WO2012174518A2 - Compositions and methods for selectively etching silicon nitride - Google Patents

Compositions and methods for selectively etching silicon nitride Download PDF

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Publication number
WO2012174518A2
WO2012174518A2 PCT/US2012/042925 US2012042925W WO2012174518A2 WO 2012174518 A2 WO2012174518 A2 WO 2012174518A2 US 2012042925 W US2012042925 W US 2012042925W WO 2012174518 A2 WO2012174518 A2 WO 2012174518A2
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WO
WIPO (PCT)
Prior art keywords
composition
ether
ammonium
glycol
silicon nitride
Prior art date
Application number
PCT/US2012/042925
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French (fr)
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WO2012174518A3 (en
Inventor
Hsing-Chen WU
Emanuel I. Cooper
Yukichi Koji
Jeffrey A. Barnes
Jieh-Hwa Shyu
Toshiyuki IDA
Yung-Hsin Huang
Heng-Kai Hsu
Wisma HSU
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Advanced Technology Materials, Inc.
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Publication of WO2012174518A2 publication Critical patent/WO2012174518A2/en
Publication of WO2012174518A3 publication Critical patent/WO2012174518A3/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31105—Etching inorganic layers
    • H01L21/31111—Etching inorganic layers by chemical means

Definitions

  • the present invention relates to a composition and process for selectively etching silicon nitride in the presence of silicon oxides, and more particularly to a composition and process for effectively and efficiently etching silicon nitride at an etch rate and selectivity that is higher than silicon oxide, particularly in a multilayer semiconductor wafer structure.
  • hot phosphoric acid etches include the corrosion of metal silicide materials, e.g., gate contact materials, the etching of silicon oxide, and process control due to the difficultly associated with maintaining a specific amount of water in the process solution.
  • metal silicide materials e.g., gate contact materials
  • etching of silicon oxide e.g., silicon oxide
  • process control due to the difficultly associated with maintaining a specific amount of water in the process solution.
  • hot phosphoric acid has been a difficult medium to adapt to single wafer tools, which have become increasingly preferred by many manufacturers.
  • Another way to selectively remove silicon nitride includes the use of a composition including hydrofluoric acid, however, said compositions also remove silicon oxides.
  • a Si 3 N 4 :Si0 2 selectivity of about 10: 1 can be achieved through dilution, however, the etch rate of silicon nitride is compromised and above-ambient pressure must be used.
  • Still another process to remove silicon nitride includes the dry etch removal using halogenated gaseous species, however, the Si 3 N 4 :Si0 2 selectivity ratio is even worse than that obtained using the aforementioned wet etch processes.
  • an object of the present invention to provide improved compositions for the selective removal of silicon nitride materials relative to silicon oxide materials while minimizing the removal or corrosion of other materials that are present, while not compromising the etch rate of the silicon nitride.
  • the present invention relates to a composition and process for selectively etching silicon nitride relative to silicon oxide from a microelectronic device comprising same.
  • Other materials e.g., metal silicides, etc., that may be present on the microelectronic device, should not be substantially removed or corroded by said compositions.
  • an etching composition comprising at least one alkoxysilane compound, at least one organic solvent, at least one oxidizing agent, at least one etchant, and water, wherein the etching composition is used to at least partially remove silicon nitride material from the surface of a microelectronic device comprising same.
  • a method of etching silicon nitride material from a surface of a microelectronic device having same thereon comprising contacting the surface with a composition comprising at least one alkoxysilane compound, at least one organic solvent, at least one oxidizing agent, at least one etchant, and water, wherein the composition at least partially removes the silicon nitride material from the surface.
  • the present invention relates to compositions that selectively remove silicon nitride relative to silicon oxide materials, and hence are useful as etchants for at least partial removal of silicon nitride material from a microelectronic device. Further, the present invention generally relates to a wet-based method for selectively removing silicon nitride relative to silicon oxide materials from a microelectronic device comprising same. Other materials, e.g., metal silicides, etc., that may be present on the microelectronic device, should not be substantially removed or corroded by said compositions.
  • microelectronic device corresponds to semiconductor substrates, flat panel displays, phase change memory devices, solar panels and other products including solar cell devices, photovoltaics, and microelectromechanical systems (MEMS), manufactured for use in microelectronic, integrated circuit, energy collection, or computer chip applications.
  • MEMS microelectromechanical systems
  • microelectronic device “microelectronic substrate” and “microelectronic device structure” are not meant to be limiting in any way and include any substrate or structure that will eventually become a microelectronic device or microelectronic assembly.
  • the microelectronic device can be patterned, blanketed, a control and/or a test device.
  • suitable for removing silicon nitride material from a microelectronic device having such nitride material thereon corresponds to at least partial removal of silicon nitride material from the microelectronic device.
  • silicon nitride and Si 3 N 4 correspond to pure silicon nitride (S1 3 N 4 ) as well as impure silicon nitride including hydrogen, carbon and/or oxygen impurities in the crystal structure.
  • silicon nitride will be referred generically as SiN x .
  • partial removal of silicon nitride material corresponds to the removal of at least a portion of the exposed silicon nitride layer.
  • partial removal of silicon nitride material includes the anisotropic removal of a silicon nitride layer that covers/protects the gate electrodes to form a SiN x sidewall.
  • the compositions described herein may be used more generally to selectively remove silicon nitride material relative to silicon oxide layers.
  • selective removal is defined as a selective removal of SiN x :Si0 2 of at least 50: 1, more preferably at least 75: 1, and most preferably at least 100:1, using the compositions described herein.
  • the "silicon oxide” or "Si0 2 " material corresponds to materials that were deposited from a silicon oxide precursor source, e.g., TEOS, thermally deposited silicon oxide, or carbon doped oxides (CDO) deposited using commercially available precursors such as SiLKTM, AURORATM, CORALTM, or BLACK DIAMONDTM.
  • silicon oxide is meant to broadly include S1O 2 , CDO's, siloxanes and thermal oxides.
  • Silicon oxide or S1O 2 material corresponds to pure silicon oxide (S1O 2 ) as well as impure silicon oxide including impurities in the structure.
  • compositions preferably possess good metal compatibility, e.g., a low etch rate on the interconnect metal and/or interconnector metal silicide material.
  • Metals of interest include, but are not limited to, copper, tungsten, cobalt, molybdenum, aluminum, tantalum, titanium and ruthenium.
  • Silicides of interest include any silicide including the species Ni, Pt, Co, Ta, Mo, W, and Ti, including but not limited to TiSi 2 , NiSi, CoSi 2 , NiPtSi, tantalum silicide, molybdenum silicide, and tungsten silicide.
  • compositions of the invention may be embodied in a wide variety of specific formulations, as hereinafter more fully described.
  • compositions wherein specific components of the composition are discussed in reference to weight percentage ranges including a zero lower limit, it will be understood that such components may be present or absent in various specific embodiments of the composition, and that in instances where such components are present, they may be present at concentrations as low as 0.001 weight percent, based on the total weight of the composition in which such components are employed.
  • composition for removing silicon nitride material from the surface of a microelectronic device having same thereon comprises, consists of, or consists essentially of at least one alkoxysilane compound, at least one organic solvent, and at least one etchant.
  • the composition for removing silicon nitride material from the surface of a microelectronic device having same thereon comprises, consists of, or consists essentially of at least one alkoxysilane compound, at least one organic solvent, at least one etchant, and at least one oxidizing agent.
  • the composition for removing silicon nitride material from the surface of a microelectronic device having same thereon comprises, consists of, or consists essentially of at least one alkoxysilane compound, at least one organic solvent, at least one etchant, at least one oxidizing agent, and water.
  • the amount of added water is no more than about 25 wt% of the total weight of the composition, preferably no more than 20 wt% of the total weight of the composition.
  • the compositions may be used to selectively remove silicon nitride material relative to silicon oxide layers, wherein the selective removal of SiN x :Si0 2 is at least 50:1, more preferably at least 75:1, and most preferably at least 100:1.
  • Organic solvents contemplated herein include, but are not limited to, glycols such as ethylene glycol, neopentyl glycol, and propylene glycol (PG), their dimers, trimers and tetramers such as dipropylene glycol, diethylene glycol (PEG), etc., alcohols such as straight chained or branched C 2 -C 6 alcohols including ethanol, propanol, butanol, pentanol, and hexanol, and glycol ethers such as 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
  • the at least one organic solvent comprises propylene glycol, diethylene glycol, or a combination thereof.
  • the alkoxysilane acts as an inhibitor of the etch rate of silicon oxide material by physisorbing and/or chemisorbing on the oxide material. This will lower the oxide etch rate thereby increasing the selectivity of the composition for silicon nitride relative to silicon oxides.
  • Alkoxysilanes contemplated have the general formula SiR ⁇ RV, wherein the R 1 , R 2 , R 3 and R 4 are the same as or different from one another and are selected from the group consisting of hydrogen, straight-chained Ci-C 6 alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl), branched Ci-C 6 alkyl groups, C r Ce alkoxy groups (e.g, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy), a phenyl group, and a combination thereof.
  • Ci-C 6 alkyl groups e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl
  • C r Ce alkoxy groups e.g, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy
  • Alkoxysilanes contemplated include trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, N-propyltrimethoxysilane, N-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, hexyltri
  • Etchants contemplated include, but are not limited to, hydrofluoric acid, ammonium fluoride, ammonium bifluoride, hexafluorosilicic acid, tetrafluoroboric acid, tetrabutylammonium tetrafluoroborate (TBA-BF 4 ), tetraalkylammonium fluoride (NR 4 F), alkyl hydrogen fluoride (NRH 3 F), dialkylammonium hydrogen fluoride (NR 2 H 2 F), trialkylammonium hydrogen fluoride (NR 3 HF), trialkylammonium trihydrogen fluoride (NR 3 :3HF), where R may be the same as or different from one another and is selected from the group consisting of straight-chained or branched Ci-C 6 alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl), and combinations thereof.
  • the fluoride source e.g.
  • Oxidizing agents contemplated herein include, but are not limited to, hydrogen peroxide (H 2 0 2 ), FeCl 3 (both hydrated and unhydrated), oxone (2KHS0 5 KHS0 4 K 2 S0 4 ), ammonium polyatomic salts (e.g., ammonium peroxomonosulfate, ammonium chlorite (NH C10 2 ), ammonium chlorate (NH C10 3 ), ammonium iodate (NH I0 3 ), ammonium nitrate (NH N0 3 ), ammonium perborate (NH B0 3 ), ammonium perchlorate (NH C10 4 ), ammonium periodate (NH 4 I0 3 ), ammonium persulfate ((NH 4 ) 2 S 2 0g), ammonium hypochlorite (NH 4 C10)), sodium polyatomic salts (e.g., sodium persulfate (Na 2 S 2 0g), sodium hypochlorite (N
  • the oxidizing agent may be introduced to the composition at the manufacturer, prior to introduction of the composition to the device wafer, or alternatively at the device wafer, i.e., in situ.
  • the oxidizing agent comprises a nitrate compound, e.g., nitric acid, ammonium nitrate, or a combination thereof.
  • the composition comprises, consists of, or consists essentially of ammonium bifluoride, propylene glycol, at least one alkoxysilane, nitric acid, and water.
  • the composition comprises, consists of, or consists essentially of ammonium bifluoride, propylene glycol, at least one alkoxysilane, ammonium nitrate, and water.
  • the composition comprises, consists of, or consists essentially of ammonium bifluoride, diethylene glycol, at least one alkoxysilane, nitric acid, and water.
  • the composition comprises, consists of, or consists essentially of ammonium bifluoride, propylene glycol, N- propyltrimethoxysilane, nitric acid, and water.
  • the composition comprises, consists of, or consists essentially of ammonium bifluoride, propylene glycol, N- propyltrimethoxysilane, ammonium nitrate, and water.
  • the composition comprises, consists of, or consists essentially of ammonium bifluoride, diethylene glycol, N-propyltrimethoxysilane, nitric acid, and water.
  • the composition is substantially devoid of abrasive material, e.g., chemical mechanical polishing material such as silica, alumina and other particulate material used for CMP, and is not used at supercritical conditions, i.e., the composition has no supercritical component. Moreover, the composition is not capable of forming a polymeric or resinous material. As defined herein, “substantially devoid” corresponds to less than about 2 wt. %, more preferably less than 1 wt. %, and most preferably less than 0.1 wt. % of the composition, based on the total weight of said composition. Moreover, when water is present, preferably the amount of added water is no more than about 25 wt% of the total weight of the composition, preferably no more than 20 wt% of the total weight of the composition.
  • abrasive material e.g., chemical mechanical polishing material such as silica, alumina and other particulate material used for CMP
  • substantially devoid corresponds to less than
  • compositions of the invention have pH value in a range from about 1 to about 7, preferably about 3 to about 7, and most preferably about 3 to about 4.
  • any of the compositions of the invention may further comprise silicon nitride material residue, wherein the silicon nitride material residue is suspended and/or dissolved in the removal composition.
  • the composition comprises, consists of, or consists essentially of at least one alkoxysilane compound, at least one organic solvent, at least one etchant, at least one oxidizing agent, and water, present in the following ranges, based on the total weight of the composition:
  • the composition may be manufactured in a more concentrated form, including at least one alkoxysilane compound, at least one organic solvent, at least one etchant, at least one oxidizing agent, and water, and thereafter diluted with at least one organic solvent at the manufacturer, before use, and/or during use at the fab.
  • Dilution ratios may be in a range from about 0.1 part diluent: 1 part composition concentrate to about 100 parts diluent: 1 part composition concentrate.
  • the compositions of the invention have pH value in a range from about 1 to about 7, preferably about 3 to about 7, and most preferably about 3 to about 4.
  • compositions described herein are easily formulated by simple addition of the respective ingredients and mixing to homogeneous condition.
  • the compositions may be readily formulated as single-package formulations or multi-part formulations that are mixed at or before the point of use, preferably multi-part formulations.
  • the individual parts of the multi-part formulation may be mixed at the tool or in a mixing region/area such as an inline mixer or in a storage tank upstream of the tool. It is contemplated that the various parts of the multi-part formulation may contain any combination of ingredients/constituents that when mixed together form the desired composition.
  • kits including, in one or more containers, one or more components adapted to form the compositions described herein.
  • the kit includes, in one or more containers, at least one alkoxysilane compound, at least one organic solvent, at least one etchant, at least one oxidizing agent, and water for combining with water and/or additional organic solvent at the fab.
  • the kit includes, in one or more containers, at least one alkoxysilane compound, at least one organic solvent, at least one etchant, and water, for combining with water, at least one organic solvent, and/or at least one oxidizing agent at the fab.
  • the containers of the kit must be suitable for storing and shipping said removal composition components, for example, NOWPak® containers (Advanced Technology Materials, Inc., Danbury, Conn., USA).
  • the one or more containers which contain the components of the composition preferably include means for bringing the components in said one or more containers in fluid communication for blending and dispense.
  • gas pressure may be applied to the outside of a liner in said one or more containers to cause at least a portion of the contents of the liner to be discharged and hence enable fluid communication for blending and dispense.
  • gas pressure may be applied to the head space of a conventional pressurizable container or a pump may be used to enable fluid communication.
  • the system preferably includes a dispensing port for dispensing the blended removal composition to a process tool.
  • Substantially chemically inert, impurity-free, flexible and resilient polymeric film materials are preferably used to fabricate the liners for said one or more containers.
  • Desirable liner materials are processed without requiring co-extrusion or barrier layers, and without any pigments, UV inhibitors, or processing agents that may adversely affect the purity requirements for components to be disposed in the liner.
  • a listing of desirable liner materials include films comprising virgin (additive-free) polyethylene, virgin polytetrafluoroethylene (PTFE), polypropylene, polyurethane, polyvinylidene chloride, polyvinylchloride, polyacetal, polystyrene, polyacrylonitrile, polybutylene, and so on.
  • Preferred thicknesses of such liner materials are in a range from about 5 mils (0.005 inch) to about 30 mils (0.030 inch), as for example a thickness of 20 mils (0.020 inch).
  • the invention relates to methods of etching silicon nitride material from the surface of the microelectronic device having same thereon using the compositions described herein.
  • silicon nitride material may be removed without substantially damaging metal and metal silicide interconnect materials.
  • the compositions preferably selectively remove silicon nitride material relative to silicon oxides.
  • a method of selectively and substantially removing silicon nitride materials relative to silicon oxide materials from the surface of the microelectronic device having same thereon is described using the compositions described herein.
  • selective removal is defined as a selective removal of SiN x :Si0 2 of at least 50:1, more preferably at least 75:1, and most preferably at least 100:1, using the compositions described herein.
  • the composition is applied in any suitable manner to the surface of the microelectronic device having the silicon nitride material thereon, e.g., by spraying the composition on the surface of the device, by dipping (in a static or dynamic volume of the composition) of the device including the silicon nitride material, by contacting the device with another material, e.g., a pad, or fibrous sorbent applicator element, that has the composition absorbed thereon, by contacting the device including the silicon nitride material with a circulating composition, or by any other suitable means, manner or technique, by which the composition is brought into removal contact with the silicon nitride material.
  • the application may be in a batch or single wafer apparatus, for dynamic or static cleaning.
  • the compositions described herein by virtue of their selectivity for silicon nitride material relative to other materials that may be present on the microelectronic device structure and exposed to the composition, such as silicon oxide(s), achieve at least partial removal of the silicon nitride material in a highly efficient and highly selective manner.
  • the composition typically is contacted with the device structure for a sufficient time of from about 1 minute to about 200 minutes, preferably about 5 minutes to about 60 minutes, at temperature in a range of from about 40°C to about 150°C, preferably about 80°C to about 120°C.
  • Such contacting times and temperatures are illustrative, and any other suitable time and temperature conditions may be employed that are efficacious to at least partially remove the silicon nitride material from the device structure.
  • the composition comprises organic solvents at the levels described herein, the method of etching silicon nitride can be carried out at higher temperatures, which allows for a higher etch rate.
  • the composition is heated inline during delivery to the device structure. By heating inline, rather than in the bath itself, the composition life increases. [0038] Following the achievement of the desired etching action, the composition can be readily removed from the microelectronic device to which it has previously been applied, e.g., by rinse, wash, or other removal step(s), as may be desired and efficacious in a given end use application of the compositions of the present invention.
  • the device may be rinsed with a rinse solution including deionized water and/or dried (e.g., spin-dry, N 2 , vapor-dry etc.).
  • compositions described herein preferably selectively etch silicon nitride material relative to silicon oxides.
  • the etch rate of silicon nitride is high (about 90 to about 100 A min "1 ), while the selectivity of SiN x :Si0 2 is moderate (about 80: 1 to about 150: 1).
  • the etch rate of silicon nitride is low (about 20 to about 50 A min "1 ), while the selectivity of SiN x :Si0 2 is high (>200: 1).
  • the etch rate of silicon nitride is moderate (about 60 to about 90 A min "1 ), while the selectivity of SiN x :Si0 2 is moderate (about 80: 1 to about 150: 1).
  • Yet another aspect of the invention relates to the improved microelectronic devices made according to the methods described herein and to products containing such microelectronic devices.
  • a still further aspect relates to methods of manufacturing an article comprising a microelectronic device, said method comprising contacting the microelectronic device with a composition for sufficient time to etchingly remove silicon nitride material from the surface of the microelectronic device having same thereon, and incorporating said microelectronic device into said article, wherein the removal composition comprises, consists of or consists essentially of at least one alkoxysilane compound, at least one organic solvent, at least one etchant, at least one oxidizing agent, and water.
  • the composition may further comprise, consist of or consist essentially of silicon nitride material.
  • Another aspect of the invention relates to an article of manufacture comprising, consisting of or consisting essentially of a microelectronic device substrate, a silicon nitride layer on said substrate, and a composition comprising, consisting of or consisting essentially of at least one alkoxysilane compound, at least one organic solvent, at least one etchant, at least one oxidizing agent, and water.

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Abstract

Compositions useful for the selective removal of silicon nitride materials relative to silicon oxide materials from a microelectronic device having same thereon. The removal compositions include at least one alkoxysilane, at least one etchant, at least one oxidizing agent, at least one organic solvent, and water.

Description

COMPOSITIONS AND METHODS FOR SELECTIVELY ETCHING SILICON
NITRIDE
FIELD
[0001] The present invention relates to a composition and process for selectively etching silicon nitride in the presence of silicon oxides, and more particularly to a composition and process for effectively and efficiently etching silicon nitride at an etch rate and selectivity that is higher than silicon oxide, particularly in a multilayer semiconductor wafer structure.
DESCRIPTION OF THE RELATED ART
[0002] Conventional wet etching techniques for selectively removing silicon nitride (Si3N4) have utilized hot (approximately 145-180°C) phosphoric acid (H3PO4) solutions with water, typically 85% phosphoric acid and 15% water (by volume). Using fresh hot phosphoric acid, the typical Si3N4:Si02 selectivity is about 40: 1. Advantageously, as the nitride layer is removed, hydrated silicon oxide forms, which consistent with Le Chatelier's principle, inhibits the additional removal of silicon oxide from the device surface; thus selectivity gradually increases with use. Disadvantages associated with the use of hot phosphoric acid etches include the corrosion of metal silicide materials, e.g., gate contact materials, the etching of silicon oxide, and process control due to the difficultly associated with maintaining a specific amount of water in the process solution. In addition, hot phosphoric acid has been a difficult medium to adapt to single wafer tools, which have become increasingly preferred by many manufacturers.
[0003] Another way to selectively remove silicon nitride includes the use of a composition including hydrofluoric acid, however, said compositions also remove silicon oxides. A Si3N4:Si02 selectivity of about 10: 1 can be achieved through dilution, however, the etch rate of silicon nitride is compromised and above-ambient pressure must be used. Still another process to remove silicon nitride includes the dry etch removal using halogenated gaseous species, however, the Si3N4:Si02 selectivity ratio is even worse than that obtained using the aforementioned wet etch processes.
[0004] Accordingly, an object of the present invention to provide improved compositions for the selective removal of silicon nitride materials relative to silicon oxide materials while minimizing the removal or corrosion of other materials that are present, while not compromising the etch rate of the silicon nitride. SUMMARY OF THE INVENTION
[0005] The present invention relates to a composition and process for selectively etching silicon nitride relative to silicon oxide from a microelectronic device comprising same. Other materials, e.g., metal silicides, etc., that may be present on the microelectronic device, should not be substantially removed or corroded by said compositions.
[0006] In one aspect, an etching composition is described, said composition comprising at least one alkoxysilane compound, at least one organic solvent, at least one oxidizing agent, at least one etchant, and water, wherein the etching composition is used to at least partially remove silicon nitride material from the surface of a microelectronic device comprising same.
[0007] In another aspect, a method of etching silicon nitride material from a surface of a microelectronic device having same thereon is described, said method comprising contacting the surface with a composition comprising at least one alkoxysilane compound, at least one organic solvent, at least one oxidizing agent, at least one etchant, and water, wherein the composition at least partially removes the silicon nitride material from the surface.
[0008] Other aspects, features and embodiments of the invention will be more fully apparent from the ensuing disclosure and appended claims.
DETAILED DESCRIPTION. AND PREFERRED EMBODIMENTS THEREOF
[0009] In general, the present invention relates to compositions that selectively remove silicon nitride relative to silicon oxide materials, and hence are useful as etchants for at least partial removal of silicon nitride material from a microelectronic device. Further, the present invention generally relates to a wet-based method for selectively removing silicon nitride relative to silicon oxide materials from a microelectronic device comprising same. Other materials, e.g., metal silicides, etc., that may be present on the microelectronic device, should not be substantially removed or corroded by said compositions.
[0010] For ease of reference, "microelectronic device" corresponds to semiconductor substrates, flat panel displays, phase change memory devices, solar panels and other products including solar cell devices, photovoltaics, and microelectromechanical systems (MEMS), manufactured for use in microelectronic, integrated circuit, energy collection, or computer chip applications. It is to be understood that the terms "microelectronic device," "microelectronic substrate" and "microelectronic device structure" are not meant to be limiting in any way and include any substrate or structure that will eventually become a microelectronic device or microelectronic assembly. The microelectronic device can be patterned, blanketed, a control and/or a test device. [0011] As used herein, "suitability" for removing silicon nitride material from a microelectronic device having such nitride material thereon corresponds to at least partial removal of silicon nitride material from the microelectronic device.
[0012] As used herein, "silicon nitride" and "Si3N4" correspond to pure silicon nitride (S13N4) as well as impure silicon nitride including hydrogen, carbon and/or oxygen impurities in the crystal structure. For the purpose of this description, silicon nitride will be referred generically as SiNx.
[0013] As used herein, "at least partial removal of silicon nitride material" corresponds to the removal of at least a portion of the exposed silicon nitride layer. For example, partial removal of silicon nitride material includes the anisotropic removal of a silicon nitride layer that covers/protects the gate electrodes to form a SiNx sidewall. Further, the compositions described herein may be used more generally to selectively remove silicon nitride material relative to silicon oxide layers. In those circumstances, "selective removal" is defined as a selective removal of SiNx:Si02 of at least 50: 1, more preferably at least 75: 1, and most preferably at least 100:1, using the compositions described herein.
[0014] As used herein, "about" is intended to correspond to ± 5 % of the stated value.
[0015] As described herein, the "silicon oxide" or "Si02" material corresponds to materials that were deposited from a silicon oxide precursor source, e.g., TEOS, thermally deposited silicon oxide, or carbon doped oxides (CDO) deposited using commercially available precursors such as SiLK™, AURORA™, CORAL™, or BLACK DIAMOND™. For the purposes of this description, "silicon oxide" is meant to broadly include S1O2, CDO's, siloxanes and thermal oxides. Silicon oxide or S1O2 material corresponds to pure silicon oxide (S1O2) as well as impure silicon oxide including impurities in the structure.
[0016] It is understood that some chemical components naturally include negligible amounts of water when in their lowest energy, i.e., stable, state, particularly as purchased commercially. For the purpose of this description, naturally present water is not considered added water.
[0017] The compositions preferably possess good metal compatibility, e.g., a low etch rate on the interconnect metal and/or interconnector metal silicide material. Metals of interest include, but are not limited to, copper, tungsten, cobalt, molybdenum, aluminum, tantalum, titanium and ruthenium. Silicides of interest include any silicide including the species Ni, Pt, Co, Ta, Mo, W, and Ti, including but not limited to TiSi2, NiSi, CoSi2, NiPtSi, tantalum silicide, molybdenum silicide, and tungsten silicide.
[0018] Compositions of the invention may be embodied in a wide variety of specific formulations, as hereinafter more fully described.
[0019] In all such compositions, wherein specific components of the composition are discussed in reference to weight percentage ranges including a zero lower limit, it will be understood that such components may be present or absent in various specific embodiments of the composition, and that in instances where such components are present, they may be present at concentrations as low as 0.001 weight percent, based on the total weight of the composition in which such components are employed.
[0020] In one aspect, a composition for removing silicon nitride material from the surface of a microelectronic device having same thereon is described, said composition including at least one alkoxysilane compound. In one embodiment, the composition for removing silicon nitride material from the surface of a microelectronic device having same thereon comprises, consists of, or consists essentially of at least one alkoxysilane compound, at least one organic solvent, and at least one etchant. In another embodiment, the composition for removing silicon nitride material from the surface of a microelectronic device having same thereon comprises, consists of, or consists essentially of at least one alkoxysilane compound, at least one organic solvent, at least one etchant, and at least one oxidizing agent. In still another embodiment, the composition for removing silicon nitride material from the surface of a microelectronic device having same thereon comprises, consists of, or consists essentially of at least one alkoxysilane compound, at least one organic solvent, at least one etchant, at least one oxidizing agent, and water. When water is present, preferably the amount of added water is no more than about 25 wt% of the total weight of the composition, preferably no more than 20 wt% of the total weight of the composition. If silicon oxide is present during the silicon nitride removal, the compositions may be used to selectively remove silicon nitride material relative to silicon oxide layers, wherein the selective removal of SiNx:Si02 is at least 50:1, more preferably at least 75:1, and most preferably at least 100:1.
[0021] Organic solvents contemplated herein include, but are not limited to, glycols such as ethylene glycol, neopentyl glycol, and propylene glycol (PG), their dimers, trimers and tetramers such as dipropylene glycol, diethylene glycol (PEG), etc., alcohols such as straight chained or branched C2-C6 alcohols including ethanol, propanol, butanol, pentanol, and hexanol, and glycol ethers such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether, propylene glycol monoethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether (DPGBE), tripropylene glycol n-butyl ether, propylene glycol phenyl ether (phenoxy-2- propanol) and combinations thereof. Preferably, the at least one organic solvent comprises propylene glycol, diethylene glycol, or a combination thereof. [0022] Although not wishing to be bound by theory, it is thought that the alkoxysilane acts as an inhibitor of the etch rate of silicon oxide material by physisorbing and/or chemisorbing on the oxide material. This will lower the oxide etch rate thereby increasing the selectivity of the composition for silicon nitride relative to silicon oxides. Alkoxysilanes contemplated have the general formula SiR^RV, wherein the R1, R2, R3 and R4 are the same as or different from one another and are selected from the group consisting of hydrogen, straight-chained Ci-C6 alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl), branched Ci-C6 alkyl groups, Cr Ce alkoxy groups (e.g, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy), a phenyl group, and a combination thereof. It should be appreciated by the skilled artisan, that to be characterized as an alkoxysilane, at least one of R1, R2, R3 or R4 must be a C1-C6 alkoxy group. Alkoxysilanes contemplated include trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, N-propyltrimethoxysilane, N-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and combinations thereof. Preferably, the alkoxysilane comprises N-propyltrimethoxysilane.
[0023] Etchants contemplated include, but are not limited to, hydrofluoric acid, ammonium fluoride, ammonium bifluoride, hexafluorosilicic acid, tetrafluoroboric acid, tetrabutylammonium tetrafluoroborate (TBA-BF4), tetraalkylammonium fluoride (NR4F), alkyl hydrogen fluoride (NRH3F), dialkylammonium hydrogen fluoride (NR2H2F), trialkylammonium hydrogen fluoride (NR3HF), trialkylammonium trihydrogen fluoride (NR3:3HF), where R may be the same as or different from one another and is selected from the group consisting of straight-chained or branched Ci-C6 alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl), and combinations thereof. Preferably, the fluoride source comprises ammonium bifluoride.
[0024] Oxidizing agents contemplated herein include, but are not limited to, hydrogen peroxide (H202), FeCl3 (both hydrated and unhydrated), oxone (2KHS05 KHS04 K2S04), ammonium polyatomic salts (e.g., ammonium peroxomonosulfate, ammonium chlorite (NH C102), ammonium chlorate (NH C103), ammonium iodate (NH I03), ammonium nitrate (NH N03), ammonium perborate (NH B03), ammonium perchlorate (NH C104), ammonium periodate (NH4I03), ammonium persulfate ((NH4)2S20g), ammonium hypochlorite (NH4C10)), sodium polyatomic salts (e.g., sodium persulfate (Na2S20g), sodium hypochlorite (NaCIO)), potassium polyatomic salts (e.g., potassium iodate (KI03), potassium permanganate (KMn04), potassium persulfate, nitric acid (HN03), potassium persulfate (K2S20g), potassium hypochlorite (KCIO)), tetramethylammonium polyatomic salts (e.g., tetramethylammonium chlorite ((N(CH3)4)C102), tetramethylammonium chlorate ((N(CH3)4)C103), tetramethylammonium iodate ((N(CH3)4)I03), tetramethylammonium perborate ((N(CH3)4)B03), tetramethylammonium perchlorate ((N(CH3)4)C10 ), tetramethylammonium periodate ((N(CH3)4)I04), tetramethylammonium persulfate ((N(CH3)4)S208)), tetrabutylammonium polyatomic salts (e.g., tetrabutylammonium peroxomonosulfate), peroxomonosulfuric acid, ferric nitrate (Fe(N03)3), urea hydrogen peroxide ((CO(NH2)2)H202), peracetic acid (CH3(CO)OOH), and combinations thereof. The oxidizing agent may be introduced to the composition at the manufacturer, prior to introduction of the composition to the device wafer, or alternatively at the device wafer, i.e., in situ. Preferably, the oxidizing agent comprises a nitrate compound, e.g., nitric acid, ammonium nitrate, or a combination thereof.
[0025] In a particularly preferred embodiment, the composition comprises, consists of, or consists essentially of ammonium bifluoride, propylene glycol, at least one alkoxysilane, nitric acid, and water. In another embodiment, the composition comprises, consists of, or consists essentially of ammonium bifluoride, propylene glycol, at least one alkoxysilane, ammonium nitrate, and water. In still another embodiment, the composition comprises, consists of, or consists essentially of ammonium bifluoride, diethylene glycol, at least one alkoxysilane, nitric acid, and water. In a particularly preferred embodiment, the composition comprises, consists of, or consists essentially of ammonium bifluoride, propylene glycol, N- propyltrimethoxysilane, nitric acid, and water. In another embodiment, the composition comprises, consists of, or consists essentially of ammonium bifluoride, propylene glycol, N- propyltrimethoxysilane, ammonium nitrate, and water. In still another embodiment, the composition comprises, consists of, or consists essentially of ammonium bifluoride, diethylene glycol, N-propyltrimethoxysilane, nitric acid, and water.
[0026] In one embodiment, the composition is substantially devoid of abrasive material, e.g., chemical mechanical polishing material such as silica, alumina and other particulate material used for CMP, and is not used at supercritical conditions, i.e., the composition has no supercritical component. Moreover, the composition is not capable of forming a polymeric or resinous material. As defined herein, "substantially devoid" corresponds to less than about 2 wt. %, more preferably less than 1 wt. %, and most preferably less than 0.1 wt. % of the composition, based on the total weight of said composition. Moreover, when water is present, preferably the amount of added water is no more than about 25 wt% of the total weight of the composition, preferably no more than 20 wt% of the total weight of the composition.
[0027] The compositions of the invention have pH value in a range from about 1 to about 7, preferably about 3 to about 7, and most preferably about 3 to about 4.
[0028] In another embodiment, any of the compositions of the invention may further comprise silicon nitride material residue, wherein the silicon nitride material residue is suspended and/or dissolved in the removal composition.
[0001] In one embodiment, the composition comprises, consists of, or consists essentially of at least one alkoxysilane compound, at least one organic solvent, at least one etchant, at least one oxidizing agent, and water, present in the following ranges, based on the total weight of the composition:
component % by weight more preferred most preferred
% by weight % by weight alkoxysilane(s) about 0.01% to about 0.1% to about 0.5% to about 5% about 3%) about 2%> organic solvent(s) about 50% to about 70% to about 75%) to about 99% about 98% about 90% etchant(s) about 0.01% to about 0.1% to about 0.1% to about 5%> about 2%> about 1%) oxidizing agent(s) about 0.01% to about 0.05% to about 0.1% to about 5%> about 1%) about 1%) water about 1%) to about about 5%> to about 10% to
35% about 25% about 20%
[0029] It will be appreciated that it is common practice to make concentrated forms of the compositions to be diluted prior to use. For example, the composition may be manufactured in a more concentrated form, including at least one alkoxysilane compound, at least one organic solvent, at least one etchant, at least one oxidizing agent, and water, and thereafter diluted with at least one organic solvent at the manufacturer, before use, and/or during use at the fab. Dilution ratios may be in a range from about 0.1 part diluent: 1 part composition concentrate to about 100 parts diluent: 1 part composition concentrate. Upon dilution, the compositions of the invention have pH value in a range from about 1 to about 7, preferably about 3 to about 7, and most preferably about 3 to about 4.
[0030] The compositions described herein are easily formulated by simple addition of the respective ingredients and mixing to homogeneous condition. Furthermore, the compositions may be readily formulated as single-package formulations or multi-part formulations that are mixed at or before the point of use, preferably multi-part formulations. The individual parts of the multi-part formulation may be mixed at the tool or in a mixing region/area such as an inline mixer or in a storage tank upstream of the tool. It is contemplated that the various parts of the multi-part formulation may contain any combination of ingredients/constituents that when mixed together form the desired composition. The concentrations of the respective ingredients may be widely varied in specific multiples of the composition, i.e., more dilute or more concentrated, and it will be appreciated that the compositions can variously and alternatively comprise, consist or consist essentially of any combination of ingredients consistent with the disclosure herein. [0031] Accordingly, another aspect relates to a kit including, in one or more containers, one or more components adapted to form the compositions described herein. Preferably, the kit includes, in one or more containers, at least one alkoxysilane compound, at least one organic solvent, at least one etchant, at least one oxidizing agent, and water for combining with water and/or additional organic solvent at the fab. Alternatively, the kit includes, in one or more containers, at least one alkoxysilane compound, at least one organic solvent, at least one etchant, and water, for combining with water, at least one organic solvent, and/or at least one oxidizing agent at the fab. It will be appreciated by one skilled in the art that other combinations are contemplated herein. The containers of the kit must be suitable for storing and shipping said removal composition components, for example, NOWPak® containers (Advanced Technology Materials, Inc., Danbury, Conn., USA). The one or more containers which contain the components of the composition preferably include means for bringing the components in said one or more containers in fluid communication for blending and dispense. For example, referring to the NOWPak® containers, gas pressure may be applied to the outside of a liner in said one or more containers to cause at least a portion of the contents of the liner to be discharged and hence enable fluid communication for blending and dispense. Alternatively, gas pressure may be applied to the head space of a conventional pressurizable container or a pump may be used to enable fluid communication. In addition, the system preferably includes a dispensing port for dispensing the blended removal composition to a process tool.
[0032] Substantially chemically inert, impurity-free, flexible and resilient polymeric film materials, such as high density polyethylene, are preferably used to fabricate the liners for said one or more containers. Desirable liner materials are processed without requiring co-extrusion or barrier layers, and without any pigments, UV inhibitors, or processing agents that may adversely affect the purity requirements for components to be disposed in the liner. A listing of desirable liner materials include films comprising virgin (additive-free) polyethylene, virgin polytetrafluoroethylene (PTFE), polypropylene, polyurethane, polyvinylidene chloride, polyvinylchloride, polyacetal, polystyrene, polyacrylonitrile, polybutylene, and so on. Preferred thicknesses of such liner materials are in a range from about 5 mils (0.005 inch) to about 30 mils (0.030 inch), as for example a thickness of 20 mils (0.020 inch).
[0033] Regarding the containers for the kits, the disclosures of the following patents and patent applications are hereby incorporated herein by reference in their respective entireties: U.S. Patent No. 7,188,644 entitled "APPARATUS AND METHOD FOR MINIMIZING THE GENERATION OF PARTICLES IN ULTRAPURE LIQUIDS;" U.S. Patent No. 6,698,619 entitled "RETURNABLE AND REUSABLE, BAG-IN-DRUM FLUID STORAGE AND DISPENSING CONTAINER SYSTEM;" and PCT/US08/63276 entitled "SYSTEMS AND METHODS FOR MATERIAL BLENDING AND DISTRIBUTION" filed on May 9, 2008. [0034] In yet another aspect, the invention relates to methods of etching silicon nitride material from the surface of the microelectronic device having same thereon using the compositions described herein. For example, silicon nitride material may be removed without substantially damaging metal and metal silicide interconnect materials. In addition, the compositions preferably selectively remove silicon nitride material relative to silicon oxides. Accordingly, in a preferred embodiment, a method of selectively and substantially removing silicon nitride materials relative to silicon oxide materials from the surface of the microelectronic device having same thereon is described using the compositions described herein. As previously defined, "selective removal" is defined as a selective removal of SiNx:Si02 of at least 50:1, more preferably at least 75:1, and most preferably at least 100:1, using the compositions described herein.
[0035] In etching applications, the composition is applied in any suitable manner to the surface of the microelectronic device having the silicon nitride material thereon, e.g., by spraying the composition on the surface of the device, by dipping (in a static or dynamic volume of the composition) of the device including the silicon nitride material, by contacting the device with another material, e.g., a pad, or fibrous sorbent applicator element, that has the composition absorbed thereon, by contacting the device including the silicon nitride material with a circulating composition, or by any other suitable means, manner or technique, by which the composition is brought into removal contact with the silicon nitride material. The application may be in a batch or single wafer apparatus, for dynamic or static cleaning. Advantageously, the compositions described herein, by virtue of their selectivity for silicon nitride material relative to other materials that may be present on the microelectronic device structure and exposed to the composition, such as silicon oxide(s), achieve at least partial removal of the silicon nitride material in a highly efficient and highly selective manner.
[0036] In use of the compositions described herein for removing silicon nitride material from microelectronic device structures having same thereon, the composition typically is contacted with the device structure for a sufficient time of from about 1 minute to about 200 minutes, preferably about 5 minutes to about 60 minutes, at temperature in a range of from about 40°C to about 150°C, preferably about 80°C to about 120°C. Such contacting times and temperatures are illustrative, and any other suitable time and temperature conditions may be employed that are efficacious to at least partially remove the silicon nitride material from the device structure. Advantageously, when the composition comprises organic solvents at the levels described herein, the method of etching silicon nitride can be carried out at higher temperatures, which allows for a higher etch rate.
[0037] In one embodiment, the composition is heated inline during delivery to the device structure. By heating inline, rather than in the bath itself, the composition life increases. [0038] Following the achievement of the desired etching action, the composition can be readily removed from the microelectronic device to which it has previously been applied, e.g., by rinse, wash, or other removal step(s), as may be desired and efficacious in a given end use application of the compositions of the present invention. For example, the device may be rinsed with a rinse solution including deionized water and/or dried (e.g., spin-dry, N2, vapor-dry etc.).
[0039] The compositions described herein preferably selectively etch silicon nitride material relative to silicon oxides. In one embodiment, the etch rate of silicon nitride is high (about 90 to about 100 A min"1), while the selectivity of SiNx:Si02 is moderate (about 80: 1 to about 150: 1). In another embodiment, the etch rate of silicon nitride is low (about 20 to about 50 A min"1), while the selectivity of SiNx:Si02 is high (>200: 1). In yet another embodiment, the etch rate of silicon nitride is moderate (about 60 to about 90 A min"1), while the selectivity of SiNx:Si02 is moderate (about 80: 1 to about 150: 1).
[0040] Yet another aspect of the invention relates to the improved microelectronic devices made according to the methods described herein and to products containing such microelectronic devices.
[0041] A still further aspect relates to methods of manufacturing an article comprising a microelectronic device, said method comprising contacting the microelectronic device with a composition for sufficient time to etchingly remove silicon nitride material from the surface of the microelectronic device having same thereon, and incorporating said microelectronic device into said article, wherein the removal composition comprises, consists of or consists essentially of at least one alkoxysilane compound, at least one organic solvent, at least one etchant, at least one oxidizing agent, and water. The composition may further comprise, consist of or consist essentially of silicon nitride material.
[0042] Another aspect of the invention relates to an article of manufacture comprising, consisting of or consisting essentially of a microelectronic device substrate, a silicon nitride layer on said substrate, and a composition comprising, consisting of or consisting essentially of at least one alkoxysilane compound, at least one organic solvent, at least one etchant, at least one oxidizing agent, and water.
[0043] The features and advantages of the invention are more fully shown by the illustrative examples discussed below.
Example 1
[0044] Five compositions were prepared as described below in Table 1. Thermal oxide and silicon nitride coupons were immersed in each composition at 110°C for 30 minutes and 10 minutes, respectively and the etch rate of each determined using ellipsometry. The results, including the selectivity of SiNx:Si02 are provided in Table 1.
Figure imgf000012_0001
* * *
[0045] While the invention has been described herein in reference to specific aspects, features and illustrative embodiments of the invention, it will be appreciated that the utility of the invention is not thus limited, but rather extends to and encompasses numerous other variations, modifications and alternative embodiments, as will suggest themselves to those of ordinary skill in the field of the present invention, based on the disclosure herein. Correspondingly, the invention as hereinafter claimed is intended to be broadly construed and interpreted, as including all such variations, modifications and alternative embodiments, within its spirit and scope.

Claims

THE CLAIMS What is claimed is:
1. An etching composition, said composition comprising at least one alkoxysilane compound, at least one organic solvent, at least one oxidizing agent, at least one etchant, and water, wherein the etching composition is used to at least partially remove silicon nitride material from the surface of a microelectronic device comprising same.
2. The etching composition of claim 1, wherein the amount of added water is less than about 25 wt%, based on the total weight of the composition
3. The etching composition of any of claims 1 -2, wherein the organic solvent comprises a species selected from the group consisting of ethylene glycol, neopentyl glycol, propylene glycol (PG), dipropylene glycol, diethylene glycol (PEG), ethanol, propanol, butanol, pentanol, hexanol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether, propylene glycol monoethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether (DPGBE), tripropylene glycol n-butyl ether, propylene glycol phenyl ether (phenoxy-2-propanol) and combinations thereof.
4. The etching composition of any of claims 1-2, wherein the at least one organic solvent comprises propylene glycol or diethylene glycol.
5. The etching composition of any of claims 1-4, wherein the alkoxysilane has the formula SiR^R , wherein the R1, R2, R3 and R4 are the same as or different from one another and are selected from the group consisting of hydrogen, straight-chained C1-C6 alkyl groups, branched C1-C6 alkyl groups, C1-C6 alkoxy groups, a phenyl group, and a combination thereof, with the proviso that at least one of R1, R2, R3 or R4 is a Ci-C6 alkoxy group.
6. The etching composition of any of claims 1-4, wherein the alkoxysilane comprises a species selected from the group consisting of trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, N-propyltrimethoxysilane, N-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and combinations thereof.
7. The etching composition of any of claims 1 -4, wherein the alkoxysilane comprises N- propyltrimethoxysilane .
8. The etching composition of any of claims 1 -7, wherein the etchant comprises a species selected from the group consisting of hydrofluoric acid, ammonium fluoride, ammonium bifluoride, hexafluorosilicic acid, tetrafluoroboric acid, tetrabutylammonium tetrafluoroborate (TBA-BF4), tetraalkylammonium fluoride (NR4F), alkyl hydrogen fluoride (NRH3F), dialkylammonium hydrogen fluoride (NR2H2F), trialkylammonium hydrogen fluoride (NR3HF), trialkylammonium trihydrogen fluoride (NR3:3HF), where R may be the same as or different from one another and is selected from the group consisting of straight-chained or branched Ci-C6 alkyl groups, and combinations thereof.
9. The etching composition of any of claims 1 -7, wherein the etchant comprises ammonium bifluoride.
10. The etching composition of any of claims 1 -9, wherein the at least one oxidizing agent comprises a species selected from the group consisting of hydrogen peroxide, FeCl3 oxone, ammonium peroxomonosulfate, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium nitrate, ammonium perborate, ammonium perchlorate, ammonium periodate, ammonium persulfate, ammonium hypochlorite, sodium persulfate, sodium hypochlorite, potassium iodate, potassium permanganate, potassium persulfate, nitric acid, potassium persulfate, potassium hypochlorite, tetramethylammonium chlorite, tetramethylammonium chlorate, tetramethylammonium iodate, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, tetramethylammonium persulfate, tetrabutylammonium peroxomonosulfate, peroxomonosulfuric acid, ferric nitrate, urea hydrogen peroxide, peracetic acid, and combinations thereof.
1 1. The etching composition of any of claims 1 -9, wherein the at least one oxidizing agent comprises nitric acid.
12. The composition of claim 1 , comprising components selected from the group consisting of: ammonium bifluoride, propylene glycol, N-propyltrimethoxysilane, nitric acid, and water; ammonium bifluoride, propylene glycol, N-propyltrimethoxysilane, ammonium nitrate; and water; and
ammonium bifluoride, diethylene glycol, N-propyltrimethoxysilane, nitric acid, and water.
13. The composition of any of claims 1 -12, wherein the pH is in a range from about 1 to about 7.
14. The composition of any of claims 1 -12, wherein the pH is in a range from about 3 to about 7.
15. The composition of any of claims 1-14, wherein the composition further comprises silicon nitride material residue.
16. A method of etching silicon nitride material from a surface of a microelectronic device having same thereon, said method comprising contacting the surface with a composition of any of claims 1-15, wherein the composition at least partially removes the silicon nitride material from the surface.
17. The method of claim 16, wherein the composition selectively removes silicon nitride material relative to silicon oxide material.
18. The method of claim 17, wherein the selectively of SiNx:Si02 removal is at least 50: 1.
19. The method of any of claims 16-18, wherein the contacting comprises time in a range from about 1 minute to about 200 minutes at temperature in a range of from about 40°C to about 150°C.
20. The method of any of claims 16-19, wherein the composition is heated inline during delivery to the device structure.
21. The method of any of claims 16-20, wherein the composition is rinsed from the surface following the desired etching action.
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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9175404B2 (en) 2011-09-30 2015-11-03 Advanced Technology Materials, Inc. Etching agent for copper or copper alloy
US9546321B2 (en) 2011-12-28 2017-01-17 Advanced Technology Materials, Inc. Compositions and methods for selectively etching titanium nitride
US9678430B2 (en) 2012-05-18 2017-06-13 Entegris, Inc. Composition and process for stripping photoresist from a surface including titanium nitride
US9765288B2 (en) 2012-12-05 2017-09-19 Entegris, Inc. Compositions for cleaning III-V semiconductor materials and methods of using same
KR20180075691A (en) * 2015-11-23 2018-07-04 엔테그리스, 아이엔씨. Compositions and methods for selectively etching p-doped polysilicon relative to silicon nitride
US10138117B2 (en) 2013-07-31 2018-11-27 Entegris, Inc. Aqueous formulations for removing metal hard mask and post-etch residue with Cu/W compatibility
US10176979B2 (en) 2012-02-15 2019-01-08 Entegris, Inc. Post-CMP removal using compositions and method of use
KR20190042516A (en) * 2019-04-15 2019-04-24 세메스 주식회사 Substrate treating apparatus and substrate treating method
US20190136090A1 (en) * 2016-12-26 2019-05-09 Soulbrain Co., Ltd. Composition for etching and manufacturing method of semiconductor device using the same
US10340150B2 (en) 2013-12-16 2019-07-02 Entegris, Inc. Ni:NiGe:Ge selective etch formulations and method of using same
US10347504B2 (en) 2013-12-20 2019-07-09 Entegris, Inc. Use of non-oxidizing strong acids for the removal of ion-implanted resist
US10428271B2 (en) 2013-08-30 2019-10-01 Entegris, Inc. Compositions and methods for selectively etching titanium nitride
US10475658B2 (en) 2013-12-31 2019-11-12 Entegris, Inc. Formulations to selectively etch silicon and germanium
US10472567B2 (en) 2013-03-04 2019-11-12 Entegris, Inc. Compositions and methods for selectively etching titanium nitride
US10557107B2 (en) 2014-01-29 2020-02-11 Entegris, Inc. Post chemical mechanical polishing formulations and method of use
WO2020185762A1 (en) * 2019-03-11 2020-09-17 Versum Materials Us, Llc Etching solution and method for selectively removing silicon nitride during manufacture of a semiconductor device
US10920141B2 (en) 2013-06-06 2021-02-16 Entegris, Inc. Compositions and methods for selectively etching titanium nitride
US11127587B2 (en) 2014-02-05 2021-09-21 Entegris, Inc. Non-amine post-CMP compositions and method of use
US11186771B2 (en) 2017-06-05 2021-11-30 Versum Materials Us, Llc Etching solution for selectively removing silicon nitride during manufacture of a semiconductor device
CN114717559A (en) * 2022-03-03 2022-07-08 深圳市金泉益科技有限公司 Titanium etching solution and application thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10995269B2 (en) * 2016-11-24 2021-05-04 Samsung Electronics Co., Ltd. Etchant composition and method of fabricating integrated circuit device using the same
CN111019659B (en) * 2019-12-06 2021-06-08 湖北兴福电子材料有限公司 Selective silicon etching liquid
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6162370A (en) * 1998-08-28 2000-12-19 Ashland Inc. Composition and method for selectively etching a silicon nitride film
KR20090030702A (en) * 2007-09-20 2009-03-25 주식회사 하이닉스반도체 Etchant for removing insulating layer
WO2009073596A2 (en) * 2007-11-30 2009-06-11 Advanced Technology Materials, Inc. Formulations for cleaning memory device structures
US20100176082A1 (en) * 2006-12-21 2010-07-15 Advanced Technology Materials, Inc. Compositions and methods for the selective removal of silicon nitride

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6162370A (en) * 1998-08-28 2000-12-19 Ashland Inc. Composition and method for selectively etching a silicon nitride film
US20100176082A1 (en) * 2006-12-21 2010-07-15 Advanced Technology Materials, Inc. Compositions and methods for the selective removal of silicon nitride
KR20090030702A (en) * 2007-09-20 2009-03-25 주식회사 하이닉스반도체 Etchant for removing insulating layer
WO2009073596A2 (en) * 2007-11-30 2009-06-11 Advanced Technology Materials, Inc. Formulations for cleaning memory device structures

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9790600B2 (en) 2011-09-30 2017-10-17 Entegris, Inc. Etching agent for copper or copper alloy
US9175404B2 (en) 2011-09-30 2015-11-03 Advanced Technology Materials, Inc. Etching agent for copper or copper alloy
US10392560B2 (en) 2011-12-28 2019-08-27 Entegris, Inc. Compositions and methods for selectively etching titanium nitride
US9546321B2 (en) 2011-12-28 2017-01-17 Advanced Technology Materials, Inc. Compositions and methods for selectively etching titanium nitride
US10176979B2 (en) 2012-02-15 2019-01-08 Entegris, Inc. Post-CMP removal using compositions and method of use
US9678430B2 (en) 2012-05-18 2017-06-13 Entegris, Inc. Composition and process for stripping photoresist from a surface including titanium nitride
US9765288B2 (en) 2012-12-05 2017-09-19 Entegris, Inc. Compositions for cleaning III-V semiconductor materials and methods of using same
US10472567B2 (en) 2013-03-04 2019-11-12 Entegris, Inc. Compositions and methods for selectively etching titanium nitride
US10920141B2 (en) 2013-06-06 2021-02-16 Entegris, Inc. Compositions and methods for selectively etching titanium nitride
US10138117B2 (en) 2013-07-31 2018-11-27 Entegris, Inc. Aqueous formulations for removing metal hard mask and post-etch residue with Cu/W compatibility
US10428271B2 (en) 2013-08-30 2019-10-01 Entegris, Inc. Compositions and methods for selectively etching titanium nitride
US10340150B2 (en) 2013-12-16 2019-07-02 Entegris, Inc. Ni:NiGe:Ge selective etch formulations and method of using same
US10347504B2 (en) 2013-12-20 2019-07-09 Entegris, Inc. Use of non-oxidizing strong acids for the removal of ion-implanted resist
US10475658B2 (en) 2013-12-31 2019-11-12 Entegris, Inc. Formulations to selectively etch silicon and germanium
US10557107B2 (en) 2014-01-29 2020-02-11 Entegris, Inc. Post chemical mechanical polishing formulations and method of use
US11127587B2 (en) 2014-02-05 2021-09-21 Entegris, Inc. Non-amine post-CMP compositions and method of use
KR102090307B1 (en) * 2015-11-23 2020-03-17 엔테그리스, 아이엔씨. Composition and method for selectively etching p-doped polysilicon compared to silicon nitride
EP3381046A4 (en) * 2015-11-23 2019-07-10 Entegris, Inc. Composition and process for selectively etching p-doped polysilicon relative to silicon nitride
KR20180075691A (en) * 2015-11-23 2018-07-04 엔테그리스, 아이엔씨. Compositions and methods for selectively etching p-doped polysilicon relative to silicon nitride
US10991809B2 (en) 2015-11-23 2021-04-27 Entegris, Inc. Composition and process for selectively etching p-doped polysilicon relative to silicon nitride
US11912902B2 (en) * 2016-12-26 2024-02-27 Soulbrain Co., Ltd. Composition for etching and manufacturing method of semiconductor device using the same
US20190136090A1 (en) * 2016-12-26 2019-05-09 Soulbrain Co., Ltd. Composition for etching and manufacturing method of semiconductor device using the same
US11186771B2 (en) 2017-06-05 2021-11-30 Versum Materials Us, Llc Etching solution for selectively removing silicon nitride during manufacture of a semiconductor device
WO2020185762A1 (en) * 2019-03-11 2020-09-17 Versum Materials Us, Llc Etching solution and method for selectively removing silicon nitride during manufacture of a semiconductor device
CN113557287A (en) * 2019-03-11 2021-10-26 弗萨姆材料美国有限责任公司 Etching solution and method for selectively removing silicon nitride in semiconductor device manufacturing process
US20220157613A1 (en) * 2019-03-11 2022-05-19 Versum Materials Us, Llc Etching Solution And Method For Selectively Removing Silicon Nitride During Manufacture Of A Semiconductor Device
CN113557287B (en) * 2019-03-11 2023-03-24 弗萨姆材料美国有限责任公司 Etching solution and method for selectively removing silicon nitride in semiconductor device manufacturing process
US11955341B2 (en) 2019-03-11 2024-04-09 Versum Materials Us, Llc Etching solution and method for selectively removing silicon nitride during manufacture of a semiconductor device
KR20190042516A (en) * 2019-04-15 2019-04-24 세메스 주식회사 Substrate treating apparatus and substrate treating method
KR102081708B1 (en) * 2019-04-15 2020-02-27 세메스 주식회사 Substrate treating apparatus and substrate treating method
CN114717559A (en) * 2022-03-03 2022-07-08 深圳市金泉益科技有限公司 Titanium etching solution and application thereof

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