JP2012504871A - Use of surfactant / antifoam mixtures for high metal loading and surface passivation of silicon substrates - Google Patents

Abstract

An improved composition and process for removing at least one material from a microelectronic device structure.
[Solution]
Removal compositions and processes for removing at least one material layer from a rejected microelectronic device structure having it on the surface. The removal composition includes hydrofluoric acid. This composition is made of material (s) that is removed without damaging the retained layer to regenerate, rework, recycle and / or reuse the structure. Realize substantial removal.
[Selection] Figure 1A

Description

[0001] The present invention generally removes a material layer, eg, a low-k dielectric, from a substrate or article having the material on its surface, thereby reclaiming, reworking, recycling, and It relates to a process useful for reuse and / or products made using it.

[0002] As device size shrinks, the growing demand for performance associated with high density ultra-large scale integrated circuit (ULSI) semiconductor interconnects is the use of low dielectric constant (low k) insulation layers due to increased signal transmission speeds. Need more and more.

[0003] Typical low-k materials include commercially available precursors such as SiLK ™, AURORA ™, CORAL ™, or BLACK DIAMOND ™, for example, the proprietary BLACK DIAMOND ( Carbon doped oxide (CDP), deposited using a trademark process. Such CDOs are typically formed from organosilane and organosiloxane precursors using chemical vapor deposition (CVD) methods. CVD carbon-doped oxide low-k dielectrics typically consist of a porous low-density material with a total dielectric constant of less than about 3.2, with other semiconductor structures such as metal interconnect lines and vias inside. Used in various semiconductor structures by forming multiple layers of CDO to be formed. For example, CDO may be used as a dielectric dielectric layer (intermetal dielectric (IMD) layer), capping layer, and / or gap-filling material.

[0004] Often, microelectronic device wafers, such as silicon semiconductor wafers, must be discarded after unacceptable layer processing during a multilayer device manufacturing process or qualification process. A number of processing problems can occur, such as non-uniform deposition of layers or subsequent etching errors. Several quality control test methods are performed after selected processing steps, rejecting and “discarding” the acceptability of semiconductor wafers for various reasons, resulting in significant non-productive costs. In addition to rejected wafers, test wafers are also often discarded because certain coating types cannot be reclaimed or recycled. Expenses for test wafers are included in the material expenses for the top three places in the factory.

[0005] In prior art approaches, a rejected or discarded process wafer must be sent to a wafer source, and a dielectric layer such as a material layer, eg, a CDO layer, is reused of the wafer. Are removed from the semiconductor wafer using chemical and mechanical methods. After successfully removing the dielectric layer and other features overlying the wafer, the wafer is recycled or reused in a new multilayer semiconductor device manufacturing process. As semiconductor wafer manufacturing moves to larger diameter wafers, such as 12 inch wafers, the disposal and recycling of wafers off-site is becoming increasingly unattractive due to high non-productive costs.

[0006] Improved compositions and processes are disclosed herein and include at least one material, such as a metal stack, an etch stop layer, a photoresist, a barrier layer, and / or a high-k and low-k. Dielectric layers, including layers, may be removed from the microelectronic device structure, thereby regenerating, reworking, recycling, and / or reusing the structure, and the compositions and processes may be Compatible with manufacturing process and ingredients. The underlying device substrate, such as silicon, is preferably not damaged by the removal composition. Preferably, the process of using the composition to remove material from a microelectronic device, eg, a low-k dielectric layer, can be performed in a single step and therefore does not require a high energy consumption oxidation step .

[0007] In addition to removing the material layer in parallel with minimizing damage to the underlying substrate material, the compositions of the present invention may be formulated to accommodate local environmental requirements. . For example, high fluoride concentrations and high organic solvent concentrations can make it difficult to use the composition in mass production due to wastewater treatment problems. Depending on the level of chemical oxygen demand (COD) of the formulation, however, the COD of the solution is the amount of organic compound that can be fully oxidized to carbon dioxide in the presence of a strong oxidant under acidic conditions. This formulation, however, cannot enter the wastewater of the facility for the purpose of returning directly to the environment. For example, in Switzerland, the COD of wastewater samples must be reduced to between 200 and 1000 mg / L before wastewater or industrial water can be returned to the environment (Pupunat, L., Sollberger, F., Rychen, P , "Efficient Reduction of Chemical Oxygen Demand in Industrial Wastewaters," http://www.csem.ch/corporate/Report2002/pdf/p56.pdf).

[0008] If the wastewater contains only a fluoride source (no organic solvent), a fluoride treatment system may be used to first remove fluoride from the wastewater and then release the water to the environment. If the wastewater contains only one or more organic solvents (no fluoride source), an organic matter disposal system such as an incinerator may be used. Unfortunately, the incineration system cannot accept wastewater samples containing high fluoride concentrations because the fluoride source can damage the incinerator material of the structure.

[0009] Accordingly, to provide an improved composition and process for removing at least one material from a microelectronic device structure for the purpose of regeneration, rework, recycling, and / or reuse of the structure. In addition, the composition and / or the process of using the composition are preferably in accordance with local regulatory standards related to the disposal of the composition.

[0010] Regenerating and reworking the microelectronic device structure, useful for removing at least one material, such as dielectric and / or other material layers, from the microelectronic device structure having the material on the surface , Recycle and / or reuse compositions and processes are disclosed herein, and use removal compositions and products or intermediates produced using them. A method is also disclosed.

[0011] In one aspect, at least one etchant, at least one surfactant / polymer source, optionally at least one organic solvent, optionally at least one chelator, optionally at least one. A removal composition is described that includes a species of oxidant, optionally at least one chloride source, optionally at least one antifoam agent, and optionally water.

[0012] In another aspect, a removal composition is described that includes at least one etchant, at least one surfactant / polymer source, water, and optionally at least one antifoam.

[0013] In yet another aspect, a defoaming composition comprising at least one etchant, at least one surfactant / polymer source, water, and at least one antifoaming agent. Describes a removal composition comprising a chemical species selected from the group consisting of ethylene oxide / propylene oxide block copolymers, alcohol alkoxylates, fatty alcohol alkoxylates, phosphate ester blends with nonionic emulsifiers, and combinations thereof. Is done.

[0014] In yet another aspect, a microelectronic device substrate and post-etch residue, low-k dielectric, high-k dielectric, etch stop material, metal laminate material, barrier layer material, ferroelectric material, silicide material, nitriding Selected from the group consisting of physical materials, oxide materials, photoresists, bottom anti-reflection coatings (BARC), sacrificial anti-reflection coatings (SARC), polymer-containing accumulators, miscellaneous materials, doped regions, and combinations thereof A microelectronic device structure comprising at least one removable material and a removal composition for a time and under conditions sufficient to substantially remove at least one material from the microelectronic device structure. A microphone comprising the step of contacting to obtain a recyclable or reusable microelectronic device structure A method of recycling a roelectronic device structure, wherein the removal composition comprises at least one etchant, at least one surfactant / polymer source, optionally at least one organic solvent, optionally at least one. Described is a process comprising a species chelating agent, optionally at least one oxidizing agent, optionally at least one chloride source, optionally at least one antifoaming agent, and optionally water. ing. In a preferred embodiment, the removal composition comprises at least one antifoaming agent, the antifoaming agent comprising ethylene oxide / propylene oxide block copolymer, alcohol alkoxylate, fatty alcohol alkoxylate, phosphoric acid with a nonionic emulsifier It includes a chemical species selected from the group consisting of ester blends, and combinations thereof.

[0015] In yet another aspect, a kit is described that includes one or more containers, one or more of the following reagents for forming a removal composition, the removal composition comprising: At least one etchant, at least one surfactant / polymer source, optionally at least one organic solvent, optionally at least one chelating agent, optionally at least one oxidizing agent, optionally Includes at least one chloride source, optionally at least one defoamer, and optionally water, the kit includes post-etch residue, low-k dielectric, high-k dielectric, etch stop Materials, metal laminate materials, barrier layer materials, ferroelectric materials, silicide materials, nitride materials, oxide materials, photoresist, bottom anti-reflection coating (BARC), sacrificial anti-reflection A material selected from the group consisting of at least one removable material selected from the group consisting of (SARC), polymer-containing accumulators, miscellaneous materials, doped regions, and combinations thereof on the surface Is adapted to form a removal composition suitable for removal from a microelectronic device structure having:

[0016] Other aspects, features, and embodiments of the invention will be more fully apparent from the ensuing disclosure and appended claims.

[0017] FIG. 4 is an electron micrograph of a tungsten wafer after immersion in Formulation E. [0018] FIG. 4 is an electron micrograph of a tungsten wafer after immersion in Formulation AB. [0019] FIG. 3 is an electron micrograph of a tungsten wafer after immersion in Formulation AC. [0020] FIG. 3 is an electron micrograph of a tungsten wafer after immersion in Formulation AD. [0021] FIG. 5 is an electron micrograph of a tungsten wafer after immersion in Formulation AE.

[0022] The present invention generally includes at least one material layer (eg, dielectric material (high-k and / or low-k), metal laminate material, etch stop layer, barrier layer material, silicide, ferroelectric, photo Resist, anti-reflective coating, post-etch residue, etc.) from the microelectronic device structure having the material on its surface, thereby reclaiming, reworking, recycling and / or reusing the microelectronic device structure It relates to removal compositions and processes useful for Said regeneration, rework, recycling and / or reuse may be remote from the site or internal.

[0023] "Microelectronic devices" are semiconductor substrates, flat panel displays, phase change memory devices, solar panels and other products including solar substrates, photovoltaic cells, and microelectromechanical systems (MEMS). Corresponding to those manufactured for use in microelectronics, integrated circuits, or computer chip applications. The terms “microelectronic device”, “microelectronic substrate”, and “microelectronic device structure” are not meant to be limiting in any way, and any substrate or a microelectronic device or microelectronic assembly that will eventually become It will be understood that it includes a structure. Microelectronic devices can be patterned, blanketed, and can be control and / or test devices. The “rejected microelectronic device” structure incorporates all microelectronic devices that can be regenerated, reworked and / or cleaned by the method of the present invention.

[0024] A "microelectronic device structure" includes a "microelectronic device substrate" having at least one material on a surface, the at least one material being a composition or crystal weight of the microelectronic device substrate. Is different. “Microelectronic device substrate” as defined herein is: bare silicon; polysilicon: germanium; III / V compounds such as aluminum nitride, gallium nitride, gallium arsenide, indium phosphide; titanium stone; 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; Single crystal silicon (doped or undoped); amorphous silicon, copper indium (gallium) diselenide; and any substrate including, but not limited to, combinations thereof Applicable. “Material” or “material layer (s)” includes doped epitaxial silicon, undoped epitaxial silicon, post-etch residue, low-k dielectric, high-k dielectric, etch stop material, metal Laminate materials, barrier layer materials, ferroelectrics, silicides, nitrides, oxides, photoresists, bottom anti-reflection coatings (BARC), sacrificial anti-reflection coatings (SARC), polymer-containing accumulators, various materials, dopes At least one material selected from the group consisting of regions and combinations thereof may be included, but is not limited thereto. At least one of the material layers may be doped with ions implanted with at least one ion such as boron, phosphorus, and arsenic. As defined herein, “miscellaneous materials” include molybdenum-containing materials, lanthanum-containing materials, rhodium-containing materials, manganese-containing materials such as MnO _x , carbon nanotubes, SrTiO ₃ , ZrO ₂ , YVO ₄ , LiNbO _3. , TeO ₃ , and combinations thereof.

[0025] As used herein, "about" shall correspond to ± 5% of the indicated value.

[0026] A "low-k dielectric material" as defined herein refers to any material used as a dielectric material in a layered microelectronic device, which material has a dielectric less than about 4.0. Has a rate. Preferably, low-k dielectric materials include silicon oxide, silicon-containing organic polymers, silicon-containing hybrid organic / inorganic materials, organosilicate glass (OSG), TEOS, fluorinated silicate glass (FSG), SiCOH, and carbon-doped oxidation. Includes low-polarity materials such as product (COD) glass It will be appreciated that the low-k dielectric material may have various densities and various porosities.

[0027] "Metal laminate material" and "metal" as defined herein are: tantalum, tantalum nitride, titanium nitride, titanium, nickel, cobalt, tungsten, tungsten nitride, and the aforementioned metals on microelectronic devices Copper-containing layer; aluminum-containing layer; Al / Cu layer; Al alloy; Cu alloy; cobalt-containing layer such as CoWP and CoWBP; gold-containing layer; Au / Pt layer; hafnium oxide; Zirconium oxide; Lanthanide oxide; Titanate; Nitrogen doped analogs thereof; Ruthenium; Iridium; Cadmium; Lead; Selenium; Silver; MoTa;

[0028] "high-k dielectric" materials as defined herein are: hafnium oxide (e.g., HfO2); zirconium oxide (e.g., ZrO _2); acid silicide hafnium; hafnium silicide; zirconium silicide; Kay Titanium oxide; aluminum oxide; lanthanum-doped analogs (eg, LaAlO ₃ ); aluminum silicide; titanate (eg, Ta ₂ O ₅ ); hafnium and silicon oxides and nitrides (eg, HfSiON) These analogs doped with lanthanum (eg HFSiON (La)); barium strontium titanate (BST); oxides of hafnium and aluminum (eg Hf _x Al _y O _z ); strontium titanate (SrTiO ₃ ); barium titanate (BaTiO ₃ ); and combinations thereof It corresponds to the alignment.

[0029] A "barrier layer material" as defined herein seals a metal line, such as a copper interconnect, so that diffusion of the metal, such as copper, into a dielectric material is minimized. For any material used in the art. Preferred barrier layer materials include silicon rich nitrides, silicon rich oxynitrides, tantalum, titanium, ruthenium, hafnium, tungsten, other refractory metals, nitrides and silicides thereof.

[0030] As defined herein, "ferroelectric" includes: barium titanate (BaTiO ₃ ); lead titanate (PbTiO ₃ ); lead zirconate titanate (PZT); lead lanthanum zirconate titanate ( PLZT); lead magnesium niobate (PMN); potassium niobate (KNbO _3); potassium sodium niobate _{(K x Na 1-x NbO} 3); potassium tantalate niobate _{(K (Ta x Nb 1-} x) O ₃ ); lead niobate (PbNb ₂ O ₆ ); bismuth titanate (Bi ₄ Ti ₃ O ₁₂ ); lead bismuth niobate (PbBi ₂ Nb ₂ O ₉ ); lithium niobate (LiNbO ₃ ); lithium tantalate ( LiTaO ₃ ); strontium bismuth tantalate; strontium bismuth tantalate niobate; strontium tantalite; Trontium; including, but not limited to, combinations and salts thereof.

The “etching stop layer” defined in this specification includes silicon carbide (SiC), silicon nitride carbon (SiCN), silicon oxide carbon (SiCO), silicon oxynitride (SiON), copper, silicon germanium ( SiGe), SiGeB, SiGeC, AlAs, InGaP, InP, InGaAs, combinations and salts thereof.

The “oxide” defined in the present specification includes any of oxide compounds defined in other layers, and a piezoelectric material such as (Pb, Sr) (Zr, Ti) O ₃ , ( Pb, Ca) (Zr, Ti) O ₃ and other pyroelectric materials, superconductors such as YBCO, electrodes such as indium tin oxide, ZrO ₂ , CeO ₂ , Y ₂ O ₃ , MgO, Al ₂ O ₃ , and SiO thermal barrier materials, such as _{2, TiO 2, Ta 2 O} 5, Y 2 O 3, and the optical coating, such as _{Sc 2 O 3, La (1} -x) Sr x Ga (1-y) M y O 3 ( However, M = Fe, Co, Ni, La _(1-x) Sr _x MnO ₃ , and La _(1-x) Ca _x MnO ₃ ) are included.

[0033] "Polymer-containing accumulator" as defined herein corresponds to a material that is constructed during fabrication on the back and edge of a microelectronic device substrate, and includes a low-k dielectric, a high-k dielectric, Etching stop materials, metal laminate materials, barrier layer materials, ferroelectrics, silicides, nitrides, oxides, photoresists, bottom anti-reflection coatings (BARC), sacrificial anti-reflection coatings (SARC), various materials, dopants And any of the materials deposited to that point on the microelectronic device including, but not limited to, and combinations thereof.

[0034] As used herein, "regenerating" a microelectronic device structure is retained (one or more) without substantially damaging the retained layer (s). Corresponding to substantially removing at least one material adjacent to the layer (s), the material (s) to be removed include post-etch residue, etch stop layer, metal laminate material, Barrier layer materials, ferroelectrics, silicides, nitrides, oxides, dielectrics (low-k and / or high-k), polymer-containing accumulators, doped regions (not including doped epitaxial layers), and these However, the present invention is not limited to these combinations. The retained layer (s) can be a microelectronic device substrate, doped epitaxial silicon, undoped epitaxial silicon, etch stop layer, metal stack material, barrier layer material, ferroelectric, silicide, Selected from the group consisting of nitrides, dielectrics (low k and / or high k), doped regions, and combinations thereof. Regeneration may be performed off site or internally. It will be appreciated that the material to be removed and the retained layer cannot be the same material. For example, the material to be removed may include a low-k dielectric material and the retained layer may be a microelectronic device substrate. One skilled in the art will appreciate that this disclosure can be used to determine which compositions and processes may be used to remove a particular material while retaining a particular layer.

[0035] As used herein, "substantial removal" or "substantially remove" means at least 90% by weight of the material (s) desired to be removed, more preferably at least This corresponds to a removal of 95% by weight, even more preferably at least 97% by weight, even more preferably at least 98% by weight, most preferably at least 99% by weight.

[0036] As used herein, "reworking" a microelectronic device structure refers to a photoresist material, an anti-reflective coating (ARC), a polymer-containing accumulator, after failure of lithographic development and quality control testing, This corresponds to substantially removing at least one of post-etch residue, electroplated copper, and combinations thereof. Alternatively, reworking includes removal of polymer-containing deposits on the backside and / or the edge of the microelectronic device structure. Rework may be performed away from the site or internally. After reworking, the microelectronic device structure may be recoated, baked, and repatterned according to photolithography techniques known in the art.

[0037] "Recycle" as defined herein regenerates, reuses or recycles the retained layer (s) of the microelectronic device after material removal as described herein. Defined as rework and reuse. For example, recycled microelectronic devices may be reintroduced into the manufacturing process flow, used as control or test devices, or used in unrelated processes or towards unrelated products. Good.

[0038] As defined herein, "substantial elimination" of pitching means that pitching is reduced compared to that typically observed using removal compositions known in the art. Point to. Preferably, the degree of pitting is less than 10%, more preferably less than 5%, and most preferably less than 2% of that observed using other removal compositions.

[0039] Regenerated microelectronic device structures are: bare silicon; polysilicon; germanium; III / V compounds such as gallium nitride, gallium arsenide, indium phosphide; titanates; II / IV compounds; CdSe, CdS, ZnS A substrate selected from the group consisting of II / VI compounds such as ZnS, ZnSe, and CdTe; silicon carbide; sapphire; silicon-on-sapphire; carbon; doped glass; undoped glass; diamond; GeAsSe glass; It will be appreciated that any diameter or thickness conventionally used in the art can be used. For example, substrate diameters conventionally used in the art include 200 mm, 300 mm, 4 inches, 6 inches and in the future include 450 mm. The 300 mm substrate has a thickness of 750 μm, and the thickness of the other substrates is directly proportional to the diameter with respect to the 300 mm substrate.

[0040] Successful regeneration requirements include zero or negligible surface, lotus edge, and / or backside pitching; less than 25 particles at 0.25 μm, less than 50 particles at 0.12 μm, Or less than 100 particles at 0.09 μm, total thickness variation (TTV) less than about 5 μm, surface metal contamination less than 1 × 10 ¹⁰ atoms cm ⁻² ; and / or regenerated substrate (other retained With no layer at all) including, but not limited to, within 5% of the original substrate thickness, preferably within 2%, most preferably within 1%. Absent. As defined herein, “total thickness variation” is the maximum and minimum thickness of a microelectronic device wafer as determined using a thickness scan or series of point thickness measurements known in the art. Corresponds to the absolute difference between.

[0041] Requirements for successful wafer rework include photoresist, polymer inclusion from the outermost edge and backside of the device substrate without substantial damage to the retained layer (s). This includes, but is not limited to, substantially removing accumulators and / or electroplated copper, thereby reducing particulate and metal contamination during subsequent processes.

[0042] The removal composition may be embodied in a wide variety of specific formulations, as described more fully below.

[0043] In all such compositions where a particular component of the composition is discussed with respect to a weight percentage range that includes a lower limit of zero, such component is present in various particular embodiments of the composition. And if 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 used. It will be understood that it is good.

[0044] In one aspect, a removal composition in accordance with national and international environmental standards, a so-called "green" removal composition is described. Diethylene glycol butyl ether and other ethylene-containing solvents are HAP chemicals and can be harmful to the environment. For example, diethylene glycol butyl ether has a very high chemical oxygen demand (COD) level, which is the mass of oxygen consumed per liter of solution. Due to its high COD level, diethylene glycol butyl ether has been banned or limited to very low levels depending on the country.

[0045] The "green" or "environmentally friendly" removal composition of the first aspect comprises an etchant source, at least one surfactant, optionally present in the following ranges relative to the total weight of the composition: Water, optionally at least one organic solvent, optionally at least one organic acid, optionally at least one oxidizing agent, optionally at least one chloride source, optionally at least one. And, optionally, at least one antifoaming agent:

[0046] The green removal composition of the first aspect comprises at least one etchant, at least one surfactant, optionally water, optionally at least one organic solvent, optionally at least one. An organic acid, optionally at least one oxidizing agent, optionally at least one chloride source, optionally at least one chelating agent, and optionally at least one antifoaming agent, It can consist of or consist essentially of these. In general, the etchant source (s), the surfactant (s), the optional water, the optional organic solvent (s), the optional organic solvent (s) Organic acid, optional oxidizing agent (s), optional chloride source (s), optional chelating agent (s), and optional ( The specific ratio and amount of antifoaming agent (s) to one another can be easily determined by those skilled in the art without undue effort, such as post-etch residue, low-k dielectric material, high-k dielectric. Composition with respect to a material selected from the group consisting of body materials, barrier layer materials, ferroelectrics, nitrides, silicides, oxides, polymer-containing accumulators, ARC materials, doped regions, miscellaneous materials, and combinations thereof The desired removal action of the object is obtained and / or It may be suitably varied so that the physical equipment can be obtained. In a preferred embodiment, the green removal composition of the first aspect is substantially free of amines. “Substantially free” as defined herein is less than about 1%, more preferably less than 0.5%, most preferably less than about 0.5% by weight of the composition relative to the total weight of the composition. Applicable to less than 1% by weight.

[0047] The green removal composition of the first aspect is about 0 to about 7, more preferably about 2.5 to about 4.5, most preferably about about when diluted 20: 1 with deionized water. It has a pH value in the range of 3 to about 3.5.

[0048] Etching agents may include, but are not limited to, fluorides, amines, and / or hydroxide salts, including but not limited to at least one of the following: Seeds: hydrogen fluoride (HF); xenon difluoride (XeF ₂ ); ammonium fluoride (NH ₄ F); tetraalkylammonium fluoride (NR ₄ F); alkyl hydrogen fluoride (NRH ₃ F); Ammonium difluoride (NH ₅ F ₂ ); Dialkylammonium hydrogen fluoride (NR ₂ H ₂ F); Trialkylammonium hydrogen fluoride (NR ₃ HF); Trialkylammonium fluoride (NR ₃ : 3HF) ); Anhydrous hydrogen fluoride pyridine complex; anhydrous hydrogen fluoride triethylamine complex; amine hydrogen fluoride complex, wherein R may be the same or different from each other Ku, linear or branched C ₁ -C ₆ alkyl group (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl) are selected from the group consisting of and the amine is a linear or branched C ₁ ~ C ₂₀ alkylamines, substituted or unsubstituted _C 6 _{-C 10} aryl amines, glycol amines are those containing an alkanolamine, and amine -N- oxides, where these: pyridine; 2-ethyl pyridine; 2- methoxypyridine 2-picoline; pyridine derivative; dimethylpyridine; piperidine; piperazine; triethylamine; triethanolamine; ethylamine, methylamine, isobutylamine, tert-butylamine, tributylamine, dipropylamine , Dimethylamine, jig Monoethanolamine; pyrrole; isoxazole; 1,2,4-triazole; bipyridine; pyrimidine; pyrazine; pyridazine; quinoline; isoquinoline; indole; imidazole; N-methylmorpholine-N-oxide (NMMO); N-oxide; triethylamine-N-oxide; pyridine-N-oxide; N-ethylmorpholine-N-oxide; N-methylpyrrolidine-N-oxide; N-ethylpyrrolidine-N-oxide; 1-methylimidazole; Diisobutylamine; aniline; aniline derivatives; and combinations thereof, including but not limited to; Alternatively, the etchant may include hydroxide salts including but not limited to alkali hydroxides, alkaline earth metal hydroxides, quaternary amine hydroxides, and combinations thereof. Preferably, the etching agent includes hydrogen fluoride.

[0049] Possible surfactants include nonionic, anionic, cationic (based on quaternary ammonium cations), and / or zwitterionic surfactants. For example, suitable nonionic surfactants include fluoroalkyl surfactants, ethoxylated fluorosurfactants, polyethylene glycol, polypropylene glycol, polyethylene or polypropylene glycol ethers, carboxylates, dodecylbenzene sulfonic acid or salts thereof, Polyacrylate polymer, dinonylphenyl polyoxyethylene, silicone or modified silicone polymer, acetylenic diol or modified acetylenic diol, alkylammonium or modified alkylammonium salt, and alkylphenol polyglycidol ether, and combinations comprising at least one of the foregoing May be included. In a preferred embodiment, the nonionic surfactant may be an ethoxylated fluorosurfactant such as ZONYL® FSO-100 fluorosurfactant (DuPont Canada Inc., Mississauga, Ontario, Canada). . Anionic surfactants contemplated in the compositions of the present invention include fluorosurfactants such as ZONYL® UR and ZONYL® FS-62 (DuPont Canada Inc., Mississauga, Ontario, Canada). Sodium alkyl sulfate such as sodium ethylhexyl sulfate (NIAPROOF® 08), ammonium alkyl sulfate, ammonium alkyl (C ₁₀ -C ₁₈ ) carboxylate, sodium sulfosuccinate and esters thereof such as dioctyl sodium sulfosuccinate, alkyl (C _10- C ₁₈ ) sulfonic acid sodium salt and dianionic sulfonate surfactant DowFax ™ (The Dow Chemical Company, Midland, Mich., USA) such as alkyl diphenyl oxide disulfonate DowFax ™ 3B2 But these Not intended to be constant. Possible cationic surfactants include alkylammonium salts such as cetyltrimethylammonium bromide (CTAB) and cetyltrimethylammonium hydrogensulfate. Suitable zwitterionic surfactants include ammonium carboxylate, ammonium sulfate, amine oxide, N-dodecyl-N, N-dimethylbetaine, betaine, sulfobetaine, and alkylammoniopropyl sulfate. Alternatively, surfactants include polyethylene glycol (PEG), polyethylene oxide (PEO), polypropylene glycol (PPG), polyvinyl pyrrolidone (PVP), cationic polymers, nonionic polymers, anionic polymers, hydroxyethyl cellulose ( HEC), acrylamide polymer, poly (acrylic acid), carboxymethylcellulose (CMC), sodium carboxymethylcellulose (Na CMC), hydroxypropylmethylcellulose, polyvinylpyrrolidone K30, BIOCARE ™ polymer, DOW ™ latex powder (DLP), ETHOCEL ™ ethyl cellulose polymer, KYTAMER ™ PC polymer, METHOCEL ™ cellulose ether, POLYOX ™ water-soluble resin, SoftCA ® water-soluble polymers including, but not limited to, polymers, UCARE ™ polymers, UCON ™ fluids, PPG-PEG-PPG block copolymers, PFG-PPG-PEG block copolymers, and combinations thereof. Also good. The water-soluble polymer may be a short chain or long chain polymer and may be combined with the nonionic, anionic, cationic, and / or zwitterionic surfactants of the present invention. Preferably, the surfactant comprises a dianionic sulfonate surfactant, a PPG-PEG-PPG block copolymer, a PEG-PPG-PEG block copolymer, and combinations thereof.

[0050] For example, water may be included in the composition because it can dissolve the fluoride species. Preferably the water is deionized.

[0051] The organic solvent (s), when present, acts as a solvent, assists in penetration and dissolution of organic residues, wets the surface of the microelectronic device structure, facilitates material removal, and / or Passivate the underlying material (eg, microelectronic device substrate) underneath. Organic solvents contemplated herein include, but are not limited to, alcohols, ethers, pyrrolidinones, glycols, carboxylic acids, glycol ethers, amines, ketones, aldehydes, alkanes, alkenes, alkynes, and amides. More preferably, alcohols, ethers, pyrrolidinones, glycols, carboxylic acids, and glycol ethers, such as methanol, ethanol, isopropanol, butanol, and higher alcohols (including diols, triols, etc.), 2,2. , 3,3,4,4,5,5-octafluoro-1-pentanol, 1H, 1H, 9H-perfluoro-1-nonanol, perfluoroheptanoic acid, 1H, 1H, 7H-dodecafluoro-1- Heptanol, perfluoropentanoic acid, 1 , 1H, 8H, 8H-dodecafluoro-1,8-octanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 5H-perfluoropentanoic acid, N-butyl heptafluorobutyrate, tetrahydrofuran (THF), N-methylpyrrolidinone (NMP), cyclohexylpyrrolidinone, N-octylpyrrolidinone, N-phenylpyrrolidinone, methyl formate, dimethylformamide (DMF), dimethylsulfoxide (DMSO), tetramethylene Sulfone (sulfolane), diethyl ether, phenoxy-2-propanol (PPh), propriophenone, ethyl lactate, ethyl acetate, ethyl benzoate, acetonitrile, acetone, ethylene glycol, propylene glycol, dioxane, butyryl lactone, butylene carbonate Ethylene carbonate, propylene carbonate, dipropylene glycol, amphiphilic species (diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, trimethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol mono Butyl ether (ie, butyl carbitol), 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 , Dipropi Lenglycol 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 Propylene glycol n-butyl ether, propylene glycol phenyl ether, and combinations thereof), branched fluorinated or non-fluorinated ether-linked carboxylic acid (CH ₃ CH ₂ ) _n O (CH ₂ ) _m COOH, where n = 1 -10 and m = 1-10. ), Unbranched fluorinated or non-fluorinated ether-linked carboxylic acid (CH ₃ CH ₂ ) _n O (CH ₂ ) _m COOH (where n = 1-10 and m = 1-10). Branched fluorinated or non-fluorinated non-ether linked carboxylic acid (CH ₃ (CH ₂ ) _n COOH, where n = 1-10), unbranched fluorinated or non-fluorinated non-ether linked carboxylic acid (CH ₃ (CH ₂ ) _n COOH, where n = 1 to 10), dicarboxylic acids, tricarboxylic acids, and combinations thereof are included, but are not limited thereto. In addition, the solvent may include other amphiphilic species, i.e., species that contain both hydrophilic and hydrophobic moieties similar to surfactants. Hydrophobic properties may be generally given by including molecular groups consisting of hydrocarbon or fluorocarbon groups, and hydrophilic properties are generally given by including ionic or uncharged polar functional groups. Also good. Preferably, the organic solvent comprises sulfolane, butyl carbitol, dipropylene propyl ether, or a mixture thereof.

[0052] The optional additional acid (s) helps break and dissolve the cross-linked polymer bonds in the low-k dielectric material. Additional acids may be organic and / or inorganic acids, boric acid, oxalic acid, succinic acid, citric acid, lactic acid, acetic acid, trifluoroacetic acid, tetrafluoroboric acid, hydrofluoric acid, hydrochloric acid, formic acid, fumaric acid Acid, acrylic acid, malonic acid, maleic acid, malic acid, L-tartaric acid, methylsulfonic acid, trifluoromethanesulfonic acid, iodic acid, mercaptoacetic acid, thioacetic acid, glycolic acid, sulfuric acid, nitric acid, propionic acid, pyruvic acid, aceto Including but not limited to acetic acid and combinations thereof.

[0053] The chelating agent (s) may be added to reduce or eliminate metal contamination species on the surface of the device during wafer regeneration. The chelating agent (s) contemplated herein include: acetylacetonate, 1,1,1-trifluoro-2,4-pentanedione, and 1,1,1,5,5, Β-diketonate compounds such as 5-hexafluoro-2,4-pentanedione; carboxylates such as formate and acetate and other long chain carboxylates; and amides (and amines) such as bis (trimethylsilylamide) tetramers However, it is not limited to these. Additional chelating agents include amines and amino acids (ie, glycine, serine, proline, leucine, alanine, asparagine, aspartic acid, glutamine, valine, and lysine), citric acid, acetic acid, maleic acid, oxalic acid, malonic acid. Succinic acid, phosphonic acid, derivatives of phosphonic acid, such as hydroxyethylidene diphosphonic acid (HEDP), 1-hydroxyethane-1,1-diphosphonic acid, nitrilo-tris (methylenephosphonic acid), nitrilotriacetic acid, iminodiacetic acid , Etidronic acid, ethylenediamine, ethylenediaminetetraacetic acid (EDTA), and (1,2-cyclohexylenedinitrilo) tetraacetic acid (CDTA), uric acid, tetraglyme, pentamethyldiethylenetriamine (PMDETA), 1,3,5-triazine- 2,4,6-thithiol trisodium salt solution, 1, , 5-triazine-2,4,6 Chichioru triammonium salt solution, sodium diethyldithiocarbamate, one alkyl group ^{(R 2} = hexyl, octyl, Deseiru, or dodecyl) and one oligoether _(R 1 ( Di-carbamate (R ₁ (CH ₂ CH ₂ O) ₂ NR ² CS ₂ Na), ammonium sulfate, mono, with CH ₂ CH ₂ O) ₂ , where R ¹ = ethyl or butyl. Ethanolamine (MEA), Dequest 2000, Dequest 2010, Dequest 2060, diethylenetriaminepentaacetic acid, propylenediaminetetraacetic acid, 2-hydroxypyridine 1-oxide, ethylenediamine disuccinic acid, sodium triphosphate pentabasic, and combinations thereof are included. Unlike non-fluorinated β-diketones, which can be required to be combined with a base to form a chelatable deprotonated compound, a fluorinated β-diketone chelator can be used in the absence of a base. Can be used. The chelating agent may be introduced into the composition at the manufacturer prior to introducing the composition into the device wafer, or at the device wafer, ie in situ. In addition to the chelating agent (s), other ingredients may be added to dilute, maintain and / or increase the concentration of other ingredients in the composition. Preferably, the chelating agent comprises at least one phosphonic acid derivative.

[0054] Oxidants contemplated herein include hydrogen peroxide (H ₂ O ₂ ), FeCl ₃ (both hydrated and non-hydrated), oxone (2KHSO ₅ · KHSO ₄ · K ₂ SO ₄ ), Ammonium polyatomic salts (eg, ammonium peroxomonosulfate, ammonium chlorite (NH ₄ ClO ₂ ), ammonium chlorate (NH ₄ ClO ₃ ), ammonium iodate (NH ₄ IO ₃ ), ammonium perborate (NH ₄ BO ₃ ), ammonium perchlorate (NH ₄ ClO ₄ ), ammonium periodate (NH ₄ IO ₃ ), ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ), ammonium hypochlorite (NH ₄ ClO )), sodium polyatomic salts (e.g., sodium persulfate _{(Na 2 S 2 O 8)} , sodium hypochlorite (NaClO)), mosquitoes Um polyatomic salts (e.g., potassium iodate _(KIO 3), potassium permanganate (KMnO _4), potassium persulfate, nitric acid _(HNO 3), potassium persulfate _{(K 2 S 2 O 8)} , hypochlorite Potassium (KClO)), tetramethylammonium polyatomic salts (for example, tetramethylammonium chlorite ((N (CH ₃ ) ₄ ) ClO ₂ ), tetramethylammonium chlorate ((N (CH ₃ ) ₄ ) ClO ₃ ) ), Tetramethylammonium iodate ((N (CH ₃ ) ₄ ) IO ₃ ), tetramethylammonium perborate ((N (CH ₃ ) ₄ ) BO ₃ ), tetramethylammonium perchlorate ((N (CH _{3) 4) ClO 4),} periodic acid tetramethylammonium _{((N (CH 3) 4} ) IO 4), persulfate tetramethylammonium Um ((N (CH ₃ ) ₄ ) S ₂ O ₈ )), tetrabutylammonium polyatomic salts (eg, tetrabutylammonium peroxomonosulfate), peroxomonosulfuric acid, iron nitrate (Fe (NO ₃ ) ₃ ), This includes, but is not limited to, urea peroxide ((CO (NH ₂ ) ₂ ) H ₂ O ₂ ), peracetic acid (CH ₃ (CO) OOH), and combinations thereof. The oxidant may be introduced into the composition at the manufacturer prior to introducing the composition into the device wafer, or at the device wafer, ie in situ. Preferably, the oxidizing agent includes a peroxide compound.

[0055] It is known in the art that HF in the presence of metallic contaminants including copper causes pitting to microelectronic device substrates including silicon. To substantially eliminate this harmful pitting action, hydrochloric acid, alkali metal chlorides (eg, NaCl, KCo, RbCl, CsCl, etc.), alkaline earth metal chlorides (eg, MgCl ₂ , CaCl ₂ , SrCl ₂ , BaCl ₂ ), ammonium chloride, formula NR ¹ R ² R ³ R ⁴ Cl (wherein R ¹ , R ² , R ³ , and R ⁴ may be the same or different from each other, H, or branched Alkyl ammonium chlorides having a linear or linear C ₁ -C ₆ alkyl (which may be, for example, methyl, ethyl, propyl, butyl, pentyl, or hexyl), combinations thereof, and the like A chloride source, not limited to, can be added to the removal composition to minimize pitting of the microelectronic device substrate during the regeneration process. It may be suppressed. Preferably, the chloride source comprises ammonium chloride.

[0056] An antifoaming agent is a substance that induces rapid foam collapse or suppresses the foaming level in a solution. Preferably, the antifoaming agent must satisfy three conditions: the antifoaming agent should be insoluble in the solution, the antifoaming agent should have a positive expansion coefficient, Should have a positive penetration coefficient. Commonly considered antifoaming agents include, but are not limited to, silicone oil based, mineral oil based, natural oil based, acetylene based, and phosphate ester based antifoaming agents. More preferably, the antifoaming agent includes Pluronic® (BASF®) products (eg, Pluronic® 17R2, Pluronic® 17R4, Pluronic® 31R1, and Pluronic ( Ethylene oxide / propylene oxide block copolymers such as 25R2), alcohol alkoxylates such as Plurafac® products (BASF®) (eg, Plurafac® PA20), Surfonic® (Huntsmen) ) (Eg, fatty alcohol alkoxylates such as Surfonic® P1), phosphate ester blends with nonionic emulsifiers such as Defamer M (Ortho Chemicals Australia Pty. Ltd.) and Super Defomer 225 (Varn Products), And combinations thereof, including but not limited to There is no. In particular, Defoamer M also acts as a wetting agent, and thus, when used, Defoamer M may be both a surfactant and an antifoam. Furthermore, diethylene glycol monobutyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether, 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, and propylene glycol are singly or effective You may use it in combination with the other antifoamer aiming at defoaming. In one embodiment, the antifoaming agent is selected from the group consisting of ethylene oxide / propylene oxide block copolymers, alcohol alkoxylates, fatty acid alkoxylates, phosphate ester blends with nonionic emulsifiers, and combinations thereof. In another embodiment, the antifoaming agent is selected from the group consisting of ethylene oxide / propylene oxide block copolymers, alcohol alkoxylates, fatty alcohol alkoxylates, and combinations thereof. In yet another embodiment, the antifoaming agent is an ethylene oxide / propylene oxide block copolymer.

[0057] In view of the nature of the green removal composition of the first aspect, preferably the composition comprises substantially an organic solvent containing an ethylene group, such as ethylene, diethylene, triethylene, and the like, and other HAP organic solvents. Not included. For example, when an organic solution is present, it preferably contains propylene and / or propylene glycol ether. It should be understood that compositions containing solvents containing ethylene groups are possible, as readily determined by those skilled in the art.

[0058] Such compositions optionally include additional components including active as well as inactive components such as rheology agents, stabilizers, passivators, dispersants, pH stabilizers and the like. May be.

[0059] In a preferred embodiment, the green removal composition of the first aspect comprises or consists of at least one etchant, at least one surfactant, and at least one antifoaming agent. Or consist essentially of these. In yet another preferred embodiment, the green removal composition of the first aspect comprises or consists of at least one etchant, at least one surfactant, water, and at least one antifoam. The antifoaming agent comprises an ethylene oxide / propylene oxide block copolymer, an alcohol alkoxylate, a fatty alcohol alkoxylate, a phosphate ester blend with a nonionic emulsifier, and combinations thereof Include species selected from the group. In another preferred embodiment, the green removal composition of the first aspect comprises at least one etchant, at least one surfactant, water, at least one antifoam, at least one chloride source. , And at least one chelating agent, or consist essentially of them. In another embodiment, the green removal composition of the first aspect comprises at least one etchant, at least one surfactant, water, at least one antifoam, at least one chloride source, And at least one chelating agent comprising, consisting of, or consisting essentially of an antifoaming agent comprising an ethylene oxide / propylene oxide block copolymer, an alcohol alkoxylate, a fatty alcohol alkoxylate, a nonionic emulsifier And a phosphate ester blend, and a species selected from the group consisting of combinations thereof. In yet another preferred embodiment, the green removal composition of the first aspect comprises at least one etchant, at least one surfactant, water, at least one antifoam, at least one chloride. A source, at least one oxidizing agent, and at least one chelating agent. In yet another preferred embodiment, the green removal composition of the first aspect comprises at least one etchant, at least one surfactant, water, at least one antifoam, at least one chloride. A source, at least one oxidant, and at least one chelating agent comprising, consisting of or consisting essentially of an antifoaming agent comprising an ethylene oxide / propylene oxide block copolymer, an alcohol alkoxylate, It includes a species selected from the group consisting of fatty alcohol alkoxylates, phosphate ester blends with nonionic emulsifiers, and combinations thereof. For example, the removal composition of the first aspect comprises water, ammonium chloride, HF, phosphonic acid-derived chelating agent, alkyl diphenylsulfate surfactant, and ethylene oxide / propylene oxide block copolymer antifoam agent, or these Or may consist essentially of these. Does another example of the removal composition of the first aspect comprise or consist of water, ammonium chloride, HF, HEDP, alkyl diphenyl oxide disulfate surfactant, and ethylene oxide / propylene oxide block copolymer antifoam? Or consist essentially of these. An oxidizing agent, such as hydrogen peroxide, may be introduced into the composition at the manufacturer or at the device wafer, i.e. in situ, prior to introducing the composition into the device wafer.

[0060] The green removal composition of the first aspect further comprises post-etch residue, low-k dielectric material, metal laminate material, high-k dielectric material, barrier layer material, ferroelectric, nitride, silicide, It may comprise a material residue selected from the group consisting of oxides, polymer-containing accumulators, ARC materials, doped regions, miscellaneous materials, and combinations thereof. Preferably, the material is dissolved and / or suspended in the green removal composition, which is still feasible for its intended use.

[0061] In one embodiment, the green removal composition of the first aspect is formulated in the following concentration embodiment, where all percentages are expressed in weight relative to the total weight of the formulation.

濃縮実施形態は、除去位置の前、及び／又は除去位置で添加してもよい少なくとも１種の酸化剤を、約０．０１〜約２０％、より好ましくは約１％〜約１５重量％含んでいてもよい。存在する場合には、有機溶媒及び／又は有機酸の下限は、配合物の全重量に対して０．０１重量％であってもよい。特に好ましい実施形態では、成分の重量パーセント比の範囲は：正味の界面活性剤に対して約１：１〜約１０：１、好ましくは約２：１〜約５：１、最も好ましくは約３：１〜約４：１の正味の（１種又は複数の）塩化物源；正味の界面活性剤に対して約１：１〜約１５：１、好ましくは約３：１〜約１０：１、最も好ましくは約７：１〜約８：１の正味のＨＦ；正味の界面活性剤に対して約１：１〜約１０：１、好ましくは約２：１〜約８：１、最も好ましくは約４：１〜約５：１の正味の（１種又は複数の）キレート剤；及び正味の界面活性剤に対して約０．０１：１〜約０．１５：１、好ましくは約０．０３：１〜約０．１２：１、最も好ましくは約０．０６：１〜約０．０９：１の正味の（１種又は複数の）消泡剤である。

Concentrated embodiments comprise from about 0.01 to about 20%, more preferably from about 1% to about 15% by weight of at least one oxidizing agent that may be added before and / or at the removal site. You may go out. When present, the lower limit of organic solvent and / or organic acid may be 0.01% by weight relative to the total weight of the formulation. In particularly preferred embodiments, the weight percent ratio ranges of the components are: about 1: 1 to about 10: 1, preferably about 2: 1 to about 5: 1, most preferably about 3 to net surfactant. : 1 to about 4: 1 net chloride source (s); about 1: 1 to about 15: 1, preferably about 3: 1 to about 10: 1 relative to the net surfactant. Most preferably about 7: 1 to about 8: 1 net HF; about 1: 1 to about 10: 1, preferably about 2: 1 to about 8: 1, most preferably relative to the net surfactant Is about 4: 1 to about 5: 1 net chelating agent (s); and about 0.01: 1 to about 0.15: 1, preferably about 0 to net surfactant. 0.03: 1 to about 0.12: 1, most preferably from about 0.06: 1 to about 0.09: 1 of the net antifoaming agent (s).

[0062] In each embodiment of the first aspect, the removal composition comprises nitric acid, sulfuric acid, lactam (eg, piperidone and / or pyrrolidone), supercritical fluid, amine, at least one aldehyde and at least one kind. At least one polymer prepared by polycondensation of aromatic compounds may be substantially free.

[0063] In one embodiment, the removal composition of the first aspect is used to regenerate a microelectronic device structure. In other words, one removable layer or multiple removable layers may be removed from the microelectronic device structure.

[0064] In another embodiment, the removal composition of the first aspect may be used to rework a microelectronic device structure, in which case the backside of the structure and / or the polymer edge of the lotus edge Accumulator is removed. The process of removing polymer-containing deposits from the backside and / or the edge of the structure may not necessarily be necessary, but may need to protect the surface of the structure from exposure to the composition. Such a process may involve positioning of this structure with a single wafer tool that uses an inert gas such as nitrogen and / or deionized water spray to protect the surface of the wafer. Alternatively, the surface may be protected by depositing a thick layer of photoresist or other protective coating polymer on the surface. In other words, the surface of the structure has been patterned and / or blanketed (1 type) that should not be exposed to the removal composition of the first aspect when cleaning its backside and / or lotus edge. This surface should be protected if it contains material (s). In another embodiment, both the front and back / foil edges are exposed to the removal composition of the first aspect so that the material from the front surface (eg, a low-k dielectric material) and the back / foil edges At the same time (eg polymer-containing accumulator and copper-containing material).

[0065] Low k dielectric materials removed using the removal compositions described herein include CORAL ™, BLACK DIAMOND ™ (hereinafter BD), CORAL derivatives, BD Derived materials, AURORA (registered trademark), derived materials of AURORA (registered trademark), SiCOH and the like. As used herein, "CORAL derived material" and "BD derived material" correspond to CORAL material and BD material, respectively, deposited using an alternative, often proprietary, deposition process. . The use of different processing techniques will result in CORAL and BD materials that are different from CORAL ™ and BLACK DIAMOND ™, respectively.

[0066] In another embodiment of the first aspect of the invention, copper ions are added to the removal composition to accelerate the removal of tungsten and tungsten-containing layers from the microelectronic device structure. When present, the amount of copper ions added is from about 0.01% to about 5% by weight, preferably from about 0.1% to about 2.5% by weight, most preferably based on the total weight of the composition. Preferably it may be in the range of about 0.2% to about 1% by weight.

[0067] In a second aspect, another green or environmentally friendly removal composition is described, the removal composition comprising an etchant source, at least one surfactant, water, and optionally at least one. Or consist essentially of, or consist essentially of these. The components in the removal composition are present in the following ranges relative to the total weight of the composition.

[0068] Etchants and optional oxidizing agents for the removal composition of the second aspect include those already described with respect to the removal composition of the first aspect. Suitable surfactant (s) for the removal composition of the second aspect include: dodecylbenzenesulfonic acid (DDBSA) or salt thereof, other linear benzenesulfonic acid (LABSA) or salt thereof, Anionic surfactants such as phosphate esters of alkoxylated fatty alcohols (eg KLEARFAC® AA270 commercially available from BASF Corporation); nonylphenol ethoxylates (eg Tergitol ™ commercially available from DOW) 15-S-9), fatty alcohol alkoxylates such as Surfonic® (Huntsmen) (eg, Surfonic® P1), polyoxyethylene glycol dodecyl ether (eg, Brij 35), and Plurafac (registered) (Trademark) products (BASF (registered trademark)) (for example, Plurafac (registered trademark) PA20) alcohol alkoxylate fat Nonionic surfactants such as fatty alcohol alkoxylates; PPG-PEG-PPG block copolymer, PEG-PPG-PEG block copolymer, ethylene oxide / propylene oxide block copolymer, Pluronic® (BASF®) Polymer surfactants such as products (eg, Pluronic® 17R2, Pluronic® 17R4, Pluronic® 31R1, and Pluronic® 25R2); and combinations thereof, including, but not limited to, It is not limited to.

[0069] Such compositions may contain active as well as inactive ingredients such as rheology agents, stabilizers, passivators, dispersants, pH stabilizers, antifoam agents, chloride sources, oxidants, chelates. Additional components including agents, co-solvents and the like may optionally be included.

[0070] The green removal composition of the second aspect includes post-etch residue, low-k dielectric material, high-k dielectric material, SiCN, aluminum-containing material, barrier layer material, ferroelectric, nitride, silicide, It may further comprise a material residue selected from the group consisting of oxides, photoresists, polymer-containing accumulators, ARC materials, doped regions, miscellaneous materials, and combinations thereof. Preferably, the material is dissolved and / or suspended in the green removal composition, which removal composition is still feasible for its intended use.

[0071] Considering the nature of the green removal composition of the second aspect, preferably the composition is: an organic solvent containing ethylene groups such as ethylene, diethylene, triethylene, and other HAP organic solvents; nitric acid; sulfuric acid : Lactam (eg piperidone and / or pyrrolidone); supercritical fluid; amine: ammonium fluoride; substantially free of polymers prepared by polycondensation of at least one aldehyde and at least one aromatic compound .

[0072] In one embodiment, the green or environmentally friendly removal composition of the second aspect is formulated in the following concentrated embodiment, where all percentages are expressed by weight relative to the total weight of the formulation.

特に好ましい実施形態では、第２の態様の除去組成物は、配合物の全重量に対して、ＨＦを約１７重量％〜約２３重量％、（１種又は複数の）界面活性剤を約４重量％〜約６重量％、及び水を約７０重量％〜約８０重量％含み、これらすべてのパーセンテージは重量によるものである。存在する場合の酸化剤の量は、好ましくは約０．０１重量％〜約１０重量％の範囲にある。特に好ましい実施形態では、成分の重量パーセント比の範囲は、正味の界面活性剤に対して約１：１〜約１０：１の正味のＨＦであり、好ましくは約２：１〜約６：１、最も好ましくは約３：１〜約５：１である。

In a particularly preferred embodiment, the removal composition of the second aspect comprises about 17 wt% to about 23 wt% HF and about 4 surfactant (s) based on the total weight of the formulation. % By weight to about 6% by weight, and water from about 70% to about 80% by weight, all percentages by weight. The amount of oxidizing agent, if present, is preferably in the range of about 0.01% to about 10% by weight. In a particularly preferred embodiment, the weight percent ratio range of the components is from about 1: 1 to about 10: 1 net HF relative to the net surfactant, preferably from about 2: 1 to about 6: 1. Most preferably from about 3: 1 to about 5: 1.

[0073] A preferred embodiment of the removal composition of the second aspect comprises, consists of, or consists essentially of HF, PEG-PPG-PEG block copolymer, and water. In another preferred embodiment, the removal composition of the second aspect comprises, consists of, or consists essentially of HF, PPG-PEG-PPG block copolymer, and water. In yet another preferred embodiment, the removal composition of the second aspect comprises, consists of, or consists essentially of HF, a polyoxyethylene glycol dodecyl ether surfactant, and water. An oxidizing agent, such as hydrogen peroxide, may be introduced into the composition at the manufacturer or at the device wafer, i.e. in situ, prior to introducing the composition into the device wafer. In another preferred embodiment, the composition of the second aspect further comprises at least one antifoaming agent.

[0074] In one embodiment, the removal composition of the second aspect is used to regenerate a microelectronic device structure. In other words, one removable layer or multiple removable layers can be removed from the microelectronic device structure. In another embodiment, the removal composition of the second aspect may be used to regenerate a microelectronic device structure, and the polymer-containing deposit on the back and / or the edge of the structure is It is removed as already described with respect to one embodiment.

[0075] The removal composition of the first and second aspects is substantially free of abrasive material typically used during CMP processing prior to contacting the removal composition with the microelectronic device. Please keep in mind.

[0076] The removal composition described herein includes a polymer-containing accumulator, a metal laminate material, a low-k dielectric layer, a high-k dielectric layer, an etch stop layer, a nitride, from the surface of the microelectronic device. Effective in removing at least one of silicide, oxide, barrier layer, photoresist, post-etch residue, miscellaneous materials, doped regions (other than doped epitaxial Si), and / or other materials simultaneously Is. For example, the removal composition can effectively remove the low-k dielectric material from the surface of the microelectronic device, as well as determine the polymer and other residues along with the microelectronic device, as readily determined by those skilled in the art. Can be removed from the backside and / or the edge of the lotus. Accordingly, as applied to microelectronic device manufacturing operations, the removal compositions described herein include low-k dielectric materials, high-k dielectric materials, etch stop layers, metal laminate materials, nitrides, silicon At least one selected from the group consisting of oxides, oxides, photoresists, barrier layers, polymer-containing accumulators, ferroelectrics, miscellaneous materials, doped regions (other than doped epitaxial Si), and combinations thereof This material is effectively used to recycle and / or reuse the structure by removing it from the microelectronic device structure in a single regeneration or rework process. The removal compositions described herein are: Total thickness variation (TTV) of less than 25 particles at 0.25 μm, less than 50 particles at 0.12 μm, or less than 100 particles at 0.09 μm (after removal) The surface metal contamination of less than 1 × 10 ¹⁰ atoms / cm ² ; and / or the thickness of the recycled substrate (without any other holding layer) is Within 5% of the thickness, preferably within 2%, most preferably within 1%; and satisfy regeneration requirements, including but not limited to rework / cleaning requirements. In addition, because of the low TTV, the typical chemical mechanical polishing (CMP) process of current regeneration techniques, i.e., the process for planarizing the substrate after wet removal of material, can be performed on the front or back surface of the wafer prior to reuse. It is thought that it is not necessary to flatten the surface. Alternatively, the CMP process parameters may be varied such that the energy requirements are substantially reduced, for example, the length of the polishing time is reduced. Most preferably, after removing material from the microelectronic device substrate, the TTV is less than 3%, more preferably less than 1%, and most preferably less than 0.5%.

[0077] The removal composition described herein also satisfies rework requirements, eg, the outermost edge of the device substrate without substantial damage to the retained layer (s). And substantial removal of photoresist, polymer-containing deposits, and / or electroplated copper from the backside. Unlike rework compositions in the prior art (eg, edge physical polishing, dry plasma etching, combustion, etc.), the at least one material removed from the microelectronic device structure is one or more It may be removed with a dampening solution.

[0078] The removal compositions described herein are easily formulated by simply adding the respective components and mixing to a homogeneous state. Further, the removal composition can be easily formulated as a single package formulation or multiple formulations mixed at the point of use. The individual portions of the multiple formulation may be mixed with the tool, in a storage tank upstream of the tool, or both. The concentration of each component may vary widely in specific multiples of the removal composition, for example, it may be more diluted or more concentrated, and the removal composition may vary or alternatively, It will be understood that any combination of components consistent with the disclosure herein may be included, consist of, or consist essentially of.

[0079] Accordingly, another aspect is a concentrated formulation of a composition described herein that is low in water and / or solvent or free of water and / or solvent, wherein the composition is removed. It relates to a formulation to which water and / or solvents may be added prior to use to form the composition. The concentrated formulation may be diluted with a solvent and concentrate in the range of about 1:10 to 100: 1, which may be water and / or an organic solvent.

[0080] Another aspect is one or more adapted to form a removal composition described herein (eg, of the first or second aspect) in one or more containers. To a kit comprising In one embodiment, the kit includes, in one or more containers, an etchant source, at least one surfactant or polymer, optionally water, optionally at least one organic solvent, optionally at least one. The organic acid, optionally at least one oxidizing agent, optionally at least one chloride source, optionally at least one chelating agent, and optionally at least one defoamer, intact Or it may be included for factory combination with diluents (eg water and / or organic solvents) and / or antifoam agents. Alternatively, the kit comprises at least one etchant, at least one surfactant or polymer, water, and optionally at least one antifoam, as such or as a diluent (eg, water and / or organic solvent). ) And / or may be included for factory combination with antifoam. In another alternative, the kit comprises at least one etchant, at least one surfactant, water, at least one chloride source, at least one chelator, and optionally at least one quencher. Foaming agents may be included as such or for factory combination with diluents (eg, water and / or organic solvents) and / or antifoaming agents. In yet another alternative, the kit comprises at least one etchant, at least one surfactant, water, at least one chloride source, at least one chelating agent, and optionally at least one kind. The antifoaming agent may be included for factory or factory combination with diluents (eg, water and / or organic solvents), antifoaming agents, and / or oxidizing agents. In yet another embodiment, the kit comprises at least one etchant, at least one surfactant or polymer, and water, neat or with a diluent (eg, water) and / or at least one oxidizing agent. May be included for combination at the factory.

[0081] The kit containers should be chemically ranked to store and dispense the component (s) contained therein. For example, the kit container may be a NOWPak® container (Advanced Technology Materials, Inc., Danbury, Conn., USA). The one or more containers containing the components of the removal composition preferably include means for fluidly communicating the components in the one or more containers for blending and dispensing. For example, when referring to NOWWPak® containers, gas pressure is applied to the outer surface of the backing material of the one or more containers to release at least a portion of the contents of the backing material, thus blending and metering. Fluid communication can be enabled for dispensing. Alternatively, the gas pressure may be added to the head space of a conventional pressurizable container, or a pump may be used to allow fluid communication. In addition, the system preferably includes a dispensing outlet for dispensing the blended removal composition into the process tool.

[0082] A substantially chemically inert, impurity-free, flexible, resilient polymer film material, such as high density polyethylene, is preferred for making the backing material of the one or more containers. used. Desirable backing materials are any pigments, UV inhibitors, or processing agents that do not require coextrusion or a barrier layer and may adversely affect the purity requirements of the components disposed on the backing. Processed without. A list of desired backing materials includes films including virgin (no additive) polyethylene, virgin polytetrafluoroethylene (PTFE), polypropylene, polyurethane, polyvinylidene chloride, polyvinyl chloride, polyacetal, polystyrene, polyacrylonitrile, polybutylene, and the like. Is included. The preferred thickness of such backing material is in the range of about 5 mils (0.005 inches) to about 30 mils (0.030 inches), for example 20 mils (0.020 inches) thick. .

[0083] With regard to the container for the kit, the disclosures of the following patents and patent applications are hereby incorporated by reference in their entirety: “APPARATUS AND METHOD FOR MINIMIZING THE GENERATION OF PARTICLES IN ULTRAPURE LIQUIDS” U.S. Pat. No. 7,188,644; U.S. Pat. No. 6,698,619, entitled “RETURNBLE AND REUSABLE, BAG-IN-DRUM FLUID STORAGE AND DISPENSING CONTAINER SYSTEM”; Q. John E. No. PCT / US08 / 63276, filed May 9, 2008, under the name of Hughes, named “SYSTEMS AND METHODS FOR MATERIAL BLENDING AND DISTRIBUTION”; Q. International application number PCT / US08 / 85826, filed December 8, 2008 under the name of Hughes et al., Entitled “SYSTEMS AND METHODS FOR DELIVERY OF FLUID-CONTAINING PROCESS MATERIAL COMMONATIONS”.

[0084] In addition to the liquid solution, the removal composition may be a foam, mist, dense fluid (ie, supercritical or subcritical, and the solvent may be in addition to water and / or solvent (s)). It is contemplated herein that it may also be formulated (or alternatively, such as CO ₂ ).

[0085] The removal compositions described herein provide post-etch residues from microelectronic device substrates, low-k dielectric materials, high-k dielectric materials, etch stop layers, nitrides, silicas in a single step. Dissolving at least one material selected from the group consisting of oxides, oxides, metal laminates, ferroelectrics, barrier layers, photoresists, ARC materials, polymer-containing accumulators, doped regions, and combinations thereof; and All of the material to be delaminated (i.e., removed) is contacted with the rejected microelectronic device substrate and a single composition for the purpose of a single immersion. Can be removed). Most preferably, the removable material is dissolved and / or delaminated in a single step, provided that mechanical polishing is not necessarily required before recycling and / or reuse. “Dissolution”, as defined herein, includes a process in which a solid solute (eg, material to be removed) enters a solvent to form a solution. “Dissolution” shall also include etching, decomposition, and / or chemical polishing of the material to be removed. Dissolution has the advantage of minimizing the generation of particulate matter that may later settle on the substrate and substantially eliminating clogging of the removal equipment.

[0086] Advantageously, the remaining layers of the microelectronic device structure after the removal process are substantially smooth and undamaged, preferably before the additional manufacturing process, ie a new material layer, eg There is no need to planarize the front and / or back surfaces prior to deposition processes such as low-k dielectric layers, high-k dielectric layers, photoresists, metal stacks, etch stop layers, and the like. For example, after regeneration, if the remaining layer comprises only a microelectronic device substrate and an epitaxial Si layer, this substrate is preferably ready for recycling / reuse without the need for costly and structurally damaged mechanical polishing. is made of. It should be understood that mechanical polishing, contact polishing, or wiping of the surface can be used where necessary.

[0087] In yet another aspect, a low-k dielectric layer, a high-k dielectric material, an etch stop layer, a metal laminate material, nitride, silicide, oxide, ferroelectric, barrier layer, photoresist, ARC material At least one material selected from the group consisting of post-etch residue, polymer-containing accumulator, doped region, and combinations thereof on the surface using the removal composition of the first or second aspect A removal method is disclosed in which the layer is removed from the microelectronic device. For example, the low-k dielectric material may be an integral part of the underlying substrate and etch stop layer (eg, SiCN, SiCO, SiC, SiON, SiGe, SiGeB, SiGeC, AlAs, InGaP, InP, InGaAs) and a metal stack material. It can be removed while maintaining the properties. Alternatively, the low-k dielectric layer and the metal laminate material can be removed while maintaining the integrity of the underlying substrate and / or etch stop layer. In another alternative, the low-k dielectric layer, etch stop layer, and metal stack material can be removed while maintaining the integrity of the underlying substrate.

[0088] In other aspects, the removal composition of the first or second aspect may be used to clean a microelectronic device structure, and contains a polymer on the backside and / or the edge of the structure. Accumulator is removed. In one embodiment, the process of removing the polymer-containing deposit from the backside and / or the edge of the structure is a simple process that uses an inert gas, such as nitrogen gas and / or deionized water spray, to protect the wafer surface. One wafer tool includes positioning the structure. Alternatively, the surface may be protected by depositing a thick layer of photoresist or other protective coating polymer on the surface. In other words, the surface of this structure, including an undamaged, blanketed or patterned layer, is not exposed to the removal composition when cleaning the backside and / or the lotus edge. In another embodiment, both the front and back / foil edges are exposed to the removal composition so that the front (eg, low-k dielectric material) and back / foil edges (eg, polymer-containing accumulator and copper-containing) The material is simultaneously removed from the material.

[0089] The microelectronic device wafer may be reworked off-site or internally. Internal rework and recycling have the advantage of increasing overall yield, reducing overall cost, and reducing the cycle time from the diagnostic process to rework.

[0090] In removal applications, the removal composition described herein may be a device containing a removable material (eg, a volume of removal composition), for example, by spraying the removal composition onto the surface of the device. Including the material to be removed by dipping (into the object) or by contacting the device with another material, such as a pad, or a fibrous adsorption applicator element having a removal composition adsorbed on the surface Remove to the surface by contacting the device with the recirculating removal composition, or any other suitable means, technique, or technique that removably contacts the removal composition and the material to be removed. The rejected microelectronic device having the material to be made is contacted in any suitable manner. Contact conditions include time and condition sufficient to remove the removable material. Furthermore, batch or single wafer processing is contemplated herein. Removal processes using the removal composition include static cleaning of the device in the removal composition, dynamic cleaning, or sequential processing steps that include static cleaning after dynamic cleaning of the device. Alternatively, each of the dynamic and static processes may be performed alternately in a cycle of such alternating processes. Any of the contact options disclosed herein may further include sonication to assist in the removal of material removed from the microelectronic device.

[0091] The removal compositions described herein include Verteq Single Wafer Megasonic Goldfinger, OnTrak System DDS (Double Sided Scrubber), Laurell Rotating Spray Tool, SEZ Single Wafer Spray Rinse, Applied Materials Mirar-Mesa ™ ) / Reflexion ™ / Reflexion LK ™ and may be used with a wide variety of conventional cleaning tools, including Megasonic batch wet bench systems. For example, the process of removing at least one material described herein can be performed on the surface of the material (s) to be removed and the material (s) and substrate or materials to be removed. One-step wet chemical processes may be supported by adding physical components such as megasonics so that mechanical failure is caused at the interface with the retained layer (s).

[0092] As applied to microelectronic device manufacturing operations, the removal composition is low-k to regenerate, rework, recycle, and / or reuse the structure from the microelectronic device structure. Dielectric layer, high-k dielectric material, etch stop layer, metal laminate material, nitride, silicide, oxide, ferroelectric, barrier layer material, photoresist, post-etch residue, ARC material, polymer-containing reservoir, Effectively used to remove at least one material selected from the group consisting of doped regions and combinations thereof. Further, the removal composition may be used during a chemical mechanical polishing process to accelerate the removal of CDO and other low k dielectric materials, or during a post CMP process to remove post CMP residual material. It should be understood.

[0093] Low-k dielectric layer, high-k dielectric material, etch stop layer, metal laminate material, nitride, silicide, oxide, ferroelectric, barrier layer, photoresist, post-etch residue, ARC material, polymer When removing at least one material selected from the group consisting of a containing reservoir, a doped region, and combinations thereof from a microelectronic device structure having them on the surface, the removal composition typically has about Over 30 seconds to about 60 minutes, more preferably over about 75 seconds to about 5 minutes, but the preferred time depends on the thickness of the layer (s) being removed and is about 20 ° C. The device structure is contacted at a temperature in the range of ~ 90 ° C, preferably in the range of about 20 ° C to about 70 ° C, and most preferably in the range of about 20 ° C to about 50 ° C. If the etch stop layer is removed, the contact time may be in the range of about 5 minutes to about 3 hours at a temperature in the range of about 20 ° C. to about 80 ° C., depending on the thickness of the etch stop layer. Such contact times and temperatures are exemplary and any other effective for substantially removing material (s) from the device structure within the broad scope of the invention. Appropriate time and temperature conditions may be used.

[0094] After achieving the desired removal operation, the removal composition may be desired, for example, rinsed, washed, dried, etc., as may be desired and effective in the field of a given end use of the compositions disclosed herein. Alternatively, other (one or more) removal steps can readily remove the composition from the pre-deposited microelectronic device. For example, the microelectronic device may be rinsed with deionized water. Furthermore, the microelectronic device may be dried with nitrogen gas, isopropanol, or SEZ (rotary process technology).

[0095] The removal composition may be monitored and controlled using statistical process control (SPC) during contact of the composition with the rejected microelectronic device structure. For example, the SPC of the removal composition bath can be monitored and controls several inputs including bath temperature, bath pH, bath main component concentration, by-product concentration, and feed chemical purity. be able to. Preferably, the removal composition is monitored using in-line monitoring and the in-line sampling device is a weight loss of the bath (which is an indicator of water and / or amine loss), fluoride concentration, H ₂ O ₂ concentration. Can be communicatively coupled with standard analytical tools to monitor pH, etc. By monitoring and / or controlling at least one of these parameters, the life of the removal composition bath can be extended, thus maximizing process efficiency. The purpose of SPC is to maintain a substantial steady state of some parameters of the removal composition as the treatment is performed over time, as readily determined by those skilled in the art. With respect to SPC, the entire disclosure of each of the following patent applications is incorporated herein by reference: US provisional filed March 31, 2007, named “METHOD FOR STRIPPPING MATERIAL FOR WAFER RECLAMATION”. Patent application 60 / 909,428, and US Provisional Patent Application 60 / 943,736, filed June 13, 2007, entitled "METHOD FOR STRIPPPING MATERIAL FOR WAFER RECLAMATION".

[0096] Surprisingly, the inventors have discovered that the same microelectronic device structure can be regenerated, eg, the material (s) is removed and the substrate is regenerated multiple times, Alternatively, the substrate and the layer (s) to be removed are regenerated. For example, the same substrate is treated such that at least one material layer is deposited, and then more than once, preferably more than 5, more preferably more than 10 times, most preferably depending on the method and material being deposited. Can be replayed 20 times or more, and the replay often satisfies the replay requirements described herein. The regeneration process is preferably a single step removal process (ie, all of the material (s) to be removed is so done using a single composition in a single step). Preferably, post-regeneration flattening is not required before subsequent processing. That said, some deposition processes and some materials can damage the substrate and thus require a large number of solutions and / or some planarization to successfully regenerate the substrate. Should be understood. Planarization has the effect of limiting the number of times the substrate can be regenerated.

[0097] It should be understood that in a multi-step removal process, it is contemplated that at least one step may require the use of at least one removal composition disclosed herein. For example, a removal process may include a microelectronic device having a first step with a substrate and at least one material to be removed and a removal composition described herein, wherein the at least one material is microelectronics. Contacting for a sufficient time and under conditions sufficient to remove from the device (e.g., as disclosed herein) and polishing the substrate to remove surface damage; This polishing condition may be a two-step process that is well known in the art.

[0098] In addition, the inventors have surprisingly discovered that the same microelectronic device structure can be reworked, eg, photoresist and ARC material (s) have been microelectronics more than 10 times. Removed from device structure. For example, the same structure can be processed by photolithography and then reworked to remove the misaligned photoresist pattern more than once, preferably more than 5 times, most preferably more than 10 times, Rework is one that does not substantially damage the retained layer (s). Furthermore, the inventors have surprisingly been able to easily clean the backside and the edge of the microelectronic device structure, for example polymer-containing accumulators and / or metals are used in the art. Have been found to be removed from the backside and the edge of the microelectronic device structure without resorting to methods (eg, physical polishing, dry plasma etching, combustion, etc.).

[0099] In another aspect, an article comprising a microelectronic device is disclosed, wherein the microelectronic device is regenerated, reprocessed, recycled, and / or recycled using the methods described herein. Including a used microelectronic structure or a microelectronic device substrate, the method comprising a microelectronic device structure and the removal composition of the first or second aspect, a low-k dielectric material, a high-k dielectric. From materials, etch stop layers, metal laminate materials, nitrides, silicides, oxides, ferroelectrics, barrier layer materials, photoresists, post-etch residues, ARC materials, polymer-containing reservoirs, doped regions, and combinations thereof When sufficient to substantially remove at least one material selected from the group And it includes the step of contacting, under conditions sufficient. Recycled or reused microelectronic device structures or microelectronic device substrates are subsequently used in subsequent microelectronic device manufacturing processes in low-k dielectric layers, high-k dielectric materials, etch stop layers, metal laminate materials, nitrides Including one or more layers deposited on the surface of the substrate, including at least one of a layer, a silicide layer, an oxide layer, a ferroelectric layer, a barrier layer material, a doped region, and combinations thereof. Also good.

[0100] In yet another aspect, a reworked microelectronic device structure or a reworked microelectronic device substrate and a low-k dielectric material, a high-k dielectric material, an etch stop layer, a metal laminate material, nitriding Articles comprising: at least one additional material layer selected from the group consisting of oxides, silicides, oxides, ferroelectrics, barrier layer materials, photoresists, ARC materials, doped regions, and combinations thereof are described. The at least one additional material layer is deposited on the microelectronic device structure or substrate after rework. The article may further include an intermediate layer positioned between the microelectronic device structure or substrate and the at least one additional material layer.

[0101] In another aspect, a microelectronic device structure or microelectronic device substrate that has been regenerated, reworked, recycled, and / or reused using the methods described herein. Disclosed is a method of manufacturing an article comprising an electronic device, the method comprising a microelectronic device structure and a removal composition of the first or second aspect, a low-k dielectric material, a high-k dielectric material, Group consisting of etch stop layer, metal laminate material, nitride, silicide, oxide, ferroelectric, barrier layer material, photoresist, post etch residue, ARC material, polymer containing reservoir, doped region, and combinations thereof For a sufficient time and under sufficient conditions so that at least one material selected from It is intended to include tactile causes process. The method of manufacturing this article includes a low-k dielectric layer, a high-k dielectric material, an etch stop layer, a metal laminate material, a nitride layer, a silicide layer, an oxide layer, a strong Depositing one or more layers comprising at least one of a dielectric layer, a barrier layer, a doped region, and combinations thereof on a recycled or reused microelectronic device structure or microelectronic device substrate. , May further be included.

[0102] In yet another aspect, the present invention relates to a method for cleaning the backside and / or lotus edge of a microelectronic device structure, said method comprising: using nitrogen gas and / or deionized water spray. Positioning the structure on a tool that protects the surface of the structure; contacting the back surface and / or the edge of the structure with the removal composition of the first or second aspect, the removal composition Substantially removes polymer-containing deposits from the back and / or the edge of the microelectronic device structure.

[0103] After treatment, the compositions described herein may be further treated to reduce the chemical oxygen demand (COD) of the wastewater stream within the fabrication facility.

[0104] In another embodiment, the antifoaming agent is added to the waste removal composition before being discarded after use.

[0105] A concentrated removal composition was prepared as follows: NH4Cl 6.75 wt%, water 43.6 wt%, HF (49%) 30 wt%, HEDP (60%) 15 wt%, Dowfax 3B2 ( 45%) 4.5% by weight (Dowfax3B2 is purchased as a 45% by weight solution and used as is), and 0.15% by weight of the antifoam, which is added to Plurafac® RA20 (Formulation A), Surfonic® Pl (Formulation B), Pluronic® 17R2 (Formulation C), Pluronic® 17R4 (Formulation D), or Pluronic® 25R2 One of (Formulation E). Each of the concentrated compositions was diluted 2: 1 with 30% hydrogen peroxide (ie, 2 parts concentrate, 1 part 30% H 2 O 2) before use.

[0106] Another set of concentrated removal compositions was prepared as follows: NH4Cl 6.75 wt%, water 47.5 wt%, HF (49%) 30 wt%, HEDP (60%) 15 wt% , And 0.75% by weight of an antifoam agent, such as Plurafac® RA20 (Formulation F), Surfonic® Pl (Formulation G), Pluronic® 17R2 ( Formulation H), Pluronic® 17R4 (Formulation I), or Pluronic® 25R2 (Formulation J). Each of the concentrated compositions was diluted 2: 1 with 30% hydrogen peroxide (ie, 2 parts concentrate, 1 part 30% H 2 O 2) before use.

[0107] Formulation K was NH4Cl 6.75 wt%, water 43.45 wt%, HF (49%) 30 wt%, HEDP (60%) 15 wt%, Dowfax3B2 (45%) 4.5 wt% And Pluronic® 25R2 0.6% by weight. Formulation K was diluted 2: 1 with 30% hydrogen peroxide before use (ie, 2 parts concentrate, 1 part 30% H2O2).

[0108] Formulation L is 6.75 wt% NH4Cl, 43. water. % By weight, HF (49%) 30% by weight, HEDP (60%) 15% by weight, Dowfax 3B2 (45%) 4.5% by weight, and Pluronic® 25R2 0.3% by weight. Formulation L was diluted 2: 1 with 30% hydrogen peroxide (ie 2 parts concentrate, 1 part 30% H 2 O 2) before use.

[0109] A blanketed wafer of SiN, TEOS, and copper was statically immersed in a formulation diluted with H 2 O 2 at room temperature (21 ± 1 ° C.) to determine the etch rate of each. The etch rate results are shown in Table 1 below:

[0110] In particular, all of the samples exhibited similar etch rates for SiN, TEOS, and copper.

[0111] Foaming tests were performed on these formulations, which were shaken in the bottle for 5 seconds at the indicated temperature, and the height of the foam above the surface of the solution was measured. The results are shown in Tables 2-4. The control does not contain an antifoam agent and uses additional water instead.

[0112] It can be seen that all of the antifoaming agents suppressed foaming of the composition to about 1 cm within only 2 minutes.

[0113] Copper loading experiments were also conducted. For example, a copper load equivalent to a 1500 wafer having a diameter of 300 mm and a Cu thickness of 5000 mm on the USG is obtained by adding one 200 mm wafer with a Cu thickness of 16 kA on the USG to 50 g of the solution at room temperature. This was achieved by submerging for a minute. Formulations containing Plurafac® RA20, Surfonic® P1, and Pluronic® 25R2 have been determined and processed to provide the best load performance at room temperature for an even 1000 wafers No clear holes and few particles were observed in the copper coupon.

[0114] A concentrated removal composition was prepared as follows: NH4Cl 4.5 wt%, HF (49%) 20 wt%, HEDP (60%) 10 wt%, Dowfax3B2 (45%) 3.04 wt% %, Pluronic® 25R2 0.104 wt%, H 2 O 2 (30%) 33.4 wt%, additional species in the amount shown in Table 5, and water as the balance, the additional species being Diethylene glycol monobutyl ether (hereinafter, BC), dipropylene glycol monopropyl ether (hereinafter, DPGPE), or propylene glycol (hereinafter, PG). The foaming height experiment described in Example 1 was performed at room temperature and the results are shown in Table 5.

[0115] The following formulations were prepared:
Formulation _M: NH 4 Cl 4.5 wt%, HF (49%) 20 wt%, HEDP (60%) 10 wt%, Dowfax3B2 (45%) 3 wt%, Super Defoamer 225 0.1 wt%, H ₂ O ₂ (30%) 33.4% by weight, water 29% by weight

Formulation _N: NH 4 Cl 4.5 wt%, HF (49%) 20 wt%, HEDP (60%) 10 wt%, Dowfax3B2 (45%) 3 wt%, Pluronic (R) 31R2 0.1 wt %, H ₂ O ₂ (30%) 33.4% by weight, water 29% by weight

Formulation _O: NH 4 Cl 4.5 wt%, HF (49%) 20 wt%, HEDP (60%) 10 wt%, Dowfax3B2 (45%) 3 wt%, Pluronic (R) 25R2 0.5 wt %, H ₂ O ₂ (30%) 33.4% by weight, toluene sodium sulfate 2% by weight, water 26.6% by weight

Formulation P: NH ₄ Cl 4.5 wt%, HF (49%) 20 wt%, HEDP (60%) 10 wt%, Dowfax3B2 (45%) 3 wt%, Super Defomer 225 0.07 wt%, H ₂ O ₂ (30%) 33.4% by weight, water 29.03% by weight

Formulation _Q: NH 4 Cl 4.5 wt%, HF (49%) 20 wt%, HEDP (60%) 10 wt%, Dowfax3B2 (45%) 3 wt%, Super Defoamer 225 0.02 wt%, H ₂ O ₂ (30%) 33.4% by weight, water 29.08% by weight

Formulation _R: NH 4 Cl 4.5 wt%, HF (49%) 20 wt%, HEDP (60%) 10 wt%, Dowfax3B2 (45%) 3 wt%, Super Defoamer 225 0.07 wt%, H ₂ O ₂ (30%) 33.4% by weight, Pluronic® 25R2 0.1% by weight, water 28.93% by weight

Formulation _S: NH 4 Cl 4.5 wt%, HF (49%) 20 wt%, HEDP (60%) 10 wt%, Dowfax3B2 (45%) 3 wt%, Super Defoamer 225 0.02 wt%, H ₂ O ₂ (30%) 33.4% by weight, Pluronic® 25R2 0.1% by weight, water 28.98% by weight

Formulation T: NH ₄ Cl 4.5 wt%, HF (49%) 20 wt%, HEDP (60%) 10 wt%, Dowfax 3B2 (45%) 3 wt%, Pluronic® 31R2 0.3 wt% %, H ₂ O ₂ (30%) 33.4% by weight, PG 2.5% by weight, water 26.3% by weight

Formulation _U: NH 4 Cl 4.5 wt%, HF (49%) 20 wt%, HEDP (60%) 10 wt%, Dowfax3B2 (45%) 3 wt%, Pluronic (R) 31R2 0.3 wt %, H ₂ O ₂ (30%) 33.4% by weight, PG 5% by weight, water 23.8% by weight

[0116] The foaming height experiment described in Example 1 was performed at room temperature, and the results are shown in Table 6.

[0117] Formulation E described in Example 1 was prepared. This formulation was diluted 2: 1 with 30% hydrogen peroxide before use (ie, 2 parts concentrate, 1 part 30% H2O2). Copper ions shown in Table 7 were added to a formulation containing H ₂ O ₂ . A tungsten wafer (about 5600 mm thick on a barrier layer about 80 nm thick) is immersed in the composition at 21 ° C. for 5 or 10 minutes, removed, rinsed with DI water, and an electron micrograph of this wafer Got.

[0118] Referring to the electron micrographs of FIGS. 1A-1E, corresponding to the results associated with immersion in Formulations E and AB-AE, respectively, on the order of 0.4% by weight relative to the total weight of the composition. It can be seen that in the presence of low concentrations of copper ions, the tungsten layer and the underlying barrier layer are completely removed within only 10 minutes at room temperature.

[0119] The following formulations were prepared:
Formulation BA: 40% by weight of HF (49%), 0.1% by weight of Brij 35, 59.9% by weight of water

Formulation BB: HF (49%) 40 wt%, Brij 35 0.5 wt%, water 59.5 wt%

Formulation BC: 40% by weight of HF (49%), 1% by weight of Brij 35, 59% by weight of water

Formulation BD: 40% by weight of HF (49%), 0.1% by weight of PEG-PPG-PEG block copolymer, 59.9% by weight of water

Formulation BE: HF (49%) 40%, PEG-PPG-PEG block copolymer 0.5%, water 59.5%

Formulation BF: HF (49%) 40% by weight, PEG-PPG-PEG block copolymer 1% by weight, water 59% by weight

Formulation BG: 40% by weight of HF (49%), 0.1% by weight of PPG-PEG-PPG block copolymer, 59.9% by weight of water

Formulation BH: 40% by weight of HF (49%), 0.5% by weight of PPG-PEG-PPG block copolymer, 59.5% by weight of water

Formulation BI: 40% by weight of HF (49%), 1% by weight of PPG-PEG-PPG block copolymer, 59% by weight of water

Formulation BJ: 40% by weight of HF (49%), 0.1% by weight of DDBSA, 59.9% by weight of water

Formulation BK: HF (49%) 40% by weight, DDBSA 0.5% by weight, water 59.5% by weight

Formulation BL: 40% by weight of HF (49%), 1% by weight of DDBSA, 59% by weight of water

Formulation BM: 40% by weight of HF (49%), 0.1% by weight of Biosoft S-100, 59.9% by weight of water

Formulation BN: 40% by weight of HF (49%), 0.5% by weight of Biosoft S-100, 59.5% by weight of water

Formulation BO: 40% by weight of HF (49%), 1% by weight of Biosoft S-100, 59% by weight of water

[0120] A BLACK DIAMOND F-20 cut specimen (coupon) (Advantiv, 5000 Å) having a k value of 2.7 or higher was immersed in the blends BA to BO at 70 ° C for 20 minutes. The same operation was repeated twice for each sample for each coupon. At the end of 20 minutes, the chemical was manually aspirated from the cell and placed in a centrifuge tube for visual analysis. Coupons and solutions were ranked (if appropriate) as having the entire film left, significant residue, slight residue (barely visible), or completely transparent. The results using BLACK DIAMOND k> 2.7 are shown in Table 8.

[0121] It can be seen that the composition comprising Brij 35 or PEG-PPG-PEG block copolymer successfully removed all of the BLACK DIAMOND from the coupon, and the resulting composition was free of residues. In addition, the composition comprising DDBSA and Biosoft S-100 successfully removed all of the BLACK DIAMOND from the coupon.

[0122] In particular, when testing a formulation using a BLACK DIAMOND coupon with a k-value of 2.4, a formulation comprising PEG-PPG-PEG or DDBSA effectively removes all of the BLACK DIAMOND from the coupon. After removal, the resulting composition contained no residue.

[0123] The following formulations CA and CB were prepared for COD testing using the COD combustion technique. Specifically, this test determines the amount of oxygen required to oxidize reducing compounds in a sample of water. The oxidant, catalyst, and sample were treated at 150 ° C. for 2 hours:

Formulation CA: HF (49%) 40%, PEG-PPG-PEG block copolymer 3%, water 57%

Formulation CB: 40% by weight of HF (49%), 5% by weight of PEG-PPG-PEG block copolymer, 55% by weight of water

[0124] Formulations CA and CB were diluted with water to 250: 1, 500: 1, and 1000: 1 to determine COD values in mg / L. The results are shown in Table 9.

[0125] Formula DA was prepared as follows to demonstrate the utility of megasonics in material removal;
Formulation DA: HF 20.1% by weight, butyl carbitol 57.5% by weight, sulfolane 1.5% by weight, H ₂ O ₂ 10% by weight, water 10.9% by weight

[0126] p-SiCOH was immersed in formulation DA at 35 ° C and placed under megasonic for 10 minutes. In p-SiCOH having a k value of 3.0, 2.7, 2.4, and 2.2, all of the p-SiCOH was peeled off and no residue remained. Furthermore, the remaining surface was smooth. Similarly, Formulation DA removed BLACK DIAMOND II from the surface of the wafer using Megasonic in just 10 minutes at 35 ° C.

[0127] As described above, the present invention has been described with reference to specific aspects, features, and exemplary embodiments of the present invention, but the usefulness of the present invention is not limited thereto. It will be understood that it extends to and encompasses numerous other aspects, features, and embodiments. Accordingly, the claims set forth below are to be construed broadly as including all such aspects, features and embodiments as are within their spirit and scope.

Claims (19)

  A removal composition comprising at least one etchant, at least one surfactant / polymer source, water, and optionally at least one antifoam.   An antifoaming agent comprising a chemical species selected from the group consisting of ethylene oxide / propylene oxide block copolymers, alcohol alkoxylates, fatty alcohol alkoxylates, phosphate ester blends with nonionic emulsifiers, and combinations thereof. Item 2. The removal composition according to Item 1.   The removal composition of claim 2 further comprising at least one chloride source.   The removal composition of claim 2 further comprising at least one chelating agent.   The removal composition of claim 2 further comprising at least one chelating agent and at least one chloride source.   The removal composition according to any one of claims 1 to 5, further comprising at least one oxidizing agent. At least one etchant comprises HF;
At least one surfactant / polymer source is a fluoroalkyl surfactant, an ethoxylated fluorosurfactant, polyethylene glycol, polypropylene glycol, polyethylene glycol ether, polypropylene glycol ether, carboxylate, dodecylbenzene sulfonic acid and salts thereof , Other linear alkylbenzene sulfonic acid (LABSA) or its salt, polyacrylate polymer, dinonylphenyl polyoxyethylene, silicone polymer, modified silicone polymer, acetylene diol, modified acetylene diol, alkyl ammonium salt, modified alkyl ammonium salts, alkylphenol glycidol ether, sodium alkyl sulfate, alkyl sulfate, alkyl _(C 10 _{~C 18)} carboxylic Ammonium salts, sodium sulfosuccinate and esters thereof, alkyl _{(C 10} ~C ₁₈₎ sodium sulfonate, two anionic sulfonate surfactant, cetyltrimethylammonium bromide, cetyltrimethylammonium hydrogen sulfate, ammonium carboxylate, ammonium sulfate, Amine oxide, N-dodecyl-N, N-dimethylbetaine, betaine, sulfobetaine, alkylammoniopropyl sulfate, polyethylene glycol (PEG), polyethylene oxide (PEO), polyvinylpyrrolidone (PVP), hydroxyethylcellulose (HEC), acrylamide Polymer, poly (acrylic acid), carboxymethylcellulose (CMC), sodium carboxymethylcellulose (Na CMC), hydroxypropylmethylcellulose, polyvinylpyrrole Don K30, latex powder, ethyl cellulose polymer, propyl cellulose polymer, cellulose ether, water-soluble resin, alkoxylated fatty alcohol phosphate ester, nonylphenol ethoxylate, fatty alcohol alkoxylate, alcohol alkoxylate, polyoxyethylene glycol dodecyl ether, Comprising a chemical species selected from the group consisting of ethylene oxide / propylene oxide block copolymers, and combinations thereof,
A removal composition according to any preceding claim.   The at least one etchant comprises HF and the at least one surfactant / polymer source is a dianionic sulfonate surfactant, a PPG-PEG-PPG block copolymer, a PEG-PPG-PEG block copolymer, and The removal composition according to any one of claims 1 to 6, comprising a chemical species selected from the group consisting of these combinations.   At least one chelating agent is acetylacetonate, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, Formate, acetate, bis (trimethylsilylamide) tetramer, glycine, serine, proline, leucine, alanine, asparagine, aspartic acid, glutamine, valine, lysine, citric acid, acetic acid, maleic acid, oxalic acid, malonic acid, succinic acid, phosphon Acid, hydroxyethylidene diphosphonic acid (HEDP), 1-hydroxyethane-1,1-diphosphonic acid, nitrilo-tris (methylenephosphonic acid), nitrilotriacetic acid, iminodiacetic acid, etidronic acid, ethylenediamine, ethylenediaminetetraacetic acid (EDTA) ), (1,2-cyclohexylenedinitrilo) four Acid (CDTA), uric acid, tetraglyme, pentamethyldiethylenetriamine (PMDETA), 1,3,5-triazine-2,4,6-thithiol trisodium salt solution, 1,3,5-triazine-2,4,6 -Thithiol triammonium salt solution, sodium diethyldithiocarbamate, disubstituted dithiocarbamate, ammonium sulfate, monoethanolamine (MEA), Quest 2000, Quest 2010, Quest 2060, diethylenetriaminepentaacetic acid, propylenediaminetetraacetic acid, 2-hydroxypyridine 1- The removal composition according to any one of claims 4 to 6, comprising a chemical species selected from the group consisting of oxide, ethylenediamine disuccinic acid, sodium triphosphate pentabasic, and combinations thereof.   The removal composition according to any one of claims 4 to 6, wherein the at least one chelating agent comprises a phosphonic acid derivative.   The removal composition of claim 3 or 6, wherein the at least one chloride source comprises hydrochloric acid, alkali metal chloride, alkaline earth metal chloride, ammonium chloride, alkylammonium chloride, and combinations thereof.   The removal composition of claim 2 comprising HF, at least one antifoaming agent, at least one dianionic sulfonate surfactant, and water.   6. The removal composition of claim 5, comprising HF, ammonium chloride, at least one antifoaming agent, at least one diionic sulfonate surfactant, at least one phosphonic acid derivative, and water.   And further comprising at least one oxidizing agent, HF, ammonium chloride, at least one antifoaming agent, at least one alkyldiphenyl oxide disulfonate surfactant, at least one phosphonic acid derivative, a peroxide compound, and 6. A removal composition according to claim 5, comprising water.   At least one surfactant selected from the group consisting of HF, water, PEG-PPG-PEG block copolymer, PPG-PEG-PPG block copolymer, polyoxyethylene glycol dodecyl ether surfactant, and combinations thereof The removal composition of claim 1 comprising: a polymer source.   Post-etch residue, low-k dielectric material residue, high-k dielectric material residue, barrier layer material residue, ferroelectric residue, nitride residue, silicide residue, oxide residue, polymer-containing accumulator residue, ARC material residue, The removal composition of any preceding claim, further comprising a material residue selected from the group consisting of doped region residues, miscellaneous material residues, and combinations thereof. Microelectronic device substrate, post-etch residue, low-k dielectric, high-k dielectric, etch stop material, metal laminate material, barrier layer material, ferroelectric material, silicide material, nitride material, oxide material, photo At least one removable material selected from the group consisting of resist, bottom anti-reflective coating (BARC), sacrificial anti-reflective coating (SARC), polymer-containing accumulator, miscellaneous materials, doped regions, and combinations thereof A microelectronic device structure and a removal composition according to any of the preceding claims for a time sufficient and sufficient conditions to substantially remove at least one material from the microelectronic device structure. Contacting under to obtain a recyclable or reusable microelectronic device substrate The method for recycling a microelectronic device structure.   Depositing at least one depositable material on the reusable substrate, wherein the at least one depositable material is a low-k dielectric, a high-k dielectric, an etch stop material, a metal Laminate material, barrier layer material, ferroelectric material, silicide material, nitride material, oxide material, photoresist, bottom anti-reflection coating (BARC), sacrificial anti-reflection coating (SARC), various materials, and these The method of claim 17, wherein the method is selected from the group consisting of:   A kit comprising one or more of the following reagents for forming a removal composition in one or more containers, the removal composition comprising at least one etchant and at least one surface active agent: An agent / polymer source, water, optionally at least one chelating agent, optionally at least one oxidizing agent, optionally at least one chloride source, and optionally at least one antifoaming agent. The kit includes post-etch residue, low-k dielectric, high-k dielectric, etch stop material, metal laminate material, barrier layer material, ferroelectric material, silicide material, nitride material, oxide material, photoresist A small number selected from the group consisting of: bottom antireflective coating (BARC), sacrificial antireflective coating (SARC), polymer-containing accumulator, miscellaneous materials, doped regions, and combinations thereof Both the one material selected from the group consisting of removable material, adapted kit to form a removal composition suitable for removing from a microelectronic device structure having said material surface.

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