WO2016042408A2 - Compositions for etching titanium nitride having compatability with silicon germanide and tungsten - Google Patents

Compositions for etching titanium nitride having compatability with silicon germanide and tungsten Download PDF

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Publication number
WO2016042408A2
WO2016042408A2 PCT/IB2015/002015 IB2015002015W WO2016042408A2 WO 2016042408 A2 WO2016042408 A2 WO 2016042408A2 IB 2015002015 W IB2015002015 W IB 2015002015W WO 2016042408 A2 WO2016042408 A2 WO 2016042408A2
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composition
ether
acid
ammonium
glycol
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PCT/IB2015/002015
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French (fr)
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WO2016042408A3 (en
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Hsing-Chen WU
Min-Chieh Yang
Sheng-Hung Tu
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Atmi Taiwan Co., Ltd.
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Publication of WO2016042408A2 publication Critical patent/WO2016042408A2/en
Publication of WO2016042408A3 publication Critical patent/WO2016042408A3/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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
    • 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
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
    • H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • H01L21/31144—Etching the insulating layers by chemical or physical means using masks

Definitions

  • the present invention relates to a composition and process for selectively etching titanium nitride and/or photoresist etch residues in the presence of semiconductor substrates, metal conductor, and insulator materials (i.e., low-k dielectrics), and more particularly to a composition and process for effectively and efficiently etching titanium nitride and/or photoresist etch residues at an etch rate and selectivity that is higher than that of exposed or underlying layers of copper, tungsten, silicon germanide, germanium, and low-k dielectric materials.
  • Photoresist masks are commonly used in the semiconductor industry to pattern materials such as semiconductors or dielectrics.
  • photoresist masks are used in a dual damascene process to form interconnects in the back-end metallization of a microelectronic device.
  • the dual damascene process involves forming a photoresist mask on a low-k dielectric layer overlying a metal conductor layer, such as a copper layer.
  • the low-k dielectric layer is then etched according to the photoresist mask to form a via and/ or trench that expose the metal conductor layer.
  • the via and trench commonly known as dual damascene structure, are usually defined using two lithography steps.
  • the photoresist mask is then removed from the low-k dielectric layer before a conductive material is deposited into the via and/or trench to form an interconnect.
  • metal hard masks are used to provide better profile control of vias and trenches.
  • the metal hard masks can comprise titanium or titanium nitride, and are removed by a wet etching process after forming the via and/or trench of the dual damascene structure. It is essential that the wet etching process uses a removal chemistry that effectively removes the metal hard mask and/or photoresist etch residues without affecting the underlying semiconductor substrates, metal conductor layer, and low-k dielectric material. In other words, the removal chemistry is required to be highly selective to the semiconductor substrates, metal conductor layer, and low-k dielectric layer.
  • an object of the present invention to provide improved compositions for the selective removal of hard mask materials relative to semiconductor substrates, metal conductor layers, and low-k dielectric layers that are present, while not compromising the etch rate of the hard mask.
  • the present invention relates to a composition and process for selectively etching hard mask layers and/or photoresist etch residues relative to semiconductor substrates, metal conductor layers, and low-k dielectric layers that are present. More specifically, the present invention relates to a composition and process for selectively etching titanium nitride and/or photoresist etch residues relative to copper, tungsten, silicon germanide, germanium, and low-k dielectric layers.
  • a composition for selectively removing titanium nitride and/or photoresist etch residue material from the surface of a microelectronic device having same thereon comprising at least one oxidizing agent, at least one etchant, at least one corrosion inhibitor, at least one Ge/SiGe passivating agent, water, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide, and wherein the at least one Ge/SiGe passivating agent comprises a species selected from the group consisting of pyruvic acid, 1,2- hexanediol, oxalacetic acid, benzalkonium chloride, polyacrylic acid, glucose, acetoacetic acid, levulinic acid, 2-oxo glutarate, polyethylene glycol (e.g., PEG 200), dodecyltrimethylammonium chloride (DTAC), and combinations thereof.
  • pyruvic acid 1,2- hexanediol, oxalacetic acid,
  • a method of etching titanium nitride material from a surface of a microelectronic device having same thereon comprising contacting the surface with a composition comprising at least one oxidizing agent, at least one etchant, at least one corrosion inhibitor, at least one Ge/SiGe passivating agent, water, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide, wherein the at least one Ge/SiGe passivating agent comprises a species selected from the group consisting of pyruvic acid, 1 ,2-hexanediol, oxalacetic acid, benzalkonium chloride, polyacrylic acid, glucose, acetoacetic acid, levulinic acid, 2-oxo glutarate, polyethylene glycol (e.g., PEG 200), dodecyltrimethylammonium chloride (DTAC), and combinations thereof, and wherein the composition selectively removes the titanium nitride
  • the present invention relates to compositions and processes for selectively etching hard mask layers and/or photoresist etch residues relative to semiconductor substrates, metal conductor layers, and low-k dielectric layers that are present. More specifically, the present invention relates to a composition and process for selectively etching titanium nitride and/or photoresist etch residues relative to copper, tungsten, silicon germanide, germanium, and low-k dielectric layers. Other materials 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.
  • Hardmask capping layer or “hardmask” as used herein corresponds to materials deposited over dielectric material to protect same during the plasma etch step. Hardmask capping layers are traditionally silicon nitrides, silicon oxynitrides, titanium nitride, titanium oxynitride, titanium and other similar compounds.
  • titanium nitride and TiN x correspond to pure titanium nitride as well as impure titanium nitride including varying stoichiometries, and oxygen content (TiO x N y )
  • low-k dielectric material corresponds to any material used as a dielectric material in a layered microelectronic device, wherein the material has a dielectric constant less than about 3.5.
  • the low-k dielectric materials include low-polarity materials such as silicon- containing organic polymers, silicon-containing hybrid organic/inorganic materials, organosilicate glass (OSG), TEOS, fluorinated silicate glass (FSG), silicon dioxide, and carbon-doped oxide (CDO) glass. It is to be appreciated that the low-k dielectric materials may have varying densities and varying porosities.
  • metal conductor layers comprise copper, tungsten, cobalt, molybdenum, aluminum, ruthenium, alloys comprising same, and combinations thereof.
  • amine species include at least one primary, secondary, and tertiary amines, with the proviso that (i) species including both a carboxylic acid group and an amine group, (ii) surfactants that include amine groups, and (iii) species where the amine group is a substituent (e.g., attached to an aryl or heterocyclic moiety) are not considered “amines" according to this definition.
  • the amine formula can be represented by NR 1 R2 R 3 , wherein R 1 , R2 and R 3 can be the same as or different from one another and are selected from the group consisting of hydrogen, straight-chained or branched Ci-C 6 alkyls (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl), C 6 -Ci 0 aryls (e.g., benzyl), straight-chained or branched Ci-C 6 alkanols (e.g., methanol, ethanol, propanol, butanol, pentanol, hexanol), and combinations thereof, with the proviso that R 1 , R 2 and R 3 cannot all be hydrogen.
  • Ci-C 6 alkyls e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl
  • photoresist etch residues corresponds to any residue comprising photoresist material, or material that is a by-product of photoresist subsequent to an etching or ashing step, as readily understood by the person skilled in the art.
  • substantially devoid is defined herein as less than 2 wt. %, preferably less than 1 wt. %, more preferably less than 0.5 wt. %, even more preferably less than 0.1 wt. %, and most preferably 0 wt.%.
  • fluoride species correspond to species including an ionic fluoride (F ) . It is to be appreciated that the fluoride species may be included as a fluoride species or generated in situ.
  • chloride species correspond to species including an ionic chloride (CI ), with the proviso that surfactants that include chloride anions are not considered “chlorides” according to this definition.
  • semi-aqueous refers to a mixture of water and organic solvent components.
  • the semi-aqueous removal compositions must not substantially damage the metal conductor layers and low-k dielectric layers that are present while the hard mask layers and/or photoresist etch residues are removed.
  • a strong base is any base having at least one pKa greater than 11, while a weak base is any base having at least one pKa less than 11.
  • semiconductor substrates include, but are not limited to, bare silicon; polysilicon; germanium; SiGe; III/V compounds such as aluminum nitride, gallium nitride, gallium arsenide, indium phosphide; titanites; II/IV compounds; II/VI compounds such as CdSe, CdS, ZnS, ZnSe and CdTe; silicon carbide; sapphire; silicon on sapphire; carbon; doped glass; undoped glass; diamond; GeAsSe glass; poly-crystalline silicon (doped or undoped); mono-crystalline silicon (doped or undoped); amorphous silicon, copper indium (gallium) diselenide; and combinations thereof.
  • germanium and SiGe are, for various MOS technologies, considered to be suitable replacements for silicon as the semiconductor material of choice to form substrates and/or gate electrodes.
  • 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.
  • Embodiments of the present invention include a chemistry for removing hard mask and/or photoresist etch residues.
  • the composition is a wet-etch solution that removes a metal hard mask and/or photoresist etch residues on a dielectric layer and is highly selective relative to a semiconductor substrate, a metal conductor layer underneath the dielectric layer and the dielectric layer itself.
  • the composition is a wet-etch solution that removes a titanium nitride layer and/or photoresist etch residues that is highly selective relative to at least one of copper, tungsten, silicon germanide, germanium, germanium, and low-k dielectric materials.
  • compositions for selectively removing titanium nitride and/or photoresist etch residue material from the surface of a microelectronic device having same thereon including at least one oxidizing agent, at least one etchant, and at least one Ge/SiGe passivating agent, wherein the composition is substantially devoid of hydrogen peroxide.
  • the composition for removing titanium nitride and/or photoresist etch residue material from the surface of a microelectronic device having same thereon comprises, consists of, or consists essentially of at least one oxidizing agent, at least one etchant, at least one Ge/SiGe passivating agent, water, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide.
  • the composition for removing titanium nitride and/or photoresist etch residue material from the surface of a microelectronic device having same thereon comprises, consists of, or consists essentially of at least one oxidizing agent, at least one etchant, water, at least one Ge/SiGe passivating agent, and at least one corrosion inhibitor, wherein the composition is substantially devoid of hydrogen peroxide.
  • the composition for removing titanium nitride and/or photoresist etch residue material from the surface of a microelectronic device having same thereon comprises, consists of, or consists essentially of at least one oxidizing agent, at least one etchant, at least one corrosion inhibitor, at least one Ge/SiGe passivating agent, at least one pH adjustor, water, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide.
  • the amount of water in the composition is in a range from about 0.1 wt% to about 50 wt%, preferably about 1 wt% to about 30 wt%, and even more preferably about 5 wt% to about 20 wt%, based on the total weight of the composition.
  • the amount of at least one organic solvent in the composition is in a range from about 0.1 wt% to about 50 wt%, preferably about 1 wt% to about 30 wt%, and even more preferably about 5 wt% to about 20 wt%, based on the total weight of the composition.
  • compositions described herein include, but are not limited to, at least one source of silica, at least one low-k passivating agent, at least one surfactant, at least one iodine scavenger, and combinations thereof.
  • these compositions have a TiN to tungsten selectivity of greater than 50:1 and a tungsten removal rate less than about 2 A min "1 , even more preferably a TiN to tungsten selectivity of greater than 75:1, and a tungsten removal rate less than about 2 A min "1 at temperatures in a range from about 45°C to about 60°C.
  • compositions have a TiN to SiGe selectivity of greater than 50:1 and a SiGe removal rate less than about 3 A min "1 , even more preferably a TiN to SiGe selectivity of greater than 75: 1, and a copper removal rate less than about 3 A min "1 at temperatures in a range from about 45°C to about 60°C.
  • compositions are substantially devoid of amines, as defined herein, chemical mechanical polishing abrasive materials, metal halides, and combinations thereof.
  • the compositions have pH value in a range from 0 to 4.
  • Etchants are added to increase the etch rate of the titanium nitride.
  • Etchants contemplated include, but are not limited to, HF, ammonium fluoride, ammonium bifluoride (ABF), tetrafluoroboric acid, hexafluorosilicic acid (HFSA), other compounds containing B-F or Si-F bonds, tetrabutylammonium tetrafluoroborate (TBA-BF 4 ), tetraalkylammonium fluoride (NR 1 R 2 R 3 R 4 F), strong bases such as tetraalkylammonium hydroxide (NR 1 R 2 R 3 R 4 OH), where Ri, R 2 , R 3 , R 4 may be the same as or different from one another and is selected from the group consisting of hydrogen, straight-chained or branched Ci-C 6 alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, e
  • the fluoride source comprises tetrafluoroboric acid, hexafluorosilicic acid, H 2 ZrF 6 , H 2 TiF 6 , HPF 6 , ammonium fluoride, ammonium bifluoride, tetramethylammonium fluoride, tetramethylammonium hydroxide, ammonium hexafluorosilicate, ammonium hexafluorotitanate, or a combination of ammonium fluoride and tetramethylammonium fluoride.
  • the etchant can comprise a strong base such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), benzyltrimethylammonium hydroxide (BTMAH), potassium hydroxide, ammonium hydroxide, benzyltriethylammonium hydroxide (BTEAH), tetrabutylphosphonium hydroxide (TBPH), (2 -hydroxyethyl) trimethylammonium hydroxide, (2 -hydroxyethyl) triethylammonium hydroxide, (2- hydroxyethyl) tripropylammonium hydroxide, (1 -hydroxypropyl) trimethylammonium hydroxide, ethyltrimethylammonium hydroxide, diethyldimethyl
  • Oxidizing agents are included to oxidize Ti 3+ in TiN x .
  • Oxidizing agents contemplated herein include, but are not limited to, FeCl 3 , FeF 3 , Fe(N0 3 ) 3 , Sr(N0 3 ) 2 , C0F 3 , MnF 3 , oxone (2KHS0 5 KHS0 4 K 2 S0 4 ), periodic acid, iodic acid, vanadium (V) oxide, vanadium (IV,V) oxide (V 6 Oi 3 ), ammonium vanadate, ammonium polyatomic salts (e.g., ammonium peroxomonosulfate, ammonium chlorite (NH 4 C10 2 ), ammonium chlorate (NH 4 C10 3 ), ammonium iodate (NH O3), ammonium nitrate (NH 4 N0 3 ), ammonium perborate (NH 4 B0 3 ), ammonium perchlorate (NH 4 C10 4
  • the oxidizing agent When the oxidizing agent is a salt it can be hydrated or anhydrous.
  • 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 for the composition comprises vanadium (IV, V) oxide (V 6 Oi 3 ), vanadium oxide, ammonium vanadate, ammonium iodate, ammonium periodate, iodic acid, periodic acid, or combinations thereof.
  • Metal corrosion inhibitors are added to block the oxidative activity of the oxidizing agent(s) and hence prevent corrosion of metals including, but not limited to, copper and tungsten.
  • Metal corrosion inhibitors contemplated herein include, but are not limited to, 5-amino-l,3,4-thiadiazole-2- thiol (ATDT), benzotriazole (BTA), 1 ,2,4-triazole (TAZ), tolyltriazole, 5-methyl-benzotriazole, 5- phenyl-benzotriazole, 5-nitro-benzotriazole, benzotriazole carboxylic acid, 3-amino-5-mercapto-l,2,4- triazole, 1 -amino- 1,2,4-triazole, hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino- 1,2,3-triazole, l-amino-5-methyl-l,2,3-triazole, 3-amino-
  • Additional corrosion inhibitors include cationic quaternary surfactant salts such as benzalkonium chloride, benzyldimethyldodecylammonium chloride, myristyltrimethylammonium bromide, dodecyltrimethylammonium bromide, hexadecylpyridinium chloride, Aliquat 336 (Cognis), benzyldimethylphenylammonium chloride, Crodaquat TES (Croda Inc.), Rewoquat CPEM (Witco), hexadecyltrimethylammonium p-toluenesulfonate, hexadecyltrimethylammonium hydroxide, 1- methyl-r-tetradecyl-4,4'-bipyridium di chloride, alkyltrimethylammonium bromide, amprolium hydrochloride, benzethonium hydroxide, benzethonium chloride, benzy
  • l-decyl-3-methylimidazolium chloride tridodecylmethylammonium bromide, dimethyldistearylammonium chloride, and hexamethonium chloride.
  • corrosion inhibitors include non-ionic surfactants such as PolyFox PF-159 (OMNOVA Solutions), polyethylene glycol) (“PEG”), polypropylene glycol) (“PPG”), PEG-PPG copolymers such as Pluronic F-127 (BASF), anionic surfactants such as dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, and combinations thereof.
  • the quaternary salts can function as both corrosion inhibitors (especially for copper and tungsten) and wetting agents. It will be obvious to those skilled in the art that, while quaternary salts are available commercially most often as chlorides or bromides, it is easy to ion-exchange the halide anion with non-halide anions such as sulfate, methanesulfonate, nitrate, hydroxide, etc. Such converted quaternary salts are also contemplated herein. In a particularly preferred embodiment, 5-methyl-lH-benzotriazole is known to block the oxidative activity of the oxidizing agents against copper.
  • preferred corrosion inhibitors include pyrazole, benzotriazole, adenosine, saccharin, the cationic quaternary surfactant salts, more preferably myristyltrimethylammonium bromide, benzalkonium chloride, hexadecyltrimethylammonium p- toluenesulfonate, and hexadecyltrimethylammonium hydroxide, tetrazoles such as 5-benzyl-lH- tetrazole, and combinations thereof.
  • the at least one organic solvent comprises at least one water-miscible organic solvent including but not limited to methanol, ethanol, isopropanol, butanol, pentanol, hexanol, 2-ethyl-l- hexanol, heptanol, octanol, ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 1,3-, and 1,4- butanediol, dipropylene glycol, diethylene glycol (DEG), 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 glycol ether
  • the at least one organic solvent comprises butylene carbonate (BC), ethylene carbonate, propylene carbonate (PC), diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, ethylene glycol, 1,2- and 1,3-propylene glycol, dipropylene glycol, diethylene glycol (DEG), DMSO, or combinations thereof.
  • the composition comprises at least two organic solvents.
  • the at least one Ge/SiGe passivating agent includes, but is not limited to, pyruvic acid, 1,2- hexanediol, oxalacetic acid, benzalkonium chloride, polyacrylic acid, glucose, acetoacetic acid, levulinic acid, 2-oxo glutarate, polyethylene glycol (e.g., PEG 200), dodecyltrimethylammonium chloride (DTAC), and combinations thereof.
  • the at least one Ge/SiGe passivating agent comprises pyruvic acid.
  • the at least one pH adjustor when present, includes, but is not limited to, tetrafluoroboric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, and combinations thereof.
  • compositions described herein can optionally include at least one low-k passivating agent to reduce the chemical attack of the low-k dielectric layers and to protect the wafer from additional oxidation.
  • Preferred low-k passivating agent include, but are not limited to, boric acid, borate salts, such as ammonium pentaborate, sodium tetraborate, 3-hydroxy-2-naphthoic acid, malonic acid, and iminodiacetic acid.
  • the composition includes about 0.01 wt% to about 2 wt% low-k passivating agent, based on the total weight of the composition. Preferably, less than 2 wt.
  • % of the underlying low-k material is etched/removed using the compositions described herein, more preferably less than 1 wt. %, most preferably less than 0.5 wt.%, based on the total weight of the underlying low-k material.
  • compositions described herein can optionally include at least one source of silica to reduce the activity of the etchant source.
  • the at least one source of silica comprises an alkoxysilane.
  • Alkoxysilanes contemplated have the general formula SiR'R 2 R 3 R 4 , 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 straight- chained Ci-C 6 alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl), branched Ci-C 6 alkyl groups, Ci-C 6 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, pen
  • R 1 , R 2 , R 3 or R 4 must be a Ci-C 6 alkoxy group.
  • Alkoxysilanes contemplated include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane (TEOS), N- propyltrimethoxysilane, N-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and combinations thereof.
  • TEOS tetraethoxysilane
  • the alkoxysilanes include ammonium hexaflurorosilicate, sodium silicate, tetramethyl ammonium silicate (TMAS), and combinations thereof.
  • TMAS tetramethyl ammonium silicate
  • the silicon-containing compound comprises TEOS, TMAS, sodium silicate, or combinations thereof.
  • the composition includes about 0.001 wt% to about 5 wt% silica source(s), based on the total weight of the composition.
  • an iodine scavenger may optionally be added to the composition.
  • an iodine scavenger may optionally be added to the composition.
  • Iodine scavengers include, but are not limited to, ketones more preferably ketones with hydrogen(s) alpha to the carbonyl such as 4-methyl-2-pentanone, 2,4-dimethyl-3-pentanone, cyclohexanone, 5-methyl-3- heptanone, 3-pentanone, 5-hydroxy-2-pentanone, 2,5-hexanedione, 4-hydroxy-4-methyl-2-pentanone, acetone, butanone, 2-methyl-2-butanone, 3,3-dimethyl-2-butanone, 4-hydroxy-2-butanone, cyclop entanone, 2-pentanone, 3-pentanone, 1 -phenyl ethanone, acetophenone, benzophenone, 2- hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 2- octanone, 3-octanone
  • the iodine scavenger includes 4-methyl-2-pentanone, 2,4-dimethyl-3-pentanone, or cyclohexanone.
  • the composition includes about 0.001 wt% to about 2 wt% iodine scavenger(s), based on the total weight of the composition.
  • a surfactant can be added to the composition, preferably an oxidation resistant, fluorinated anionic surfactant.
  • Anionic surfactants contemplated in the compositions of the present invention include, but are not limited to, fluorosurfactants such as ZONYL® UR and ZONYL® FS-62 (DuPont Canada Inc., Mississauga, Ontario, Canada), and ammonium fluoroalkylsulfonates such as NovecTM 4300 (3M).
  • fluorosurfactants such as ZONYL® UR and ZONYL® FS-62 (DuPont Canada Inc., Mississauga, Ontario, Canada)
  • ammonium fluoroalkylsulfonates such as NovecTM 4300 (3M).
  • the etchant used comprises a fluoride
  • any of the compositions described herein may further comprise titanium nitride and/or photoresist etch material residue, wherein the residue is suspended and/or dissolved in the composition.
  • the composition of the first aspect comprises, consists of, or consists essentially of at least one oxidizing agent, at least one etchant, at least one corrosion inhibitor, at least one Ge/SiGe passivating agent, water, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide, present in the following ranges, based on the total weight of the composition:
  • component % by weight more preferred % most preferred % by weight by weight oxidizing agent(s) about 0.0001 wt% about 0.001 wt% about 0.001 wt% to about 2 wt% to about 1 wt% to about 0.2 wt% etchant(s) about 0.01 wt% to about 0.01 wt% to about 0.01 wt% to about 10 wt% about 5 wt% about 2.5 wt% corrosion inhibitor(s) about 0.0001 wt% about 0.0001 wt% about 0.001 wt% to about 10 wt% to about 5 wt% to about 2 wt%
  • Ge/SiGe passivating about 0.001 wt% about 0.01 wt% to about 0.01 wt% to agent(s) to about 5 wt% about 3 wt% about 2 wt% organic solvent(s/ about 23 wt% to about 56 wt% to about 73.3 wt% to about 99.8888 about 98.9789 about 94.888 wt% wt% wt% wt%
  • the at least one oxidizing agent comprises vanadium (IV,V) oxide ( ⁇ 6 ⁇ 3 ), vanadium oxide, ammonium vanadate, ammonium iodate, ammonium periodate, iodic acid, periodic acid, or combinations thereof;
  • the at least one etchant comprises HF, ammonium bifluoride, hexafluorosilicic acid, tetrafluoroboric acid, or combinations thereof;
  • the at least one corrosion inhibitor comprises 5-methyl-lH-benzotriazole, pyrazole, benzotriazole, myristyltrimethylammonium bromide, benzalkonium chloride, hexadecyltrimethylammonium p-toluenesulfonate, hexadecyltrimethylammonium hydroxide, 5- benzyl-lH-tetrazole, or combinations thereof;
  • the at least one Ge/SiGe passivating agent comprises pyruvic acid
  • the composition of the first aspect comprises, consists of, or consists essentially of at least one oxidizing agent, at least one etchant, at least one corrosion inhibitor, at least one Ge/SiGe passivating agent, water, at least one pH adjustor, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide, present in the following ranges, based on the total weight of the composition:
  • oxidizing agent(s) about 0.0001 wt% about 0.001 wt% about 0.001 wt% to about 2 wt% to about 1 wt% to about 0.2 wt% etchant(s) about 0.01 wt% to about 0.01 wt% to about 0.1 wt% to about 10 wt% about 5 wt% about 2.5 wt% corrosion inhibitor(s) about 0.0001 wt% about 0.0001 wt% about 0.001 wt% to about 10 wt% to about 5 wt% to about 2 wt% Ge/SiGe passivating about 0.001 wt% about 0.01 wt% to about 0.01 wt% to agent(s) to about 5 wt% about 3 wt% about 2 wt% pH adjustor(s) about 0.001 wt% about 0.01 wt% to about 0.01 wt% to about 0.01 wt% to to
  • the at least one oxidizing agent comprises vanadium (IV,V) oxide ( " ⁇ On), vanadium oxide, ammonium vanadate, ammonium iodate, ammonium periodate, iodic acid, periodic acid, or combinations thereof;
  • the at least one etchant comprises HF, ammonium bifluoride, or combinations thereof;
  • the at least one corrosion inhibitor comprises 5-methyl-lH-benzotriazole, pyrazole, benzotriazole, myristyltrimethylammonium bromide, benzalkonium chloride, hexadecyltrimethylammonium p-toluenesulfonate, hexadecyltrimethylammonium hydroxide, 5-benzyl-lH-tetrazole, or combinations thereof;
  • the at least one Ge/SiGe passivating agent comprises pyruvic acid
  • the at least one pH adjustor comprises tetrafluoroboric acid, sulfuric acid, or
  • the composition of the first aspect comprises, consists of, or consists essentially of at least one oxidizing agent, at least one etchant, at least one corrosion inhibitor, at least one Ge/SiGe passivating agent, water, at least one pH adjustor, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide, present in the following ranges, based on the total weight of the composition:
  • component % by weight more preferred % most preferred % by weight by weight oxidizing agent(s) about 0.0001 wt% about 0.001 wt% about 0.001 wt% to about 2 wt% to about 1 wt% to about 0.2 wt% etchant(s) about 0.01 wt% to about 0.01 wt% to about 0.1 wt% to about 10 wt% about 5 wt% about 2.5 wt% corrosion inhibitor(s) about 0.0001 wt% about 0.0001 wt% about 0.001 wt% to about 10 wt% to about 5 wt% to about 2 wt%
  • the at least one oxidizing agent comprises vanadium (IV,V) oxide ( " V ⁇ On), vanadium oxide, ammonium vanadate, ammonium iodate, ammonium periodate, i
  • the composition of the first aspect comprises, consists of, or consists essentially of at least one oxidizing agent, at least one etchant, at least one corrosion inhibitor, at least one Ge/SiGe passivating agent, water, at least one pH adjustor, at least one low-k passivating agent, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide, present in the following ranges, based on the total weight of the composition:
  • component % by weight more preferred % most preferred % by weight by weight oxidizing agent(s) about 0.0001 wt% about 0.001 wt% about 0.001 wt% to about 2 wt% to about 1 wt% to about 0.2 wt% etchant(s) about 0.01 wt% to about 0.01 wt% to about 0.1 wt% to about 10 wt% about 5 wt% about 2.5 wt% corrosion inhibitor(s) about 0.0001 wt% about 0.0001 wt% about 0.001 wt% to about 10 wt% to about 5 wt% to about 2 wt%
  • Ge/SiGe passivating about 0.001 wt% about 0.01 wt% to about 0.01 wt% to agent(s) to about 5 wt% about 4 wt% about 3 wt% pH adjustor(s) about 0.001 wt% about 0.01 wt% to about 0.01 wt% to to about 7 wt% about 6 wt% about 5 wt% low-k passivating agent(s) about 0.01 wt% to about 0.01 wt% to about 0.01 wt% to about 2 wt% about 1 wt% about 0.5 wt% organic solvent(s/ about 1 wt% to about 5 wt% to about 10 wt% to about 50 wt% about 30 wt% about 20 wt% water about 14 wt% to about 48 wt% to about 66.8 wt% to about 99 wt% about 95 wt% about 89.9 wt%
  • the at least one oxidizing agent comprises vanadium (IV,V) oxide ( " V ⁇ On), vanadium oxide, ammonium vanadate, ammonium iodate, ammonium periodate, iodic acid, periodic acid, or combinations thereof;
  • the at least one etchant comprises HF, ammonium bifluoride, or combinations thereof;
  • the at least one corrosion inhibitor comprises 5-methyl-lH-benzotriazole, pyrazole, benzotriazole, myristyltrimethylammonium bromide, benzalkonium chloride, hexadecyltrimethylammonium p-toluenesulfonate, hexadecyltrimethylammonium hydroxide, 5-benzyl-lH-tetrazole, or combinations thereof;
  • the at least one Ge/SiGe passivating agent comprises pyruvic acid
  • the at least one pH adjustor comprises hydrochloric acid, sulfuric acid, or combinations thereof, the
  • the composition may be manufactured in a more concentrated form and thereafter diluted with at least one solvent, e.g., water and/or 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 described herein include oxidizing agents, which can be unstable over time. Accordingly, the concentrated form can be substantially devoid of oxidizing agent(s) and the oxidizing agent can be introduced to the concentrate or the diluted composition by the manufacturer before use and/or during use at the fab.
  • 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.
  • compositions can variously and alternatively comprise, consist or consist essentially of any combination of ingredients consistent with the disclosure herein.
  • a second aspect relates to a kit including, in one or more containers, one or more components adapted to form the compositions described herein.
  • the containers of the kit must be suitable for storing and shipping said 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 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, polyvinyl chloride, 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 titanium nitride material from the surface of the microelectronic device having same thereon using the composition described herein.
  • titanium nitride material may be removed without substantially damaging/removing semiconductor substrates, metal conductor, and insulator materials that are present on the microelectronic device.
  • a method of selectively and substantially removing titanium nitride and/or photoresist etch residue materials relative to semiconductor substrates, metal conductor, and insulator materials from the surface of the microelectronic device having same thereon is described using the composition described herein.
  • a method of selectively and substantially removing titanium nitride and/or photoresist etch residue materials relative to metal conductor e.g., copper
  • metal conductor e.g., copper
  • tungsten, germanium, silicon germanide, and insulator materials from the surface of the microelectronic device having same thereon is described using the compositions described herein.
  • 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 titanium nitride and/or photoresist etch residue material relative to other materials that may be present on the microelectronic device structure and exposed to the composition, such as semiconductor substrates, metals, and insulating materials (i.e., low-k dielectrics), achieve at least partial removal of the titanium nitride and/or photoresist etch residue material in a highly efficient and highly selective manner.
  • the composition typically is contacted with the device structure in a single wafer tool for a sufficient time of from about 0.3 minute to about 30 minutes, preferably about 0.5 minutes to about 3 minutes, at temperature in a range of from about 20°C to about 100°C, preferably about 45°C to about 60°C.
  • 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 titanium nitride and/or photoresist etch residue material from the device structure.
  • the composition is heated inline during delivery to the device structure. By heating inline, rather than in the bath itself, the composition life increases.
  • 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 described herein.
  • 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 preferably selectively etch titanium nitride material relative to semiconductor substrates, metal conductor, and insulating (i.e., low-k dielectric) materials.
  • the etch rate of titanium nitride is high (upwards of 50 A min "1 , preferably upwards of about 35 A min "1 at 50°C and, while the etch rate of metal (e.g., Cu and W) is low ( less about 10 A min "1 , preferably less than about 5 A min "1 ) and the etch rate of low-k dielectric is low (less than about 10 A min "1 , preferably less than about 5 A min "1 ) at the same temperature.
  • metal e.g., Cu and W
  • a fourth aspect relates to the improved microelectronic devices made according to the methods described herein and to products containing such microelectronic devices.
  • a fifth 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 titanium nitride and/or photoresist etch residue material from the surface of the microelectronic device having same thereon, and incorporating said microelectronic device into said article, wherein the composition comprises, consists of or consists essentially of at least one oxidizing agent, at least one etchant, at least one corrosion inhibitor, at least one Ge/SiGe passivating agent, water, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide.
  • the composition may further comprise, consist of or consist essentially of titanium nitride material.
  • a sixth aspect of the invention relates to an article of manufacture comprising, consisting of or consisting essentially of a microelectronic device substrate, a titanium nitride layer on said substrate, and a composition described herein.
  • Formulations comprising 0.8 wt% HBF 4 (as pH adjuster), 0.5 wt % pyrazole, 0.01 wt% periodic acid (50%), and the other constituents (in wt. %) recited in Table 1 were prepared. SiGe, tungsten, TiN and PETEOS coupons were immersed in each formulation at 50°C for time indicated and the etch rates determined.
  • the pyruvic acid kept the SiGe etch rate relatively low. Without the additional V 6 Oi 3 oxidizer, the SiGe etch rate was as high as 12.5 A min "1 .
  • Formulations comprising 0.8 wt% HBF 4 (as pH adjuster), 0.5 wt % pyrazole, and the other constituents (in wt. %) recited in Table 2 were prepared, wherein at least one of the two oxidizers was present in an amount of at least 0.001 wt%.
  • SiGe, tungsten, TiN and PETEOS coupons were immersed in each formulation at 50°C for time indicated and the etch rates determined.
  • Table 1 Formulations prepared and etch rates.
  • Table 2 Formulations prepared and etch rates.
  • Formulations Y and Z recited in Table 3 were prepared. SiGe, tungsten, TiN, PETEOS, and low-k dielectric (BD-II) coupons were immersed in each formulation at 60°C for time indicated and the etch rates determined.
  • SiGe, tungsten, TiN, PETEOS, and low-k dielectric (BD-II) coupons were immersed in each formulation at 60°C for time indicated and the etch rates determined.
  • Table 3 Formulations prepared and etch rates.

Abstract

Compositions useful for the selective removal of titanium nitride and/or photoresist etch residue materials relative to metal conducting, e.g., tungsten and copper, and insulating materials from a microelectronic device having same thereon. The compositions contain at least one oxidant, at least one etchant, and at least one organic solvent, may contain various corrosion inhibitors to ensure selectivity.

Description

COMPOSITIONS FOR ETCHING TITANIUM NITRIDE HAVING COMPATABILITY WITH SILICON GERMANIDE AND TUNGSTEN
FIELD
[0001] The present invention relates to a composition and process for selectively etching titanium nitride and/or photoresist etch residues in the presence of semiconductor substrates, metal conductor, and insulator materials (i.e., low-k dielectrics), and more particularly to a composition and process for effectively and efficiently etching titanium nitride and/or photoresist etch residues at an etch rate and selectivity that is higher than that of exposed or underlying layers of copper, tungsten, silicon germanide, germanium, and low-k dielectric materials.
DESCRIPTION OF THE RELATED ART
[0002] Photoresist masks are commonly used in the semiconductor industry to pattern materials such as semiconductors or dielectrics. In one application, photoresist masks are used in a dual damascene process to form interconnects in the back-end metallization of a microelectronic device. The dual damascene process involves forming a photoresist mask on a low-k dielectric layer overlying a metal conductor layer, such as a copper layer. The low-k dielectric layer is then etched according to the photoresist mask to form a via and/ or trench that expose the metal conductor layer. The via and trench, commonly known as dual damascene structure, are usually defined using two lithography steps. The photoresist mask is then removed from the low-k dielectric layer before a conductive material is deposited into the via and/or trench to form an interconnect.
[0003] With the decreasing size of microelectronic devices, it becomes more difficult to achieve the critical dimensions for vias and trenches. Thus, metal hard masks are used to provide better profile control of vias and trenches. The metal hard masks can comprise titanium or titanium nitride, and are removed by a wet etching process after forming the via and/or trench of the dual damascene structure. It is essential that the wet etching process uses a removal chemistry that effectively removes the metal hard mask and/or photoresist etch residues without affecting the underlying semiconductor substrates, metal conductor layer, and low-k dielectric material. In other words, the removal chemistry is required to be highly selective to the semiconductor substrates, metal conductor layer, and low-k dielectric layer.
[0004] Accordingly, an object of the present invention to provide improved compositions for the selective removal of hard mask materials relative to semiconductor substrates, metal conductor layers, and low-k dielectric layers that are present, while not compromising the etch rate of the hard mask. SUMMARY OF THE INVENTION
[0005] The present invention relates to a composition and process for selectively etching hard mask layers and/or photoresist etch residues relative to semiconductor substrates, metal conductor layers, and low-k dielectric layers that are present. More specifically, the present invention relates to a composition and process for selectively etching titanium nitride and/or photoresist etch residues relative to copper, tungsten, silicon germanide, germanium, and low-k dielectric layers.
[0006] In one aspect, a composition for selectively removing titanium nitride and/or photoresist etch residue material from the surface of a microelectronic device having same thereon is described, said composition comprising at least one oxidizing agent, at least one etchant, at least one corrosion inhibitor, at least one Ge/SiGe passivating agent, water, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide, and wherein the at least one Ge/SiGe passivating agent comprises a species selected from the group consisting of pyruvic acid, 1,2- hexanediol, oxalacetic acid, benzalkonium chloride, polyacrylic acid, glucose, acetoacetic acid, levulinic acid, 2-oxo glutarate, polyethylene glycol (e.g., PEG 200), dodecyltrimethylammonium chloride (DTAC), and combinations thereof.
[0007] In another aspect, a method of etching titanium 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 oxidizing agent, at least one etchant, at least one corrosion inhibitor, at least one Ge/SiGe passivating agent, water, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide, wherein the at least one Ge/SiGe passivating agent comprises a species selected from the group consisting of pyruvic acid, 1 ,2-hexanediol, oxalacetic acid, benzalkonium chloride, polyacrylic acid, glucose, acetoacetic acid, levulinic acid, 2-oxo glutarate, polyethylene glycol (e.g., PEG 200), dodecyltrimethylammonium chloride (DTAC), and combinations thereof, and wherein the composition selectively removes the titanium nitride material from the surface relative to semiconductor substrates, metals, and insulating materials.
[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 and processes for selectively etching hard mask layers and/or photoresist etch residues relative to semiconductor substrates, metal conductor layers, and low-k dielectric layers that are present. More specifically, the present invention relates to a composition and process for selectively etching titanium nitride and/or photoresist etch residues relative to copper, tungsten, silicon germanide, germanium, and low-k dielectric layers. Other materials 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] "Hardmask capping layer" or "hardmask" as used herein corresponds to materials deposited over dielectric material to protect same during the plasma etch step. Hardmask capping layers are traditionally silicon nitrides, silicon oxynitrides, titanium nitride, titanium oxynitride, titanium and other similar compounds.
[0012] As used herein, "titanium nitride" and "TiNx" correspond to pure titanium nitride as well as impure titanium nitride including varying stoichiometries, and oxygen content (TiOxNy)
[0013] As used herein, "about" is intended to correspond to + 5 % of the stated value.
[0014] As defined herein, "low-k dielectric material" corresponds to any material used as a dielectric material in a layered microelectronic device, wherein the material has a dielectric constant less than about 3.5. Preferably, the low-k dielectric materials include low-polarity materials such as silicon- containing organic polymers, silicon-containing hybrid organic/inorganic materials, organosilicate glass (OSG), TEOS, fluorinated silicate glass (FSG), silicon dioxide, and carbon-doped oxide (CDO) glass. It is to be appreciated that the low-k dielectric materials may have varying densities and varying porosities.
[0015] As defined herein, "metal conductor layers" comprise copper, tungsten, cobalt, molybdenum, aluminum, ruthenium, alloys comprising same, and combinations thereof.
[0016] As defined herein, "amine" species include at least one primary, secondary, and tertiary amines, with the proviso that (i) species including both a carboxylic acid group and an amine group, (ii) surfactants that include amine groups, and (iii) species where the amine group is a substituent (e.g., attached to an aryl or heterocyclic moiety) are not considered "amines" according to this definition. The amine formula can be represented by NR 1 R2 R 3 , wherein R 1 , R2 and R 3 can be the same as or different from one another and are selected from the group consisting of hydrogen, straight-chained or branched Ci-C6 alkyls (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl), C6-Ci0 aryls (e.g., benzyl), straight-chained or branched Ci-C6 alkanols (e.g., methanol, ethanol, propanol, butanol, pentanol, hexanol), and combinations thereof, with the proviso that R1, R2 and R3 cannot all be hydrogen.
[0017] As defined herein, "photoresist etch residues" corresponds to any residue comprising photoresist material, or material that is a by-product of photoresist subsequent to an etching or ashing step, as readily understood by the person skilled in the art.
[0018] "Substantially devoid" is defined herein as less than 2 wt. %, preferably less than 1 wt. %, more preferably less than 0.5 wt. %, even more preferably less than 0.1 wt. %, and most preferably 0 wt.%.
[0019] As used herein, "fluoride" species correspond to species including an ionic fluoride (F ) . It is to be appreciated that the fluoride species may be included as a fluoride species or generated in situ.
[0020] As used herein, "chloride" species correspond to species including an ionic chloride (CI ), with the proviso that surfactants that include chloride anions are not considered "chlorides" according to this definition.
[0021] As used herein, the term "semi-aqueous" refers to a mixture of water and organic solvent components. The semi-aqueous removal compositions must not substantially damage the metal conductor layers and low-k dielectric layers that are present while the hard mask layers and/or photoresist etch residues are removed.
[0022] As defined herein, a strong base is any base having at least one pKa greater than 11, while a weak base is any base having at least one pKa less than 11.
[0023] As defined herein, "semiconductor substrates" include, but are not limited to, bare silicon; polysilicon; germanium; SiGe; III/V compounds such as aluminum nitride, gallium nitride, gallium arsenide, indium phosphide; titanites; II/IV compounds; II/VI compounds such as CdSe, CdS, ZnS, ZnSe and CdTe; silicon carbide; sapphire; silicon on sapphire; carbon; doped glass; undoped glass; diamond; GeAsSe glass; poly-crystalline silicon (doped or undoped); mono-crystalline silicon (doped or undoped); amorphous silicon, copper indium (gallium) diselenide; and combinations thereof. For example, due to their electronic properties, germanium and SiGe are, for various MOS technologies, considered to be suitable replacements for silicon as the semiconductor material of choice to form substrates and/or gate electrodes.
[0024] Compositions of the invention may be embodied in a wide variety of specific formulations, as hereinafter more fully described.
[0025] 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.
[0026] Embodiments of the present invention include a chemistry for removing hard mask and/or photoresist etch residues. In one embodiment, the composition is a wet-etch solution that removes a metal hard mask and/or photoresist etch residues on a dielectric layer and is highly selective relative to a semiconductor substrate, a metal conductor layer underneath the dielectric layer and the dielectric layer itself. In a more specific embodiment, the composition is a wet-etch solution that removes a titanium nitride layer and/or photoresist etch residues that is highly selective relative to at least one of copper, tungsten, silicon germanide, germanium, germanium, and low-k dielectric materials.
[0027] Accordingly, in one aspect, a composition for selectively removing titanium nitride and/or photoresist etch residue material from the surface of a microelectronic device having same thereon is described, said composition including at least one oxidizing agent, at least one etchant, and at least one Ge/SiGe passivating agent, wherein the composition is substantially devoid of hydrogen peroxide. In one embodiment, the composition for removing titanium nitride and/or photoresist etch residue material from the surface of a microelectronic device having same thereon comprises, consists of, or consists essentially of at least one oxidizing agent, at least one etchant, at least one Ge/SiGe passivating agent, water, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide. In another embodiment, the composition for removing titanium nitride and/or photoresist etch residue material from the surface of a microelectronic device having same thereon comprises, consists of, or consists essentially of at least one oxidizing agent, at least one etchant, water, at least one Ge/SiGe passivating agent, and at least one corrosion inhibitor, wherein the composition is substantially devoid of hydrogen peroxide. In yet another embodiment, the composition for removing titanium nitride and/or photoresist etch residue material from the surface of a microelectronic device having same thereon comprises, consists of, or consists essentially of at least one oxidizing agent, at least one etchant, at least one corrosion inhibitor, at least one Ge/SiGe passivating agent, at least one pH adjustor, water, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide. In one embodiment, the amount of water in the composition is in a range from about 0.1 wt% to about 50 wt%, preferably about 1 wt% to about 30 wt%, and even more preferably about 5 wt% to about 20 wt%, based on the total weight of the composition. In another embodiment, the amount of at least one organic solvent in the composition is in a range from about 0.1 wt% to about 50 wt%, preferably about 1 wt% to about 30 wt%, and even more preferably about 5 wt% to about 20 wt%, based on the total weight of the composition. Other components contemplated for inclusion in the compositions described herein include, but are not limited to, at least one source of silica, at least one low-k passivating agent, at least one surfactant, at least one iodine scavenger, and combinations thereof. Advantageously, these compositions have a TiN to tungsten selectivity of greater than 50:1 and a tungsten removal rate less than about 2 A min"1, even more preferably a TiN to tungsten selectivity of greater than 75:1, and a tungsten removal rate less than about 2 A min"1 at temperatures in a range from about 45°C to about 60°C. Furthermore, these compositions have a TiN to SiGe selectivity of greater than 50:1 and a SiGe removal rate less than about 3 A min"1, even more preferably a TiN to SiGe selectivity of greater than 75: 1, and a copper removal rate less than about 3 A min"1 at temperatures in a range from about 45°C to about 60°C. These compositions are substantially devoid of amines, as defined herein, chemical mechanical polishing abrasive materials, metal halides, and combinations thereof. The compositions have pH value in a range from 0 to 4.
[0028] Etchants are added to increase the etch rate of the titanium nitride. Etchants contemplated include, but are not limited to, HF, ammonium fluoride, ammonium bifluoride (ABF), tetrafluoroboric acid, hexafluorosilicic acid (HFSA), other compounds containing B-F or Si-F bonds, tetrabutylammonium tetrafluoroborate (TBA-BF4), tetraalkylammonium fluoride (NR1R2R3R4F), strong bases such as tetraalkylammonium hydroxide (NR1R2R3R4OH), where Ri, R2, R3, R4 may be the same as or different from one another and is selected from the group consisting of hydrogen, straight-chained or branched Ci-C6 alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl), Ci- C6 alkoxy groups (e.g., hydroxyethyl, hydroxypropyl) substituted or unsubstitued aryl groups (e.g., benzyl), weak bases, and combinations thereof. Preferably, the fluoride source comprises tetrafluoroboric acid, hexafluorosilicic acid, H2ZrF6, H2TiF6, HPF6, ammonium fluoride, ammonium bifluoride, tetramethylammonium fluoride, tetramethylammonium hydroxide, ammonium hexafluorosilicate, ammonium hexafluorotitanate, or a combination of ammonium fluoride and tetramethylammonium fluoride. Alternatively, or in addition to fluoride sources, the etchant can comprise a strong base such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), benzyltrimethylammonium hydroxide (BTMAH), potassium hydroxide, ammonium hydroxide, benzyltriethylammonium hydroxide (BTEAH), tetrabutylphosphonium hydroxide (TBPH), (2 -hydroxyethyl) trimethylammonium hydroxide, (2 -hydroxyethyl) triethylammonium hydroxide, (2- hydroxyethyl) tripropylammonium hydroxide, (1 -hydroxypropyl) trimethylammonium hydroxide, ethyltrimethylammonium hydroxide, diethyldimethylammonium hydroxide (DEDMAH), 1, 1,3,3- tetramethylguanidine (TMG), guanidine carbonate, arginine, and combinations thereof. Most preferably, the etchant comprises HF, ammonium bifluoride, hexafluorosilicic acid, tetrafluoroboric acid, or combinations thereof.
[0029] Oxidizing agents are included to oxidize Ti3+ in TiNx. Oxidizing agents contemplated herein include, but are not limited to, FeCl3, FeF3, Fe(N03)3, Sr(N03)2, C0F3, MnF3, oxone (2KHS05 KHS04 K2S04), periodic acid, iodic acid, vanadium (V) oxide, vanadium (IV,V) oxide (V6Oi3), ammonium vanadate, ammonium polyatomic salts (e.g., ammonium peroxomonosulfate, ammonium chlorite (NH4C102), ammonium chlorate (NH4C103), ammonium iodate (NH O3), ammonium nitrate (NH4N03), ammonium perborate (NH4B03), ammonium perchlorate (NH4C104), ammonium periodate (NH4I04), ammonium persulfate ((NH4)2S208), ammonium hypochlorite (NH4C10)), ammonium tungstate ((NH4)i0H2(W2O7)), sodium polyatomic salts (e.g., sodium persulfate (Na2S208), sodium hypochlorite (NaCIO), sodium perborate), potassium polyatomic salts (e.g., potassium iodate (KI03), potassium permanganate (KMn04), potassium persulfate, nitric acid (HN03), potassium persulfate (K2S208), potassium hypochlorite (KCIO)), tetramethylammonium polyatomic salts (e.g., tetramethylammonium chlorite ((N(CH3)4)C102), tetramethylammonium chlorate ((N(CH3)4)C103), tetramethylammonium iodate ((N(CH3)4)I03), tetramethylammonium perborate ((N(CH3)4)B03), tetramethylammonium perchlorate ((N(CH3)4)C104), tetramethylammonium periodate ((N(CH3)4)I04), tetramethylammonium persulfate ((N(CH3)4)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), 1 ,4-benzoquinone, toluquinone, dimethyl-l,4-benzoquinone, chloranil, alloxan, N-methylmorpholine N-oxide (NMMO), trimethylamine N-oxide, and combinations thereof. When the oxidizing agent is a salt it can be hydrated or anhydrous. 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 for the composition comprises vanadium (IV, V) oxide (V6Oi3), vanadium oxide, ammonium vanadate, ammonium iodate, ammonium periodate, iodic acid, periodic acid, or combinations thereof.
[0030] Metal corrosion inhibitors are added to block the oxidative activity of the oxidizing agent(s) and hence prevent corrosion of metals including, but not limited to, copper and tungsten. Metal corrosion inhibitors contemplated herein include, but are not limited to, 5-amino-l,3,4-thiadiazole-2- thiol (ATDT), benzotriazole (BTA), 1 ,2,4-triazole (TAZ), tolyltriazole, 5-methyl-benzotriazole, 5- phenyl-benzotriazole, 5-nitro-benzotriazole, benzotriazole carboxylic acid, 3-amino-5-mercapto-l,2,4- triazole, 1 -amino- 1,2,4-triazole, hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino- 1,2,3-triazole, l-amino-5-methyl-l,2,3-triazole, 3-amino-l,2,4-triazole, 3-mercapto-l,2,4-triazole, 3- isopropyl- 1,2,4-triazole, 5-phenylthiol-benzotriazole, halo-benzotriazoles (halo = F, CI, Br or I), naphthotriazole, 2-mercaptobenzimidazole (MBI), 2-mercaptobenzothiazole, 4-methyl-2- phenylimidazole, 2-mercaptothiazoline, 5-aminotetrazole, pentylenetetrazole, 5-phenyl-lH-tetrazole, 5-benzyl-lH-tetrazole, Ablumine O (Taiwan Surfactant), 2-benzylpyridine, succinimide, maleimide, phthalimide, glutarimide, 2,4-diamino-6-methyl-l,3,5-triazine, thiazole, triazine, methyltetrazole, 1,3- dimethyl-2-imidazolidinone, 1 ,5-pentamethylenetetrazole, 1 -phenyl-5-mercaptotetrazole, diaminomethyltriazine, imidazoline thione, 4-methyl-4H-l,2,4-triazole-3-thiol, benzothiazole, imidazole, pyrazole, indiazole, adenosine, carbazole, saccharin, and benzoin oxime. Additional corrosion inhibitors include cationic quaternary surfactant salts such as benzalkonium chloride, benzyldimethyldodecylammonium chloride, myristyltrimethylammonium bromide, dodecyltrimethylammonium bromide, hexadecylpyridinium chloride, Aliquat 336 (Cognis), benzyldimethylphenylammonium chloride, Crodaquat TES (Croda Inc.), Rewoquat CPEM (Witco), hexadecyltrimethylammonium p-toluenesulfonate, hexadecyltrimethylammonium hydroxide, 1- methyl-r-tetradecyl-4,4'-bipyridium di chloride, alkyltrimethylammonium bromide, amprolium hydrochloride, benzethonium hydroxide, benzethonium chloride, benzyldimethylhexadecylammonium chloride, benzyldimethyltetradecylammonium chloride, benzyldodecyldimethylammonium bromide, benzyldodecyldimethylammonium chloride, cetylpyridinium chloride, choline p-toluenesulfonate salt, dimethyldioctadecylammonium bromide, dodecylethyldimethylammonium bromide, dodecyltrimethylammonium chloride, ethylhexadecyldimethylammonium bromide, Girard's reagent, hexadecyl(2- hydroxyethyl)dimethylammonium dihydrogen phosphate, dexadecylpyridinium bromide, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, methylbenzethonium chloride, Hyamine® 1622, Luviquat™, Ν,Ν',Ν'-polyoxyethylene (lO)-N-tallow- 1,3-diaminopropane liquid, oxyphenonium bromide, tetraheptylammonium bromide, tetrakis(decyl)ammonium bromide, thonzonium bromide, tridodecylammonium chloride, trimethyloctadecylammonium bromide, l-methyl-3-n-octylimidazolium tetrafluoroborate, l-decyl-3- methylimidazolium tetrafluoroborate. l-decyl-3-methylimidazolium chloride, tridodecylmethylammonium bromide, dimethyldistearylammonium chloride, and hexamethonium chloride. Other corrosion inhibitors include non-ionic surfactants such as PolyFox PF-159 (OMNOVA Solutions), polyethylene glycol) ("PEG"), polypropylene glycol) ("PPG"), PEG-PPG copolymers such as Pluronic F-127 (BASF), anionic surfactants such as dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, and combinations thereof. The quaternary salts can function as both corrosion inhibitors (especially for copper and tungsten) and wetting agents. It will be obvious to those skilled in the art that, while quaternary salts are available commercially most often as chlorides or bromides, it is easy to ion-exchange the halide anion with non-halide anions such as sulfate, methanesulfonate, nitrate, hydroxide, etc. Such converted quaternary salts are also contemplated herein. In a particularly preferred embodiment, 5-methyl-lH-benzotriazole is known to block the oxidative activity of the oxidizing agents against copper. Alternatively, or in addition to the 5-methyl-lH-benzotriazole (mBTA), preferred corrosion inhibitors include pyrazole, benzotriazole, adenosine, saccharin, the cationic quaternary surfactant salts, more preferably myristyltrimethylammonium bromide, benzalkonium chloride, hexadecyltrimethylammonium p- toluenesulfonate, and hexadecyltrimethylammonium hydroxide, tetrazoles such as 5-benzyl-lH- tetrazole, and combinations thereof.
[0031] The at least one organic solvent comprises at least one water-miscible organic solvent including but not limited to methanol, ethanol, isopropanol, butanol, pentanol, hexanol, 2-ethyl-l- hexanol, heptanol, octanol, ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 1,3-, and 1,4- butanediol, dipropylene glycol, diethylene glycol (DEG), diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether (TPGME),dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n- propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, tetrahydrofurfuryl alcohol (THFA), butyl ene carbonate (BC), ethylene carbonate, propylene carbonate (PC), 2,3-dihydrodecafluoropentane, ethyl perfluorobutylether, methyl perfluorobutylether, 4-methyl- 2-pentanol, tetramethylene glycol dimethyl ether, dimethyl sulfoxide (DMSO), sulfolane, methanesulfonic acid (MSA), and combinations thereof. Preferably, the at least one organic solvent comprises butylene carbonate (BC), ethylene carbonate, propylene carbonate (PC), diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, ethylene glycol, 1,2- and 1,3-propylene glycol, dipropylene glycol, diethylene glycol (DEG), DMSO, or combinations thereof. In a particularly preferred embodiment, the composition comprises at least two organic solvents.
[0032] The at least one Ge/SiGe passivating agent includes, but is not limited to, pyruvic acid, 1,2- hexanediol, oxalacetic acid, benzalkonium chloride, polyacrylic acid, glucose, acetoacetic acid, levulinic acid, 2-oxo glutarate, polyethylene glycol (e.g., PEG 200), dodecyltrimethylammonium chloride (DTAC), and combinations thereof. Preferably, the at least one Ge/SiGe passivating agent comprises pyruvic acid.
[0033] The at least one pH adjustor, when present, includes, but is not limited to, tetrafluoroboric acid, sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, and combinations thereof.
[0034] The compositions described herein can optionally include at least one low-k passivating agent to reduce the chemical attack of the low-k dielectric layers and to protect the wafer from additional oxidation. Preferred low-k passivating agent include, but are not limited to, boric acid, borate salts, such as ammonium pentaborate, sodium tetraborate, 3-hydroxy-2-naphthoic acid, malonic acid, and iminodiacetic acid. When present, the composition includes about 0.01 wt% to about 2 wt% low-k passivating agent, based on the total weight of the composition. Preferably, less than 2 wt. % of the underlying low-k material is etched/removed using the compositions described herein, more preferably less than 1 wt. %, most preferably less than 0.5 wt.%, based on the total weight of the underlying low-k material.
[0035] The compositions described herein can optionally include at least one source of silica to reduce the activity of the etchant source. In one embodiment, the at least one source of silica comprises an alkoxysilane. Alkoxysilanes contemplated have the general formula SiR'R2R3R4, wherein the R1, R2, R3 and R4 are the same as or different from one another and are selected from the group consisting of straight- chained Ci-C6 alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl), branched Ci-C6 alkyl groups, Ci-C6 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 Ci-C6 alkoxy group. Alkoxysilanes contemplated include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane (TEOS), N- propyltrimethoxysilane, N-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and combinations thereof. Other sources of silica that can be used instead or in addition to the alkoxysilanes include ammonium hexaflurorosilicate, sodium silicate, tetramethyl ammonium silicate (TMAS), and combinations thereof. Preferably, the silicon-containing compound comprises TEOS, TMAS, sodium silicate, or combinations thereof. When present, the composition includes about 0.001 wt% to about 5 wt% silica source(s), based on the total weight of the composition.
[0036] When the oxidizing agent comprises iodate or periodate, an iodine scavenger may optionally be added to the composition. Although not wishing to be bound by theory, it is thought that as the iodate or periodate are reduced, iodine accumulates, which increases the rate of copper etch. Iodine scavengers include, but are not limited to, ketones more preferably ketones with hydrogen(s) alpha to the carbonyl such as 4-methyl-2-pentanone, 2,4-dimethyl-3-pentanone, cyclohexanone, 5-methyl-3- heptanone, 3-pentanone, 5-hydroxy-2-pentanone, 2,5-hexanedione, 4-hydroxy-4-methyl-2-pentanone, acetone, butanone, 2-methyl-2-butanone, 3,3-dimethyl-2-butanone, 4-hydroxy-2-butanone, cyclop entanone, 2-pentanone, 3-pentanone, 1 -phenyl ethanone, acetophenone, benzophenone, 2- hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 2- octanone, 3-octanone, 4-octanone, dicyclohexyl ketone, 2, 6-dimethyl cyclohexanone, 2- acetylcyclohexanone, 2,4-pentanedione, menthone, and combinations thereof. Preferably, the iodine scavenger includes 4-methyl-2-pentanone, 2,4-dimethyl-3-pentanone, or cyclohexanone. When present, the composition includes about 0.001 wt% to about 2 wt% iodine scavenger(s), based on the total weight of the composition.
[0037] To ensure wetting, especially when the pH is low, a surfactant can be added to the composition, preferably an oxidation resistant, fluorinated anionic surfactant. Anionic surfactants contemplated in the compositions of the present invention include, but are not limited to, fluorosurfactants such as ZONYL® UR and ZONYL® FS-62 (DuPont Canada Inc., Mississauga, Ontario, Canada), and ammonium fluoroalkylsulfonates such as Novec™ 4300 (3M). When the etchant used comprises a fluoride, it is contemplated to use a long-chain tetraalkylammonium fluoride that can be used as a surfactant and the etchant.
[0038] In another embodiment, any of the compositions described herein may further comprise titanium nitride and/or photoresist etch material residue, wherein the residue is suspended and/or dissolved in the composition.
[0039] In one embodiment, the composition of the first aspect comprises, consists of, or consists essentially of at least one oxidizing agent, at least one etchant, at least one corrosion inhibitor, at least one Ge/SiGe passivating agent, water, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide, present in the following ranges, based on the total weight of the composition:
component % by weight more preferred % most preferred % by weight by weight oxidizing agent(s) about 0.0001 wt% about 0.001 wt% about 0.001 wt% to about 2 wt% to about 1 wt% to about 0.2 wt% etchant(s) about 0.01 wt% to about 0.01 wt% to about 0.01 wt% to about 10 wt% about 5 wt% about 2.5 wt% corrosion inhibitor(s) about 0.0001 wt% about 0.0001 wt% about 0.001 wt% to about 10 wt% to about 5 wt% to about 2 wt%
Ge/SiGe passivating about 0.001 wt% about 0.01 wt% to about 0.01 wt% to agent(s) to about 5 wt% about 3 wt% about 2 wt% organic solvent(s/ about 23 wt% to about 56 wt% to about 73.3 wt% to about 99.8888 about 98.9789 about 94.888 wt% wt% wt%
water about 0.1 wt% to about 1 wt% to about 5 wt% to about 50 wt% about 30 wt% about 20 wt%
In a particularly preferred embodiment of the composition, the at least one oxidizing agent comprises vanadium (IV,V) oxide (ν6Οι3), vanadium oxide, ammonium vanadate, ammonium iodate, ammonium periodate, iodic acid, periodic acid, or combinations thereof; the at least one etchant comprises HF, ammonium bifluoride, hexafluorosilicic acid, tetrafluoroboric acid, or combinations thereof; the at least one corrosion inhibitor comprises 5-methyl-lH-benzotriazole, pyrazole, benzotriazole, myristyltrimethylammonium bromide, benzalkonium chloride, hexadecyltrimethylammonium p-toluenesulfonate, hexadecyltrimethylammonium hydroxide, 5- benzyl-lH-tetrazole, or combinations thereof; the at least one Ge/SiGe passivating agent comprises pyruvic acid, and the at least one organic solvent comprises butylene carbonate (BC), ethylene carbonate, propylene carbonate (PC), ethylene glycol, 1,2- and 1,3-propylene glycol, dipropylene glycol, diethylene glycol (DEG), DMSO, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, or combinations thereof.
[0040] In another embodiment, the composition of the first aspect comprises, consists of, or consists essentially of at least one oxidizing agent, at least one etchant, at least one corrosion inhibitor, at least one Ge/SiGe passivating agent, water, at least one pH adjustor, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide, present in the following ranges, based on the total weight of the composition:
component % by weight more preferred % most preferred % by weight by weight oxidizing agent(s) about 0.0001 wt% about 0.001 wt% about 0.001 wt% to about 2 wt% to about 1 wt% to about 0.2 wt% etchant(s) about 0.01 wt% to about 0.01 wt% to about 0.1 wt% to about 10 wt% about 5 wt% about 2.5 wt% corrosion inhibitor(s) about 0.0001 wt% about 0.0001 wt% about 0.001 wt% to about 10 wt% to about 5 wt% to about 2 wt% Ge/SiGe passivating about 0.001 wt% about 0.01 wt% to about 0.01 wt% to agent(s) to about 5 wt% about 3 wt% about 2 wt% pH adjustor(s) about 0.001 wt% about 0.01 wt% to about 0.01 wt% to to about 5 wt% about 3 wt% about 2 wt% organic solvent(s/ about 18 wt% to about 53 wt% to about 71.3 wt% to about 99.8878 about 98.9689 about 94.878 wt% wt% wt%
water about 0.1 wt% to about 1 wt% to about 5 wt% to about 50 wt% about 30 wt% about 20 wt%
In a particularly preferred embodiment of the composition, the at least one oxidizing agent comprises vanadium (IV,V) oxide (" ^On), vanadium oxide, ammonium vanadate, ammonium iodate, ammonium periodate, iodic acid, periodic acid, or combinations thereof; the at least one etchant comprises HF, ammonium bifluoride, or combinations thereof; the at least one corrosion inhibitor comprises 5-methyl-lH-benzotriazole, pyrazole, benzotriazole, myristyltrimethylammonium bromide, benzalkonium chloride, hexadecyltrimethylammonium p-toluenesulfonate, hexadecyltrimethylammonium hydroxide, 5-benzyl-lH-tetrazole, or combinations thereof; the at least one Ge/SiGe passivating agent comprises pyruvic acid, the at least one pH adjustor comprises tetrafluoroboric acid, sulfuric acid, or combinations thereof, and the at least one organic solvent comprises butylene carbonate (BC), ethylene carbonate, propylene carbonate (PC), ethylene glycol, 1,2- and 1,3-propylene glycol, dipropylene glycol, di ethylene glycol (DEG), DMSO, di ethylene glycol monobutyl ether, diethylene glycol monohexyl ether, or combinations thereof.
[0041] In yet another embodiment, the composition of the first aspect comprises, consists of, or consists essentially of at least one oxidizing agent, at least one etchant, at least one corrosion inhibitor, at least one Ge/SiGe passivating agent, water, at least one pH adjustor, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide, present in the following ranges, based on the total weight of the composition:
component % by weight more preferred % most preferred % by weight by weight oxidizing agent(s) about 0.0001 wt% about 0.001 wt% about 0.001 wt% to about 2 wt% to about 1 wt% to about 0.2 wt% etchant(s) about 0.01 wt% to about 0.01 wt% to about 0.1 wt% to about 10 wt% about 5 wt% about 2.5 wt% corrosion inhibitor(s) about 0.0001 wt% about 0.0001 wt% about 0.001 wt% to about 10 wt% to about 5 wt% to about 2 wt%
Ge/SiGe passivating about 0.001 wt% about 0.01 wt% to about 0.01 wt% to agent(s) to about 5 wt% about 4 wt% about 3 wt% pH adjustor(s) about 0.001 wt% about 0.01 wt% to about 0.01 wt% to to about 7 wt% about 6 wt% about 5 wt% organic solvent(s/ about 1 wt% to about 5 wt% to about 10 wt% to about 50 wt% about 30 wt% about 20 wt% water about 16 wt% to about 49 wt% to about 67.3 wt% to about 99 wt% about 95 wt% about 89.9 wt% In a particularly preferred embodiment of the composition, the at least one oxidizing agent comprises vanadium (IV,V) oxide ("V^On), vanadium oxide, ammonium vanadate, ammonium iodate, ammonium periodate, iodic acid, periodic acid, or combinations thereof; the at least one etchant comprises HF, ammonium bifluoride, or combinations thereof; the at least one corrosion inhibitor comprises 5-methyl-lH-benzotriazole, pyrazole, benzotriazole, myristyltrimethylammonium bromide, benzalkonium chloride, hexadecyltrimethylammonium p-toluenesulfonate, hexadecyltrimethylammonium hydroxide, 5-benzyl-lH-tetrazole, or combinations thereof; the at least one Ge/SiGe passivating agent comprises pyruvic acid, the at least one pH adjustor comprises hydrochloric acid, sulfuric acid, or combinations thereof, and the at least one organic solvent comprises butylene carbonate (BC), ethylene carbonate, propylene carbonate (PC), ethylene glycol, 1,2- and 1,3-propylene glycol, dipropylene glycol, di ethylene glycol (DEG), DMSO, di ethylene glycol monobutyl ether, diethylene glycol monohexyl ether, or combinations thereof.
[0042] In still another embodiment, the composition of the first aspect comprises, consists of, or consists essentially of at least one oxidizing agent, at least one etchant, at least one corrosion inhibitor, at least one Ge/SiGe passivating agent, water, at least one pH adjustor, at least one low-k passivating agent, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide, present in the following ranges, based on the total weight of the composition:
component % by weight more preferred % most preferred % by weight by weight oxidizing agent(s) about 0.0001 wt% about 0.001 wt% about 0.001 wt% to about 2 wt% to about 1 wt% to about 0.2 wt% etchant(s) about 0.01 wt% to about 0.01 wt% to about 0.1 wt% to about 10 wt% about 5 wt% about 2.5 wt% corrosion inhibitor(s) about 0.0001 wt% about 0.0001 wt% about 0.001 wt% to about 10 wt% to about 5 wt% to about 2 wt%
Ge/SiGe passivating about 0.001 wt% about 0.01 wt% to about 0.01 wt% to agent(s) to about 5 wt% about 4 wt% about 3 wt% pH adjustor(s) about 0.001 wt% about 0.01 wt% to about 0.01 wt% to to about 7 wt% about 6 wt% about 5 wt% low-k passivating agent(s) about 0.01 wt% to about 0.01 wt% to about 0.01 wt% to about 2 wt% about 1 wt% about 0.5 wt% organic solvent(s/ about 1 wt% to about 5 wt% to about 10 wt% to about 50 wt% about 30 wt% about 20 wt% water about 14 wt% to about 48 wt% to about 66.8 wt% to about 99 wt% about 95 wt% about 89.9 wt%
In a particularly preferred embodiment of the composition, the at least one oxidizing agent comprises vanadium (IV,V) oxide ("V^On), vanadium oxide, ammonium vanadate, ammonium iodate, ammonium periodate, iodic acid, periodic acid, or combinations thereof; the at least one etchant comprises HF, ammonium bifluoride, or combinations thereof; the at least one corrosion inhibitor comprises 5-methyl-lH-benzotriazole, pyrazole, benzotriazole, myristyltrimethylammonium bromide, benzalkonium chloride, hexadecyltrimethylammonium p-toluenesulfonate, hexadecyltrimethylammonium hydroxide, 5-benzyl-lH-tetrazole, or combinations thereof; the at least one Ge/SiGe passivating agent comprises pyruvic acid, the at least one pH adjustor comprises hydrochloric acid, sulfuric acid, or combinations thereof, the at least one low-k passivating agent comprises boric acid, and the at least one organic solvent comprises butylene carbonate (BC), ethylene carbonate, propylene carbonate (PC), ethylene glycol, 1,2- and 1,3-propylene glycol, dipropylene glycol, diethylene glycol (DEG), DMSO, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, or combinations thereof.
[0043] It will be appreciated that it is common practice to make concentrated forms of the composition to be diluted prior to use. For example, the composition may be manufactured in a more concentrated form and thereafter diluted with at least one solvent, e.g., water and/or 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. It should further be appreciated that the compositions described herein include oxidizing agents, which can be unstable over time. Accordingly, the concentrated form can be substantially devoid of oxidizing agent(s) and the oxidizing agent can be introduced to the concentrate or the diluted composition by the manufacturer before use and/or during use at the fab.
[0044] 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.
[0045] Accordingly, a second aspect relates to a kit including, in one or more containers, one or more components adapted to form the compositions described herein. The containers of the kit must be suitable for storing and shipping said 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 composition to a process tool.
[0046] 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, polyvinyl chloride, 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).
[0047] 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.
[0048] In a third aspect, the invention relates to methods of etching titanium nitride material from the surface of the microelectronic device having same thereon using the composition described herein. For example, titanium nitride material may be removed without substantially damaging/removing semiconductor substrates, metal conductor, and insulator materials that are present on the microelectronic device. Accordingly, in a preferred embodiment, a method of selectively and substantially removing titanium nitride and/or photoresist etch residue materials relative to semiconductor substrates, metal conductor, and insulator materials from the surface of the microelectronic device having same thereon is described using the composition described herein. In another preferred embodiment, a method of selectively and substantially removing titanium nitride and/or photoresist etch residue materials relative to metal conductor (e.g., copper), tungsten, germanium, silicon germanide, and insulator materials from the surface of the microelectronic device having same thereon is described using the compositions described herein.
[0049] In application, the composition is applied in any suitable manner to the surface of the microelectronic device having the titanium nitride and/or photoresist etch residue 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 titanium nitride and/or photoresist etch residue 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 titanium nitride and/or photoresist etch residue 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 titanium nitride and/or photoresist etch residue 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 titanium nitride and/or photoresist etch residue material relative to other materials that may be present on the microelectronic device structure and exposed to the composition, such as semiconductor substrates, metals, and insulating materials (i.e., low-k dielectrics), achieve at least partial removal of the titanium nitride and/or photoresist etch residue material in a highly efficient and highly selective manner.
[0050] In use of the compositions described herein for removing titanium nitride and/or photoresist etch residue material from microelectronic device structures having same thereon, the composition typically is contacted with the device structure in a single wafer tool for a sufficient time of from about 0.3 minute to about 30 minutes, preferably about 0.5 minutes to about 3 minutes, at temperature in a range of from about 20°C to about 100°C, preferably about 45°C to about 60°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 titanium nitride and/or photoresist etch residue material from the device structure.
[0051] 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.
[0052] Following the achievement of the desired removal 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 described herein. 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.).
[0053] The compositions preferably selectively etch titanium nitride material relative to semiconductor substrates, metal conductor, and insulating (i.e., low-k dielectric) materials. In one embodiment, the etch rate of titanium nitride is high (upwards of 50 A min"1, preferably upwards of about 35 A min"1 at 50°C and, while the etch rate of metal (e.g., Cu and W) is low ( less about 10 A min"1, preferably less than about 5 A min"1) and the etch rate of low-k dielectric is low (less than about 10 A min"1, preferably less than about 5 A min"1) at the same temperature.
[0054] A fourth aspect relates to the improved microelectronic devices made according to the methods described herein and to products containing such microelectronic devices.
[0055] A fifth 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 titanium nitride and/or photoresist etch residue material from the surface of the microelectronic device having same thereon, and incorporating said microelectronic device into said article, wherein the composition comprises, consists of or consists essentially of at least one oxidizing agent, at least one etchant, at least one corrosion inhibitor, at least one Ge/SiGe passivating agent, water, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide. The composition may further comprise, consist of or consist essentially of titanium nitride material.
[0056] A sixth aspect of the invention relates to an article of manufacture comprising, consisting of or consisting essentially of a microelectronic device substrate, a titanium nitride layer on said substrate, and a composition described herein.
[0057] The features and advantages of the invention are more fully shown by the illustrative examples discussed below.
Example 1
[0058] Formulations comprising 0.8 wt% HBF4 (as pH adjuster), 0.5 wt % pyrazole, 0.01 wt% periodic acid (50%), and the other constituents (in wt. %) recited in Table 1 were prepared. SiGe, tungsten, TiN and PETEOS coupons were immersed in each formulation at 50°C for time indicated and the etch rates determined.
[0059] It can be seen that the pyruvic acid kept the SiGe etch rate relatively low. Without the additional V6Oi3 oxidizer, the SiGe etch rate was as high as 12.5 A min"1.
Example 2
[0060] Formulations comprising 0.8 wt% HBF4 (as pH adjuster), 0.5 wt % pyrazole, and the other constituents (in wt. %) recited in Table 2 were prepared, wherein at least one of the two oxidizers was present in an amount of at least 0.001 wt%. SiGe, tungsten, TiN and PETEOS coupons were immersed in each formulation at 50°C for time indicated and the etch rates determined.
[0061] The importance of the etchant for the removal of the TiN, as well as the Ge/SiGe passivating agent is readily evidenced in Table 2.
Table 1 : Formulations prepared and etch rates.
Figure imgf000019_0001
Table 2: Formulations prepared and etch rates.
Figure imgf000020_0001
Example 3
[0062] Formulations Y and Z recited in Table 3 were prepared. SiGe, tungsten, TiN, PETEOS, and low-k dielectric (BD-II) coupons were immersed in each formulation at 60°C for time indicated and the etch rates determined.
Table 3: Formulations prepared and etch rates.
Figure imgf000021_0001
* * *
[0063] 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. A composition for selectively removing titanium nitride and/or photoresist etch residue material from the surface of a microelectronic device having same thereon, said composition comprising at least one oxidizing agent, at least one etchant, at least one corrosion inhibitor, at least one Ge/SiGe passivating agent, water, and at least one organic solvent, wherein the composition is substantially devoid of hydrogen peroxide, wherein the at least one Ge/SiGe passivating agent comprises a species selected from the group consisting of pyruvic acid, 1,2-hexanediol, oxalacetic acid, benzalkonium chloride, polyacrylic acid, glucose, acetoacetic acid, levulinic acid, 2-oxo glutarate, polyethylene glycol (e.g., PEG 200), dodecyltrimethylammonium chloride (DTAC), and combinations thereof.
2. The composition of claim 1, wherein the etchant comprises a species selected from the group consisting of H2ZrF6, H2TiF6, HPF6, HF, ammonium fluoride, ammonium bifluoride, tetrafluoroboric acid, hexafluorosilicic acid, tetrabutylammonium tetrafluoroborate (TBA-BF4), ammonium hexafluorosilicate, ammonium hexafluorotitanate, tetraalkylammonium fluoride (NR1R2R3R4F), tetraalkylammonium hydroxide (NR1R2R3R4OH), where Ri, R2, R3, R4 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, weak bases, and combinations thereof, preferably a species selected from the group consisting of HF, ammonium bifluoride, tetrafluoroboric acid, hexafluorosilicic acid, and combinations thereof.
3. The composition of any of the preceding claims, wherein the oxidizing agent comprises a species selected from the group consisting of FeCl3 (both hydrated and unhydrated), Fe(N03)3, Sr(N03)2, C0F3, FeF3, MnF3, oxone (2KHSO5 KHSO4 K2SO4), periodic acid, iodic acid, vanadium (V) oxide, vanadium (IV, V) oxide, ammonium vanadate, ammonium peroxomonosulfate, ammonium chlorite (NH4CIO2), ammonium chlorate (NH4CIO3), ammonium iodate (NH4IO3), ammonium nitrate (NH4NO3), ammonium perborate (NH4BO3), ammonium perchlorate ( H4CIO4), ammonium periodate (NH4IO3), ammonium persulfate ((NH4)2S208), ammonium hypochlorite (NH4CIO), ammonium tungstate ((NH4)i0H2(W2O7)), sodium persulfate (Na2S208), sodium hypochlorite (NaCIO), sodium perborate, potassium iodate (KJO3), potassium permanganate (KMn04), potassium persulfate, nitric acid (HNO3), potassium persulfate (K2S208), potassium hypochlorite (KCIO), tetramethylammonium chlorite ((N(CH3)4)C102), tetramethylammonium chlorate ((N(CH3)4)C103), tetramethylammonium iodate ((N(CH3)4)I03), tetramethylammonium perborate ((N(CH3)4)B03), tetramethylammonium perchlorate ((N(CH3)4)C104), tetramethylammonium periodate ((N(CH3)4)I04), tetramethylammonium persulfate ((N(CH3)4)S208), tetrabutylammonium peroxomonosulfate, peroxomonosulfuric acid, ferric nitrate (Fe(N03)3), peracetic acid (CH3(CO)OOH), 1,4-benzoquinone, toluquinone, dimethyl-l,4-benzoquinone, chloranil, alloxan, N-methylmorpholine N-oxide, trimethylamine N-oxide, and combinations thereof, preferably a species selected from the group consisting of V6Oi3, vanadium oxide, ammonium iodate, ammonium periodate, ammonium vanadate, periodic acid, iodic acid, and combinations thereof.
4. The composition of any of the preceding claims, wherein the oxidizing agent comprises a species selected from the group consisting of ν6Οι3> periodic acid, and combinations thereof.
5. The composition of any of the preceding claims, wherein the at least one corrosion inhibitor comprises a species selected from the group consisting of 5-amino-l,3,4-thiadiazole-2 -thiol (ATDT), benzotriazole (BTA), 1 ,2,4-triazole (TAZ), tolyltriazole, 5-methyl-benzotriazole (mBTA), 5-phenyl- benzotriazole, 5-nitro-benzotriazole, benzotriazole carboxylic acid, 3-amino-5-mercapto-l,2,4- triazole, 1 -amino- 1,2,4-triazole, hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino- 1,2,3-triazole, l-amino-5-methyl-l,2,3-triazole, 3-amino-l,2,4-triazole, 3-mercapto-l,2,4-triazole, 3- isopropyl- 1,2,4-triazole, 5-phenylthiol-benzotriazole, halo-benzotriazoles (halo = F, CI, Br or I), naphthotriazole, 2-mercaptobenzimidazole (MBI), 2-mercaptobenzothiazole, 4-methyl-2- phenylimidazole, 2-mercaptothiazoline, 5-aminotetrazole, pentylenetetrazole, 5-phenyl-lH-tetrazole, 5-benzyl-lH-tetrazole, Ablumine O, 2-benzylpyridine, succinimide, maleimide, phthalimide, glutarimide, 2,4-diamino-6-methyl-l,3,5-triazine, thiazole, pyrazole, triazine, methyltetrazole, 1,3- dimethyl-2-imidazolidinone, 1 ,5-pentamethylenetetrazole, 1 -phenyl-5-mercaptotetrazole, diaminomethyltriazine, imidazoline thione, 4-methyl-4H-l,2,4-triazole-3 -thiol, benzothiazole, imidazole, indiazole, adenosine, carbazole, saccharin, benzoin oxime, PolyFox PF-159, poly( ethylene glycol), poly(propylene glycol), PEG-PPG copolymers, dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, benzalkonium chloride, benzyldimethyldodecylammonium chloride, myristyltrimethylammonium bromide, dodecyltrimethylammonium bromide, hexadecylpyridinium chloride, Aliquat 336, benzyldimethylphenylammonium chloride, Crodaquat TES, Rewoquat CPEM, hexadecyltrimethylammonium p-toluenesulfonate, hexadecyltrimethylammonium hydroxide, 1- methyl-r-tetradecyl-4,4'-bipyridium di chloride, alkyltrimethylammonium bromide, amprolium hydrochloride, benzethonium hydroxide, benzethonium chloride, benzyldimethylhexadecylammonium chloride, benzyldimethyltetradecylammonium chloride, benzyldodecyldimethylammonium bromide, benzyldodecyldimethylammonium chloride, cetylpyridinium chloride, choline p-toluenesulfonate salt, dimethyldioctadecylammonium bromide, dodecylethyldimethylammonium bromide, dodecyltrimethylammonium chloride, ethylhexadecyldimethylammonium bromide, Girard's reagent, hexadecyl(2- hydroxyethyl)dimethylammonium dihydrogen phosphate, dexadecylpyridinium bromide, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, methylbenzethonium chloride, Hyamine® 1622, Luviquat™, Ν,Ν',Ν'-polyoxyethylene (lO)-N-tallow- 1,3-diaminopropane liquid, oxyphenonium bromide, tetraheptylammonium bromide, tetrakis(decyl)ammonium bromide, thonzonium bromide, tridodecylammonium chloride, trimethyloctadecylammonium bromide, l-methyl-3-n-octylimidazolium tetrafluoroborate, l-decyl-3- methylimidazolium tetrafluoroborate. l-decyl-3-methylimidazolium chloride, tridodecylmethylammonium bromide, dimethyldistearylammonium chloride, hexamethonium chloride, and combinations thereof, preferably a species selected from the group consisting of pyrazole, a benzotriazole derivative, a cationic quaternary surfactant, and a combination thereof.
6. The composition of any of the preceding claims, wherein the at least one organic solvent comprises a species selected from the group consisting of methanol, ethanol, isopropanol, butanol, pentanol, hexanol, 2-ethyl-l-hexanol, heptanol, octanol, ethylene glycol, 1,2- and 1,3 -propylene glycol, 1,2-, 1,3-, and 1 ,4-butanediol, tetrahydrofurfuryl alcohol (THFA), butylene carbonate, ethylene carbonate, propylene carbonate, dipropylene glycol, diethylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether (TPGME),dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n- propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, 2,3-dihydrodecafluoropentane, ethyl perfluorobutyl ether, methyl perfluorobutylether, alkylene carbonates, 4-methyl-2-pentanol, tetramethylene glycol dimethyl ether, dimethyl sulfoxide, sulfolane, methanesulfonic acid (MSA), and combinations thereof, preferably diethylene glycol monoethyl ether, diethylene glycol methyl ether, propylene glycol, ethylene glycol, tetraethylene glycol dimethyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, or combinations thereof, preferably a species selected from the group consisting of butylene carbonate (BC), ethylene carbonate, propylene carbonate (PC), ethylene glycol, 1,2- and 1,3-propylene glycol, dipropylene glycol, diethylene glycol (DEG), DMSO, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, and combinations thereof.
7. The composition of any of the preceding claims, wherein the composition further comprises at least one additional component selected from the group consisting of at least one source of silica, at least one low-k passivating agent, at least one surfactant, at least one iodine scavenger, and combinations thereof.
8. The method of claim 7, wherein the composition further comprises at least one low-k passivating agent selected from the group consisting of boric acid, ammonium pentaborate, sodium tetraborate, 3- hydroxy-2 -naphthoic acid, malonic acid, iminodiacetic acid, and combinations thereof.
9. The composition of any of the preceding claims, wherein the composition is substantially devoid of amines, chemical mechanical polishing abrasive materials, metal halides, and combinations thereof.
10. The composition of any of the preceding claims, wherein the composition has a TiN to tungsten selectivity of greater than 50:1 and a tungsten removal rate less than about 2 A min"1 at temperatures in a range from about 45°C to about 60°C.
11. The composition of any of the preceding claims, wherein the composition has a TiN to SiGe selectivity of greater than 50: 1 and a SiGe removal rate less than about 3 A min"1 at temperatures in a range from about 45°C to about 60°C.
12. The composition of any of the preceding claims, wherein the pH of the composition is in a range from about 0 to about 4.
13. The composition of any of the preceding claims, wherein the amount of water in the composition is in a range from about 0.1 wt% to about 50 wt%, preferably about 1 wt% to about 30 wt%, and even more preferably about 5 wt% to about 20 wt%, based on the total weight of the composition.
14. The composition of any of claims 1-12, wherein the amount of organic solvent in the composition is in a range from about 0.1 wt% to about 50 wt%, preferably about 1 wt% to about 30 wt%, and even more preferably about 5 wt% to about 20 wt%, based on the total weight of the composition.
15. A method of etching titanium 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 - 14, wherein the composition selectively removes the titanium nitride material from the surface relative to semiconductor substrates, metals, and insulating materials.
16. The method of claim 15, wherein the contacting comprises time in a range from about 0.3 minute to about 30 minutes at temperature in a range of from about 20°C to about 100°C.
17. The method of any of claims 15-16, wherein the composition is rinsed from the surface following the desired etching action.
18. The method of any of claims 15-17, wherein the metals comprise copper, tungsten or both.
19. The method of any of claims 15-18, wherein the semiconductor substrates comprise germanium or silicon germanide.
20. The method of any of the claims 15-19, wherein the composition has a TiN to tungsten selectivity of greater than 50:1 and a tungsten removal rate less than about 2 A min"1 at temperatures in a range from about 45°C to about 60°C.
21. The method of any of the claims 15-19, wherein the composition has a TiN to SiGe selectivity of greater than 50:1 and a SiGe removal rate less than about 3 A min"1 at temperatures in a range from about 45°C to about 60°C.
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