Patent Description:
During laser ablation of polymeric films, debris is invariably formed and the amount and type depends on the composition of the film and processing conditions of ablation. This debris is mostly deposited on the terrace but some can find way to the structure's bottom and walls. Thorough removal is essential to enable further component build steps such as soldering and metal deposition. Chemical cleaning of such debris without affecting the film is one of the focuses of the present invention. Moreover, the design of the compositions of the present invention allows the compositions to act as an efficient stripper at an elevated temperature. <CIT> describes a remover composition obtained by adding a cyclic urea compound to water, water-soluble organic solvent, or a mixture of water and water-soluble organic solvent. <CIT> describes compositions for cleaning integrated circuit substrates and a two-step method for removal of photoresist, post etch residue, and/or post planarization residue from substrates comprising copper, where one of the compositions comprises a basic compound.

The present invention is defined by independent claim <NUM> and independent claims <NUM> to <NUM>. The present disclosure describes a cleaning composition, which can be used for a post laser ablation cleaning process at room temperature (e.g., <NUM>), and which can also serve as a stripping composition for a polymeric layer for either a rework process and/or after subsequent processing at an elevated temperature (e.g., <NUM>-<NUM>).

The composition comprises:
(a) <NUM> - <NUM> percent by weight an alkaline compound; (b) <NUM> - <NUM> percent by weight an alcohol amine compound; (c) <NUM> - <NUM> percent by weight a hydroxylammonium compound (d) <NUM> - <NUM> percent by weight an organic solvent; (e) <NUM> - <NUM> percent by weight a corrosion inhibitor compound, wherein the corrosion inhibitor compound is triazole, benzotriazole, substituted triazole, or substituted benzotriazole; and (f) <NUM> -<NUM> percent by weight water. The composition is free of a urea and urea derivatives and has a pH of at least <NUM>.

In some embodiments, this disclosure features a composition wherein the pH of the composition is at least about <NUM>, and the organic solvent has a relative energy difference (RED) of from about <NUM> to about <NUM> relative to water. In such embodiments, the composition can have a kinematic viscosity at <NUM> from about <NUM><NUM>s-<NUM> (<NUM> cSt) to about <NUM> cm2s-<NUM> (<NUM> cSt).

The present disclosure also describes a method for manufacturing a semiconductor device using the composition, and a process wherein post laser debris and non-ablated areas of the patterned polymeric film are removed.

A unique aspect in the design of the composition of this disclosure is that at room temperature, this composition acts as a cleaner to remove post laser ablation debris, and at elevated temperature acts as an extremely efficient stripper.

This disclosure relate to compositions suitable for cleaning residues after a laser ablation process, and under different treatment conditions, also suitable for stripping a polymeric layer. When used as a cleaning composition after the post laser ablation process, it is essential that little, if any, of the polymeric layer on a semiconductor substrate be removed. When used in a stripping process, it is critical that all of the polymeric layer be removed and the underlying substrate be clean. The inventors discovered unexpectedly that the compositions described herein can be used effectively in both cleaning and stripping processes described above.

The cleaning/stripping compositions described herein include: (a) <NUM> - <NUM> percent by weight an alkaline compound; (b) <NUM> - <NUM> percent by weight an alcohol amine compound; (c) <NUM> - <NUM> percent by weight a hydroxylammonium compound; (d) <NUM>-<NUM> percent by weight an organic solvent; (e) <NUM> - <NUM> percent by weight a corrosion inhibitor compound, wherein the corrosion inhibitor compound is triazole, benzotriazole, substituted triazole, or substituted benzotriazole; and (f) <NUM> -<NUM> percent by weight water. The composition is free of a urea and urea derivatives and has a pH of at least <NUM>.

The alkaline compounds (a) that can be used in the cleaning/stripping composition of the disclosure are not particularly limited. In some embodiments, the alkaline compounds include inorganic bases, such as, potassium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate; and organic bases, such as, quaternary ammonium hydroxides. Preferred alkaline compounds are quaternary ammonium hydroxides. Examples of the quaternary ammonium hydroxides include, but are not limited to, quaternary ammonium hydroxides, which can be selected from a group consisting of tetramethyl ammonium hydroxide (TMAH), <NUM>-hydroxyltrimethyl ammonium hydroxide, tetraethyl ammonium hydroxide (TEAH), tetrapropyl ammonium hydroxide (TPAH), tetrabutyl ammonium hydroxide (TBAH), and a mixture thereof. The preferred quaternary ammonium hydroxides are tetramethyl ammonium hydroxide and <NUM>-hydroxyltrimethyl ammonium hydroxide. A more preferred quaternary ammonium hydroxide is tetramethyl ammonium hydroxide.

The alkaline compounds (a) used in the cleaning/stripping composition of this disclosure are present in an amount of at least about <NUM> weight % (e.g., at least about <NUM> weight %, at least about <NUM> weight % or at least about <NUM> weight %) to at most about <NUM> weight % (e.g., at most about <NUM> weight %, at most about <NUM> weight %, at most about <NUM> weight %, at most about <NUM> weight %, or at most about <NUM> weight %) relative to the total amount of the composition of the disclosure.

The alcohol amine compounds (b) used in the cleaning/stripping composition of this disclosure are not particularly limited. These alcohol amine compounds include, but are not limited to, monoethanolamine (MEA), diethanolamine, triethanolamine, diglycolamine, <NUM>-(<NUM>-aminoethoxy)ethanol, <NUM>-amino-<NUM>-propanol amino-<NUM>-propanol, <NUM>-amino-<NUM>-butanol, <NUM>-amino-<NUM>-pentanol, <NUM>-amino-<NUM>-methyl-<NUM>-propanol, <NUM>-methylamino-<NUM>-propanol, <NUM>-amino-<NUM>-butanol, tris(hydroxymethyl)amino ethane, <NUM>-dimethylamino-<NUM>-propanol, <NUM>-amino-<NUM>-cyclopentanemethanol, monoisopropanolamine, diisopropanolamine, triisopropanolamine, <NUM>-isopropylamino ethanol, <NUM>-propylamino ethanol, <NUM>-(tert-butylamino)ethanol, <NUM>-amino-<NUM>,<NUM>-dimethyl pentanol, <NUM>-amino-<NUM>-methyl-<NUM>-butanol, N-methylaminoethanol, N-methyldiethanolamine, N-ethylethanolamine, N-butyl ethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, N-methyl-N-ethyl ethanolamine and a mixture of two or more of these alcohol amines.

The alcohol amine compounds (b) used in the cleaning/stripping composition of this disclosure are present in an amount of at least about <NUM> weight % (e.g., at least about <NUM> weight %, at least about <NUM> weight % or at least about <NUM> weight %) to at most about <NUM> weight % (e.g., at most about <NUM> weight %, at most about <NUM> weight %, at most about <NUM> weight % at most about <NUM> weight %, at most about <NUM> weight %, at most about <NUM> weight %, at most about <NUM> weight %, or at most about <NUM> weight %) relative to the total amount of composition.

The hydroxylammonium compounds (c) that can be used in the cleaning/stripping composition of this disclosure are not particularly limited. The examples of hydroxylammonium compounds include but are not limited to hydroxylammonium sulfate, hydroxylammonium hydrochloride, hydroxylammonium nitrate, hydroxylammonium phosphate, hydroxyammonium perchlorate, hydroxylammonium citrate, and hydroxylammonium acetate.

The hydroxyl ammonium compounds used in in the cleaning/stripping composition of this disclosure are present in an amount of at least about <NUM> weight % (e.g., at least about <NUM> weight %, at least about <NUM> weight %, at least about <NUM> weight %, or at least about <NUM> weight %) to at most about <NUM> weight % (e.g., at most about <NUM> weight %, at most about <NUM> weight %, at most about <NUM> weight%, at most about <NUM> weight %, or at most about <NUM> weight %) relative to the total amount of the composition.

The organic solvents (d) (e.g., water miscible organic solvents) in the composition of this disclosure can include those highly compatible with water, which are, for example, N-methyl pyrrolidone (NMP), N-ethyl pyrrolidone (NEP), gamma-butyrolactone, methyl ethyl ketone (MEK), dimethyl sulfoxide (DMSO), dimethyl sulfone, dimethylformamide, N-methylformamide, formamide, tetrametyl urea, tetrahydrofurfuryl alcohol (THFA) and a mixture thereof. In some embodiments, the organic solvents are selected from those having a relative energy difference, RED, of at most about <NUM> (e.g., at most about <NUM>, at most about <NUM>) and/or at least about <NUM> (e.g., at least about <NUM>, at least about <NUM>, or at least about <NUM>) relative to water. RED is the ratio of distance (Ra) between Hansen parameters in Hansen Space and the interaction radius (Ro) in Hansen space. Ra is defined by the following formulation: (Ra)<NUM> = <NUM>(δd2 - δd1)<NUM> + (δp2 - δp1)<NUM> + (δh2 - δh1)<NUM> in which δd, δp and δh are respectively the energy between dispersion, intermolecular force and hydrogen bonds between molecules. More detail on Hansen parameters can be found in the following reference: "Hansen, Charles (<NUM>). Hansen Solubility Parameters: A user's handbook, Second Edition. Boca Raton, Fla: CRC Press. ISBN <NUM>-<NUM>-<NUM>-<NUM>-<NUM>".

In certain embodiments, the organic solvent (e.g., a water miscible organic solvent) may be a glycol ether. The glycol ethers can include glycol mono (C<NUM>-C<NUM>) alkyl ethers and glycol di(C<NUM>-C<NUM>) alkyl ethers, including but not limited to, (C<NUM>-C<NUM>) alkane diols, (C<NUM>-C<NUM>) alkyl ethers, and (C<NUM>-C<NUM>) alkane diol di(C<NUM>-C<NUM>)alkyl ethers. Examples of glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monobenzyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, polyethylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol ethylene glycol monomethyl ether acetate, ethylene glycol monethyl ether acetate, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monobutyl ether, propylene glycol, monoproply ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, diproplylene glycol diisopropyl ether, tripropylene glycol monomethyl ether, <NUM>-methoxy-<NUM>-butanol, <NUM>-methoxy-<NUM>-butanol, <NUM>-methoxy-<NUM>-methylbutanol, <NUM>,<NUM>-dimethoxyethane and <NUM>-(<NUM>-butoxyethoxy) ethanol. More typical examples of glycol ethers are propylene glycol monomethyl ether, propylene glycol monopropyl ether, tri(propylene glycol) monomethyl ether and <NUM>-(<NUM>-butoxyethoxy) ethanol.

Preferred solvents in the composition of this disclosure are dimethyl sulfoxide (DMSO) and tetrahydrofurfuryl alcohol (THFA). More preferred solvent is tetrahydrofurfuryl alcohol (THFA).

The solvent used in the cleaning/stripping composition of this disclosure is present in an amount of at least about <NUM> weight % (e.g., at least about <NUM> weight %, at least about <NUM> weight %, at least about <NUM> weight %, at least about <NUM> weight %, at least about <NUM> weight %, at least about <NUM> weight %, at least about <NUM> weight %, or at least about <NUM> weight %) to at most about <NUM> weight % (e.g., at most about <NUM> weight %, at most about <NUM> weight %, at most about <NUM> weight %, at most about <NUM> weight %, at most about <NUM> weight %, at most about <NUM> weight %, at most about <NUM> weight %, at most about <NUM> weight % or at most about <NUM> weight %) relative to the total amount of the composition.

Corrosion inhibitor compounds (e) used in the cleaning/stripping composition of this disclosure include triazole, benzotriazole, substituted triazole, and substituted benzotriazole compounds.

Examples of triazole compounds include, but are not limited to, <NUM>,<NUM>,<NUM>-triazole, <NUM>,<NUM>,<NUM>-triazole, or triazoles substituted with substituents such as C<NUM>-C<NUM> alkyl (e.g., <NUM>-methyltriazole), amino, thiol, mercapto, imino, carboxy and nitro groups. Specific examples include benzotriazole, tolyltriazole, <NUM>-methyl-<NUM>,<NUM>,<NUM>-triazole, <NUM>-phenyl-benzotriazole, <NUM>-nitro-benzotriazole, <NUM>-amino-<NUM>-mercapto-<NUM>,<NUM>,<NUM>-triazole, <NUM>-amino-<NUM>,<NUM>,<NUM>-triazole, hydroxybenzotriazole, <NUM>-(<NUM>-amino-pentyl)-benzotriazole, <NUM>-amino-<NUM>,<NUM>,<NUM>-triazole, <NUM>-amino-<NUM>-methyl-<NUM>,<NUM>,<NUM>-triazole, <NUM>-amino-<NUM>,<NUM>,<NUM>-triazole, <NUM>-mercapto-<NUM>,<NUM>,<NUM>-triazole, <NUM>-isopropyl-<NUM>,<NUM>,<NUM>-triazole, <NUM>-phenylthiol-benzotriazole, halo-benzotriazoles (halo = F, Cl, Br or I), naphthotriazole, and the like.

In some examples not forming part of the claimed invention, the corrosion inhibitor is an oxime compound of Structure (I):
<CHM>
in which R<NUM> is selected from the group consisting of hydrogen, substituted or unsubstituted C<NUM>-C<NUM> linear or branched alkyl, substituted or unsubstituted C<NUM>-C<NUM> cycloalkyl or heterocycloalkyl, and substituted or unsubstituted C<NUM>-C<NUM> aryl or heteroaryl; and R<NUM> to R<NUM> are each independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted C<NUM>-C<NUM> linear or branched alkyl, substituted or unsubstituted C<NUM>-C<NUM> cycloalkyl or heterocycloalkyl, and substituted or unsubstituted C<NUM>-C<NUM> aryl or heteroaryl; or any two adjacent R<NUM> to R<NUM> (e.g., R<NUM> and R<NUM>, R<NUM> and R<NUM>, or R<NUM> and R<NUM>), together with the ring carbon atoms to which they are attached, form a six-membered ring.

In some of these examples, R<NUM> is hydrogen, substituted or unsubstituted C<NUM>-C<NUM> linear or branched alkyl, or substituted or unsubstituted C<NUM>-C<NUM> aryl. Examples of R<NUM> groups include, but are not limited to, hydrogen, methyl, and phenyl. In some embodiments, each of R<NUM> to R<NUM>, independently, is hydrogen, halogen, substituted or unsubstituted C<NUM>-C<NUM> linear or branched alkyl, substituted or unsubstituted C<NUM>-C<NUM> cycloalkyl or heterocycloalkyl, or substituted or unsubstituted C<NUM>-C<NUM> aryl or heteroaryl. Examples of R<NUM> - R<NUM> groups include, but are not limited to, hydrogen, halogen, nonyl, dodecyl, phenyl, iso-propyl, t-butyl, cyclopentyl, <NUM>,<NUM>-dimethylcyclohexyl, and tolyl. The substituents on the compounds of Structure (I) are chosen to optimize a variety of parameters including, but not limited to, the solubility and activity of the oxime compound in a given composition and the storage stability of the composition.

Examples of suitable compounds of Structure (I) include, but are not limited to,
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

The corrosion inhibitor compound used in the cleaning/stripping composition of this disclosure is present in an amount of at least about <NUM> weight% (e.g., at least about <NUM> weight %, at least about <NUM> weight %, at least about <NUM> weight%, at least about <NUM> weight % or at least about <NUM> weight %) to at most about <NUM> weight % (e.g., at most about <NUM> weight %, at most about <NUM> weight %, at most about <NUM> weight %, at most about <NUM> weight %, at most about <NUM> weight %, at most about <NUM> weight %, or at most about <NUM> weight %) relative to the total amount of the composition. In some embodiments, the preferred amount for the corrosion inhibitor is from <NUM> weight % to <NUM> weight % relative to the total amount of the composition.

The amount of water (such as deionized water, pure water, ultrapure water, etc.) used in the cleaning/stripping composition of this disclosure is at least about <NUM> weight % (e.g., at least about <NUM> weight %, at least about <NUM> weight % or at least about <NUM> weight %) to at most about <NUM> weight % (e.g., at most about <NUM> weight %, at most about <NUM> weight %, at most about <NUM> weight %, at most about <NUM> weight % or at most about <NUM> weight %) relative to the total amount of the composition.

The cleaning/stripping composition of the present disclosure may also include one or more of the following additives provided that these additives do not adversely affect the stripping and/or cleaning performance of the composition, nor damage the underlying substrate surface: surfactants, chelating agents, coupling agent, chemical modifiers, dyes, biocides, and/or other additives in amounts up to a total of <NUM> percent by weight based on the total weight of the composition.

Suitable surfactants in the cleaning/stripping composition of this disclosure include, without limitation: fluoroalkyl surfactants; polyethylene glycols; polypropylene glycols; polyethylene glycol ethers; polypropylene glycol ethers; carboxylic acid salts; dodecylbenzenesulfonic acid and salts thereof; polyacrylate polymers; dinonylphenyl polyoxyethylene; silicone polymers; modified silicone polymers; acetylenic diols; modified acetylenic diols, alkylammonium salts; modified alkylarnmonium salts; alkylammonium suflonic acid inner salts and combinations of two or more of the foregoing. Examples of suitable surfactants include, but are not limited to, the surfactants described in <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT> and <CIT>.

Examples of chelating agents include, but are not limited to, ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), penicillamine, <NUM>,<NUM>-dimercapto-<NUM>-propanesulfonic acid (DMPS), dimercaptosuccinic acid (DMSA), gluconic acid, acrylic acid, nitrilotriacetic acid (NTA), glutamic acid diacetic acid (GLDA; DISSOLVINE(R) GL from AkzoNobel, Chicago, III. ), tetrasodium iminodisuccinate, iminosuccinic acid, pentasodium diethylenetriamine pentacetate, and polyaspartate. For example, the chelating agent can be EDTA.

The cleaning/stripping composition of this disclosure can further include a coupling agent. A coupling agent may aid in stabilization of the composition, such as maintaining shelf life. Examples of coupling agents include, but are not limited to, sodium xylene sulfonate (SXS), sodium cumene sulfonate (SCS), and ethyl hexyl sulfonate (EHS). In certain embodiments, the coupling agent is sodium xylene sulfonate.

In some embodiments, one or more of the following materials are excluded from the cleaning/stripping compositions of this disclosure. Examples include active fluorine containing compounds which hydrolyses to release fluorine (e.g. latent HF sources such as carboxyl fluorides), fluoride salts such as ammonium or quaternary ammonium fluorides, oxidizing reagents such as peroxides and inorganic oxidizing agents, amidine salts such as guanidinium salt, acetamidinium salt, and formamidinium salt, urea and urea derivatives, and phenolic compounds.

The cleaning/stripping composition of this disclosure has a basic pH of at least <NUM>. The pH is at least about <NUM> (e.g., at least about <NUM>, at least about <NUM>, at least about <NUM>, at least about <NUM>, at least about <NUM>, at least about <NUM>, at least about <NUM>, or at least about <NUM>) and/or at most about <NUM> (e.g., at most about <NUM>, at most about <NUM>, at most about <NUM>, at most about <NUM>, at most about <NUM>, at most about <NUM>, at most about <NUM>, at most about <NUM>, or at most about <NUM>). The preferred pH range is from <NUM> to <NUM>. The most preferred pH range is from <NUM> to <NUM>. The pH value of the composition can be measured by a pH meter which can be calibrated using standard aqueous buffer solutions. Without wishing to be bound by theory, it is believed that a relatively high pH (i.e., a strong basic condition) can facilitate the composition to remove post laser ablation debris in a cleaning process or remove a polymeric layer in a stripping process. For example, in a cleaning process to remove post laser ablation debris, the basic condition can neutralize acidic species and make them soluble in the aqueous solution. In a stripping process to remove a polymeric layer, the basic condition can facilitate breaking the polymer chains or cross-linking networks and therefore help remove the polymeric layer.

In some embodiments, the cleaning/stripping composition of this disclosure can have a relatively low kinematic viscosity. In some embodiments, the kinematic viscosity of the cleaning/stripping composition in this disclosure can be at least about <NUM> cm2s-<NUM> (<NUM> cSt) (e.g., least about <NUM> cm2s-<NUM> (<NUM> cSt), at least about <NUM> cm2s-<NUM> (<NUM> cSt), at least about <NUM> cm2s-<NUM> (<NUM> cSt), at least about <NUM> cm2s-<NUM> (<NUM> cSt), at least about <NUM><NUM>s-<NUM> (<NUM> cSt), at least about <NUM> cm2s-<NUM> (<NUM> cSt), at least about <NUM> cm2s-<NUM> (<NUM> cSt), at least about <NUM><NUM>s-<NUM> (<NUM> cSt), at least about <NUM> cm2s-<NUM> (<NUM> cSt), at least about <NUM> cm2s-<NUM> (<NUM> cSt), or at least about <NUM> cm2s-<NUM> (<NUM> cSt)) and/or at most about <NUM><NUM>s-<NUM> (<NUM> cSt) (e.g., at most about <NUM> cm2s-<NUM> (<NUM> cSt), at most about <NUM><NUM>s-<NUM> (<NUM> cSt), at most about <NUM> cm2s-<NUM> (<NUM> cSt), at most about <NUM><NUM>s-<NUM> (<NUM> cSt), at most about <NUM><NUM>s-<NUM> (<NUM> cSt), at most about <NUM> cm2s-<NUM> (<NUM> cSt), at most about <NUM><NUM>s-<NUM> (<NUM> cSt), at most about <NUM><NUM>s-<NUM> (<NUM> cSt), or at most about <NUM><NUM>s-<NUM> (<NUM> cSt)). As used herein, kinematic viscosity is measured at <NUM> by using a calibrated Cannon-Fenske Routine viscometer. Without wishing to be bound by theory, it is believed that a composition having a relatively high kinematic viscosity can have a lower cleaning/stripping power at least because the diffusion of active ingredients in the composition into the polymeric layer can have a relatively low rate (compared to a composition having a relatively low kinematic viscosity), which can result in a lower stripping and/or cleaning power.

The cleaning/stripping composition of this disclosure can be prepared by mixing various components in any suitable order using conventional mixing methods. The components may be mixed cold, without the addition of heat.

In some embodiments, the cleaning/stripping composition of this disclosure can be used in processes for cleaning after laser ablation of a polymeric film on a semiconductor substrate. In some embodiments, this composition can be also used in a process for stripping unexposed photosensitive polymeric films, exposed, crosslinked polymeric films, or non-photosensitive polymeric films on semiconductor substrates.

Semiconductor substrates could be circular (such as wafers) or could be panels. In some embodiments, the semiconductor substrate could be a silicon substrate, a copper substrate, an aluminum substrate, a silicon oxide substrate, a silicon nitride substrate, a glass substrate, an organic laminate substrate, or a dielectric material substrate.

The polymeric composition used to form a polymeric film on a semiconductor substrate is not particularly limited except by absorbance of the polymeric film at the particulate wavelength used for laser ablation. The polymeric layer can be a polyimide layer, a polyimide precursor layer, a poly(meth)acrylate layer, a polyurethane layer, a polybenzoxazole layer, a polybenzothiozole layer, a novolac layer, an epoxy layer, a polyamide layer or a polyester layer. The polymeric layer can be photosensitive or non-photosensitive, and can be formed by spin coating, spray coating, roller coating, dip coating of solution containing a polymer composition, or lamination of a photosensitive or non-photosensitive dry film composition using a laminator. The preferred polymeric layers are photosensitive polyimide layer and photosensitive polyimide precursor layer. Photosensitive polyimide compositions or photosensitive precursor compositions that can be used to form such a layer are not particularly limited and include, but are not limited to, the compositions disclosed in <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT> and <CIT>.

In some embodiments, a preferred polymeric composition includes: (a) at least one soluble polyimide polymer optionally with end-capped groups having at least one functional group selected from a substituted or unsubstituted linear alkenyl group (e.g., a C<NUM>-C<NUM> linear alkenyl group) and a substituted or unsubstituted linear alkenyl group (e.g., a C<NUM>-C<NUM> linear alkynyl group); (b) at least one reactive functional compound (RFC), (c) at least one initiator and; (d) at least one solvent.

Soluble polyimide polymer is defined as a polymer that has <NUM> wt% or higher solubility in an organic solvent, such as gamma-butyrolactone (GBL), caprolactone, sulfolane, N-methyl-<NUM>-pyrrolidone (NMP), N-ethyl-<NUM>-pyrrolidone, N-butyl-<NUM>-pyrrolidone, N-formylmorpholine, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-diethylfornamide, diethylacetamide, tetrahydrofurfuryl alcohol (THFA), propylene carbonate, <NUM>-phenoxyethanol, propylene glycol phenyl ether, benzyl alcohol, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), <NUM>-heptanone, cyclopentanone (CP), cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), n-butyl acetate (n-BA), or a mixture thereof.

The reactive functional compound (RFC) in the polymeric composition described herein generally possesses at least one functional group capable of reacting with the optional end-capped functional group on the polyimide polymer (e.g., the end-capped functional group on the polyimide polymer described above) or with another reactive functional group on the polyimide polymer. The RFC can be a monomer or an oligomer. The oligomer can contain many monomer units and is capable of further reactions to be incorporated in the final material. Examples of such monomer units/oligomers are based on one or more of the following types: acrylate, ester, vinyl alcohol, urethane, urea, imide, amide, carboxazole, carbonate, pyranose, siloxane, ureaformaldehyde and melamine-formaldehyde. The RFC generally contains at least one terminal and/or pendant reactive functional group capable of radical, thermal, or acid catalyzed reaction with the at least one functional group selected from a substituted or unsubstituted linear alkenyl group and a substituted or unsubstituted linear alkynyl group on the polyimide polymer. In one embodiment, the reactive functional group on the RFC includes an unsaturated double or triple bond.

Suitable examples of reactive functional groups on the RFC include, but are not limited to, a vinyl group, an allyl group, a vinyl ether group, a propenyl ether group, a (meth)acryloyl group, an epoxy group, a -SiH group and a -SH (thiol) group.

In one embodiment, a suitable example of an RFC includes, but is not limited to, an urethane acrylate oligomer. The term "urethane acrylate oligomer" refers to a class of compounds that contain urethane linkages and have (meth)acrylate (e.g., acrylate or methacrylate) functional groups such as urethane multi(meth)acrylate, multiurethane (meth)acrylate, and multiurethane multi(meth)acrylate. Types of urethane (meth)acrylate oligomers have been described by, for example, <CIT> and <CIT>. Other specific examples of RFC include <NUM>,<NUM>-hexanediol di(meth)acrylate, tetraethyleneglycol di(meth)acrylate, divinylbenzene, ethoxylated bisphenol-A-di(meth)acrylate, diethylene glycol bis(allyl carbonate), trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta-/hexa-(meth)acrylate, isocyanurate tri(meth)acrylate, bis(<NUM>-hydroxyethyl)-isocyanurate di(meth)acrylate, <NUM>,<NUM>-butanediol tri(meth)acrylate, <NUM>,<NUM>-butanediol tri(meth)acrylate, methyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl(meth)acrylate, neopentyl glycol di(meth)acrylate, (meth)acrylate modified-urea-formaldehyde resins, (meth)acrylate modified melamine-formaldehyde resins and (meth)acrylate modified cellulose.

In some embodiments, RFC compounds are silicon containing di(meth)acrylate compounds.

Examples of RFC compounds containing thiol groups include, but are not limited to, trimethylolpropane tris(mercaptoacetate), pentaerythritol tetrakis(mercaptoacetate), dipentaerythritol hexakis(<NUM>-mercaptopropionate), and ethoxylated trimethylolpropane tri-<NUM>-mercaptopropionate. Examples of RFC compounds containing vinyl ether groups include, but are not limited to, <NUM>,<NUM>-butanediol divinyl ether, <NUM>,<NUM>-cyclohexanedimethanol divinyl ether, di(ethylene glycol) vinyl ether, polyethylene glycol) divinyl ether, and bis[<NUM>-(vinyloxy)butyl] (<NUM>-methyl-<NUM>,<NUM>-phenylene)biscarbamate. One example of a RFC compound containing a SiH group is octasilane POSS® SH1310 available from Hybrid Plastics.

The initiator (e.g., photoinitiator) in component (c) used in a polymeric composition is a compound that is capable of initiating a reaction between a functional group on the polyimide polymer and the reactive functional compound, when the composition or a portion of the composition is exposed to light and/or heat. Some initiators used in the composition function by generating free radicals when heated or by absorbing light at the wavelength of exposure. Other initiators used in the composition function by generating acid when heated or by absorbing light at the wavelength of exposure. Other initiators used in the composition function by generating a basic compound when heated or by absorbing light at the wavelength of exposure. In some embodiments, the initiators described herein can also catalyze the reaction between a functional group on the polyimide polymer and the reactive functional compound and therefore also serves as a catalyst.

Specific examples of initiators that generate free radicals when heated include, but are not limited to, peroxides (such as benzoyl peroxide, cyclohexanone peroxide, lauroyl peroxide, tert-amyl peroxybenzoate, tert-butyl hydroperoxide, dicumyl peroxide, cumene hydroperoxide, succinic acid peroxide, or di(n-propyl)peroxydicarbonate), azo compounds (e.g., <NUM>,<NUM>-azobis(isobutyronitrile), <NUM>,<NUM>-azobis(<NUM>,<NUM>-dimethylvaleronitrile), dimethyl-<NUM>,<NUM>-azobisisobutyrate, <NUM>,<NUM>-azobis(<NUM>-cyanopentanoic acid), azobiscyclohexanecarbonitrile, or <NUM>,<NUM>-azobis(<NUM>-methylbutyronitrile)), α-hydroxy ketones (e.g.,<NUM>-hydroxy-cyclohexyl-phenyl-ketone (Irgacure <NUM>)) and mixtures thereof.

A patterned polymeric film containing opening vias in said polymeric film can be formed by irradiating said polymeric film with a laser beam. This process is called laser drilling or laser ablation. Direct laser ablation with a laser beam is a dry, one step material removal according to the mask pattern of fine via with high aspect ratio. This technique is commonly used in industry. In some embodiments, laser ablation can be accomplished using one or more mask based projection excimer lasers. In some embodiments, this process can be done by a maskless direct ablation solid state laser. In some embodiments, the wavelength of the laser is <NUM> or less. In some embodiments, the wavelength of the laser is <NUM> or less. Examples of suitable laser ablation methods include, but are not limited to, the methods described in <CIT>, <CIT>, and <CIT>.

A by-product of said laser ablation process is a residue or dust (debris) that is generated as a result of the laser ablation process. The debris accumulates in the side walls and bottom of vias. It also accumulates on the mirrors and optics of the laser imaging device. This can have adversely effects on the performance of the laser ablation process. A vacuum device fitted into an imager may capture a significant amount of residues on optics and mirror. Several techniques are used for post laser ablation cleaning of vias. These techniques includes using a sacrificial layer, solvent cleaning, oxygen plasma cleaning, CO2 snow cleaning and DPSS cleaning (diode pump solid state) using pico second DPSS laser. Examples of suitable post laser ablation cleaning methods include, but are not limited to, the methods described in <CIT>, <CIT>, <CIT>, <CIT>, and <CIT>.

In one embodiment, the method for manufacturing a semiconductor device comprises the steps of (i) exposing a polymeric film to a laser under ablating conditions, and (ii) cleaning the laser ablation debris using one or more of the compositions of the disclosure.

The polymeric composition is not particularly limited except by absorbance of the polymeric film at the particulate wavelength used for laser ablation. The ability of the material to absorb laser energy limits the depth to which that energy can perform useful ablation. Ablation depth is determined by, for example, the absorption depth of the material and the heat of vaporization of the work material. The depth is also a function of beam energy density, the laser pulse duration, and the laser wavelength. Laser energy per unit area on the work material is measured in terms of the energy fluence. In one embodiment, the polymeric composition can be adjusted to have absorbance from <NUM> per µm (micron) to <NUM> per µm (micron) at <NUM>. In another embodiment, the polymeric composition can be adjusted to have absorbance from <NUM> per µm (micron) to <NUM> per µm (micron) at <NUM>. In yet another embodiment, the polymeric composition can be adjusted to have absorbance from <NUM> per µm (micron) to <NUM> per µm (micron) at <NUM>. In some embodiments, the amount of absorption can be adjusted by addition of a dye. In all these three embodiments, energy fluence is at most <NUM> mJ/cm<NUM> (e.g., at most <NUM> mJ/cm<NUM>, at most <NUM> mJ/cm<NUM>, at most <NUM> mJ/cm<NUM> or at most <NUM> mJ/cm<NUM>) and/or at least <NUM> mJ/cm<NUM> (e.g., <NUM> mJ/cm<NUM>, at least <NUM> mJ/cm<NUM> or at least <NUM> mJ/cm<NUM>). The film thickness of the polymeric layer formed by such a polymeric composition can be at least about <NUM> (micron) (e.g., at least about <NUM> (microns), at least about <NUM> (microns), at least about <NUM> (microns), at least about <NUM> (microns), at least about <NUM> (microns), at least about <NUM> (microns), at least about <NUM> (microns), at least about <NUM> (microns), at least about <NUM> (microns) or at least about <NUM> (microns)) to at most about <NUM> (microns) (e.g., at most about <NUM> (microns), at most about <NUM> (microns), at most about <NUM> (microns), at most about <NUM> (microns), at most about <NUM> (microns) or at most about <NUM> (microns)).

The post laser ablation cleaning process can be accomplished by treating the object to be cleaned with the compositions of this disclosure using known techniques, such as immersion, centrifugal spray, megasonic cleaning and ultrasonic cleaning. Examples of such cleaning procedures are disclosed in <CIT>, <CIT> and <CIT>.

Temperatures employed in the cleaning process can be at least about <NUM> (e.g., at least about <NUM>, at least about <NUM>, at least about <NUM>, at least about <NUM>, at least about <NUM>, at least about <NUM>, at least about <NUM>, or at least about <NUM>) and/or at most about <NUM> (e.g., at most about <NUM>, at most about <NUM>, at most about <NUM>, at most about <NUM> or at most about <NUM>). Time employed in the cleaning process can be at least about <NUM> minutes (e.g., at least about <NUM> minutes or at least about <NUM> minutes) and at most about <NUM> minutes (e.g., at most about <NUM> minutes or at most about <NUM> minutes).

Optional steps in the cleaning process include rinsing and drying steps. The semiconductor substrate may be rinsed with water or an aqueous solution. Aqueous solutions that can be used in this process could be a mixture of Dl-water and a surfactant, a slightly basic aqueous solution containing a surfactant, or an aqueous solution containing linear or branched C1 - C4 alcohols to remove the composition described in this disclosure and/or other residues. This step can also be accomplished by using known techniques such as immersion, centrifugal spray, megasonic cleaning and ultrasonic cleaning. The cleaned semiconductor substrate can be dried using drying means known to those skilled in the art.

Surprisingly, the composition described in this disclosure shows unexpected effectiveness on completely removal of post laser ablation debris from said patterned polymeric film at a low temperature without any damage to said film.

The compositions of this disclosure also are used at a temperature of <NUM> to <NUM> in in a process for stripping unexposed photosensitive polymeric films, exposed, crosslinked polymeric films, or non-photosensitive polymeric films from semiconductor substrates. Stripping processes can be accomplished by treating the object from which the polymeric film is to be stripped using known techniques, such as immersion, centrifugal spray, megasonic cleaning and ultrasonic cleaning.

Temperatures employed in the stripping process are at least <NUM> (e.g., at least about <NUM> or at least about <NUM>) to at most <NUM> (e.g., at most about <NUM> or at most about <NUM>). The stripping time can be at least about <NUM> minutes (e.g., at least about <NUM> minutes, at least about <NUM> minutes, at least about <NUM> minutes, or at least about <NUM> minutes) and/or at most about <NUM> minutes (e.g., at most about <NUM> minutes, at most about <NUM> minutes, at most about <NUM> minutes, at most about <NUM> minutes, or at most about <NUM> minutes).

Optional steps in the stripping process include rinsing and drying steps as described above in the cleaning process.

A unique aspect in the design of the compositions of the disclosure is that the compositions of this disclosure can act as a cleaner for post laser ablation debris at room temperature and can act as an extremely efficient strippers for complete stripping of non-ablated areas of polymeric film at an elevated temperature.

A method for manufacturing a semiconductor device is disclosed as well. This method is performed by (i) patterning a photosensitive polymeric film containing at least one epolyimide polymer or a polyimide precursor polymer on top of a substrate (e.g., formed by coating the substrate with a polymeric composition) to form a pattered film, layer, (ii) treating the patterned film with ion implantation (e.g., to form a transistor), plasma or wet etching to form a pattern in a photosensitive polymeric film, or metal deposition and (iii) stripping said photosensitive polymeric film using the composition at a temperature of <NUM> to <NUM>. Each of the above three steps can be performed by methods known in the art. In some embodiments, the polymeric layer can be formed by a polyimide composition or a polyimide precursor composition. In some embodiments, the polyimide composition or polyimide precursor composition can be photosensitive.

Additionally, a disclosed process includes:
(i) providing semiconductor substrate containing a polymeric film; (ii) optionally flood exposing said polymeric film by using light, or other radiation sources; (iii) optionally subjecting said polymeric film after the light-exposure treatment to a post-exposure baking treatment; (iv) optionally subjecting the post exposure baked polymeric film to hard bake; (v) opening vias into said polymeric film by a laser ablation process using a laser to form a patterned polymeric film; (vi) removing post laser ablation debris from said patterned polymeric film using the composition of this disclosure at a temperature of <NUM> to <NUM>, (vii) forming a conductive post in a region including an inner side of vias by applying a molten conductive paste on vias; (viii) optionally rinsing the patterned polymeric film with a conductive paste remover solution to remove the conductive paste from top of polymeric film, (ix) removing non-ablated areas of polymeric film using the composition of this disclosure at at a temperature of <NUM> to <NUM>, and (x) optionally, rinsing the patterned polymeric film with water or an aqueous solution to remove any remaining cleaning/stripping composition of this disclosure and other residues. The cleaning/stripping composition used in the cleaning step (vi) can be the same as or different from the cleaning/stripping composition used in the stripping step (ix).

The polymeric film is photosensitive. In some embodiments, the photosensitive film is negative tone. In some embodiments, the photosensitive negative tone film is formed from a polyimide composition or a polyimide precursor composition.

In some embodiments of this process, a photosensitive polymeric coated substrate is exposed to radiation in step (ii). The exposure is typically a flood exposure, done under non-ablating conditions. In general, this exposure step results in the curing or crosslinking of the photosensitive polymeric coating in the exposed area. This exposure step uses light, or other radiation sources (e.g., ultraviolet light, visible light, electron beam radiation, or X-rays), as is suitable for the initiator in the specific polymeric composition. The use of i-line (<NUM>), h-line (<NUM>), or g-line (<NUM>) UV light is preferred. One skilled in the art will know which type of high energy radiation is appropriate for a given application. The energy dose used in the present disclosure can be at least about <NUM> mJ/cm<NUM> (e.g., at least about <NUM> mJ/cm<NUM>, at least about <NUM> mJ/cm<NUM>, at least about <NUM> mJ/cm<NUM>, at least about <NUM> mJ/cm<NUM>, at least about <NUM> mJ/cm<NUM> or at least about <NUM> mJ/cm<NUM>) to at most about <NUM> mJ/cm<NUM> (e.g., at most about <NUM> mJ/cm<NUM>, at most about <NUM> mJ/cm<NUM>, at most about <NUM> mJ/cm<NUM>, at most about <NUM> mJ/cm<NUM> or at most about <NUM> mJ/cm<NUM>).

In some embodiments, a short post exposure bake is performed. The post exposure baking temperature can be at least about <NUM> (e.g., at least about <NUM>, at least about <NUM> or at least about <NUM>) and/or at most about <NUM> (e.g., at most about <NUM>, at most about <NUM>, at most about <NUM> and at most about <NUM>). The post exposure baking time can be at least about <NUM> seconds (e.g., at least about <NUM> seconds or at least about <NUM> seconds) and/or at most about <NUM> seconds (e.g., at most about <NUM> seconds or at most about <NUM> seconds).

In some embodiments, a hard baking step can be incorporated. In some embodiments, the hard baking temperature can be at least about <NUM> (e.g., at least about <NUM> or at least about <NUM>) to at most about <NUM> (e.g., at most about <NUM> or at most about <NUM>). The hard baking time can be at least about <NUM> minutes (e.g., at least about <NUM> minutes or at least about <NUM> minutes) and/or at most about <NUM> minutes (e.g., at most about <NUM> minutes or at most about <NUM> minutes).

The laser ablation step and the post laser ablation cleaning step can be done as described earlier.

In the next step of this process, an electrical connection between one surface of the semiconductor substrate and one surface of another substrate can be provided by formation of the conductive layer in the vias produced by laser ablation process. Formation of said conductive layer without having to fill the through-via with a molten material (e.g., a molten conductive paste or solder paste) is one of the possible ways to ensure highly reliable electrical connections. The conducting paste or solder paste include metals or alloys such as nickel, copper, beryllium copper, alloys of nickel, alloys of copper, alloys of beryllium copper, nickel-cobalt-iron alloys and iron-nickel alloys with a polymeric binder. Further details of the composition and application of conductive paste are described in <CIT>, <CIT>, <CIT>, and <CIT>. Cleaning compositions for removal of conductive paste after reflow are described in <CIT> and <CIT>. The cleaning process can be accomplished by using known techniques, such as immersion, centrifugal spray, megasonic cleaning and ultrasonic cleaning as discussed earlier.

The complete removal (stripping) of the polymeric film can be done by using the cleaning/stripping compositions of this disclosure as described above in the stripping process, including the optional rinsing and drying steps.

The cleaned semiconductor substrate is ready for subsequent integration processes to create semiconductor devices, such as semiconductor packages (e.g., memory packages, microprocessor packages, tablets packages and packages that are used for mobile devices). In some embodiments, a semiconductor package can be prepared by a multi-step process that includes at least one step that removes post laser ablation or drilling debris using a cleaning/stripping composition described herein. In some embodiments, a semiconductor package can be prepared by a multi-step process that includes at least one step that strips or removes of a polymeric film using a cleaning/stripping composition described herein.

The disclosure will now be further elucidated with reference to the following non-limiting examples.

The polymerization reaction was performed in an one liter three-neck, jacketed round bottomed flask equipped with a mechanical agitator, a thermocouple and a nitrogen inlet to keep positive nitrogen pressure throughout the reaction. The flask was charged with <NUM> grams of benzophenone-<NUM>,<NUM>',<NUM>,<NUM>'-tetracarboxylic dianhydride (BTDA), <NUM> grams of hexafluoroisopropylidenediphthalic anhydride (6FDA) and <NUM> grams of anhydrous NMP. The contents were agitated at <NUM>-<NUM>. <NUM> grams of <NUM>-(<NUM>-aminophenyl)-<NUM>,<NUM>,<NUM>-trimethylindan-<NUM>-amine (DAPI), and <NUM> grams of <NUM>,<NUM>-diamino-<NUM>,<NUM>,<NUM>-trimethylbenzene (DAM) were dissolved in <NUM> grams of dry NMP in a bottle. The diamine solution was added to the flask by pump for <NUM> hour at room temperature. The mixture was warmed to <NUM> and agitated for <NUM> hours to produce a polyamic acid.

To endcap the polyamic acid formed above, <NUM> grams of <NUM>-acryloyloxy-<NUM>,<NUM>-bis[(acryloyloxy)methyl]propyl <NUM>,<NUM>-dioxo-<NUM>,<NUM>-dihydro-<NUM>-benzofuran-<NUM>-carboxylate (PETA) and <NUM> of pyridine were charged to the flask. The mixture was agitated at <NUM> for <NUM> hours to form an endcapped polyamic acid.

To perform the imidization reaction of the above endcapped polyamic acid, <NUM> grams of acetic anhydride and <NUM> grams of pyridine were charged to the flask. The reaction mixture was warmed to <NUM> and agitated for <NUM> hours. A small sample (<NUM>) was withdrawn and precipitated into <NUM>:<NUM> methanol:water (<NUM>). The solid was isolated by filtration and dried. FTIR analysis showed that the imidization reaction was complete (showed absence of amide and anhydride peaks).

The solution was cooled to room temperature and added dropwise to <NUM> liters of vigorously stirred de-ionized water to precipitate the polymer. The polymer was collected by filtration and washed with one liter of de-ionized water. The cake was re-slurried with four liters of methanol and filtered. The wet cake was dried in air for <NUM> hours and then the polymer was dried under vacuum at <NUM> for <NUM> hours. The molecular weight of the resultant polyimide polymer was measured by GPC.

To a <NUM>-neck round bottom flask equipped with a mechanical stirrer was added <NUM> parts of GBL, <NUM> parts of the polymer obtained in Synthesis Example <NUM>, <NUM> parts of (<NUM>-glycidyloxypropyl)trimethoxy silane, <NUM> parts of NCI-<NUM> (trade name, available from ADEKA corporation), <NUM> parts of (<NUM>,<NUM>,<NUM>-trimethylbenzoyl)phosphine oxide, <NUM> parts of tetraethylene diacrylate, <NUM> of pentacrylthritol triacrylate and <NUM> of polyamic ester of Structure PAE-<NUM>. The composition was mechanically stirred for <NUM> hours. This composition was then filtered by using a <NUM> filter (Ultradyne from Meissner Filtration Product, Inc. <NUM>-44B1).

The filtered photosensitive solution (F-<NUM>) was applied via slot-die coater from Frontier Industrial Technologies (Towanda, PA) with line speed of <NUM> feet/minutes (<NUM> per minutes) onto a polyethylene terephthalate (PET) film TA <NUM> (manufactured by Toray Plastics America, Inc. ) having a thickness of <NUM> used as a carrier substrate without online corona treatment and dried at <NUM>-<NUM>°F to obtain polymeric layers with thickness of <NUM> (microns). The lamination pressure was <NUM> psi and the vacuum was <NUM> Pa (<NUM> Torr). On this polymeric layer, a biaxially oriented polypropylene (BOPP) films (manufactured by IMPEX GLOBAL LLC, trade name 80ga BOPP) was laminated by a roll compression to act as a protective layer.

After the removal of the protective layer by peeling, the polymeric layer of dry film structure DF-<NUM> (<NUM>"x <NUM>") was placed on a <NUM>" copper wafer (Wafernet). The polymeric layer was laminated onto Cu coated wafer by vacuum lamination at <NUM> followed by being subjected to a pressure of <NUM> psi. Lamination process was done by using a DPL-24A Differential Pressure Laminator manufactured by OPTEK, NJ.

After the removal of the protective layer by peeling, the polymeric layer of dry film structure DF-<NUM> (<NUM>"x <NUM>") was placed on an <NUM>" copper wafer (Wafernet, item # S45102). The polymeric layer was laminated onto Cu coated wafer by vacuum lamination at <NUM> followed by being subjected to a pressure of <NUM> psi. Lamination process was done by using a DPL-24A Differential Pressure Laminator manufactured by OPTEK, NJ.

Laminated dry film (L-<NUM>) was flood exposed at <NUM> mJ/cm<NUM> using SUSS broad band exposure tool. The wafer was then heated at <NUM> for <NUM> seconds. The laminated dry film was then baked at <NUM> for one hour under vacuum.

The laser ablation procedure was performed on exposed, baked wafer by EPL300 Gen2 at wavelength of <NUM> using a via mask with a via diameter of <NUM> (microns) and pitch of <NUM> (microns). The printing energy of <NUM> laser was fixed at <NUM> mJ/cm<NUM> and N = <NUM> pulse.

A composition was prepared by using <NUM> parts of tetramethyl ammonium hydroxide (TMAH), <NUM> parts of monoethanolamine, <NUM> parts of hydroxylammonium sulfate, <NUM> parts of tetrahydrofurfuryl alcohol (THFA), <NUM> parts of <NUM>-methyl-<NUM>-benzotriazole and <NUM> prats of water. The pH of this cleaning/stripping composition was measured at <NUM> by using a Metrohm Model <NUM> base unit equipped with a Metrohm pH Electrode part# <NUM>/<NUM>. Kinematic viscosity of the cleaning/stripping composition was measured by using a Cannon Fenske viscometer size <NUM> at <NUM>. The kinematic viscosity was <NUM><NUM>s-<NUM> (<NUM> cSt).

The laminated wafer LA-<NUM> was cut into <NUM>" x <NUM>" pieces and placed vertically in a <NUM> beaker containing <NUM> of the cleaning/stripping composition obtained above. The contents of the beaker were stirred using a magnetic bar at <NUM>. The temperature was maintained constant by using a temperature controller. After <NUM> minutes, the wafer pieces were removed and immediately rinsed with water and dried by using nitrogen purge. The effectiveness of cleaning was determined by using an optical microscope and by SEM after gold sputtering. Both top-down and cross-section Images of wafer revealed no residue after cleaning. The extent of film thickness loss was determined by measuring the thickness of the remaining film using Dektak profilometer. Ablation debris was completely removed without any damage to film. No film thickness loss was observed.

Claim 1:
A composition, comprising:
(a) <NUM> - <NUM> percent by weight an alkaline compound;
(b) <NUM>-<NUM> percent by weight an alcohol amine compound;
(c) <NUM> - <NUM> percent by weight a hydroxylammonium compound;
(d) <NUM>-<NUM> percent by weight an organic solvent;
(e) <NUM> - <NUM> percent by weight a corrosion inhibitor compound, wherein the corrosion inhibitor compound is triazole, benzotriazole, substituted triazole, or substituted benzotriazole; and
(f) <NUM> -<NUM> percent by weight water;
wherein the composition is free of a urea and urea derivatives and has a pH of at least <NUM>.