Selective wet etching compositions and methods

Abstract

Compositions and methods are provided for etching molybdenum-containing films on microelectronic device substrates. The microelectronic device substrate is contacted with the compositions of the invention for a time sufficient to at least partially remove the molybdenum-containing film. The compositions include at least one oxidizing agent, at least one complexing agent, and at least one cationic surfactant, and have a pH of about 7.5 to about 13. The etchant compositions selectively remove molybdenum at room temperature at an etch rate of about 20 to 50 Å / min with improved uniformity of removal.

Description

[Technical Field]

[0001] FIELD OF THE INVENTION The present invention pertains generally to etching or removing molybdenum-containing materials from microelectronic device substrates. [Background technology]

[0002] Typically, tungsten and tungsten-based materials are used as electrodes in 3D-NAND manufacturing. However, tungsten materials have been found to be sensitive to various etchant compositions. For example, in processes using W electrodes, acidic compositions containing phosphoric acid and nitric acid (so-called "W recess") used for electrode separation have been found to cause partial etching of the tungsten layer.

[0003] Currently, 3D-NAND structures are finding utility in memory devices. To achieve better memory performance efficiency, 3D-NAND manufacturers have been investigating other materials that can provide superior performance in memory devices. In particular, many 3D-NAND manufacturers are replacing the W layer with molybdenum. As a result, manufacturers need etchant compositions that can selectively remove Mo in the recesses without removing materials such as TEOS and aluminum oxide. Of particular interest are etchant compositions that can selectively remove molybdenum at an etch rate that allows each recess to achieve substantially the same target etch depth under controlled etching conditions. Summary of the Invention

[0004] Compositions and methods are provided for selectively etching molybdenum-containing films on microelectronic device substrates. The microelectronic device substrate is contacted with the composition of the present invention for a time sufficient to at least partially remove the molybdenum-containing film. The composition comprises, consists of, or consists essentially of at least one oxidizing agent, at least one cationic surfactant, water, and an amount of a pH adjuster necessary to achieve a pH of about 7 to about 13. The etchant composition selectively removes molybdenum at room temperature at an etch rate of about 20 to 50 Å / min, with improved removal uniformity. [Brief explanation of the drawings]

[0005] [Figure 1] 1 is a simplified diagram of a microelectronic device substrate having molybdenum, TEOS, and aluminum oxide surfaces. The data provided in the Examples characterize the amount and uniformity of etching relative to device depth from the top, center, and bottom. [Figure 2] 1 is a bar graph showing the Z ranges of various experiments reflected in the Examples, illustrating the improved roughness parameters of molybdenum-containing films subjected to etching using the compositions of the present invention. (Rz is the average value of the roughness depth a for successive sampling lengths. Z is the sum of the height of the highest peak and the depth of the lowest valley within the sampling length.) [Figure 3] 1A-1C are scanning electron micrographs (SEM) of various sample surfaces as shown in the examples, showing that the roughness (Rz) is much higher in samples etched with compositions that do not contain cationic surfactants. DETAILED DESCRIPTION OF THE INVENTION

[0006] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. As used in this specification and the appended claims, the term "or" is generally used in its sense including "and / or" unless the context clearly dictates otherwise.

[0007] The term "about" generally refers to a range of numbers that are considered equivalent to a recited value (e.g., having the same function or result). In many instances, the term "about" can include numbers that are rounded to the nearest significant figure.

[0008] Numerical ranges expressed using endpoints include all numbers subsumed within that range (eg, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0009] The present invention provides at least one oxidizing agent; at least one cationic surfactant; Water and and a pH adjuster in an amount necessary to achieve a pH of about 7 to about 13, and optionally at least one complexing agent, at least one pH buffering agent, or At least one oxidant stabilizer and one or more of:

[0010] The compositions of the present invention are useful for etching, i.e., removing, molybdenum-containing films from the surface of microelectronic device substrates. In particular, the compositions exhibit excellent selectivity to molybdenum-containing materials while limiting damage to surfaces including TEOS and aluminum oxide.

[0011] As used herein, the term "microelectronic device" corresponds to semiconductor substrates, including 3D NAND structures, flat panel displays, and microelectromechanical systems (MEMS), fabricated for use in microelectronic, integrated circuit, or computer chip applications. It should be understood that the term "microelectronic device" is not meant to be limiting in any way and includes, for example, any substrate that contains N-type metal oxide semiconductor (nMOS) and / or P-type metal oxide semiconductor (pMOS) transistors and that ultimately becomes a microelectronic device or microelectronic assembly. Such microelectronic devices generally include at least one substrate that can be selected from, for example, silicon, SiO2, Si3N4, OSG, FSG, silicon carbide, hydrogenated silicon carbide, silicon nitride, hydrogenated silicon nitride, silicon carbonitride, hydrogenated silicon carbonitride, boron nitride, antireflective coatings, photoresist, germanium, germanium-containing, boron-containing, Ga / As, flexible substrates, porous inorganic materials, metals such as copper and aluminum, and diffusion barrier layers such as, but not limited to, TiN, Ti(C)N, TaN, Ta(C)N, Ta, W, or WN. The films are compatible with various subsequent processing steps, such as, for example, chemical mechanical planarization (CMP) and anisotropic etching processes.

[0012] Microelectronic devices include molybdenum-containing materials. As used herein, "molybdenum-containing materials" and "molybdenum" include any material containing more than 50% by weight of elemental molybdenum, based on the total weight of the material. Examples of molybdenum-containing materials include, but are not limited to, pure molybdenum (Mo) and alloys or mixtures containing molybdenum, as well as molybdenum oxide and molybdenum carbide. For example, molybdenum deposited during the fabrication of microelectronic devices may also generally contain less than 5% by weight of aluminum (Mo-Al) or titanium (Mo-Ti), and "molybdenum" is known to include these materials. It should be understood by those skilled in the art that the chemical formulas of various molybdenum species can vary based on the oxidation state of the molybdenum ion, with common oxidation states of molybdenum being -3, -1, +1, +2, +3, +4, +5, or +6.

[0013] The oxidizing agent of the composition is a species capable of oxidizing molybdenum to produce soluble molybdenum species, for example, under alkaline pH conditions. Examples include hydrogen peroxide (H2O2), FeCl3, FeF3, Fe(NO3)3, Sr(NO3)2, CoF3, MnF3, oxone, (2KHSO5·KHSO4·K2SO4), nitric acid (HNO3), ammonium peroxomonosulfate, ammonium chlorite (NH4ClO2), ammonium chlorate (NH4ClO3), ammonium iodate (NH4IO3), ammonium nitrate (NH4NO3), ammonium perborate (NH4BO3), ammonium perchlorate (NH4ClO4), ammonium periodate (NH4IO4), ammonium persulfate ((NH4)2S2O8), ammonium hypochlorite (NH4ClO), ammonium tungstate ((NH4) 10H2(W2O7)), sodium persulfate (Na2S2O8), sodium hypochlorite (NaClO), sodium perborate, potassium iodate (KIO3), potassium permanganate (KMnO4), potassium persulfate (K2S2O8), potassium hypochlorite (KClO), tetramethylammonium chlorite ((N(CH3)4)ClO2), tetramethylammonium chlorate ((N(CH3)4)ClO3), tetramethylammonium iodate ((N(CH3)4)IO3), tetramethylammonium perborate ((N(CH3)4)BO3), tetramethylammonium perchlorate Examples of suitable oxidizing agents include ammonium peroxide ((N(CH3)4)ClO4), tetramethylammonium periodate ((N(CH3)4)1O4), tetramethylammonium persulfate ((N(CH3)4)SO8), tetrabutylammonium peroxomonosulfate, peroxomonosulfate, urea hydrogen peroxide ((CO(NH2)2)HO2), peracetic acid (CH3(CO)OOH), t-butyl hydroperoxide, nitrobenzene sulfonate, 1,4-benzoquinone, toluquinone, dimethyl-1,4-benzoquinone, chloranil, alloxan, periodic acid, and combinations thereof. In one embodiment, the oxidizing agent is selected from hydrogen peroxide, urea hydrogen peroxide, ammonium persulfate, periodic acid, peracetic acid, or t-butyl hydroperoxide.

[0014] The oxidizing agent can be present in any amount effective to remove molybdenum from the microelectronic device, especially in the presence of other metal layers. In one embodiment, the etchant composition can include about 0.1 weight percent to about 5 weight percent oxidizing agent. In other embodiments, the amount of oxidizing agent is about 0.1 weight percent to about 2 weight percent, or about 0.1 weight percent to about 1 weight percent. The oxidizing agent can be introduced directly into the composition or prepared as part of an oxidizing agent solution, which can then be combined with the remaining ingredients before contacting the microelectronic device. In the latter case, decomposition of the oxidizing agent is further prevented by minimizing the amount of time the oxidizing agent is exposed to alkaline conditions.

[0015] The composition comprises at least one pH adjusting agent in an amount necessary to provide a pH of the composition of at least about 7. In one embodiment, the pH of the composition is from about 7.5 to about 13, and in another embodiment, from about 8 to about 11. Examples of suitable pH adjusters include, but are not limited to, alkali metal hydroxides, alkaline earth metal hydroxides, tetraalkylammonium hydroxides (e.g., tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), and tetrabutylammonium hydroxide (TBAH)), tributylmethylammonium hydroxide (TBMAH), benzyltrimethylammonium hydroxide (BTMAH), choline hydroxide, ethyltrimethylammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, diethyldimethylammonium hydroxide, tetraalkylphosphonium hydroxides (e.g., tetrabutylphosphonium hydroxide (TBPH), tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, and tetrapropylphosphonium hydroxide), benzyltriphenylphosphonium hydroxide, methyltriphenylphosphonium hydroxide, ethyltriphenylphosphonium hydroxide, N-propyltriphenylphosphonium hydroxide, and combinations thereof. In one embodiment, the pH adjuster is selected from tetramethylammonium hydroxide or choline hydroxide.

[0016] In certain embodiments, the pH adjuster used herein is present in an amount of from about 0.1% to about 10% by weight, or from about 0.1% to about 8% by weight, or from about 0.1% to about 5% by weight.

[0017] The compositions described herein may be, and in one embodiment are substantially devoid of, ammonia or ammonium hydroxide. In another embodiment, the etchant composition is free of ammonia and ammonium hydroxide. While these bases are effective in raising the pH to a desired level, they present substantial health and environmental concerns and significantly increase the costs of managing and mitigating these issues.

[0018] Cationic surfactants are generally salts of quaternary ammonium salts and can be useful for passivating surfaces to allow for selective and uniform removal of molybdenum-containing materials. Exemplary cationic surfactants include cetyltrimethylammonium bromide (CTAB) (also known as hexadecyltrimethylammonium bromide), hexadecyltrimethylammonium chloride (CTAC), heptadecanefluorooctanesulfonic acid, tetraethylammonium halide, stearyltrimethylammonium chloride, 4-(4-diethylaminophenylazo)-1-(4-nitrobenzyl)pyridium bromide, cetylpyridinium chloride monohydrate, benzalkonium chloride, benzethonium chloride, benzyldimethyldodecylammonium chloride, benzyldimethylhexadecylammonium chloride, hexadecyltrimethylammonium bromide, and hexadecyltrimethylammonium bromide. ammonium bromide, dimethyldioctadecyl ammonium chloride, dodecyltrimethyl ammonium chloride, didodecyl dimethyl ammonium bromide, di(hydrogenated tallow)dimethyl ammonium chloride, tetraheptyl ammonium bromide, tetrakis(decyl)ammonium bromide, and oxyphenonium bromide, dimethyldioctadecyl ammonium chloride, dimethyldihexadecyl ammonium bromide, di(hydrogenated tallow)dimethyl ammonium chloride, hexamethonium chloride, trimethyltetradecyl ammonium chloride, decyltrimethyl ammonium chloride, and benzyl dimethyl ammonium chloride (BDAC).

[0019] In addition to the components described above, the compositions of the present disclosure may further comprise, consist of, or consist essentially of any additional components present to further improve and / or enhance the performance of the composition for selectively removing molybdenum from microelectronic devices. For example, the etchant composition may optionally further comprise one or more of at least one complexing agent, at least one pH buffer, or at least one oxidant stabilizer. The composition may include one or more of these components alone or in any combination. For example, the composition may include both a complexing agent and a pH buffer. Additionally or additionally, the composition may further include an oxidant stabilizer added to the composition before or in combination with the oxidant.

[0020] As used herein, "complexing agent" includes compounds understood by those skilled in the art to be complexing agents, chelating agents, and / or sequestering agents. When present, the complexing agent chemically bonds with or physically retains the molybdenum atoms and / or ions being removed from the microelectronic device using the compositions described herein, improving the etch rate of this material. Suitable complexing agents include aminoethylethanolamine, N-methylaminoethanol, aminoethoxyethanol, dimethylaminoethoxyethanol, diethanolamine, N-methyldiethanolamine, monoethanolamine (MEA), triethanolamine (TEA), 1-amino-2-propanol, 2-amino-1-butanol, isobutanolamine, triethylenediamine, 4-(2-hydroxyethyl)morpholine (HEM), ethylenediaminetetraacetic acid (EDTA), m-xylenediamine (MXDA), iminodiacetic acid (IDA), 2-(hydroxyethyl)iminodiacetic acid (HIDA), nitrilotriacetic acid, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, uric acid, alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, histidine, isoleucine, leucine, and lysine. , methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), 1,5,9-triazacyclododecane-N,N',N''-tris(methylenephosphonic acid) (DOTRP), 1,4,7,10-tetraazacyclododecane-N,N',N'',N'''-tetrakis(methylenephosphonic acid) (DOTP), nitrilotriazole Tris(methylene)triphosphonic acid, diethylenetriaminepentakis(methylenephosphonic acid) (DETAP), aminotri(methylenephosphonic acid), bis(hexamethylene)triaminepentamethylenephosphonic acid, 1,4,7-triazacyclononane-N,N',N''-tris(methylenephosphonic acid (NOTP), hydroxyethyl diphosphonate, nitrilotris(methylene)phosphonic acid, 2-phosphonobutane-1,2,3,Examples of suitable complexing agents include, but are not limited to, 4-tetracarboxylic acid, carboxyethylphosphonic acid, aminoethylphosphonic acid, glyphosate, ethylenediaminetetra(methylenephosphonic acid), phenylphosphonic acid, oxalic acid, succinic acid, maleic acid, malic acid, malonic acid, adipic acid, phthalic acid, lactic acid, citric acid, sodium citrate, potassium citrate, ammonium citrate, tricarballylic acid, trimethylolpropionic acid, tartaric acid, glucuronic acid, 2-carboxypyridine, 4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt, and combinations thereof. In one embodiment, the complexing agent is selected from 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), lactic acid, or citric acid.

[0021] The complexing agent can be present in any amount effective to improve the etching rate of molybdenum. For example, if used, the composition can include from about 0.1% to about 20% by weight of the complexing agent. In another embodiment, the amount of complexing agent is from about 0.5% to about 15% by weight, and in another embodiment, from about 1.0% to about 10% by weight.

[0022] When present, a pH buffering agent can be used to maintain and stabilize the pH of the composition, particularly when used to selectively remove molybdenum-containing materials. The pH buffering agent can be a metal corrosion inhibitor, which protects the metal layer from oxidation and thereby stabilizes the pH during molybdenum layer removal, or an ammonium salt, which can buffer the composition from pH changes and extend the composition's shelf life. Combinations of these agents can also be used.

[0023] For example, in one optional embodiment, the composition includes at least one metal corrosion inhibitor as a pH buffer, such as 5-aminotetrazole, 5-phenyl-benzotriazole, 1H-tetrazole-5-acetic acid, 1-phenyl-2-tetrazoline-5-thione, benzimidazole, methyltetrazole, pyrazole, 5-amino-1,3,4-thiadiazole-2-thiol (ATDT), benzotriazole (BTA), 1,2,4-triazole (TAZ), 1,2,3-triazole, tolyltriazole, 5-methyl-benzotriazole (mBTA), 5-phenyl-benzotriazole (mBTA), 5-phenyl-benzotriazole (mBTA), 5-amino-1,3,4-thiadiazole-2-thiol (ATDT ... Triazole, 5-nitro-benzotriazole, benzotriazolecarboxylic acid, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-amino-1,2,4-triazole (3-ATA), 3-mercapto-1,2,4-triazole, 3-isopropyl -1,2,4-triazole, 5-phenylthiol-benzotriazole, halo-benzotriazole (halo = F, Cl, Br or I), naphthotriazole, 2-mercaptobenzimidazole (MBI), 2-mercaptobenzothiazole, 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 5-amino-1,2,4-triazole (5-ATA), 3-amino-5-mercapto-1,2,4-triazole, pentylenetetrazole, 5-phenyl-1H-tetrazoline 4-methyl-4H-1,2,4-triazole, 5-benzyl-1H-tetrazole, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, triazine, methyltetrazole, 1,3-dimethyl-2-imidazolidinone, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, diaminomethyltriazine, imidazolinethione, 4-methyl-4H-1,2,4-triazole-3-thiol, 4-amino-4H-1,2,4-triazole, 3-amino-5-methylthio-1H-1,2,The metal corrosion inhibitor may comprise, consist of, or consist essentially of, but is not limited to, 4-triazole, benzothiazole, imidazole, indiazole, adenine, adenosine, carbazole, N-cyclohexyl-3-aminopropanesulfonic acid, and combinations thereof. Preferably, the metal corrosion inhibitor comprises an azole compound having a pKa of about 9. For example, the metal corrosion inhibitor may be tolyltriazole.

[0024] The optional metal corrosion inhibitor may be present in any amount effective to protect the metal layer from corrosion without significantly affecting the molybdenum etch rate. Thus, the amount of corrosion inhibitor in the etchant composition is an amount that provides an essentially inhibitor-independent Mo etch rate. Specifically, if used, the etchant composition may include from about 0.001 to about 1.0 wt. % of the corrosion inhibitor. In one embodiment, the amount of corrosion inhibitor is from about 0.05 to about 0.5 wt. %, and in another embodiment, from about 0.01 to about 0.10 wt. %.

[0025] In another optional embodiment, the selective etching composition includes an ammonium salt as a pH buffer. Examples of suitable ammonium salts include, for example, ammonium acetate, ammonium bicarbonate, ammonium butyrate, ammonium trifluoroacetate, diammonium monohydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphonate, and combinations thereof.

[0026] In another optional embodiment, the composition further comprises an oxidant stabilizer added to the composition before or in combination with the oxidant. Exemplary stabilizers include glycine, serine, proline, leucine, alanine, asparagine, aspartic acid, glutamine, valine, and lysine, nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid (EDTA), (1,2-cyclohexylenedinitrilo)tetraacetic acid (CDTA), uric acid, tetraglyme, diethylenetriaminepentaacetic acid, propylenediminetetraacetic acid, ethylenediaminedisuccinic acid, sulfanilamide, and combinations thereof. In one embodiment, the oxidant stabilizer is selected from CDTA and EDTA. In one embodiment, the composition may comprise from about 0.0001% to about 1.0% by weight of the oxidant stabilizer. In other embodiments, the amount of oxidant stabilizer present in the composition is from about 0.0005% to about 0.5% by weight, or from about 0.001% to about 0.1% by weight.

[0027] As mentioned above, the composition may be an aqueous composition or a semi-aqueous composition. Thus, in some embodiments, the composition comprises water without any additional solvent, while in other embodiments, the composition further comprises water with at least one water-soluble or water-miscible organic solvent. The inclusion of at least one solvent in combination with water can further improve the performance of the composition, such as improving the planarity of the resulting etched molybdenum surface. Suitable solvents include, for example, methanol, ethanol, isopropanol, butanol, pentanol, hexanol, 2-ethyl-1-hexanol, heptanol, octanol, ethylene glycol, propylene glycol, butylene glycol, butylene carbonate, ethylene carbonate, propylene carbonate, dipropylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol 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 perfluorobutyl ether, alkyl carbonate, alkylene carbonate, 4-methyl-2-pentanol, diethylene glycol isopropyl methyl ether, and combinations thereof.In one embodiment, at least one solvent comprises propylene glycol. If used, the solvent may be present in an amount of about 10% to about 90% by weight of the total solvent (water and solvent) used, or about 30% to about 85% by weight of the total solvent, or about 50% to about 85% by weight of the total solvent, with the remainder being water.

[0028] It will be appreciated that it is common practice to create concentrated forms of compositions that are diluted before use. For example, compositions may be manufactured in a more concentrated form and then diluted with at least one solvent by the manufacturer prior to use and / or during use at the manufacturing plant. The dilution ratio may range from about 0.1 parts diluent:1 part composition concentrate to about 100 parts diluent:1 part composition concentrate. It will be further appreciated that the compositions described herein contain an oxidizing agent that may be unstable over time. Thus, the concentrated form may be substantially free of oxidizing agent, and an oxidizing agent may be introduced into the concentrate or diluted composition by the manufacturer prior to use and / or during use at the manufacturing plant.

[0029] The compositions described herein are easily formulated by simply adding each component and mixing to a homogeneous state. Furthermore, the compositions can be easily formulated as single-package formulations or multi-component formulations, preferably multi-component formulations, that are mixed at or before the time of use. Individual portions of a multi-component formulation can be mixed at the tool, or in a mixing zone / area such as an in-line mixer, or in a storage tank upstream of the tool. It is contemplated that the various portions of a multi-component formulation can contain any combination of ingredients / components that are mixed together to form the desired composition. It is understood that the concentration of each component can vary widely, depending on the specific multiple of the composition, i.e., whether it is more dilute or more concentrated, and that the composition can variously and alternatively comprise, consist of, or consist essentially of any combination of components consistent with the disclosure herein.

[0030] Thus, in a further aspect, the present invention provides a kit comprising, in one or more containers, one or more components adapted to form the compositions described herein. The containers of the kit should be suitable for storing and transporting the aforementioned removal composition components, e.g., a NOWPak® container (Advanced Technology Materials, Inc., Danbury, Connecticut, USA). The one or more containers containing the composition components preferably include a means for fluidly connecting the components within the one or more containers for blending and dispensing. For example, with reference to a NOWPak® container, gas pressure can be applied to the outside of a liner within the one or more containers to expel at least a portion of the liner's contents, thus enabling fluid communication for blending and dispensing. Alternatively, gas pressure can be applied to the headspace of a conventional pressurized container, or a pump can be used to enable fluid communication. Additionally, the system preferably includes a dispense port for dispensing the blended composition to a process tool.

[0031] Substantially chemically inert, impurity-free, flexible, and resilient polymeric film materials, such as high-density polyethylene, can be used to manufacture liners for one or more of the aforementioned containers. Desirable liner materials are processed without the need for coextrusion or barrier layers, and without pigments, UV inhibitors, or processing agents that may adversely affect the purity requirements of the components disposed within the liner. The list of desirable liner materials includes films containing virgin (i.e., unadded) polyethylene, virgin polytetrafluoroethylene (PTFE), polypropylene, polyurethane, polyvinylidene chloride, polyvinyl chloride, polyacetal, polystyrene, polyacrylonitrile, polybutylene, and the like. Preferred thicknesses of such liner materials range from about 5 mils (0.005 inches) to about 30 mils (0.030 inches), e.g., 20 mils (0.020 inches) thick.

[0032] With respect to containers for kits, the disclosures of the following patents and patent applications are each incorporated herein by reference in their entirety: U.S. Pat. No. 7,188,644, entitled "APPARATUS AND METHOD FOR MINIMIZING THE GENERATION OF PARTICLES IN ULTRAPURE LIQUIDS," and U.S. Pat. No. 6,698,619, entitled "RETURNABLE AND REUSABLE, BAG-IN-DRUM FLUID STORAGE AND DISPENSING CONTAINER SYSTEM," each of which is incorporated herein by reference.

[0033] In a further aspect, the present invention provides a method for etching molybdenum from a microelectronic device substrate having a molybdenum-containing film thereon, the method comprising: at least one oxidizing agent, at least one cationic surfactant, water, and A composition comprising a pH adjuster in an amount necessary to achieve a pH of about 7 to about 13, and optionally at least one complexing agent, at least one pH buffering agent, or At least one oxidant stabilizer and a composition comprising one or more of: contacting the molybdenum-containing film for a time sufficient to at least partially remove the film.

[0034] In the methods of the present invention, the composition is as described herein. [Example]

[0035] Example 1 The compositions shown in Table 1 were prepared by combining the various ingredients and adjusting the pH to 9.5-11.5 using (TEAH) as a pH adjuster. The mixture was stirred at room temperature for 15 minutes to obtain a clear solution.

[0036] Molybdenum layered pattern specimens similar to those shown in the simplified diagram in Figure 1 were placed in 200 grams of the specified composition in a 500 mL Teflon beaker equipped with a stir bar and thermocouple. For this series of experiments, the temperature was set at 50 °C with stirring at 600 rpm. Once the temperature stabilized, the specimens were left in the solution for the specified time, followed by a 30-second static DIW rinse followed by a 1-minute DIW flow. The rinsed specimens were dried with in-house nitrogen and analyzed by SEM. The results obtained for the top, middle, and bottom sections of the layered pattern are shown in Table 1. TIFF0007729988000001.tif76170

[0037] As can be seen from this data, the known etching compositions PAN, SC-1, and SPM (comparative example) exhibited higher etch rates but undesirable uniformity. Samples containing the cationic surfactant BDAC showed a significant impact on micro- and macro-uniformity. Furthermore, it is expected that target recess depths and process times can be achieved by adjusting the concentration of the cationic surfactant.

[0038] Example 2 Compositions of the present disclosure were prepared similar to those described in Example 1 and are shown in Table 2. TIFF0007729988000002.tif129170

[0039] As the data in Table 2 show, the surface roughness of the surfaces etched using the disclosed compositions was lower than that obtained from the control composition. The surface roughness before etching was 3.4. Furthermore, Figure 2 is a bar graph showing the Z range of these compositions, demonstrating the improved roughness parameter of molybdenum-containing films etched using the disclosed compositions. (Rz is the average roughness depth a of successive sampling lengths. Z is the sum of the height of the highest peak and the depth of the lowest valley within the sampling length.) Furthermore, Figure 3 shows scanning electron micrographs (SEMs) of some of these surfaces, demonstrating that the roughness (Rz) is much higher for samples etched with compositions that do not contain cationic surfactants.

[0040] Additional compositions of the present disclosure are shown in Table 3, which also provided improved surface roughness. TIFF0007729988000003.tif109170

[0041] Aspects In a first aspect, the present disclosure provides a method for manufacturing a semiconductor device comprising: at least one oxidizing agent; at least one cationic surfactant; Water and and a pH adjuster in an amount necessary to achieve a pH of about 7 to about 13, and optionally at least one complexing agent, at least one pH buffering agent, or At least one oxidant stabilizer and one or more of: A selective etching composition is provided for removing molybdenum-containing films from microelectronic devices relative to aluminum oxide.

[0042] In a second aspect, the present disclosure provides a method for treating a leukemia disease, the leukemia disease, or a leukemia comprising administering to a patient an effective amount of an oxidizing agent selected from the group consisting of hydrogen peroxide, FeCl3, FeF3, Fe(NO3)3, Sr(NO3)2, CoF3, MnF3, oxone, (2KHSO5·KHSO4·K2SO4), nitric acid, ammonium peroxomonosulfate, ammonium chlorite (NH4ClO2), ammonium chlorate (NH4ClO3), ammonium iodate (NH4IO3), ammonium nitrate (NH4NO3), ammonium perborate (NH4BO3), ammonium perchlorate (NH4ClO4), ammonium periodate (NH4IO4), ammonium persulfate ((NH4)2S2O8), ammonium hypochlorite (NH4ClO), ammonium tungstate ((NH4 10 H2(W2O7)), sodium persulfate (Na2S2O8), sodium hypochlorite (NaClO), sodium perborate, potassium iodate (KIO3), potassium permanganate (KMnO4), potassium persulfate (K2S2O8), potassium hypochlorite (KClO), tetramethylammonium chlorite ((N(CH3)4)ClO2), tetramethylammonium chlorate ((N(CH3)4)ClO3), tetramethylammonium iodate ((N(CH3)4)IO3), tetramethylammonium perborate ((N(CH3)4)BO3), tetramethylammonium perchlorate ammonium ((N(CH3)4)ClO4), tetramethylammonium periodate ((N(CH3)4)lO4), tetramethylammonium persulfate ((N(CH3)4)S2O8), tetrabutylammonium peroxomonosulfate, peroxomonosulfuric acid, urea hydrogen peroxide ((CO(NH2)2)H2O2), peracetic acid, t-butyl hydroperoxide, nitrobenzenesulfonate, 1,4-benzoquinone, toluquinone, dimethyl-1,4-benzoquinone, chloranil, alloxan, periodic acid, and combinations thereof.

[0043] In a third aspect, the present disclosure provides the composition of the first or second aspect, wherein the oxidizing agent is selected from hydrogen peroxide, periodic acid, t-butyl hydroperoxide, potassium iodate, and peracetic acid.

[0044] In a fourth aspect, the present disclosure provides a method for treating a skin ulcer, wherein the cationic surfactant is selected from the group consisting of cetyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, heptadecanefluorooctanesulfonic acid, tetraethylammonium halide, stearyltrimethylammonium chloride, 4-(4-diethylaminophenylazo)-1-(4-nitrobenzyl)pyridium bromide, cetylpyridinium chloride monohydrate, benzalkonium chloride, benzethonium chloride, benzyldimethyldodecylammonium chloride, benzyldimethylhexadecylammonium chloride, hexadecyltrimethylammonium bromide, and hexadecyltrimethylammonium bromide. The present invention provides the compositions of the first to third aspects, wherein the hydroxybenzoate is selected from oxyphenonium bromide, dimethyldioctadecylammonium chloride, dimethyldihexadecylammonium bromide, di(hydrogenated tallow)dimethylammonium chloride, benzyldimethylammonium chloride, and benzyldimethylammonium bromide.

[0045] In a fifth aspect, the present disclosure provides the composition of any one of the first to fourth aspects, wherein the cationic surfactant is selected from benzyldimethylammonium chloride, cetyltrimethylammonium bromide, hexamethonium chloride, trimethyltetradecylammonium chloride, decyltrimethylammonium chloride, and benzyldimethyldodecylammonium chloride.

[0046] In a sixth aspect, the present disclosure provides a composition of any one of the first to fifth aspects, wherein the pH adjuster is selected from alkali metal hydroxides, alkaline earth metal hydroxides, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), tributylmethylammonium hydroxide (TBMAH), benzyltrimethylammonium hydroxide (BTMAH), choline hydroxide, ethyltrimethylammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, diethyldimethylammonium hydroxide, tetrabutylphosphonium hydroxide (TBPH), tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, benzyltriphenylphosphonium hydroxide, methyltriphenylphosphonium hydroxide, ethyltriphenylphosphonium hydroxide, N-propyltriphenylphosphonium hydroxide, and combinations thereof.

[0047] In a seventh aspect, the present disclosure provides the composition of any one of the first to sixth aspects, wherein the pH adjuster is selected from tetramethylammonium hydroxide, choline hydroxide, or a combination thereof.

[0048] In an eighth aspect, the present disclosure provides a composition of any one of the first to seventh aspects, comprising at least one complexing agent.

[0049] In a ninth aspect, the present disclosure provides a method for preparing a complexing agent comprising the steps of: preparing a complexing agent selected from the group consisting of aminoethylethanolamine, N-methylaminoethanol, aminoethoxyethanol, dimethylaminoethoxyethanol, diethanolamine, N-methyldiethanolamine, monoethanolamine, triethanolamine, 1-amino-2-propanol, 2-amino-1-butanol, isobutanolamine, triethylenediamine, 4-(2-hydroxyethyl)morpholine, ethylenediaminetetraacetic acid, m-xylenediamine, iminodiacetic acid, 2-(hydroxyethyl)iminodiacetic acid , nitrilotriacetic acid, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, uric acid, alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,5,9-triazacyclododecane-N,N',N''-tris(methylenephosphonic acid), 1,4,7,10-tetraazacyclododeca N,N',N'',N'''-tetrakis(methylenephosphonic acid), nitrilotris(methylene)triphosphonic acid, diethylenetriaminepentakis(methylenephosphonic acid), aminotri(methylenephosphonic acid), bis(hexamethylene)triaminepentamethylenephosphonic acid, 1,4,7-triazacyclononane-N,N',N''-tris(methylenephosphonic acid), hydroxyethyl diphosphonate, nitrilotris(methylene)phosphonic acid, 2-phosphonobutane-1,2,3,4-tetracarboxylic acid, carboxyethylphosphonic acid , aminoethylphosphonic acid, glyphosate, ethylenediaminetetra(methylenephosphonic acid)phenylphosphonic acid, oxalic acid, succinic acid, maleic acid, malic acid, malonic acid, adipic acid, phthalic acid, lactic acid, citric acid, sodium citrate, potassium citrate, ammonium citrate, tricarballylic acid, trimethylolpropionic acid, tartaric acid, glucuronic acid, 2-carboxypyridine, 4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt, and combinations thereof.

[0050] In a tenth aspect, the present disclosure provides the composition of the first to ninth aspects, wherein the complexing agent is selected from 1-hydroxyethylidene-1,1-diphosphonic acid, lactic acid, and citric acid.

[0051] In an eleventh aspect, the present disclosure provides the composition of any one of the first to tenth aspects, wherein the at least one pH buffering agent is a metal corrosion inhibitor or an ammonium salt.

[0052] In a twelfth aspect, the present disclosure provides a metal corrosion inhibitor comprising 5-aminotetrazole, 5-phenyl-benzotriazole, 1H-tetrazole-5-acetic acid, 1-phenyl-2-tetrazoline-5-thione, benzimidazole, methyltetrazole, pyrazole, 5-amino-1,3,4-thiadiazole-2-thiol, benzotriazole, 1,2,4-triazole, 1,2,3-triazole, tolyltriazole, 5-methyl-benzotriazole, 5-phenyl-benzotriazole, 5-nitro-benzotriazole, ... Triazolecarboxylic acid, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, 5-phenylthiol-benzotriazole, halo-benzotriazole, naphthyl triazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 5-amino-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, pentylenetetrazole, 5-phenyl-1H-tetrazole, 5-benzyl-1H-tetrazole, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, triazine, methyltetrazole, 1,3-dimethyl-2-imidazolidinone, 1,5-pentylenetetrazole, 5-phenyl-1H-tetrazole, 5-benzyl-1H-tetrazole, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, triazine, methyltetrazole, 1,3-dimethyl-2-imidazolidinone, The composition of an eleventh aspect is provided, wherein the hydroxybenzoate is selected from tamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, diaminomethyltriazine, imidazolinethione, 4-methyl-4H-1,2,4-triazole-3-thiol, 4-amino-4H-1,2,4-triazole, 3-amino-5-methylthio-1H-1,2,4-triazole, benzothiazole, imidazole, indiazole, adenine, adenosine, carbazole, N-cyclohexyl-3-aminopropanesulfonic acid, and combinations thereof.

[0053] In a thirteenth aspect, the present disclosure provides the composition of the eleventh or twelfth aspect, wherein the metal corrosion inhibitor is tolyltriazole.

[0054] In a fourteenth aspect, the present disclosure provides the composition of the 11th aspect, wherein the ammonium salt is selected from salts of ammonium acetate, ammonium bicarbonate, ammonium butyrate, ammonium trifluoroacetate, diammonium monohydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphonate, and combinations thereof.

[0055] In a fifteenth aspect, the present disclosure provides a composition of any one of the first to fourteenth aspects, further comprising an oxidant stabilizer.

[0056] In a sixteenth aspect, the present disclosure provides the composition of the fifteenth aspect, wherein the oxidant stabilizer is selected from glycine, serine, proline, leucine, alanine, asparagine, aspartic acid, glutamine, valine, and lysine, nitrilotriacetic acid, iminodiacetic acid, etidronic acid, ethylenediaminetetraacetic acid (EDTA), (1,2-cyclohexylenedinitrilo)tetraacetic acid (CDTA), uric acid, tetraglyme, diethylenetriaminepentaacetic acid, propylenediaminetetraacetic acid, ethylenediaminedisuccinic acid, sulfanilamide, and combinations thereof.

[0057] In a seventeenth aspect, the present disclosure provides the composition of the fifteenth or sixteenth aspect, wherein the oxidant stabilizer is selected from ethylenediaminetetraacetic acid, (1,2-cyclohexylenedinitrilo)tetraacetic acid, and tetraglyme.

[0058] In an eighteenth aspect, the present disclosure provides a composition of any one of the first to seventeenth aspects, further comprising at least one organic solvent.

[0059] In a nineteenth aspect, the present disclosure provides the composition of the eighteenth aspect, wherein the organic solvent is propylene glycol.

[0060] In a twentieth aspect, the present disclosure provides a method for etching molybdenum from a microelectronic device substrate having a molybdenum-containing film and aluminum oxide thereon, the method comprising: at least one oxidizing agent, at least one cationic surfactant, water, and A composition comprising a pH adjuster in an amount necessary to achieve a pH of about 7 to about 13, and optionally at least one complexing agent, at least one pH buffering agent, or At least one oxidant stabilizer and a composition comprising one or more of: contacting the molybdenum-containing film with aluminum oxide for a time sufficient to at least partially remove the film.

[0061] Having thus described several exemplary embodiments of the present disclosure, those skilled in the art will readily appreciate that still other embodiments may be made and used within the scope of the appended claims. Many advantages of the present disclosure, which are covered by this document, have been set forth in the foregoing description. It will be understood, however, that this disclosure is in many respects merely illustrative. The scope of the present disclosure is, of course, defined in the language in which the appended claims are expressed.

Claims

1. 0.1% by weight to 5% by weight of periodic acid; at least one cationic surfactant; Water and and a pH adjuster in an amount necessary to achieve a pH of 7 to 13, and optionally 0.1% to 20% by weight of at least one complexing agent; at least one pH buffer that is a metal corrosion inhibitor or an ammonium salt; or 0.0001% to 1.0% by weight of at least one oxidant stabilizer and one or more of: A selective etching composition for removing molybdenum-containing films from microelectronic devices relative to aluminum oxide.

2. Cationic surfactants include cetyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, heptadecanefluorooctanesulfonic acid, tetraethylammonium halide, stearyltrimethylammonium chloride, 4-(4-diethylaminophenylazo)-1-(4-nitrobenzyl)pyridium bromide, cetylpyridinium chloride monohydrate, benzalkonium chloride, benzethonium chloride, benzyldimethyldodecylammonium chloride, benzyldimethylhexadecylammonium chloride, hexadecyltrimethylammonium bromide, 2. The composition of claim 1, wherein the ammonium salt is selected from dimethyldioctadecyl ammonium chloride, dodecyltrimethyl ammonium chloride, didodecyl dimethyl ammonium bromide, di(hydrogenated tallow)dimethyl ammonium chloride, tetraheptyl ammonium bromide, tetrakis(decyl)ammonium bromide, and oxyphenonium bromide, dimethyldioctadecyl ammonium chloride, dimethyldihexadecyl ammonium bromide, di(hydrogenated tallow)dimethyl ammonium chloride, benzyl dimethyl ammonium chloride, and benzyl dimethyl ammonium bromide.

3. The composition of claim 1 comprising at least one complexing agent.

4. The composition of claim 1 further comprising at least one organic solvent.

5. 1. A method for etching molybdenum from a microelectronic device substrate having a molybdenum-containing film and aluminum oxide thereon, comprising: 0.1% to 5% by weight of periodic acid, at least one cationic surfactant, 0.0001% to 1.0% by weight of at least one oxidant stabilizer; water, and 1. A composition comprising a pH adjuster in an amount necessary to achieve a pH of 7 to 13, and optionally 0.1% to 20% by weight of at least one complexing agent, or at least one pH buffering agent and a composition comprising one or more of: contacting the molybdenum-containing film with aluminum oxide for a time sufficient to at least partially remove the film.

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