JP2008538013A - Removal of high-dose ion-implanted photoresist using self-assembled monolayers in solvent systems - Google Patents

Abstract

  A method and self-assembled monolayer (SAM) containing composition for removing bulk and hardened photoresist materials from microelectronic devices has been developed. The SAM-containing composition includes at least one solvent, at least one catalyst, at least one SAM component, and optionally a surfactant. SAM-containing compositions passivate the underlying silicon-containing layer while effectively removing the hardened photoresist material in a one-step process.

Description

FIELD OF THE INVENTION This invention relates to self-assembled monolayer (SAM) containing compositions useful for the removal of bulk and hardened photoresist from the surface of microelectronic devices, and methods of using the compositions for their removal. .

2. Description of Related Art As semiconductor devices become more integrated and miniaturized, dopant atoms, eg, As, B, and P, are used to accurately control impurity distribution in microelectronic devices and Ion implantation is widely used in front-end-of-line (FEOL) processing for addition to exposed device layers. The concentration and depth of the dopant impurity is controlled by varying the dopant dose, acceleration energy, and ion current. Prior to subsequent processing, the ion-implanted photoresist layer must be removed. Conventionally, various processes including, but not limited to, a wet chemical etching process in a mixed solution of sulfuric acid and hydrogen peroxide and a dry plasma etching process, for example, in an oxygen plasma ashing process, remove the cured photoresist. Has been used.

Unfortunately, high doses of ions at low implantation energy (5 keV), medium implantation energy (10 keV), high implantation energy (20 keV) (e.g., a dose greater than about 1 × 10 ¹⁵ atm / cm ² ) in the desired layer When injected into the photoresist, they are also implanted into the photoresist layer, particularly the entire exposed surface of the photoresist, which becomes physically and chemically hard. Hard ion-implanted photoresist layers, also referred to as carbonized regions or “crusts”, have proven difficult to remove.

  Currently, removal of ion-implanted photoresist and other contaminants is usually done by plasma etching, followed by a multi-step wet strip process, typically using an aqueous-based etchant formulation, Residues and other contaminants after etching are removed. Wet strip processing in the art generally involves the use of strong acids, bases, solvents and oxidizing agents. Unfortunately, wet stripping also etches the underlying silicon-containing layer, such as the substrate and gate oxide, and / or increases the gate oxide thickness.

  As feature sizes continue to decrease, it becomes very difficult to meet the above removal requirements using prior art aqueous based etchant formulations. Since water has a high surface tension and limits or prevents access to smaller image nodes with high aspect ratios, it becomes more difficult to remove residues in the gaps or grooves. Furthermore, aqueous based etchant formulations often evaporate to dry, leaving previously dissolved solutes in the trenches or vias, which inhibits conduction and reduces device yield. Furthermore, the underlying porous low-k dielectric material does not have sufficient mechanical strength to withstand the capillary stress of high surface tension liquids such as water, resulting in pattern collapse of the structure. Aqueous etchant formulations can also strongly change important material properties of low-k materials, including dielectric constant, mechanical strength, moisture absorption, coefficient of thermal expansion, and adhesion to different substrates.

  Accordingly, it would be a significant advance in the art to provide improved compositions that overcome the deficiencies of the prior art associated with removing bulk and hardened photoresists from microelectronic devices. The improved composition effectively removes bulk and hardened photoresists in a one-step or multi-step process without the need for plasma etching steps and without substantially over-etching the underlying silicon-containing layer It shall be.

SUMMARY OF THE INVENTION The present invention is a self-assembled monolayer (SAM) containing composition useful for the removal of bulk and hardened photoresist from the surface of microelectronic devices, and a method for producing said composition for their removal. And methods of use, and improved microelectronic devices made using them.

  In one aspect, the present invention provides a self-assembled monolayer (SAM) -containing composition comprising at least one solvent, at least one catalyst, at least one SAM component, and optionally at least one surfactant. The SAM composition relates to a self-assembled monolayer (SAM) containing composition suitable for removing the photoresist material from a microelectronic device having bulk and hardened photoresist material thereon. .

  In another aspect, the present invention is a kit comprising a SAM-containing composition reagent in one or more containers, the SAM-containing composition comprising at least one solvent, at least one catalyst, and at least one A SAM-containing composition comprising a SAM component and optionally at least one surfactant, wherein the kit is suitable for removing said photoresist material from a microelectronic device having bulk and cured photoresist material thereon. The kit is configured to form.

  In a further aspect, the invention provides a method of removing the photoresist material from a microelectronic device having bulk and hardened photoresist material thereon, the method comprising at least removing the photoresist material from the microelectronic device. Contacting the microelectronic device with the SAM-containing composition for a time sufficient to partially remove and under sufficient contact conditions, the SAM-containing composition comprising at least one solvent, at least one catalyst, It relates to a method comprising at least one SAM component and optionally at least one surfactant.

  In yet a further aspect, the present invention is a method of removing said photoresist material from a microelectronic device having bulk and cured photoresist material thereon, said method comprising silicon-containing underlayers of the photoresist material Contacting the microelectronic device with the SAM-containing composition for a time sufficient to at least partially passivate the layer and contacting the microelectronic device with the etchant-containing removal composition to remove the photo from the microelectronic device. And at least partially removing the resist material, wherein the SAM-containing composition comprises a halide-free SAM component.

  In another aspect, the invention provides a method for removing the photoresist material from a microelectronic device having bulk and cured photoresist material thereon, the method comprising at least removing the photoresist material from the microelectronic device. Contacting a microelectronic device with a SAM-containing composition for a time sufficient to partially remove, wherein the SAM-containing composition lacks an etchant component.

  In yet another aspect, the invention is a method of manufacturing a microelectronic device, sufficient to at least partially remove the photoresist material from a microelectronic device having bulk and cured photoresist material thereon. Contacting the microelectronic device with the SAM-containing composition in a short time, the SAM-containing composition comprising at least one solvent, at least one catalyst, at least one SAM component, and optionally at least one A method comprising a surfactant and optionally incorporating the cleaned microelectronic device into a product.

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

Detailed Description of the Invention and Preferred Embodiments The present invention is a self-assembly that is highly effective in removing bulk and hardened photoresist from the surface of a microelectronic device while maintaining the integrity of the underlying silicon-containing layer. It is based on the discovery of monolayer (SAM) containing compositions.

  As used herein, “bulk photoresist” corresponds to a non-carbonized photoresist on the surface of a microelectronic device, specifically adjacent to the underside of the cured photoresist crust.

  As used herein, a “cured photoresist” refers to a photoresist that has been plasma etched during, for example, a back-end-of-line (BEOL) dual damascene process of an integrated circuit, such as a suitable semiconductor wafer. Photoresist that has been ion-implanted during front-end-of-line (FEOL) processing and / or carbonized or highly cross-linked crusts in the bulk photoresist to inject dopant species into the layer This includes, but is not limited to, photoresist by any other technique that forms on the exposed surface.

As used herein, “underlying silicon-containing” layers include silicon; gate oxide (eg, thermally or chemically grown SiO ₂ ) and silicon oxide including TEOS; silicon nitride; and low-k Corresponds to the layer immediately below the bulk photoresist and / or hardened photoresist containing the silicon-containing material. A “low-k silicon-containing material” as defined herein corresponds to any material used as a dielectric material in a layered microelectronic device having a dielectric constant of less than about 3.5. Preferably, as a low-k dielectric material, silicon-containing organic polymer, silicon-containing hybrid organic / inorganic material, organosilicate glass (OSG), TEOS, fluorinated silicate glass (FSG), Low polarity materials such as silicon dioxide and carbon-doped oxide (CDO) glass may be mentioned. It should be understood that low-k dielectric materials can have a variety of densities and a variety of porosities.

  “Microelectronic devices” correspond to semiconductor substrates, flat panel displays, and microelectromechanical systems (MEMS) manufactured for use in microelectronics, integrated circuits, or computer chip applications. It should be understood that the term “microelectronic device” is in no way intended to be limiting and includes any substrate that eventually becomes a microelectronic device or microelectronic assembly.

  As defined herein, “substantially overetching” means after contacting a microelectronic device having an adjacent underlying silicon-containing layer with a SAM-containing composition of the invention according to the process of the invention. This corresponds to greater than about 10% removal of the underlying layer, more preferably greater than about 5% removal, and most preferably greater than about 2% removal. In other words, most preferably 2% or less of the underlying silicon-containing layer is etched for a predetermined time using the composition of the present invention.

  As used herein, “about” is intended to correspond to ± 5% of the stated value.

  As used herein, “adequacy” for removing the photoresist material from a microelectronic device having bulk and cured photoresist material thereon is at least part of the photoresist material from the microelectronic device. Corresponds to removal. Preferably, at least 90% of the photoresist material is removed from the microelectronic device using the composition of the present invention, more preferably at least 95% of the photoresist material, most preferably at least 99% of the photoresist material, Removed.

As used herein, “dense fluid” corresponds to a supercritical fluid or a subcritical fluid. The term “supercritical fluid” is used herein to indicate a material that is under conditions above the critical temperature T _{c and} above the critical pressure P _c in the pressure-temperature diagram of the compound of interest. Preferred supercritical fluid employed in the present invention is CO _2, which is alone _{or, Ar, NH 3, N 2} , CH 4, C 2 H 4, CHF 3, C 2 H 6, n-C Used in a mixture with another additive such as ₃ H ₈ , H ₂ O, N ₂ O. The term “subcritical fluid” refers to a solvent that is in a subcritical state, ie, below the critical temperature and / or below the critical pressure for that particular solvent. Preferably, the subcritical fluid is a high pressure liquid of varying density.

  Importantly, the SAM-containing composition of the present invention must have good metal-containing material compatibility, for example, a low etch rate on the metal-containing material. Metal-containing materials of interest include, but are not limited to, copper, tungsten, cobalt, aluminum, tantalum, titanium, and ruthenium, their silicides, and nitrides.

  Self-assembled monolayers (SAMs) passivate metals (eg, copper, gold, etc.) and various surfaces including but not limited to oxides of titanium, hafnium, silicon, and aluminum. It has been known. The SAM includes a silane having at least one leaving group, such as a silane having a halide, which readily forms a covalent bond at an oxygen group on the silicon-containing surface (ie, via a silylation reaction). The silane itself can further contain a covalently bound inert molecule such as polyethylene glycol (PEG), so that after binding to a silicon-containing surface, the PEG-silane binds other molecules to the surface. Can be prevented. PEG-silane SAMs are well known because they are thin (ie, not bulky) hydrophilic and the association of the PEG molecules with the silicon-containing surface forms a non-tacky aqueous layer. On the other hand, if necessary, a hydrophobic surface can be formed using alkylchlorosilane.

  The compositions of the present invention can be embodied in a wide variety of specific formulations, as described more fully below.

  In all compositions where a particular component of the composition is described for a mass percent range that includes a lower limit of zero, that component is present even if present in various particular embodiments of that composition. And, if present, that component may be present at a concentration as low as 0.01% by weight, based on the total weight of the composition employed. Will be done.

  In one aspect, the present invention relates to a liquid SAM-containing composition useful for removing bulk and cured photoresists from microelectronic devices. A liquid composition according to one embodiment includes at least one SAM component, optionally at least one solvent, optionally at least one catalyst, and optionally at least one surfactant. A liquid composition according to another embodiment comprises at least one SAM component, at least one catalyst, optionally at least one solvent, and optionally at least one surfactant. A liquid composition according to yet another embodiment comprises at least one SAM component, at least one solvent, at least one catalyst, and optionally at least one surfactant. Importantly, depending on the nature of the solvent selected, the solvent may simultaneously act as a catalyst.

  In one embodiment, the present invention relates to a liquid SAM-containing composition useful for removing bulk and cured photoresist from a microelectronic device, wherein the catalyst simultaneously acts as a solvent. . The liquid composition according to this embodiment comprises, based on the total mass of the composition, at least one catalyst, at least one SAM component, and optionally at least one surfactant present within the following range: .

  In particularly preferred embodiments, the present invention relates to liquid SAM-containing compositions useful for removing bulk and hardened photoresists from microelectronic devices. The liquid composition according to this embodiment comprises, based on the total mass of the composition, at least one solvent, at least one catalyst, at least one SAM component, and optionally at least one existing within the following range: And a surfactant.

  In one embodiment, the range of the molar ratio of SAM to catalyst in the liquid SAM-containing composition is from about 1:10 to about 5: 1, more preferably from about 1: 5 to about 1: 1; The range of the molar ratio of the liquid solvent is from about 1: 200 to about 1:50, more preferably from about 1: 125 to about 1:75; the range of the molar ratio of SAM to surfactant (if present) Is about 1:10 to about 5: 1.

  In a broad implementation of the invention, the liquid SAM-containing composition may comprise at least one solvent, at least one catalyst, at least one SAM component, and optionally at least one surfactant. Or may consist essentially of them. In general, bulk and cured photoresists and / or processing equipment so that specific proportions and amounts of solvents, catalysts, SAM components and optional surfactants can be readily determined within the skill in the art without undue effort. Can be appropriately varied in relation to each other to provide the desired removal effect of the liquid SAM-containing composition.

  Solvent species useful in the compositions of the present invention may actually be nonpolar or polar. Examples of non-polar species include, but are not limited to, toluene, decane, dodecane, octane, pentane, hexane, tetrahydrofuran (THF), and carbon dioxide (subcritical or supercritical). Examples of polar species include methanol, ethanol, isopropanol, N-methylpyrrolidinone, N-octylpyrrolidinone, N-phenylpyrrolidinone, dimethyl sulfoxide (DMSO), sulfolane, ethyl lactate, ethyl acetate, toluene, acetone, methyl carbitol, Examples include butyl carbitol, hexyl carbitol, monoethanolamine, butyrollactone, diglycolamine, alkylammonium fluoride, γ-butyrolactone, butylene carbonate, ethylene carbonate, and propylene carbonate, and mixtures thereof. Preferably the solvent comprises a nonpolar species. Toluene is particularly preferred.

The SAM component may include alkoxyhalosilanes including (RO) ₃ SiX, (RO) ₂ SiX ₂ , (RO) SiX ₃ , where X may be the same or different from each other, F , Cl, Br, or I, ROs may be the same or different from each other, and linear or branched C ₁ -C such as methoxy, ethoxy, propoxy, etc., or combinations thereof Selected from the group consisting of ₂₀ alkoxy species. Preferably, the SAM component comprises alkylhalosilanes of the type (R) ₃ SiX, (R) ₂ SiX ₂ , (R) SiX ₃ , where X may be the same or different from each other , F, Cl, Br, or I, and R may be the same or different from each other, methyl, ethyl, propyl, butyl, octyl, decyl, dodecyl, etc., or combinations thereof linear as, branched, or is selected from the group consisting of cyclic _C 1 _{-C 20} alkyl species. Fluorinated alkyl derivatives and fluorinated alkoxy derivatives may be used. Preferably, the SAM component comprises an alkylhalosilane, where X = Cl and R = methyl. In another alternative, the SAM component has a PEG molecule attached to it.

  Without wishing to be bound by theory, a catalyst is included in the composition of the present invention to initiate the silylation reaction and accelerate the passivation of the underlying silicon-containing layer. Preferably, the catalyst includes amines such as trimethylamine, triethylamine, butylamine, pyridine, and other nucleophilic compounds that assist in removing the halogen leaving group from the SAM component. If the amine catalyst promotes in situ silylation reaction, whereby the SAM silane is covalently bonded to the oxygen atom on the underlying silicon-containing layer and at the same time accompanied by the generation of a protonated leaving group such as HX Conceivable. Thus, the underlying silicon-containing layer is passivated by the covalently bonded silane, while the generated protonated leaving group is available for removal of the cured photoresist material. Importantly, depending on the nature of the solvent selected, the solvent can simultaneously act as a catalyst.

  The liquid SAM-containing composition of the present invention may further comprise a surfactant to help remove the resist from the surface of the microelectronic device. Examples of surfactants include fluoroalkyl surfactants, polyethylene glycol, polypropylene glycol, polyethylene or polypropylene glycol ether, carboxylates, dodecylbenzenesulfonic acid or salts thereof, polyacrylate polymers, dinonylphenyl polyoxyethylene, silicones Examples include, but are not limited to, polymers or modified silicone polymers, acetylenic diols or modified acetylenic diols, alkylammonium salts or modified alkylammonium salts, and combinations of the above surfactants.

  In a preferred embodiment, the liquid SAM-containing composition is less than about 1% water, more preferably less than about 0.5% water, most preferably about 0.25%, based on the total weight of the composition. Contains less than mass% water. More preferably, the at least one SAM component does not undergo substantial polymerization at the microelectronic device surface. For example, preferably less than 5% by weight of the SAM component polymerizes on the surface of the microelectronic device, more preferably less than 2% by weight of the SAM component, even more preferably less than 1% by weight, most preferably less than 0.1% by weight, Polymerizes on the surface of microelectronic devices.

  In general, specific proportions and amounts of at least one solvent, at least one catalyst, at least one SAM component, and optionally at least one surfactant are liquid for the bulk and cured photoresist to be removed from the microelectronic device. Can be appropriately varied in relation to each other to provide the desired cleaning and passivating effects of the SAM-containing composition. Such specific proportions and amounts can be readily determined by simple experimentation within the skill of the art without undue effort. Most preferably, the SAM-containing component and the catalyst are present in an amount effective to remove the material from the microelectronic device having the bulk and cured photoresist material thereon.

  The phrase “removing the bulk and cured photoresist material from the microelectronic device” is not intended to be limiting in any way and includes the removal of the bulk and cured photoresist material from any substrate that eventually becomes a microelectronic device. Should be understood.

  Using the liquid SAM-containing composition of the present invention, cured photoresists such as BEOL cured photoresist, bottom anti-reflective coating (BARC) material, post-CMP residue, BARC residue, and / or post-ashing / etching It is also contemplated herein to remove the later photoresist while at the same time passivating the underlying silicon-containing layer or any other hydrophilic surface having hydroxyl end groups that require passivation. Furthermore, the liquid SAM-containing composition of the present invention may be used to remove contaminants from the material for reuse of the photomask material.

  The liquid SAM-containing composition of the present invention may be used to further improve the passivation and removal capabilities of the composition or otherwise improve the composition characteristics, i.e., to provide metal passivation. Optionally, additional ingredients may be formulated. Thus, the composition may be formulated with stabilizers, complexing agents, passivating agents such as Cu passivating agents and / or corrosion inhibitors.

  The liquid SAM-containing composition of the present invention is easily formulated by mixing the solvent, catalyst, SAM component and optional surfactant with gentle agitation. The solvent, catalyst, SAM component and optional surfactant are easily formulated as a single package formulation or a multi-component formulation that is mixed at the point of use. The individual components of the multi-component formulation can be mixed in the tool or in a storage tank upstream of the tool. In a broad implementation of the invention, the concentration of individual components of a single package formulation or a multi-component formulation can vary widely by a specific multiple, i.e., more dilute or more concentrated, and the liquid form of the present invention. It is understood that the SAM-containing composition of the present invention may include, consist of, or consist essentially of any combination of ingredients that are diverse and alternatively consistent with the disclosure herein. Will.

  Accordingly, another aspect of the invention relates to a kit comprising one or more components configured to form a composition of the invention in one or more containers. Preferably, the kit comprises at least one solvent, at least one SAM component, and optionally at least one surfactant in one or more containers for combination with at least one catalyst in a manufacturing plant. According to another embodiment, the kit comprises at least one SAM component and optionally at least one surfactant for combination with at least one solvent and at least one catalyst in a manufacturing plant. In a container. In yet another embodiment, the kit includes at least one SAM component in a solvent in one container and at least one catalyst in the solvent in another container for combination in a manufacturing plant. For example, the kit container is a NOWPak® container (Advanced Technology Materials, Inc., Danbury, Conn., USA), Danbury, Connecticut, USA. Also good.

  In yet another embodiment, the present invention is a liquid SAM-containing composition useful for removing bulk and cured photoresist from a microelectronic device, wherein the liquid SAM-containing composition comprises at least one solvent and A liquid SAM-containing composition comprising at least one catalyst, at least one SAM component, optionally at least one surfactant, and a photoresist residue, wherein the photoresist is a bulk and / or cured photoresist Related to things. Importantly, the residual material may be dissolved and / or suspended in the liquid SAM-containing composition of the present invention. In yet another embodiment, the photoresist residue includes ions selected from the group consisting of boron ions, arsenic ions, phosphorus ions, indium ions, and antimony ions.

In yet another aspect, the present invention relates to a dense SAM-containing composition comprising a dense fluid, such as a supercritical fluid (SCF), as the main solvent system. Supercritical carbon dioxide (SCCO ₂ ) is the preferred SCF because of its easily manufactured characteristics, its lack of toxicity and negligible environmental impact. Since SCCO ₂ has both liquid and gaseous characteristics, SCCO ₂ is an attractive reagent for the removal of microelectronic device process contaminants. Like gas, it diffuses rapidly, has low viscosity, nearly zero surface tension, and easily penetrates into deep trenches and vias. Like a liquid, it has a bulk flow capability as a “cleaning” medium. SCCO ₂ has a density comparable to organic solvents and has the advantage of being recyclable, thus minimizing waste storage and processing requirements.

液状のＳＡＭ含有組成物は、約７５．０％〜約９０．０％の共溶媒と、約０．０１％〜約１０．０％のＳＡＭ成分と、約０．０１％〜約１０．０％の触媒と、任意に０〜約１０．０％の界面活性剤とを含み、企図される共溶媒、ＳＡＭ成分、触媒及び任意の界面活性剤は上述の種を含む。 A high density SAM-containing composition according to one embodiment comprises SCCO ₂ and a liquid SAM-containing composition, ie a SAM-containing concentrate, within the following range, based on the total mass of the composition:

The liquid SAM-containing composition comprises about 75.0% to about 90.0% co-solvent, about 0.01% to about 10.0% SAM component, and about 0.01% to about 10.0. % Catalyst and optionally 0 to about 10.0% surfactant, and contemplated co-solvents, SAM components, catalysts and optional surfactants include the species described above.

In one embodiment, the molar ratio range of the liquid SAM-containing composition to SCCO ₂ in the high-density SAM-containing composition ranges from about 1: 200 to about 1: 4, more preferably from about 1: 100 to about 1. : 6.

In a broad implementation of the invention, the high density SAM-containing composition comprises SCCO ₂ , a liquid SAM-containing composition, ie, at least one additional solvent, at least one catalyst, at least one SAM component, and optionally May comprise, consist of, or consist essentially of at least one surfactant. In general, the specific proportions and amounts of SCCO ₂ and liquid SAM-containing compositions are high density in bulk and cured photoresists and / or processing equipment so that they can be readily determined within the skill of the art without undue effort. Appropriate changes can be made in relation to each other to provide the desired removal effect of the SAM-containing composition. Importantly, the liquid SAM-containing composition may be at least partially dissolved and / or suspended in the dense fluid of the dense SAM-containing composition.

In yet another embodiment, the present invention is a high density SAM-containing composition useful for removing bulk and hardened photoresist from a microelectronic device, wherein the high density SAM-containing composition comprises at least SCCO ₂ and A high solvent comprising at least one catalyst, at least one catalyst, at least one SAM component, optionally at least one surfactant, and a photoresist residue, wherein the photoresist is a bulk and / or cured photoresist; It relates to a density SAM-containing composition. Importantly, the residual material may be dissolved and / or suspended in the high density SAM-containing composition of the present invention. In yet another embodiment, the photoresist residue includes ions selected from the group consisting of boron ions, arsenic ions, phosphorus ions, indium ions, and antimony ions.

  Using the high density SAM-containing composition of the present invention, a cured photoresist, such as BEOL cured photoresist, bottom antireflective coating (BARC) material, post-CMP residue, BARC residue, and / or post-ashing It is also contemplated herein that the post-etch photoresist can be removed and at the same time passivating the underlying silicon-containing layer or any other hydrophilic surface with hydroxyl end groups that require passivation. Is done. In addition, the dense SAM-containing composition of the present invention can be used to remove contaminating material from a photomask material for reuse.

  In yet another aspect, the invention relates to a method for removal of bulk and hardened photoresist from microelectronic devices using the SAM-containing compositions described herein. For example, SAM passivation can be used to clean trench and via structures on patterned devices while maintaining the structural integrity of the underlying silicon-containing layer. It should be understood by those skilled in the art that the SAM-containing composition may be used in a one-step or multi-step removal process.

  The SAM-containing composition of the present invention overcomes the disadvantages of conventional removal techniques by reversibly passivating the underlying silicon-containing layer while simultaneously removing the bulk and hardened photoresist deposited thereon.

  The liquid SAM-containing composition of the present invention is easily formulated by simple mixing of the components, for example, under gentle agitation in a mixing or washing tank. High density SAM-containing compositions are easily formulated by static or dynamic mixing at the appropriate temperature and pressure.

  In passivation and removal applications, the liquid SAM-containing composition can be applied in any suitable manner to a microelectronic device having a photoresist material thereon, for example, spraying the composition onto the surface of the device. By immersing (in a volume of the composition) the device containing the photoresist material, another material impregnated with the composition, such as a pad or a fibrous adsorbent application member, and the device By contacting the circulating removal composition with the device containing the material, or any other suitable means by which the liquid SAM-containing composition contacts the photoresist material on the microelectronic device. , Depending on the mode or technique. Passivation and removal applications may be static or dynamic, as readily determined by one skilled in the art.

  In using the composition of the present invention to remove the material from the surface of the microelectronic device having the photoresist material thereon, the liquid SAM-containing composition is typically about 1 to about 60 minutes. While the device surface is in contact, the preferred time depends on the dopant ion dose and implantation energy used during ion implantation, the higher the dopant ion dose and / or implantation energy, the longer the contact time required. Preferably, the temperature is in the range of about 20 ° C to about 80 ° C, preferably about 30 ° C to about 80 ° C, and most preferably about 70 ° C. Such contact times and temperatures are exemplary, and any other suitable time and temperature conditions that are effective to at least partially remove the photoresist material from the device surface within the broad practice of the invention. Can be used. “At least partial removal” as defined herein corresponds to at least 90% removal, preferably at least 95% removal of bulk and hardened photoresist. Most preferably, at least 99% of the bulk and cured photoresist material is removed using the composition of the present invention.

  After achieving the desired passivating and cleaning effects, the microelectronic device can be thoroughly rinsed with a large amount of ethanol and / or THF to remove any residual chemical additives.

The SAM-containing composition of the present invention comprises 100% of a highly doped photoresist (thickness 500-700 nm) (2 × 10 ¹⁵ As ions cm ⁻² ) with a cured crosslinked carbonized crust that is 30-70 nm thick. Selectively remove. Importantly, the hardened crust is removed without substantially overetching the underlying silicon-containing layer.

  For passivation and cleaning applications using high density SAM-containing compositions, the microelectronic device surface with the photoresist thereon is suitable high pressure, for at least partial removal of the photoresist from the microelectronic device surface. For example, contacting a dense SAM-containing composition in a pressurized contact chamber, but the dense SAM-containing composition is fed to the pressurized contact chamber at an appropriate volumetric rate and amount to effect the desired contact operation. Is called. The chamber may be a batch or single wafer chamber for continuous, pulsed, or static cleaning. Passivation and removal of the cured photoresist with the high density SAM-containing composition can be improved by using high temperature and / or high pressure conditions during contact of the photoresist with the high density SAM containing composition.

  With a suitable high density SAM-containing composition, at a pressure in the range of about 1,500 to about 4,500 psi, for a time sufficient to effect the desired removal of the photoresist, for example, about 5 minutes to about 30. Contact times in the range of minutes, and temperatures from about 40 ° C. to about 75 ° C., may be contacted with microelectronic device surfaces having photoresist thereon, but in larger implementations of the invention, larger or smaller Contact time and contact temperature may be advantageously used.

  The removal process using a high density SAM-containing composition can be a static soak step, a dynamic cleaning mode step, or a dynamic flow of a high density SAM containing composition on a microelectronic device surface followed by a high density SAM containing composition. In the alternative process cycle, each of the dynamic flow process and the static soak process are alternately and repeatedly performed.

  The “dynamic” contact mode includes a continuous flow of the composition over the device surface to maximize mass transfer gradient and achieve complete removal of resist from the surface. The “static soak” contact mode includes contacting the device surface with a static volume of composition and maintaining contact with it for a continuous (soak) time.

After contact of the dense SAM-containing composition to the surface of the microelectronic device, preferably the device is then aliquoted with a rinsing solution, such as an SCF / cosolvent solution, such as an SCCO ₂ / methanol (80% / 20%) solution, And cleaning with pure SCF to remove any residual precipitating chemical additives from the areas of the device surface where the resist removal has been performed.

  The liquid SAM-containing composition and the high-density SAM-containing composition of the present invention were used while achieving the desired passivation of the underlying silicon-containing layer and the desired removal of the cured photoresist material on the surface of the microelectronic device. It is understood that specific contact conditions can be readily determined within the skill of the art based on the disclosure herein, and that specific proportions and concentrations of ingredients in the compositions of the present invention may vary widely. It will be.

Another aspect of the invention is a method for removal of bulk and hardened photoresist from a microelectronic device on a microelectronic device surface using a halide-free SAM component such as hexamethyldisilazane (HMDS). And passivating the underlying silicon-containing layer and removing bulk and cured photoresist from the microelectronic device using an etchant-containing removal composition. Suitable etchant-containing removal compositions include, but are not limited to, hydrogen fluoride (HF), ammonium fluoride (NH ₄ F), alkyl hydrofluoride (NRH ₃ F), dialkyl ammonium fluoride _{(dialkylammonium hydrogen fluoride) (NR 2} H 2 F), hydrogen fluoride trialkylammonium _{(trialkylammonium hydrogen fluoride) (NR 3} HF), fluoride trihydric trialkylammonium _{(trialkylammonium trihydrogen fluoride) (NR 3} (3HF)), Tetraalkylammonium fluoride (NR ₄ F), pyridine-HF complex, pyridine / HCl complex, pyridine / H In the above R-substituted species, including Br complex, triethylamine / HF complex, triethylamine / HCl complex, monoethanolamine / HF complex, triethanolamine / HF complex, triethylamine / formic acid complex, and xenon difluoride (XeF ₂ ) Each R in is independently selected from C ₁ -C ₈ alkyl and C ₆ -C ₁₀ aryl. An additional species is Pamelin, a "Dense Fluid Formulation for Cleaning Ion-Implanted Photolayers from Microelectronic Devices". M. Vistin) et al., Co-pending US Provisional Patent Application No. 60 / 672,157, filed April 15, 2005, hereby incorporated by reference in its entirety. Incorporate.

  In yet another aspect, the invention provides a method of removing said photoresist material from a microelectronic device having bulk and cured photoresist material thereon, wherein the SAM-containing composition is hydrogen fluoride, ammonium fluoride, The method at least partially removes the photoresist material from the microelectronic device, provided that it lacks an etchant component selected from the group consisting of ammonium bifluoride and other known fluoride etchant species. It relates to a method comprising contacting a microelectronic device with a SAM-containing composition for a sufficient time.

  Regardless of the method used to remove the cured photoresist from the microelectronic device, a further aspect of the present invention is to remove the photoresist material from the surface of the microelectronic device, referred to herein as “depassivation”. Including removal of the SAM passivation layer from the surface of the microelectronic device after removal.

If carbon contamination by passivated alkyl groups on the wafer surface is unacceptable (for SAMs where Cl ₃ SiMe is used, a monolayer of about 3-10 cm of methyl groups), a strong acid such as H ₂ SO ₄ may be used. Can be used to remove the SAM, but this can cause unwanted oxidation of the underlying silicon-containing layer. Accordingly, dilute inorganic acids containing halide ions such as HCl and HF are preferred under optimized process conditions. Halide ions readily attack passivated Si—O—Si bonds at the SAM-device surface interface and thus “depassivate” the device surface. However, special care must be taken to minimize overetching of the silicon-containing layer on the device surface.

The inventors have found that an aqueous solution of HF / pyridine (1: 1 molar ratio) in DMSO is a thermal oxide, TEOS, silicon nitride, and polysilicon at a rate of less than 0.1 kg · min− ^1. It has been shown previously that it is known to etch. Thus, to passivate the device surface with only slight fluorination and overetching of the underlying silicon-containing layer, the depassivation solution is about 0.01% to about 2% by weight in the solvent. Or a dilute inorganic acid / amine complex. Diluted inorganic acid / amine complexes contemplated herein include pyridine / HF complexes, pyridine / HCl complexes, pyridine / HBr complexes, triethylamine / HF complexes, triethylamine / HCl complexes, triethylamine / formic acid complexes, and peroxides. In combination with concentrated HCl, ammonium hydroxide, and mixtures thereof. Solvents contemplated herein for depassivation solutions include, but are not limited to, DMSO, methanol, and ethyl acetate.

  Yet another aspect of the present invention relates to an improved microelectronic device made by the method of the present invention, and a product containing such a microelectronic device.

  A further aspect of the present invention is a method of manufacturing an article comprising a microelectronic device for at least partially removing said photoresist material from a microelectronic device having bulk and cured photoresist material thereon. Contacting the microelectronic device with the SAM-containing composition for a sufficient time; and incorporating the microelectronic device into the article, wherein the SAM-containing composition comprises at least one solvent, at least one catalyst, It relates to a method comprising at least one SAM component and optionally at least one surfactant. Alternatively, the SAM-containing composition may further comprise a dense fluid.

  The features and advantages of the invention are more fully shown by the specific examples described below.

Example 1
Perform atomic force microscopy (AFM) and surface energy measurements before and after contact of the sample device surface with the SAM-containing composition of the present invention to remove the cured photoresist and form a monolayer on the surface of the device. I examined the degree. The sample device surface is (from top to bottom) an ion-implanted photoresist layer (2 × 10 ¹⁵ As ions cm ⁻² ; 10 keV implantation energy), a bulk photoresist layer, a silicon-containing gate oxide layer, and a silicon substrate Including a wafer consisting of Samples were processed with different SAM functionality (functionality) at different times and at different temperatures, and contact angles were measured. The results are shown in Tables 1 to 3 below.

  Passivation of the underlying silicon-containing layer is evidenced by an increase in contact angle after application of the SAM-containing composition to the device surface. It can be seen from Table 1 that a process time of less than 10 minutes is required to convert a hydroxyl-terminated hydrophilic device surface with a contact angle of 35 ° to a methyl-terminated hydrophobic surface with a contact angle of 77 °. Is recognized.

  The corresponding AFM images shown in FIGS. 1A-1D at contact times equal to 10 minutes, 30 minutes, 1 hour, and 15 hours, respectively, increase in time (while keeping all other process parameters constant). It clearly shows that polymerization (or cross-linking) of multi-substituted chlorosilanes forms small islands on silicon-containing surfaces. As the process time increases, the islands gradually coalesce or agglomerate, and 15 hours show signs of bulk polymerization on the surface.

  Preliminary temperature studies were conducted to determine the most effective temperature for surface passivation and cleaning efficiency. Regarding cleaning efficiency, four different microelectronic device layers: bulk coated photoresist; 30-45 nm ion implantation crust on bulk coated photoresist; bulk patterned photoresist; and bulk An ion implantation crust on patterned photoresists was studied. Comparing the results reported in Table 2 (contact angles) with the percent removal efficiency shown in FIG. 2, temperatures higher than 60 ° C. resulted in a maximum amount of passivation and almost 100% removal of the photoresist. It is allowed to bring. Therefore, all subsequent experiments as a function of time and SAM functionality were performed at 70 ° C.

The signs of cross-linking are better shown in FIGS. 3A-3C, which show the SAM functionality at a temperature of 70 ° C. and a time of 30 minutes, specifically the function of cross-linking as a function of the number of chloride leaving groups. Showing change. In ClSiMe ₃ (FIG. 3A), it can be seen that there is no cross-linking ability of SAM and a smooth monolayer (rms = 0.415 nm; control rms = 0.131 nm) is formed on the surface. However, as shown by the island formation described above, cross-linking occurs in Cl ₂ SiMe ₂ (FIG. 3B) and Cl ₃ SiMe (FIG. 3C), resulting in a rougher film surface (di- and tri-chlorosilane, respectively). For rms = 0.465 and 1.573 nm). Island formation indicates the need for more aggressive depassivation techniques (eg, more concentrated compositions, longer contact times, etc.).

Example 2
4A-4C are optical microscopes (FIG. 4) of a sample device surface comprising a layer of densely patterned, highly doped (2 × 10 ¹⁵ As ions cm ⁻² ; 10 keV implantation energy) photoresist consisting of parallel line regions. 4A) and scanning electron microscope (SEM) images are shown. A cured crust of ˜30 nm thickness is clearly visible in the 90 ° viewpoint image (FIG. 4C). The cleaning efficiency of the crust as a function of chloride substitution on the SAM component is shown in FIG. 5A (ClSiMe ₃ ), FIG. 5B (Cl ₂ SiMe ₂ ), and FIG. 5C (Cl ₃ SiMe). The optical microscopic images of FIGS. 5A-5C show that as the number of chloride leaving groups on the SAM component increases, the amount of cured photoresist removed also increases. In fact, greater than 90% removal of four different microelectronic device layers is achieved using Cl ₃ SiMe-containing compositions (see FIG. 6). The increase in crust removal is believed to be the result of the increase in HCl generated when the SAM-containing composition is applied to the device surface.

  Additional experiments were performed whereby a non-halide-containing SAM-containing composition was contacted with a sample device surface comprising a highly patterned highly doped photoresist and an underlying silicon-containing layer. As indicated by the 63 ° contact angle, the cured photoresist was not removed when the sample was passivated. Accordingly, our results indicate that some amount of leaving group, such as chloride, is necessary for removal of the cured photoresist.

Example 3
Further aspects of the invention include removal of the passivation layer from the surface of the microelectronic device, or “depassivation”. FIG. 7A is an optical microscope image of a densely patterned device surface with a contact angle of 36 ° and rms = 0.15 nm. FIG. 7B is an optical image of the device surface of FIG. 7A after application of a SAM-containing composition comprising Cl ₃ SiMe at 70 ° C. for 30 minutes. The contact angle of the passivated surface was measured as 79 ° (at rms = 1.10 nm), indicating passivation of the silicon-containing surface. It can be seen that at least 90% of the cured photoresist has been removed. FIG. 7C is an optical image of the device surface of FIG. 7B after depassivation at 50 ° C. for 2 minutes with a composition of NEt ₃ : HF (1: 3 molar ratio) in DMSO. The contact angle of the depassivated surface was measured as 35 ° (at rms = 0.25 nm). The depassivation process is essentially complete when the contact angle of the surface matches the contact angle of the surface prior to contact with the SAM-containing composition.

  It will be appreciated that the depassivation process should be optimized to eliminate fluorination and / or overetching of the underlying silicon-containing layer. For example, depassivation is performed at 30 second intervals for SAM removal from device structures containing thermal oxide, and depassivation is performed at 20 second intervals for SAM removal from TEOS-based device structures. You may go on.

8A-8E provide another view of the results of passivation and cleaning, and depassivation after removal of the cured photoresist. FIG. 8A is a pre-process SEM of a device surface comprising a densely patterned highly doped (2 × 10 ¹⁵ As ions cm ⁻² ; 10 keV implantation energy) photoresist layer. FIG. 8B is the SEM of the densely patterned surface of FIG. 8A after applying a SAM-containing composition comprising Cl ₃ SiMe for 30 minutes at 70 ° C., with successful and efficient removal of the cured photoresist ( And passivation). 8C and 8D are SEMs of the device surface of FIG. 8B after depassivation with a composition of NEt ₃ : HF (1: 3 molar ratio) in DMSO at 50 ° C. for 2 minutes. The SEM images of FIGS. 8C and 8D do not show any sign of substantial over-etching of the underlying silicon-containing layer during the depassivation process (compare with the over-etched sample in FIG. 8E). ).

  The improved SAM-containing composition taught herein can be bulk and cured in a one-step or multi-step process without the need for plasma etching steps and without substantially over-etching the underlying silicon-containing layer. Effectively remove the photoresist.

  Thus, while the invention has been described herein with reference to specific aspects, features and exemplary embodiments of the invention, the usefulness of the invention is not limited thereto, but rather numerous other aspects. It will be understood that this extends to and encompasses the features and embodiments. Accordingly, the appended claims should be construed broadly to include all such aspects, features, and embodiments within their spirit and scope.

Brief Description of Drawings
After contacting a microelectronic device surface with a SAM-containing composition comprising 1 mmol of Cl ₃ SiMe and 2 mmol of Et ₃ N in 10 mL of toluene at a contact temperature of 70 ° C., contact time = 1 micron It is an atomic force microscope photograph of the surface of an electronic device. After contacting a microelectronic device surface with a SAM-containing composition comprising 1 mmol Cl ₃ SiMe and 2 mmol Et ₃ N in 10 mL toluene at a contact temperature of 70 ° C., the contact time = 30 minutes It is an atomic force microscope photograph of the surface of an electronic device. At a contact temperature of 70 ° C., after contacting a SAM-containing composition comprising 1 mmol of Cl ₃ SiMe and 2 mmol of Et ₃ N in 10 mL of toluene to the surface of the microelectronic device, contact time = 1 microsecond It is an atomic force microscope photograph of the surface of an electronic device. After contacting a microelectronic device surface with a SAM-containing composition comprising 1 mmol of Cl ₃ SiMe and 2 mmol of Et ₃ N in 10 mL of toluene at a contact temperature of 70 ° C., the contact time = 15 hours of micro It is an atomic force microscope photograph of the surface of an electronic device. Bulk coated photoresist layer (bulk PR), coated ion-implanted photoresist layer (crust), bulk patterned photoresist layer (patterned PR), and patterned ion-implanted photoresist layer Figure 4 shows the cleaning efficiency of the inventive SAM-containing composition as a function of temperature for four different microelectronic device layers including (patterned crust). Atomic force microscopy of the surface of the microelectronic device after contacting the surface of the microelectronic device with a SAM-containing composition comprising ClSiMe ₃ in 2 mmol of Et ₃ N in 10 mL of toluene at a contact temperature of 70 ° C. It is a photograph. At the contact temperature of 70 ° C., the atoms on the microelectronic device surface after contacting the microelectronic device surface with a SAM-containing composition comprising Cl ₂ SiMe ₂ in ₂ mmol Et ₃ N in 10 mL toluene for 30 minutes. It is a force micrograph. Atomic force on the surface of the microelectronic device after contacting the surface of the microelectronic device with a SAM-containing composition comprising Cl ₃ SiMe in 2 mmol of Et ₃ N in 10 mL of toluene at a contact temperature of 70 ° C. It is a micrograph. 2 is an optical microscopic image of a densely patterned ion-implanted photoresist on a microelectronic device surface. 2 is a scanning electron microscope (SEM) image of a densely patterned ion-implanted photoresist on a microelectronic device surface. 2 is a scanning electron microscope (SEM) image of a densely patterned ion-implanted photoresist on a microelectronic device surface. The SAM-containing composition comprising the ClSiMe ₃ after contacting for 30 minutes at 70 ° C., is an optical microscope image of a microelectronic device surface. The SAM-containing composition comprising Cl ₂ SiMe ₂ after contact for 30 minutes at 70 ° C., is an optical microscope image of a microelectronic device surface. The SAM-containing composition comprising Cl ₃ SiMe after contacting for 30 minutes at 70 ° C., is an optical microscope image of a microelectronic device surface. Bulk coated photoresist layer (bulk PR), coated ion implanted photoresist layer (crust), bulk patterned photoresist layer (patterned PR), and patterned ion implanted photoresist layer 4 shows the removal efficiency of the SAM-containing composition of the present invention as a function of SAM functionality for four different microelectronic device layers including (patterned crust). It is an optical microscope image of a control surface. It is the optical microscope image of the surface after washing | cleaning and passivation using the SAM containing composition of this invention. Figure 3 is an optical microscopic image of a surface after depassivation according to the present invention. It is a scanning electron micrograph of a control surface. It is a scanning electron micrograph of the surface after washing | cleaning and passivation using the SAM containing composition of this invention. It is the scanning electron micrograph of the surface after depassivation in a 90 degree viewpoint. It is the scanning electron micrograph of the surface after the depassivation in a 60 degree viewpoint. It is a scanning electron micrograph of the surface intentionally over-etched after depassivation.

Claims (43)

  A self-assembled monolayer (SAM) -containing composition comprising at least one solvent, at least one catalyst, at least one SAM component, and optionally at least one surfactant, the SAM-containing composition A self-assembled monolayer (SAM) -containing composition suitable for removing said photoresist material from a microelectronic device having bulk and cured photoresist material thereon.   The SAM-containing composition of claim 1, wherein the molar ratio of SAM to catalyst in the liquid SAM-containing composition is in the range of about 1:10 to about 5: 1.   The SAM-containing composition of claim 1, wherein the molar ratio of SAM to solvent is in the range of about 1: 200 to about 1:50.   2. The solvent of claim 1, wherein the solvent comprises at least one non-polar solvent selected from the group consisting of toluene, decane, dodecane, octane, pentane, hexane, tetrahydrofuran (THF), carbon dioxide, and mixtures thereof. SAM-containing composition.   Methanol, ethanol, isopropanol, N-methylpyrrolidinone, N-octylpyrrolidinone, N-phenylpyrrolidinone, dimethyl sulfoxide (DMSO), sulfolane, ethyl lactate, ethyl acetate, toluene, acetone, butyl carbitol, monoethanolamine, butyrolol lactone The SAM-containing composition of claim 4, further comprising an additional solvent selected from the group consisting of: diglycolamine, alkylammonium fluoride, γ-butyrolactone, butylene carbonate, ethylene carbonate, propylene carbonate, and mixtures thereof. object.   The SAM-containing composition according to claim 1, wherein the solvent comprises toluene.   The SAM-containing composition according to claim 1, wherein the solvent comprises high density carbon dioxide. The SAM component is (RO) ₃ SiX, (RO) ₂ SiX ₂ , (RO) SiX ₃ , (R) ₃ SiX, (R) ₂ SiX ₂ , and (R) SiX _3.
(Where X = F, Cl, Br, and I, R = methyl, ethyl, propyl, butyl, octyl, decyl, and dodecyl; fluorinated derivatives thereof; and combinations thereof)
The SAM-containing composition of claim 1 comprising a silane selected from the group consisting of: The SAM-containing composition according to claim 1, wherein the SAM component comprises an alkylchlorosilane selected from the group consisting of Cl ₃ SiMe, Cl ₂ SiMe ₂ , and ClSiMe ₃ .   The SAM-containing composition of claim 1, wherein the catalyst comprises an amine selected from the group consisting of trimethylamine, triethylamine, butylamine, pyridine, and combinations thereof.   The SAM-containing composition according to claim 1, comprising at least one surfactant.   The surfactant is a fluoroalkyl surfactant, polyethylene glycol, polypropylene glycol, polyethylene glycol ether, polypropylene glycol ether, carboxylate, dodecylbenzenesulfonic acid, dodecylbenzenesulfonate, polyacrylate polymer, dinonylphenyl polyoxy 12. The SAM of claim 11, comprising a surfactant species selected from the group consisting of ethylene, silicone polymers, modified silicone polymers, acetylenic diols, modified acetylenic diols, alkyl ammonium salts, modified alkyl ammonium salts, and combinations thereof. Containing composition. The SAM-containing composition according to claim 1, wherein the composition comprises toluene, Cl ₃ SiMe, and triethylamine.   The SAM-containing composition of claim 1, wherein the microelectronic device comprises an article selected from the group consisting of a semiconductor substrate, a flat panel display, and a microelectromechanical system (MEMS).   The SAM-containing composition of claim 1, wherein the bulk and hardened photoresist material comprises dopant ions selected from the group consisting of arsenic ions, boron ions, phosphorus ions, indium ions, and antimony ions.   The at least one SAM component and the at least one catalyst passivate the silicon-containing layer on the microelectronic device while simultaneously removing the material from the microelectronic device having bulk and hardened photoresist material thereon. The SAM-containing composition of claim 1, wherein the SAM-containing composition is present in an effective amount.   The silicon-containing layer is silicon; silicon dioxide; TEOS; silicon nitride; silicon-containing organic polymer; silicon-containing hybrid organic / inorganic material; organosilicate glass (OSG); fluorosilicate glass (FSG); The SAM-containing composition of claim 16 comprising a silicon-containing compound selected from the group consisting of oxide (CDO) glass; and combinations thereof.   The SAM-containing composition according to claim 7, wherein the carbon dioxide is supercritical.   The SAM-containing composition of claim 1 further comprising a photoresist residue.   The SAM-containing composition of claim 19, wherein the photoresist comprises a bulk photoresist, a cured photoresist, or a combination thereof.   21. The SAM-containing composition according to claim 20, wherein the photoresist comprises ions selected from the group consisting of boron ions, arsenic ions, phosphorus ions, indium ions, and antimony ions.   A kit comprising a SAM-containing composition reagent in one or more containers, the SAM-containing composition comprising at least one solvent, at least one catalyst, at least one SAM component, and optionally at least one A kit, wherein the kit is configured to form a SAM-containing composition suitable for removing the photoresist material from a microelectronic device having bulk and cured photoresist material thereon. kit.   A method of removing the photoresist material from a microelectronic device having bulk and hardened photoresist material thereon, the method being sufficient to at least partially remove the photoresist material from the microelectronic device. Contacting the microelectronic device with a SAM-containing composition for a sufficient amount of time and under sufficient contact conditions, wherein the SAM-containing composition comprises at least one solvent, at least one catalyst, and at least one SAM component. Optionally comprising at least one surfactant.   24. The method of claim 23, wherein the contacting is performed for a time of about 1 minute to about 60 minutes.   24. The method of claim 23, wherein the contacting is performed at a temperature of about 30 <0> C to about 80 <0> C. The solvent is toluene, decane, octane, dodecane, pentane, hexane, tetrahydrofuran (THF), carbon dioxide, methanol, ethanol, isopropanol, N-methylpyrrolidinone, N-octylpyrrolidinone, N-phenylpyrrolidinone, dimethylsulfoxide (DMSO). , Sulfolane, ethyl lactate, ethyl acetate, toluene, acetone, butyl carbitol, monoethanolamine, butyrolollactone, diglycolamine, alkylammonium fluoride, γ-butyrolactone, butylene carbonate, ethylene carbonate, propylene carbonate, and their Including at least one solvent selected from the group consisting of a mixture;
The catalyst comprises an amine selected from the group consisting of trimethylamine, triethylamine, butylamine, pyridine, and combinations thereof;
The SAM component is (RO) ₃ SiX, (RO) ₂ SiX ₂ , (RO) SiX ₃ , (R) ₃ SiX, (R) ₂ SiX ₂ , and (R) SiX _3.
(Where X = F, Cl, Br, and I, R = methyl, ethyl, propyl, butyl, octyl, decyl, and dodecyl; fluorinated derivatives thereof; and combinations thereof)
24. The method of claim 23, comprising a silane selected from the group consisting of:   The molar ratio of SAM to catalyst in the liquid SAM-containing composition is in the range of about 1:10 to about 5: 1, and the molar ratio of SAM to solvent is about 1: 200 to about 1:50. 24. The method of claim 23, which is within range.   24. The method of claim 23, wherein the microelectronic device comprises an article selected from the group consisting of a semiconductor substrate, a flat panel display, and a microelectromechanical system (MEMS).   24. The method of claim 23, wherein the bulk and hardened photoresist material comprises dopant ions selected from the group consisting of arsenic ions, boron ions, phosphorus ions, indium ions, and antimony ions.   The contacting comprises spraying the SAM-containing composition onto a surface of the microelectronic device; immersing the microelectronic device in a sufficient volume of the SAM-containing composition; soaking the SAM-containing composition Contacting the surface of the microelectronic device with another deposited material; contacting the microelectronic device with a circulating SAM-containing composition; contacting the microelectronic device with a continuous stream of the SAM-containing composition 24. and a process selected from the group consisting of contacting a surface of the microelectronic device with a static volume of the SAM-containing composition for a continuous period of time.   24. The method of claim 23, further comprising rinsing the microelectronic device after contact with the SAM-containing composition.   The at least one SAM component and the at least one catalyst passivate the silicon-containing layer on the microelectronic device while simultaneously removing the material from the microelectronic device having bulk and hardened photoresist material thereon. 24. The method of claim 23, wherein the method is present in an effective amount.   The silicon-containing layer is silicon; silicon dioxide; TEOS; silicon nitride; silicon-containing organic polymer; silicon-containing hybrid organic / inorganic material; organosilicate glass (OSG); fluorosilicate glass (FSG); 35. The method of claim 32, comprising a silicon-containing compound selected from the group consisting of oxide (CDO) glass; and combinations thereof.   35. The method of claim 32, wherein the underlying silicon-containing layer has a contact angle in the range of about 60 degrees to about 120 degrees after formation of the SAM passivation layer.   24. After at least partial removal of the photoresist material from the microelectronic device, further comprising removing the SAM passivation layer from the microelectronic device using a depassivation composition. The method described in 1.   The depassivation composition comprises a pyridine / HF complex, a pyridine / HCl complex, a pyridine / HBr complex, a triethylamine / HF complex, a triethylamine / HCl complex, a triethylamine / formic acid complex, a peroxide derivative thereof, concentrated HCl, water 36. The method of claim 35, comprising a compound selected from the group consisting of ammonium oxide, and combinations thereof.   24. The method of claim 23, wherein the solvent comprises high density carbon dioxide.   38. The method of claim 37, wherein the contact conditions include high pressure.   40. The method of claim 38, wherein the high pressure comprises a pressure in the range of about 1500 to about 4500 psi.   38. The method of claim 37, wherein the contact time is in the range of about 5 to about 30 minutes.   38. The method of claim 37, wherein the contact conditions comprise a temperature in the range of about 40 ° C to about 75 ° C.   A method of removing the photoresist material from a microelectronic device having bulk and hardened photoresist material thereon, the method at least partially passivating a silicon-containing layer underlying the photoresist material. Contacting the microelectronic device with a SAM-containing composition for a time sufficient to contact the microelectronic device with an etchant-containing removal composition to at least partially remove the photoresist material from the microelectronic device. Removing, wherein the SAM-containing composition comprises a halide-free SAM component.   A method of removing the photoresist material from a microelectronic device having bulk and hardened photoresist material thereon, the method being sufficient to at least partially remove the photoresist material from the microelectronic device. Contacting the microelectronic device with a SAM-containing composition in a short time, wherein the SAM-containing composition lacks an etchant component.

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