Surfactants for electronic products

Abstract

The pre-texturing agent, etchant, and photoresist stripper can be formulated to include one or more surfactants from one or more surfactant classes, such as siloxane derivatives of amino acids having surface-active properties.

Description

[0001] Cross - Reference to Related Applications

[0002] This application claims priority to U.S. Provisional Application No. 62 / 970,356, filed Feb. 5, 2020, the disclosure of which is hereby incorporated by reference in its entirety. Technical Field

[0003] The present disclosure relates to surfactants for electronic products. More particularly, the present disclosure relates to surfactants in the preparation of circuit boards by etching and removing photoresist coatings. Such surfactants can include siloxane derivatives of amino acids, where the siloxane derivative has surface-active properties. Background Art

[0004] Surfactants (molecules having surface-active properties) are widely used in cleaners, etchants, and photoresist strippers for the manufacture of circuit boards. Surfactants can be included as emulsifiers, wetting agents, foaming agents, dispersants, and / or agents to improve spreading.

[0005] Surfactants can be uncharged, zwitterionic, cationic, or anionic. Although in principle any surfactant class (e.g., cationic, anionic, nonionic, amphoteric) is suitable, formulations can include combinations of two or more surfactants from two or more surfactant classes.

[0006] Typically, surfactants are amphiphilic molecules having a relatively water-insoluble hydrophobic "tail" group and a relatively water-soluble hydrophilic "head" group. These compounds can adsorb at interfaces, such as the interface between two liquids, a liquid and a gas, or a liquid and a solid. In a system comprising relatively polar and relatively nonpolar components, the hydrophobic tail preferentially interacts with the relatively nonpolar component or components, while the hydrophilic head preferentially interacts with the relatively polar component or components. In the case of an interface between water and oil, the hydrophilic head group preferentially extends into the water, while the hydrophobic tail preferentially extends into the oil. When added to a water-gas interface, the hydrophilic head group preferentially extends into the water, while the hydrophobic tail preferentially extends into the gas. The presence of the surfactant disrupts at least some of the intermolecular interactions between water molecules, replacing at least some of the interactions between water molecules with generally weaker interactions between at least some water molecules and the surfactant. This results in a lowering of the surface tension and can also be used to stabilize the interface.

[0007] At sufficiently high concentrations, surfactants may form aggregates that serve to limit the exposure of hydrophobic tails to polar solvents. One such aggregate is a micelle. In a typical micelle, the molecules are arranged in a spherical shape, with the hydrophobic tails of one or more surfactants preferentially located inside the sphere, while the hydrophilic heads of one or more surfactants are preferentially located on the outside of the micelle, where the heads preferentially interact with the more polar solvent. The effect of the given compound on surface tension and the concentration at which it forms micelles can serve as defining characteristics of a surfactant. Summary of the Invention

[0009] The present disclosure provides formulations for pre-texturing agents, etchants, and photoresist strippers. These products can be formulated to include one or more surfactants from one or more of the surfactant classes disclosed herein. The surfactant can be used as an emulsifier, wetting agent, dispersant, and / or a reagent to improve spreadability.

[0010] The present disclosure provides surfactants in the form of siloxane derivatives of amino acids having surface-active properties for pre-texturing agents, etchants, and photoresist strippers. The amino acid can be a naturally occurring or synthetic amino acid, or they can be obtained via ring-opening reactions of molecules such as lactams (e.g., caprolactam). The amino acid can be functionalized with different types of siloxane groups to form compounds having surface-active properties. Characteristically, these compounds can have a low critical micelle concentration (CMC) and / or the ability to lower the surface tension of a liquid.

[0011] The present disclosure provides a formulation for a pre-texturing agent, comprising at least one surfactant of formula I,

[0012]

[0013] wherein R 1 and R 2 can be the same or different and comprise at least one group selected from C 1 -C 6 alkyl groups, optionally the C 1 -C 6 alkyl group can contain one or more oxygen, nitrogen, or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain can optionally be substituted with one or more substituents selected from hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1 to 12; the terminal nitrogen is optionally further substituted by R 3 wherein R 3 is selected from hydrogen, oxygen, hydroxyl, and C 1 -C 6An alkyl group; an optional counterion associated with the compound, which if present is selected from chloride, bromide, and iodide ions; one or more defoamers, optional one or more acids, optional one or more bases, optional one or more chelating agents, and one or more solvents.

[0014] The present disclosure further provides a formulation for an etchant, comprising at least one surfactant of Formula I,

[0015]

[0016] wherein R 1 and R 2 may be the same or different and comprise at least one group selected from C 1 -C 6 alkyl groups, optionally the C 1 -C 6 alkyl group may contain one or more oxygen, nitrogen, or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain may optionally be substituted by one or more substituents selected from hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1 to 12; the terminal nitrogen is optionally further substituted by R 3 wherein R 3 is selected from hydrogen, oxygen, hydroxyl, and C 1 -C 6 alkyl groups; an optional counterion associated with the compound, which if present is selected from chloride, bromide, and iodide ions; hydrofluoric acid (HF), one or more solvents, optional one or more oxidizing agents, and one or more complexing agents.

[0017] The present disclosure also provides a formulation for a photoresist stripper, comprising at least one surfactant of Formula I,

[0018]

[0019] wherein R 1 and R 2 may be the same or different and comprise at least one group selected from C 1 -C 6 alkyl groups, optionally the C 1 -C 6 alkyl group may contain one or more oxygen, nitrogen, or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain may optionally be substituted by one or more substituents selected from hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1 to 12; the terminal nitrogen is optionally further substituted by R 3 wherein R 3 is selected from hydrogen, oxygen, hydroxyl, and C 1 -C 6An alkyl group; an optional counterion associated with the compound, which, if present, is selected from chloride, bromide, and iodide ions; an alkanolamine; a sulfoxide or sulfone compound; and a glycol ether.

[0020] The above and other features of the present disclosure and the manner of achieving them will become more apparent and will be better understood by reference to the following description of embodiments in conjunction with the accompanying drawings.

[0021] Summary of the Drawings

[0022] Figure 1 A graph showing the surface tension vs. concentration of surfactant 2 with a chloride counterion measured at pH = 7 as described in Example 1b.

[0023] Figure 2 shows a graph of the surface tension vs. concentration of surfactant 3 as described in Example 2b.

[0024] Figure 3 A graph showing the dynamic surface tension of surfactant 3 as a change in surface tension vs. time as described in Example 2b.

[0025] Figure 4 A graph showing the surface tension vs. concentration of surfactant 4 as described in Example 3b.

[0026] Figure 5 A graph showing the dynamic surface tension of surfactant 4 as a change in surface tension vs. time as described in Example 3b.

[0027] Figure 6 A graph showing the surface tension vs. concentration of surfactant 5 as described in Example 4b.

[0028] Figure 7 A graph showing the dynamic surface tension of surfactant 5 as a change in surface tension vs. time as described in Example 4b. Detailed Description of the Invention

[0030] As used herein, the phrase "within any range using these endpoints" literally means that any range can be selected from any two values listed before this phrase, whether these values are in the lower half or the upper half of the list. For example, a pair of values can be selected from two lower values, two higher values, or a lower value and a higher value.

[0031] As used herein, the term "alkyl group" refers to any saturated carbon chain, which can be straight-chain or branched-chain.

[0032] As used herein, the phrase "surface active" means that the relevant compound is capable of reducing the surface tension of the medium in which it is at least partially soluble and / or the interfacial tension with other phases, and can thus be at least partially adsorbed at the liquid / vapor and / or other interfaces. The term "surfactant" can be applied to such compounds.

[0033] Regarding terms of imprecision, the terms "about" and "substantially" are used interchangeably to refer to a measured value that includes the stated measured value and also includes any measured value that is reasonably close to the stated measured value. As understood and readily determined by one of ordinary skill in the relevant art, a measured value that is reasonably close to the stated measured value differs from the stated measured value by a reasonably small amount. For example, such deviations can be attributed to measurement errors or minor adjustments made to optimize performance. In cases where one of ordinary skill in the relevant art cannot readily ascertain the value of such a reasonably small difference, the terms "about" and "substantially" can be understood to mean ±10% of the stated value.

[0034] The present disclosure provides formulations of pre-texturing agents, etchants, and photoresist strippers.

[0035] I. Prefabricating Agent

[0036] The present disclosure provides formulations and methods for texturing the surface of photovoltaic wafers. To improve the efficiency of converting light energy into electrical energy, a silicon surface with very low reflectivity is required. For example, for single-crystalline silicon, this is achieved by anisotropically etching a (100) Si wafer to form pyramid structures on the surface, a method known as texturing. A uniform and dense distribution of pyramids is required on the surface of the silicon wafer to achieve low reflectivity, with the pyramid height being less than 10 μm and the size being uniform. Smaller and uniform pyramid structures ensure good coverage of the passivation layer, which is again deposited on top of the textured surface to prevent efficiency losses. Smaller and uniform pyramid structures also ensure that the metal contact lines printed on the silicon surface are narrower, allowing more light to reach the silicon surface for photoelectric conversion.

[0037] The pre-texturing formulations of the present disclosure can be used to process silicon wafers, substrates, or silicon films deposited on different types of substrates (the terms substrate or wafer can be used interchangeably herein) in the texturing methods described herein. Silicon wafers processed with the pre-texturing formulations and / or methods of the present disclosure can be used to manufacture photovoltaic cells. Compared to wafers that have not been subjected to this treatment, wafers subjected to the pre-texturing formulations and / or methods of the present disclosure can show improvements in texturing uniformity and reduced reflectivity.

[0038] Additional benefits achievable by using the methods and / or formulations of the present disclosure may include one or more of the following: 1) generating pyramid structures on the wafer surface with a high density and an average height of less than 10 μm, or less than 8 μm, or less than 5 μm, or less than 4 μm; 2) reducing the reflectivity of the textured surface; 3) reducing the time required to form pyramids and / or form a textured surface with low reflectivity; 4) reducing the sensitivity of the texturing quality to the concentration of isopropanol in the texturing method, and in some embodiments, texturing can be performed without any isopropanol or any other additives required to promote texturing in one or more texturing compositions; 5) when the pre-textured formulations and / or methods of the present disclosure are used in a texturing method, the need for additives in the texturing (etching) composition or etching solution for improving the quality and throughput of texturing can be reduced or eliminated; 6) the total amount of silicon etched in the texturing step can be reduced; 7) the bath life of the texturing composition (also referred to as the texturing or etching solution) can be increased; 8) the coverage of the passivation layer can be improved; 9) the metal contact lines printed on the front of the wafer can be narrower; and 10) the wettability of the silicon surface before texturing can be improved.

[0039] Compared with known methods and formulations, the pre-texturing using the pre-textured formulations of the present disclosure and the texturing methods described herein can reduce the time used for texturing. This can result in reduced processing time and thus increased throughput of wafer processing. In addition, when the pre-textured formulations and / or methods of the present disclosure are employed, they may change little over time or show little sensitivity to the concentration of one or more texturing compositions in one or more texturing baths during the texturing method, thereby improving the robustness of the process; thus, if there is a process upset, longer or shorter texturing times can be employed without compromising the performance of the photovoltaic device.

[0040] The processing of photovoltaic monocrystalline silicon wafers typically involves one or more first steps (usually in a concentrated alkali solution) of cleaning to remove any contaminants and removing saw damage from the cut wafers (cut from the ingot), followed by texturing in a dilute alkali solution to produce a pyramid texture on the surface, which reduces the surface reflectivity and converts more light into electrical energy, thereby increasing the efficiency of the wafer. For polycrystalline silicon wafers, the processing may involve one or more first steps of cleaning to remove any contaminants, followed by direct texturing. It is desirable to have as low a reflectivity as possible. The present disclosure provides pre-texturing formulations and methods for improving the surface texturing of wafers. The present disclosure provides a method of treating a wafer surface with a pre-texturing formulation that includes one or more surfactants or one or more surfactants in solution. The formulation modifies the wafer surface and, in the case of texturing monocrystalline silicon wafers, results in a high nucleation density of pyramids, thereby producing a uniform distribution of the desired small pyramids. For polycrystalline silicon wafers, the surface modification improves the uniformity of the textured surface and can result in a lower surface reflectivity.

[0041] The pre-texturing formulations provided by the present disclosure may include one or more surfactants selected from one or more surfactant classes, one or more defoamers, optionally one or more acids, optionally one or more bases, optionally one or more chelating agents, and one or more solvents.

[0042] 1. Surfactant

[0043] The pre-texturing agent of the present disclosure includes one or more surfactants, also referred to as a surfactant system. The selection of the one or more surfactants may depend on its or their ability to modify the wafer surface to nucleate pyramids and clean the wafer surface.

[0044] Surfactants suitable for the pre-texturing formulations of the present disclosure include one or more surfactants and / or co-surfactants of Formula I,

[0045]

[0046] wherein R 1 and R 2 may be the same or different and include at least one group selected from C 1 -C 6 alkyl groups, optionally the C 1 -C 6 alkyl group may include one or more oxygen, nitrogen, or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain may optionally be substituted with one or more substituents selected from hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1 to 12; the terminal nitrogen is optionally further substituted with R 3is replaced, where R 3 is selected from hydrogen, oxygen, hydroxyl, and C 1 -C 6 alkyl; and an optional counterion associated with the compound, which if present is selected from chloride, bromide, and iodide ions.

[0047] In particular, suitable surfactants or co-surfactants can include one or more of any of the surfactants 1-6 described herein.

[0048] The amount of the surfactant system in the pre-textured formulation can be about 0.01 wt% or greater, about 0.1 wt% or greater, about 1 wt% or greater, about 5 wt% or greater, about 10 wt% or greater, about 15 wt% or greater, or about 20 wt% or less, about 25 wt% or less, about 30 wt% or less, or within any range using these endpoints.

[0049] 2. Defoaming Agent

[0050] The pre-textured formulation of the present disclosure can further comprise one or more defoamers / antifoaming agents. The defoamer can be selected from, but not limited to: silicone, organophosphate, ethylene oxide / propylene oxide (EO / PO)-based defoamers containing polyethylene glycol and polypropylene glycol copolymers, alcohols, white oil or vegetable oil and wax, long-chain fatty alcohols, fatty acid soaps or esters. Some reagents, such as some silicone surfactants and the surfactants of the present disclosure, can act as both defoamers and surfactants.

[0051] The defoamer can be present in the pre-textured formulation in an amount of about 0.0001 wt% or greater, about 0.001 wt% or greater, about 0.01 wt% or greater, about 0.1 wt% or greater, about 0.2 wt% or greater, about 0.5 wt% or greater, or about 1.0 wt% or less, about 1.5 wt% or less, about 2.0 wt% or less, about 3.0 wt% or less, about 3.5 wt% or less, about 4.0 wt% or less, about 4.5 wt% or less, about 5.0 wt% or less, or within any range using these endpoints.

[0052] 3. Acid

[0053] Organic acids are used to improve the removal of trace metals, organic and inorganic residues. The organic acid can be selected from a variety of acids, including but not limited to: oxalic acid, citric acid, maleic acid, malic acid, malonic acid, gluconic acid, glutaric acid, ascorbic acid, formic acid, acetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycine, alanine, cystine, sulfonic acid, various derivatives of sulfonic acid, or mixtures thereof. Salts of these acids can also be used. Mixtures of these acid / salts can also be used.

[0054] The pre-textured formulation can further comprise an inorganic acid and / or their salts. The inorganic acid and / or their salts can be used in combination with other organic acids and / or their salts. Suitable inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, sulfamic acid, etc. Mixtures of these acid / salts can also be used.

[0055] The pre-textured composition of the present disclosure can comprise an amount of acid and / or their salts (acid / salts) of about 0 wt% or greater, about 0.1 wt% or greater, about 5 wt% or greater, about 10 wt% or greater, or about 15 wt% or less, about 20 wt% or less, about 25 wt% or less, about 30 wt% or less, or within any range using these endpoints.

[0056] The combination of acid and salt can also be used to buffer the solution at the desired pH level. When adding the acid / salt to the pre-textured formulation, they can be present in an amount of about 0.2 wt% or greater, about 0.3 wt% or greater, about 0.5 wt% or greater, about 1 wt% or greater, about 3 wt% or greater, or about 5 wt% or less, about 7 wt% or less, about 9 wt% or less, about 10 wt% or less, or within any range using these endpoints.

[0057] 4. Base

[0058] The pre-textured formulation of the present disclosure can further comprise one or more bases. Suitable bases include but not limited to: ammonium hydroxide, potassium hydroxide, quaternary ammonium hydroxides, amines, guanidine carbonate, and organic bases. The bases can be used alone or in combination with other bases. Examples of suitable organic bases include but not limited to: hydroxylamine, ethylene glycol, glycerol, organic amines such as primary, secondary or tertiary aliphatic amines, cycloaliphatic amines, aromatic amines and heterocyclic amines, ammonia water and quaternary ammonium hydroxides, such as hydroxylamine (NH 2OH), N-methylhydroxylamine, N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, monoethanolamine, ethylenediamine, 2-(2-aminoethylamino)ethanol, diethanolamine, N-methylethanolamine, dipropylamine, 2-ethylaminoethanol, dimethylaminoethanol, ethyldiethanolamine, cyclohexylamine, dicyclohexylamine, benzylamine, dibenzylamine, N-methylbenzylamine, pyrrole, pyrrolidine, pyrrolidone, pyridine, morpholine, pyrazine, piperidine, N-hydroxyethylpiperidine, oxazole, thiazole, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, trimethylethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide, (2-hydroxyethyl)triethylammonium hydroxide, (2-hydroxyethyl)tripropylammonium hydroxide, and (1-hydroxypropyl)trimethylammonium hydroxide.

[0059] The pre-textured formulation can contain the base in an amount of about 0 wt% or greater, about 1 wt% or greater, about 5 wt% or greater, or about 10 wt% or less, about 15 wt% or less, about 20 wt% or less, or within any range using these end points.

[0060] The pH of the pre-textured formulation can also be controlled by adjusting the concentrations of the acid and the base. The pH can be a factor in controlling the adsorption of the surfactant on the surface of the substrate and thus the quality of the resulting texture in the texturing step.

[0061] 5. Optional Chelating Agent

[0062] The pre-textured and / or textured compositions of the present invention may further comprise one or more chelating agents. The chelating agent may be selected from, but not limited to: ethylenediaminetetraacetic acid (EDTA), N-hydroxyethyl ethylenediaminetriacetic acid (NHEDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DPTA), ethanol diglycine, citric acid, gluconic acid, oxalic acid, phosphoric acid, tartaric acid, methylenediphosphonic acid, aminotrimethylenephosphonic acid, ethylenediphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, ethylaminobis(methylenephosphonic acid), dodecylaminobis(methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediaminebis(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, and 1,2-propanediaminetetramethylenephosphonic acid or ammonium salts, organic amine salts, malonic acid, succinic acid, dimercaptosuccinic acid, glutaric acid, maleic acid, phthalic acid, fumaric acid, polycarboxylic acids such as tricarbaryl acid, propane-1,1,2,3-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, pyromellitic acid, oxycarboxylic acids such as glycolic acid, β-hydroxypropionic acid, citric acid, malic acid, tartaric acid, pyruvic acid, diglycolic acid, salicylic acid, gallic acid, polyphenols such as catechol, pyrogallol, phosphoric acids such as pyrophosphoric acid, polyphosphoric acid, heterocyclic compounds such as 8-hydroxyquinoline, and diketones such as α-dipyridyl acetylacetone.

[0063] The pre-textured formulations of the present disclosure may contain the chelating agent in an amount of about 0 wt% or greater, about 1 wt% or greater, about 2 wt% or greater, about 3 wt% or greater, about 4 wt% or greater, about 5 wt% or greater, or about 6 wt% or less, about 7 wt% or less, about 8 wt% or less, about 9 wt% or less, about 10 wt% or less, or within any range using these endpoints.

[0064] 6. Solvent

[0065] The pre-formulation may be an aqueous composition containing water (such as water, deionized water, or purified water) as a solvent; however, as known to those skilled in the art, common solvents may be used instead of water or in combination with water, including alcohols, diols, acetone, etc. The pre-textured formulation may contain greater than 50 wt% water based on the total weight of the formulation.

[0066] 7. Other Additives

[0067] The pre-textured composition containing a surfactant may further contain one or more additives to facilitate cleaning and / or texturing (etching) of the wafer surface. Even after, for example, a saw damage removal step (if any), the cleaning additives help remove debris remaining on the surface. Optionally, the pre-textured composition of the present invention may contain one or more additional components, including inorganic or organic acids, bases, chelating agents, dispersants, and defoaming agents or mixtures thereof. Acids, bases, and other additives can be added to the pre-textured composition, for example, to improve its cleaning performance.

[0068] The pre-textured formulation of the present disclosure may further contain one or more dispersants. Suitable dispersants include the surfactants of the present disclosure, as well as triethanolamine lauryl sulfate, ammonium lauryl sulfate, triethanolamine polyoxyethylene alkyl ether sulfate, acrylamide-methyl-propane sulfonate, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene derivatives, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tetraoleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene alkylamine, polyoxyethylene hydrogenated castor oil, alkyl alkanolamide, polyvinylpyrrolidone, coconut amine acetate, stearyl amine acetate, lauryl betaine, stearyl betaine, lauryl dimethylamine oxide, and 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine.

[0069] The dispersant may be present in the pre-textured formulation in an amount of about 0 wt% or greater, about 0.1 wt% or greater, about 0.5 wt% or greater, about 1.0 wt% or greater, about 1.5 wt% or greater, or about 2.0 wt% or less, about 2.5 wt% or less, about 3.0 wt% or less, about 3.5 wt% or less, about 4.0 wt% or less, about 4.5 wt% or less, about 5.0 wt% or less, or within any range using these endpoints.

[0070] The pre-textured formulation may further contain other additives, such as sugars or sugar alcohols, such as xylitol, mannose, glucose, etc. The pre-textured formulation may contain these additives in an amount of about 0 wt% or greater, about 1 wt% or greater, about 10 wt% or greater, about 20 wt% or greater, or about 30 wt% or less, about 40 wt% or less, about 50 wt% or less, or within any range using these endpoints.

[0071] The pre-textured formulation may also include oxidizing agents such as nitric acid, peroxides, and hypochlorites. The oxidizing agent may be present in an amount of about 0 wt% or greater, about 1 wt% or greater, about 10 wt% or greater, about 20 wt% or greater, or about 30 wt% or less, about 40 wt% or less, about 50 wt% or less, or within any range using these endpoints.

[0072] The pre-textured formulation may also include corrosion inhibitors to protect the materials of the process equipment from corrosion caused by exposure to the pre-textured treatment composition or the textured etchant composition.

[0073] Suitable corrosion inhibitors may include compounds such as 1,2,4-triazole, aminotriazole, benzotriazole, tolyltriazole, mercaptobenzothiazole. The formulation may also include corrosion inhibitors that are chemically reducing in nature, such as ascorbic acid.

[0074] 8. Method of Use

[0075] The pre-textured formulations of the present disclosure can be used in at least one pre-texturing step in a multi-step process for texturing wafers, which may be single-crystal substrates (e.g., Si<100> or Si<111>), microcrystalline silicon substrates, polycrystalline silicon substrates, strained silicon substrates, amorphous silicon substrates, doped or undoped polycrystalline silicon substrates, glass, sapphire, or any type of silicon-containing substrate. The substrate may also be a silicon film deposited on different types of substrates such as metals, glass, or polymers. The pre-texturing step prior to the texturing step is a pretreatment step involving the use of the formulation of the present disclosure, which contains a surfactant or a mixture of more than one surfactant in solution.

[0076] It is believed that the pre-textured formulation containing one or more surfactants improves (lowers) the reflectivity of the wafer after or during one or more pre-texturing steps and one or more texturing steps. The pre-texturing step will use the pre-textured formulation of the present disclosure containing a surfactant, and the texturing step may be any standard texturing or etching step using any known etching composition or etching solution (commonly also referred to as a wet etchant). For example, the texturing step may use a standard texturing solution in a standard texturing bath.

[0077] The pre-textured formulations of the present disclosure can provide the additional benefit of cleaning the silicon surface when used in the pre-texturing step. After the texturing process is completed, the texturing quality is improved, forming a high density of small pyramids in the case of single-crystalline silicon and a more uniform textured surface in the case of polycrystalline silicon, resulting in a lower reflectivity.

[0078] The present disclosure further provides a method of textured silicon wafers including the step of wetting the wafer with one or more of the pre-textured formulations disclosed herein, and a method of textured silicon wafers including the step of wetting the wafer with the pre-textured formulation described herein. The method of textured silicon wafers includes the following steps: wetting the wafer with the pre-textured formulation described herein; wetting the wafer with an etching composition. Any of the above pre-textured formulations can be used in the methods of the present disclosure.

[0079] The texturing method of the present disclosure can be a multi-step texturing method including at least a pre-texturing step and a subsequent texturing step. The multi-step texturing method can further include one or more rinsing steps, one or more cleaning steps, one or more optional saw damage removal steps, and / or other steps. The wafer can be wetted with the pre-textured formulation of the present disclosure before the saw damage removal step, before the texturing (etching) step, or before both the saw damage removal step and the texturing step.

[0080] The wafer can be rinsed in a separate rinsing step before and after the pre-texturing and / or texturing steps. Wetting can be carried out at room temperature or an elevated temperature. The wafer can be wetted with the pre-textured formulation of the present disclosure for a period of time, which can vary depending on the method of applying the pre-textured formulation of the present disclosure to the wafer.

[0081] II. Etching Agent

[0082] The present disclosure provides an etchant formulation. The semiconductor industry is rapidly reducing the size and increasing the density of electronic circuits and components in microelectronic devices, silicon chips, liquid crystal displays, MEMS (microelectromechanical systems), printed circuit boards, etc. The integrated circuits therein are layered or stacked, where the thickness of the insulating layer between each circuit layer is continuously decreasing and the feature size is getting smaller. As the feature size shrinks, the patterns become smaller, and the device performance parameters are closer and more robust. As a result, due to the smaller feature size, various problems that were previously tolerable can no longer be tolerated or have become greater problems.

[0083] In the production of advanced integrated circuits, in order to minimize problems associated with higher density and optimize performance, high-k and low-k insulators and various barrier layer materials have been adopted.

[0084] Tantalum (Ta) and tantalum nitride (TaN) are used in semiconductor devices, liquid crystal displays, MEMS (microelectromechanical systems), printed circuit boards, etc., and are used as ground layers and capping layers for noble metals, aluminum (Al), and copper (Cu) wiring. In semiconductor devices, it can be used as a barrier metal, hard mask, or gate material.

[0085] In the construction of devices for these applications, it is often necessary to etch Ta and TaN. In various types of uses and device environments of Ta and TaN, other layers are contacted or otherwise exposed while etching these two materials. High selectivity etching of Ta and TaN in the presence of these other materials (such as metal conductors, dielectrics, and hard masks) is required for device yield and long life.

[0086] The present disclosure includes formulations for etchants for methods of selectively etching Ta and / or TaN relative to metal conductor layers, hard mask layers, and low-k dielectric layers present in semiconductor devices. More specifically, the present disclosure relates to compositions and methods for selectively etching Ta and / or TaN relative to copper and low-k dielectric layers.

[0087] The etchant formulations of the present disclosure can have relatively high Ta / Cu and / or TaN / Cu etch selectivities (i.e., high ratios of Ta etch rate to Cu etch rate and / or high ratios of TaN etch rate to Cu etch rate). In some embodiments, the etch composition can have a Ta / Cu and / or TaN / Cu etch selectivity of about 2 or greater, about 3 or greater, about 4 or greater, about 5 or greater, about 6 or greater, about 7 or greater, about 8 or greater, about 9 or greater, about 10 or greater, about 15 or greater, about 20 or greater, about 30 or greater, about 40 or greater, about 50 or greater, or about 60 or less, about 70 or less, about 80 or less, about 90 or less, about 100 or less, or within any range using these endpoints.

[0088] The etchant formulations of the present disclosure can have relatively high Ta / dielectric material (such as SiO 2 or low-k material) and / or TaN / dielectric material etch selectivities (i.e., high ratios of Ta etch rate to dielectric material etch rate and / or high ratios of TaN etch rate to dielectric material etch rate). In some embodiments, the etch composition can have a Ta / dielectric material and / or TaN / dielectric material etch selectivity of about 2 or greater, about 3 or greater, about 4 or greater, about 5 or greater, about 6 or greater, about 7 or greater, about 8 or greater, about 9 or greater, about 10 or greater, about 15 or greater, about 20 or greater, about 30 or greater, about 40 or greater, about 50 or greater, or about 60 or less, about 70 or less, about 80 or less, about 90 or less, about 100 or less, or within any range using these endpoints.

[0089] The etchant of the present disclosure may comprise hydrofluoric acid (HF), one or more surfactants selected from one or more surfactant classes, one or more solvents, optionally one or more oxidizing agents, and one or more complexing agents.

[0090] 1. Hydrofluoric Acid

[0091] It is believed that hydrofluoric acid may promote and enhance the removal of Ta and / or TaN on the semiconductor substrate during the etching process.

[0092] Hydrofluoric acid may be present in the etchant formulation in an amount of about 0.1 wt% or greater, about 0.2 wt% or greater, about 0.4 wt% or greater, 0.5 wt% or greater, about 0.6 wt% or greater, about 0.8 wt% or greater, about 1.0 wt% or greater, about 1.2 wt% or greater, about 1.4 wt% or greater, about 1.5 wt% or greater, or about 2.0 wt% or less, about 2.5 wt% or less, about 3 wt% or less, about 3.5 wt% or less, about 4.0 wt% or less, about 4.5 wt% or less, about 5.0 wt% or less, or within any range using these endpoints.

[0093] 2. Surfactant

[0094] The etchant formulation of the present disclosure comprises one or more surfactants, also referred to as a surfactant system. The surfactant may promote the uniformity of the etching composition and assist in dissolving components (such as sulfonic acid) in the solvent.

[0095] Surfactants suitable for the etchant formulation of the present disclosure include one or more surfactants and / or co-surfactants of Formula I,

[0096]

[0097] wherein R 1 and R 2 may be the same or different and comprise at least one group selected from C 1 -C 6 alkyl, optionally the C 1 -C 6 alkyl may contain one or more oxygen, nitrogen or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain may optionally be substituted by one or more substituents selected from hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl and carboxylate; n is an integer from 1 to 12; the terminal nitrogen is optionally further substituted by R 3 wherein R 3 is selected from hydrogen, oxygen, hydroxyl and C 1 -C 6an alkyl group; and an optional counterion associated with the compound, which if present is selected from chloride, bromide, and iodide ions.

[0098] In particular, suitable surfactants or co-surfactants can include one or more of any of the surfactants 1-6 described herein.

[0099] The surfactant can be present in the etchant formulation in an amount of about 0.0001 wt% or greater, about 0.01 wt% or greater, about 0.1 wt% or greater, about 0.2 wt% or greater, about 0.3 wt% or greater, about 0.4 wt% or greater, about 0.5 wt% or greater, or about 0.6 wt% or less, about 0.7 wt% or less, about 0.8 wt% or less, about 0.9 wt% or less, about 1.0 wt% or less, or within any range using these endpoints.

[0100] 3. Solvent

[0101] The etchant formulations of the present disclosure can include one or more solvents. The etch composition can include a first solvent that is a carboxylic acid. The carboxylic acid used as the first solvent can facilitate and enhance the removal of Ta and / or TaN on the semiconductor substrate during the etching process.

[0102] Suitable first solvents can include carboxylic acids of the formula: R—COOH, where R is H or C 1 -C 6 alkyl groups, such as formic acid, acetic acid, trifluoroacetic acid, propionic acid, lactic acid, butyric acid, valeric acid, and caproic acid.

[0103] The first solvent can be a major component of the etchant formulation of the present disclosure. For example, the first solvent can be present in the etchant formulation in an amount of about 70 wt% or greater, about 75 wt% or greater, about 80 wt% or greater, about 85 wt% or greater, or about 90 wt% or less, about 95 wt% or less, about 96 wt% or less, about 97 wt% or less, about 98 wt% or less, about 99 wt% or less, about 99.9 wt% or less, or within any range using these endpoints.

[0104] Alternatively, the etchant formulations of the present disclosure can include two or more solvents. For example, the etch composition can include at least one second solvent selected from organic solvents (which are not carboxylic acids) and inorganic solvents. Suitable inorganic solvents include water and aqueous solutions. The water can be deionized and ultrapure, free of organic contaminants, and have a minimum resistivity of about 4 to about 17 megohms, or at least about 17 megohms.

[0105] The at least one second solvent (such as water) may be present in an amount of about 0.01 wt% or greater, about 0.1 wt% or greater, about 0.5 wt% or greater, about 1 wt% or greater, about 2 wt% or greater, about 4 wt% or greater, about 5 wt% or greater, or about 6 wt% or less, about 7 wt% or less, about 8 wt% or less, about 9 wt% or less, about 10 wt% or less, or in any range using these endpoints.

[0106] The second solvent may be an organic solvent that is not a carboxylic acid. For example, the organic solvent may be a hydrophobic organic solvent having a partition coefficient (logP) of about 0 or greater, about 0.1 or greater, about 0.2 or greater, about 0.3 or greater, about 0.5 or greater, about 1.0 or greater, about 1.5 or greater, about 2.0 or greater, or about 2.5 or less, about 3.0 or less, about 3.5 or less, about 4.0 or less, about 4.5 or less, about 5.0 or less, or in any range using these endpoints.

[0107] As used herein, the partition coefficient log P is obtained from a two-phase system of n-octanol and water. In some embodiments, the organic solvent may be an alcohol or an ether. The ether may be an alkylene glycol ether (such as a diethylene glycol ether, a triethylene glycol ether, and a tetraethylene glycol ether). Examples of such organic solvents include benzyl alcohol, diethylene glycol butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl ether, tetraethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether. Without wishing to be bound by theory, it is believed that using a hydrophobic organic solvent can inhibit the removal of Cu during the etching process without reducing the removal of Ta or TaN.

[0108] The at least one second solvent (such as an organic solvent) may be present in an amount of about 0.1 wt% or greater, about 0.2 wt% or greater, about 0.4 wt% or greater, about 0.5 wt% or greater, about 0.6 wt% or greater, about 0.8 wt% or greater, about 1.0 wt% or greater, about 1.5 wt% or greater, about 2.0 wt% or greater, about 2.5 wt% or greater, about 5.0 wt% or greater, or about 6.0 wt% or less, about 8.0 wt% or less, about 10 wt% or less, about 15 wt% or less, about 20 wt% or less, or in any range using these endpoints.

[0109] 4. Oxidizing Agent

[0110] The etchant formulation of the present disclosure may optionally include any oxidizing agent suitable for microelectronic applications. The oxidizing agent can promote and enhance the removal of Ta and / or TaN on a semiconductor substrate. Suitable oxidizing agents include, but are not limited to, oxidizing acids or their salts (such as nitric acid, permanganic acid, or potassium permanganate), peroxides (such as hydrogen peroxide, dialkyl peroxides, urea hydrogen peroxide), peroxysulfonic acids (such as hexafluoropropane peroxysulfonic acid, methane peroxysulfonic acid, trifluoromethane peroxysulfonic acid, or p-toluenesulfonic acid) and their salts, ozone, percarbonic acids (such as peracetic acid) and their salts, perphosphoric acids and their salts, persulfuric acids and their salts (such as ammonium persulfate or tetramethylammonium persulfate), perchloric acid and its salts (such as ammonium perchlorate, sodium perchlorate, or tetramethylammonium perchlorate), and periodic acid and its salts (such as periodic acid, ammonium periodate, or tetramethylammonium periodate). These oxidizing agents can be used alone or in combination.

[0111] The oxidizing agent can be present in the etchant formulation in an amount of about 0.01 wt% or greater, about 0.02 wt% or greater, about 0.04 wt% or greater, about 0.05 wt% or greater, about 0.06 wt% or greater, about 0.08 wt% or greater, about 0.1 wt% or greater, about 0.15 wt% or greater, about 0.2 wt% or greater, or about 0.25 wt% or less, about 0.3 wt% or less, about 0.35 wt% or less, about 0.4 wt% or less, about 0.45 wt% or less, about 0.5 wt% or less, or in any range between these endpoints.

[0112] Alternatively, the etchant formulation of the present disclosure may not include an oxidizing agent (such as nitric acid). In such embodiments, the etch composition is still capable of selectively etching Ta and / or TaN relative to other materials (such as metal conductor layers, hard mask layers, and low-k dielectric layers) in a patterned semiconductor substrate (such as a patterned wafer).

[0113] 5. Complexing Agent

[0114] The etchant formulations of the present disclosure may include any suitable complexing agent. The complexing agent can promote and enhance the removal of Ta and / or TaN on a semiconductor substrate during an etching process while inhibiting the removal of Cu exposed to the etching composition. Suitable complexing agents can be selected from polycarboxylic acids and hydroxycarboxylic acids. As used herein, the term "polycarboxylic acid" refers to a compound containing two or more (such as two, three, or four) carboxyl groups (COOH). Examples of suitable polycarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid. As used herein, the term "hydroxycarboxylic acid" refers to a compound containing at least one (such as two, three, or four) hydroxyl group (OH) and at least one (such as two, three, or four) carboxyl group (COOH). Examples of suitable hydroxycarboxylic acids include citric acid and 2-hydroxybenzoic acid. In some embodiments, the polycarboxylic acid does not contain a hydroxyl group. In some embodiments, the hydroxycarboxylic acid contains only one hydroxyl group.

[0115] The complexing agent can be included in the etchant formulation in an amount of about 0.1 wt% or greater, about 0.2 wt% or greater, about 0.4 wt% or greater, about 0.5 wt% or greater, about 0.6 wt% or greater, about 0.8 wt% or greater, about 1.0 wt% or greater, about 1.5 wt% or greater, about 2.0 wt% or greater, about 2.5 wt% or greater, about 5.0 wt% or greater, or about 6.0 wt% or less, about 6.5 wt% or less, about 7.0 wt% or less, about 7.5 wt% or less, about 8.0 wt% or less, about 8.5 wt% or less, about 9.0 wt% or less, about 9.5 wt% or less, about 10 wt% or less, or in any range using these endpoints.

[0116] 6. Other Additives

[0117] The etchant formulations of the present disclosure may further include at least one hexafluorosilicate compound. The following hexafluorosilicate compounds can promote and enhance the removal of Ta and / or TaN on a semiconductor substrate during an etching process while inhibiting the removal of dielectric materials (SiO 2 ) exposed to the etching composition. Suitable hexafluorosilicate compounds include hexafluorosilicic acid (H 2 SiF 6 ) and its salts. Specific examples of hexafluorosilicate compounds include H 2 SiF 6 , Na 2 SiF 6 , K 2 SiF 6 and (NH 4 ) 2 SiF 6 .

[0118] The hexafluorosilicate compound may be present in the etchant formulation in an amount of about 0.1 wt% or greater, about 0.2 wt% or greater, about 0.4 wt% or greater, 0.5 wt% or greater, about 0.6 wt% or greater, about 0.8 wt% or greater, about 1.0 wt% or greater, about 1.2 wt% or greater, about 1.4 wt% or greater, about 1.5 wt% or greater, or about 2.0 wt% or less, about 2.5 wt% or less, about 3 wt% or less, about 3.5 wt% or less, about 4.0 wt% or less, about 4.5 wt% or less, about 5.0 wt% or less, or in any range using these endpoints.

[0119] The etchant formulation of the present disclosure may further comprise at least one sulfonic acid. The sulfonic acid may promote and enhance the removal of Ta and / or TaN on the semiconductor substrate during the etching process. Examples of suitable sulfonic acids include p-toluenesulfonic acid, methanesulfonic acid, or dodecylbenzenesulfonic acid.

[0120] The sulfonic acid may be present in the etchant formulation in an amount of about 0.1 wt% or greater, about 0.2 wt% or greater, about 0.4 wt% or greater, about 0.5 wt% or greater, about 0.6 wt% or greater, about 0.8 wt% or greater, about 1.0 wt% or greater, about 1.5 wt% or greater, about 2.0 wt% or greater, about 2.5 wt% or greater, about 5.0 wt% or greater, or about 6.0 wt% or less, about 6.5 wt% or less, about 7.0 wt% or less, about 7.5 wt% or less, about 8.0 wt% or less, about 8.5 wt% or less, about 9.0 wt% or less, about 9.5 wt% or less, about 10 wt% or less, or in any range using these endpoints.

[0121] In addition, the etchant formulation of the present disclosure may contain additional additives such as pH regulators, corrosion inhibitors, additional surfactants, additional organic solvents, biocides, and antifoaming agents as optional components.

[0122] 7. Manufacturing Method

[0123] The etch composition of the present disclosure can be prepared by simply mixing the components, or can be prepared by blending two compositions in a kit. The first composition in the kit may be an aqueous solution of an oxidant (such as nitric acid). The second composition in the kit may contain the remaining components of the etch composition of the present disclosure in concentrated form at a predetermined ratio such that blending of the two compositions will produce the desired etch composition of the present disclosure.

[0124] 8. Method of Use

[0125] The present disclosure provides a method for etching a semiconductor substrate containing Ta and / or TaN (e.g., a feature containing Ta and / or TaN). The method includes contacting the semiconductor substrate containing Ta and / or TaN with an etching composition of the present disclosure to remove Ta and / or TaN. The method may further include rinsing the semiconductor substrate with a rinse solvent after the contacting step and / or drying the semiconductor substrate after the rinsing step. In some embodiments, the method substantially does not remove Cu or dielectric material (e.g., SiO 2 ) in the semiconductor substrate. For example, the method does not remove more than about 5 wt% (e.g., more than about 3 wt% or more than about 1 wt%) of Cu or dielectric material in the semiconductor substrate.

[0126] The etching method may include the following steps: 1) providing a semiconductor substrate containing Ta and / or TaN; 2) contacting the semiconductor substrate with the etching composition described herein; 3) rinsing the semiconductor substrate with one or more suitable rinse solvents; and 4) optionally, drying the semiconductor substrate (e.g., by any suitable means of removing the rinse solvent without compromising the integrity of the semiconductor substrate).

[0127] The semiconductor substrate containing Ta and / or TaN to be etched in the method may contain organic and organometallic residues, as well as a series of metal oxides that may also be removed during the etching process. The semiconductor substrate (e.g., a wafer) is typically composed of silicon, silicon germanium, group III-V compounds (such as GaAs), or any combination thereof. The semiconductor substrate may additionally contain exposed integrated circuit structures, such as interconnect features (e.g., metal lines and dielectric materials). Metals and metal alloys used for interconnect features include, but are not limited to, aluminum, aluminum alloyed with copper, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten. The semiconductor substrate may also contain interlayer dielectrics, layers of silicon oxide, silicon nitride, silicon carbide, titanium oxide, and carbon-doped silicon oxide.

[0128] The semiconductor substrate can be contacted with the etching composition by any suitable method, such as placing the etching composition in a bath and submerging and / or dipping the semiconductor substrate in the etching composition, spraying the etching composition onto the semiconductor substrate, flowing the etching composition onto the semiconductor substrate, or any combination thereof.

[0129] III. Photoresist Stripper

[0130] The present disclosure further provides a formulation of a photoresist stripper. The semiconductor integrated circuits and device circuits of liquid crystal panels have very fine structures. The fine circuits are generally fabricated by uniformly coating a photoresist on an insulating film or a conductive metal film (such as an oxide film or an Al alloy film, respectively) coated on a substrate, exposing and developing the photoresist to form a specific pattern, etching the metal film or the insulating film by using the patterned photoresist as a mask, and then removing the unwanted photoresist.

[0131] The photoresist stripping formulation is used to remove photoresist from a substrate. Generally, the photoresist stripping formulation should have a high stripping force both at low and high temperatures and should leave no residue on the substrate. In addition, considering the use of a large amount of stripping composition in the manufacture of large-scale liquid crystal display panel circuits, the desirable stripper should not corrode the metal film and should be of little harm to humans and the environment.

[0132] The present disclosure provides a photoresist stripping formulation suitable for single-wafer processing methods and dipping methods for stripping photoresist, particularly a formulation that leaves no impurities on the substrate even when applying a single-wafer processing method using an air knife method to strip the photoresist.

[0133] The present disclosure further provides a photoresist stripping composition that has a good stripping force for various types of films coated on a substrate and prevents the formation of impurity particles when cleaning bare glass.

[0134] To be suitable for single-wafer processing photoresist stripping methods and dipping methods using high gas pressure (air knife), the photoresist stripping formulation must have a good stripping force, be non-corrosive, and not form impurity particles on the substrate.

[0135] To effectively prevent any impurities on the substrate, the stripping formulation should be easily absorbed by various LCD layers, such as indium tin oxide (ITO) films, aluminum, chromium, silicon nitride films, and amorphous silicon films. In addition, the stripping formulation should exhibit a uniform low surface tension with the LCD layers. In addition, it should have low volatility and viscosity. In addition, the contact angle between the LCD layer surface and the stripping formulation falling on the surface should be small and remain constant.

[0136] In addition, it is desirable that the stripping formulation shows uniform physical properties for various types of LCD layers and that the stripping formulation can prevent the formation of impurity particles on bare glass when testing for the presence of impurity particles in an LCD manufacturing facility.

[0137] The photoresist stripping formulation of the present disclosure comprises an alkanolamine, a sulfoxide or sulfone compound, a glycol ether, and one or more surfactants selected from one or more surfactant classes.

[0138] 1. Alkanolamine

[0139] Alkanolamines strip the photoresist from the substrate. Suitable alkanolamines include monoisopropanolamine and monoethanolamine.

[0140] The alkanolamine is present in the photoresist stripper formulation in an amount of about 5 wt% or greater, about 6 wt% or greater, about 7 wt% or greater, about 8 wt% or greater, about 9 wt% or greater, or about 10 wt% or less, about 11 wt% or less, about 12 wt% or less, about 13 wt% or less, about 14 wt% or less, about 15 wt% or less, or within any range using these endpoints.

[0141] 2. Sulfoxide or Sulfone

[0142] Sulfoxides or sulfone compounds are provided as solvents for dissolving the photoresist and control the surface tension between the stripping composition and the LCD layer. Suitable compounds include diethyl sulfoxide, dimethyl sulfoxide, diethyl sulfone, or dimethyl sulfone.

[0143] The sulfoxide or sulfone compound may be included in the photoresist stripping formulation in an amount of about 35 wt% or greater, about 40 wt% or greater, or about 45 wt% or less, about 50 wt% or less, about 55 wt% or less, or within any range using these endpoints.

[0144] 3. Glycol Ether

[0145] Glycol ethers are combined with the aforementioned sulfoxide or sulfone compounds to dissolve the photoresist and control the surface tension between the compound and the LCD layer, so as to greatly enhance the air knife photoresist stripping ability compared to a composition composed of dimethyl sulfoxide and monoethanolamine. Even though dimethyl sulfoxide itself is used to enhance the air knife photoresist stripping ability, its combination with monoethanolamine greatly reduces the air knife photoresist stripping ability. However, adding glycol ethers to the compound composed of dimethyl sulfoxide and monoethanolamine improves the air knife photoresist stripping ability and the photoresist stripping force of the compound.

[0146] Suitable glycol ether compounds include ethyl diglycol, methyl diglycol, or butyl diglycol.

[0147] The glycol ether may be included in the photoresist stripping formulation in an amount of about 35 wt% or greater, about 40 wt% or greater, or about 45 wt% or less, about 50 wt% or less, about 55 wt% or less, or within any range using these endpoints.

[0148] 4. Surfactant

[0149] One or more surfactants may be included in the photoresist stripper formulation. The surfactant can prevent the generation and residue of impurity particles on the substrate when rinsing the bare glass. Surfactants suitable for the photoresist stripper formulation of the present disclosure include one or more surfactants of formula I and / or co-surfactants,

[0150]

[0151] wherein R 1 and R 2 may be the same or different and include at least one group selected from C 1 -C 6 alkyl groups, optionally the C 1 -C 6 alkyl group may contain one or more oxygen, nitrogen or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain may optionally be substituted by one or more substituents selected from hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl and carboxylate; n is an integer from 1 to 12; the terminal nitrogen is optionally further substituted by R 3 wherein R 3 is selected from hydrogen, oxygen, hydroxyl and C 1 -C 6 alkyl; and an optional counterion associated with the compound, which if present is selected from chloride, bromide and iodide ions.

[0152] In particular, suitable surfactants or co-surfactants may include one or more of any of the surfactants 1-6 described herein.

[0153] The photoresist stripper formulation may contain one or more surfactants in an amount of about 0.05 wt% or greater, about 0.1 wt% or greater, about 0.2 wt% or greater, or about 0.3 wt% or less, about 0.4 wt% or less, about 0.5 wt% or less, or within any range using these endpoints.

[0154] 5. Other Additives

[0155] The photoresist stripper formulation of the present disclosure may further contain tetramethylammonium hydroxide in an amount of 1 wt% or greater, about 2 wt% or greater, about 3 wt% or greater, about 4 wt% or greater, about 5 wt% or greater, or about 6 wt% or less, about 7 wt% or less, about 8 wt% or less, about 9 wt% or less, about 10 wt% or less, or within any range using these endpoints.

[0156] The photoresist stripper formulation may also contain hydroquinone in an amount of about 3 wt% or greater, about 4 wt% or greater, about 5 wt% or greater, about 6 wt% or greater, about 7 wt% or greater, about 8 wt% or greater, about 9 wt% or greater, or about 10 wt% or less, about 11 wt% or less, about 12 wt% or less, about 13 wt% or less, about 14 wt% or less, about 15 wt% or less, or within any range using these endpoints.

[0157] The photoresist stripping formulation may also contain an alkylsulfonic acid in an amount of about 1 wt% or greater, about 2 wt% or greater, about 3 wt% or greater, about 4 wt% or greater, about 5 wt% or greater, about 6 wt% or greater, about 7 wt% or greater, about 8 wt% or greater, about 9 wt% or greater, or about 10 wt% or less, about 11 wt% or less, about 12 wt% or less, about 13 wt% or less, about 14 wt% or less, about 15 wt% or less, or within any range using these endpoints.

[0158] VI. Surfactant

[0159] The present disclosure provides surfactants in the form of siloxane derivatives of amino acids for use as pre-texturing agents, etchants, and photoresist strippers. The amino acids can be naturally occurring or synthetic, or they can be obtained from the ring-opening reaction of lactams such as caprolactam. The compounds of the present disclosure have been shown to have surface-active properties and can be used, for example, as surfactants and wetting agents. In particular, the present disclosure provides compounds of Formula I shown below:

[0160]

[0161] wherein R 1 and R 2 can be the same or different and contain at least one group selected from C 1 -C 6 alkyl groups, optionally the C 1 -C 6 alkyl group can contain one or more oxygen, nitrogen, or sulfur atoms or substituents containing at least one of these atoms, and the alkyl chain can be optionally substituted with one or more substituents selected from hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate;

[0162] n is an integer from 1 to 12;

[0163] The terminal nitrogen is optionally further substituted by R 3 wherein R 3 is selected from hydrogen, oxygen, hydroxyl, and C 1 -C6 an alkyl group; and

[0164] an optional counterion associable with the compound, and if present, the counterion is selected from chloride, bromide, and iodide ions.

[0165] The present disclosure further provides a compound of formula Ia:

[0166]

[0167] wherein R 1 and R 2 may be the same or different and each contains at least one group selected from C 1 -C 6 alkyl groups, optionally the C 1 -C 6 alkyl group may contain one or more oxygen, nitrogen, or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain may optionally be substituted with one or more substituents selected from hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate;

[0168] m is an integer from 1 to 6;

[0169] The terminal nitrogen is optionally further substituted with R 3 wherein R 3 is selected from hydrogen, oxygen, and C 1 -C 6 alkyl groups, wherein the alkyl chain is optionally substituted with one or more substituents selected from carboxyl, carboxylate, and sulfonate; and

[0170] an optional counterion associable with the compound, and if present, the counterion is selected from chloride, bromide, and iodide ions.

[0171] The present disclosure additionally provides a compound of formula Ib:

[0172]

[0173] wherein R 1 and R 2 may be the same or different and each contains at least one group selected from C 1 -C 6 alkyl groups, optionally the C 1 -C 6 alkyl group may contain one or more oxygen, nitrogen, or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain may optionally be substituted with one or more substituents selected from hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate;

[0174] p is 5;

[0175] The terminal nitrogen is optionally further substituted by R 3 wherein R 3 is selected from hydrogen, oxygen, and C 1 -C 6 alkyl, wherein the alkyl chain is optionally substituted by one or more substituents selected from carboxyl, carboxylate, and sulfonate; and

[0176] an optional counterion that can associate with the compound, and if present, the counterion is selected from chloride, bromide, and iodide ions.

[0177] A specific compound provided by the present disclosure is 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)hexanamide (Surfactant 1), which has the following formula:

[0178] .

[0179] A second specific compound provided by the present disclosure is 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)hexanammonium chloride (Surfactant 2), which has the following formula:

[0180] .

[0181] A third specific compound provided by the present disclosure is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide (Surfactant 3), which has the following formula:

[0182] .

[0183] A fourth specific compound provided by the present disclosure is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-amine oxide (Surfactant 4), which has the following formula:

[0184] .

[0185] In the above structures, the symbol "N→O" is intended to represent a non-ionic bonding interaction between nitrogen and oxygen.

[0186] The fifth specific compound provided by the present disclosure is 4-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)butane-1-sulfonate (Surfactant 5), which has the following formula:

[0187] .

[0188] The sixth specific compound provided by the present disclosure is 5-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)pentane-1-sulfonate (Surfactant 6), which has the following formula:

[0189] .

[0190] These compounds can be synthesized by various methods. One such method involves reacting an amino acid, such as an N-alkylated or N-acylated amino acid, with a siloxane to convert the C-terminus of the amino acid into the desired siloxane derivative. The N-terminus of the amino acid can be further protonated, alkylated, or oxidized to produce, for example, a quaternary amine or an N-oxide.

[0191] The amino acid can be naturally occurring or synthetic, or can be derived from the ring-opening reaction of a lactam (such as caprolactam). The ring-opening reaction can be an acid- or base-catalyzed reaction, and an example of an acid-catalyzed reaction is shown in Scheme 1 below.

[0192] Scheme 1

[0193]

[0194] The amino acid can have as few as 1 or as many as 12 carbons between the N-terminus and the C-terminus. The alkyl chain can be branched or straight-chain. The alkyl chain can be interrupted by nitrogen, oxygen, or sulfur. The alkyl chain can be further substituted by one or more substituents selected from hydroxy, amino, amido, sulfonyl, sulfonate, carboxy, and carboxylate. The N-terminal nitrogen can be acylated or alkylated with one or more alkyl groups. For example, the amino acid can be 6-(dimethylamino)hexanoic acid.

[0195] The siloxane can be substituted by one or more alkoxy groups such as methoxy, ethoxy, isopropoxy, tert-butoxy, etc. The siloxane can be further substituted by one or more alkyl groups such as propyl, where the alkyl can be further substituted by a suitable functional group (such as nitrogen) to allow coupling of the siloxane with the amino acid. For example, the siloxane can be 3-aminopropyltris(trimethylsilyloxy)silane.

[0196] The siloxane derivative of the amino acid can be synthesized as shown in Scheme 2 below. As shown, 6-aminohexanoic acid is treated with formaldehyde in formic acid under reflux to obtain 6-(dimethylamino)hexanoic acid. Subsequently, the free carboxylic acid is coupled to 3-aminopropyl(trimethylsilyloxy)silane in refluxing toluene to obtain the desired siloxane derivative.

[0197] Scheme 2

[0198]

[0199] The N-terminal nitrogen can be further derivatized to alter or improve the water solubility and surface activity properties. A sample synthesis scheme is shown in Scheme 3 below, where the N-terminal nitrogen is treated with hydrochloric acid to obtain the corresponding hydrochloride salt.

[0200] Scheme 3

[0201]

[0202] The N-terminal nitrogen can be alkylated. A sample synthesis scheme is shown below, where the N-terminal nitrogen is treated with methyl iodide to obtain the corresponding quaternary ammonium salt.

[0203] Scheme 4

[0204]

[0205] The N-terminal nitrogen can be treated with hydrogen peroxide in water under reflux to obtain the corresponding N-oxide, as shown in Sample Synthesis Scheme 5 below.

[0206] Scheme 5

[0207]

[0208] The compounds of the present disclosure exhibit surface activity properties. These properties can be measured and described by various methods. One way to describe a surfactant is through the critical micelle concentration (CMC) of the molecule. The CMC can be defined as the concentration of the surfactant at which micelles form, and above which all additional surfactant is incorporated into the micelles.

[0209] As the surfactant concentration increases, the surface tension decreases. Once the surface is completely covered by surfactant molecules, micelles begin to form. This point represents the CMC and the minimum surface tension. Further addition of surfactant will not further affect the surface tension. Therefore, the CMC can be determined by observing the change in surface tension with surfactant concentration. One such method for measuring this value is the Wilhemy plate method. The Wilhemy plate is typically a thin iridium-platinum plate that is connected to a balance by a wire and placed perpendicular to the air-liquid interface. The balance is used to measure the force exerted on the plate due to wetting. Subsequently, this value is used to calculate the surface tension (γ) according to Equation 1:

[0210] Equation 1: γ = F / l cos θ

[0211] where l is equal to the wetting perimeter (2w + 2d, where w and d are the thickness and width of the plate, respectively), and cosθ, the contact angle between the liquid and the plate, is assumed to be 0 in the absence of existing literature values.

[0212] Another parameter used to evaluate surfactant performance is the dynamic surface tension. The dynamic surface tension is the surface tension value for a specific surface or interface lifetime. In the case of a liquid to which a surfactant has been added, this may differ from the equilibrium value. Immediately after the surface is created, the surface tension is equal to that of the pure liquid. As described above, the surfactant reduces the surface tension; thus, the surface tension decreases until the equilibrium value is reached. The time required to reach equilibrium depends on the diffusion rate and adsorption rate of the surfactant.

[0213] One method for measuring the dynamic surface tension relies on a bubble pressure tensiometer. This device measures the maximum internal pressure of a bubble formed in a liquid through a capillary. The value measured corresponds to the surface tension at a specific surface lifetime (i.e., the time from bubble formation to the appearance of the maximum pressure). The dependence of the surface tension on the surface lifetime can be measured by varying the rate at which the bubbles are generated.

[0214] Surface-active compounds can also be evaluated by their wetting ability on a solid substrate, which is measured by the contact angle. When a liquid droplet comes into contact with a solid surface in a third medium such as air, a three-phase line is formed between the liquid, gas, and solid. The angle between the unit vector of the surface tension acting on the three-phase line and tangent to the droplet and the surface is described as the contact angle. The contact angle (also known as the wetting angle) is a measure of the wetting of the solid by the liquid. In the case of complete wetting, the liquid spreads completely over the solid and the contact angle is 0°. The wetting properties of a given compound are typically measured at concentrations of 1 - 100×CMC, however, since it is not a concentration-dependent property, the wetting properties can be measured at higher or lower concentrations.

[0215] In one method, an optical contact angle goniometer can be used to measure the contact angle. The device uses a digital camera and software to extract the contact angle by analyzing the profile shape of a sessile droplet on the surface.

[0216] Potential applications of the surface-active compounds of the present disclosure include formulations used as shampoos, conditioners, detergents, spotless rinsing liquids, floor and carpet cleaners, cleaners for removing graffiti, wetting agents for crop protection, adjuvants for crop protection, and wetting agents for aerosol spraying.

[0217] Those skilled in the art will understand that small differences between compounds can result in significantly different surfactant properties, such that different compounds can be used with different substrates in different applications.

[0218] The following non-limiting embodiments are provided to illustrate the different properties of different surfactants. In Table 1 below, the abbreviations of the surfactants are related to their corresponding chemical structures.

[0219] Table 1

[0220]

[0221] Each of the five compounds can effectively act as a surfactant and can be used in wetting agents or foaming agents, dispersants, emulsifiers, detergents, etc.

[0222] Surfactants 1 and 2 are candidates for foaming agents or wetting agents in various surface cleaning and personal care product formulations.

[0223] Surfactant 3 is cationic. These surfactants can be used in the above applications and some other special applications such as surface treatment, such as personal hair care products, and can also be used to generate water-repellent surfaces.

[0224] Surfactant 4 is non-ionic and can be used in shampoos, detergents, hard surface cleaners, and a variety of other surface cleaning formulations.

[0225] Surfactant 5 is zwitterionic. These surfactants can be used as co-surfactants in all of the above applications.

[0226] The amount of the compounds disclosed herein in the formulation can be as low as about 0.001 wt%, about 0.05 wt%, about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 2 wt%, or about 5 wt%, or as high as about 8 wt%, about 10 wt%, about 15 wt%, about 20 wt%, or about 25 wt%, or within any range between any two of the foregoing values. Examples

[0227] Nuclear magnetic resonance (NMR) spectroscopy was carried out on a Bruker 500 MHz spectrometer. The critical micelle concentration (CMC) was determined at 23 °C by the Wilhelmy plate method using a tensiometer (DCAT 11, DataPhysics Instruments GmbH) equipped with a Pt-Ir plate. The dynamic surface tension was measured at 23 °C using a bubble pressure tensiometer (Krüss BP100, Krüss GmbH). The contact angle was measured using an optical contact angle goniometer (OCA 15 Pro, DataPhysics GmbH) equipped with a digital camera.

[0228] Example 1a:

[0229] Synthesis of 6 - (dimethylamino) - N - (3 - (1,1,1,5,5,5 - hexamethyl - 3 - ((trimethylsilyl)oxy)trisiloxan - 3 - yl)propyl)hexanamide (Surfactant 1) and 6 - ((3 - (1,1,1,5,5,5 - hexamethyl - 3 - ((trimethylsilyl)oxy)trisiloxan - 3 - yl)propyl)amino) - N,N - dimethyl - 6 - oxohexan - 1 - aminium salt (Surfactant 2) δ Example 1b: Determination of the Critical Micelle Concentration (CMC) of Surfactant 2

[0230]

[0231] In a 100 mL round-bottom flask equipped with a Dean Stark trap, 6-(dimethylamino)hexanoic acid (2.00 g, 12.56 mmol, 1 equiv) was dissolved in toluene (50 mL), and then 3-aminopropyltris(trimethylsilyloxy)silane (5.48 mL, 13.81 mmol, 1.1 equiv) was added. The reaction vessel was heated and the reactants were refluxed for 24 h until no more water was separated in the Dean Stark tube. The solvent was removed under vacuum to give surfactant 1 as a yellow oil in 94% yield. 1 HNMR (500 MHz, DMSO) Figure 1 : 0.09 (s, 27H), 0.28 - 0.31 (m, 2H), 1.12 - 1.26 (m, 2H), 1.27 - 1.30 (m, 4H), 1.38 - 1.41 (m, 2H), 1.94 (t, J = 7.3 Hz, 2H), 2.00 (s, 6H), 2.06 – 2.03 (m, 2H), 2.89 (dd, J = 12.9, 6.8 Hz, 2H).

[0232] In its neutral form, surfactant 1 is slightly soluble in pure water without the addition of a hydrotropic agent or other surfactants, but upon protonation under slightly acidic conditions, it becomes interfacially active (surfactant 2). This acidic condition can be generated by adding any acid or acidic buffer in the pH range of 4 - 7. Surfactant 2 can also be prepared in a non-aqueous solution, for example, by bubbling gaseous HCl into toluene in the presence of surfactant 1.

[0233] Example 2a:

[0234] Synthesis of 6 - ((3 - (1,1,1,5,5,5 - hexamethyl - 3 - ((trimethylsilyl)oxy)trisiloxan - 3 - yl)propyl)amino) - N,N,N - trimethyl - 6 - oxohexane - 1 - iodide ammonium (Surfactant 3)

[0235] The critical micelle concentration (CMC) of surfactant 2 was tested with chloride counterions and determined to be approximately 2 millimoles. The plateau value of the minimum surface tension achievable with this surfactant is approximately 23 mN / m. Example 2b: is a graph of these results showing surface tension vs concentration.

[0236] Determination of the Physical Properties of Surfactant 3

[0237] Figure 2 Figure 3

[0238]

[0239] In a 100 mL round-bottom flask, surfactant 1 (1.00 g, 2.02 mmol, 1 equiv) was dissolved in acetonitrile (10 mL). Then Na 2 CO 3 (0.26 g, 2.42 mmol, 1.2 equiv) was added and the mixture was stirred for 10 minutes. Methyl iodide (0.377 mL, 6.06 mmol, 3 equiv) was added and the reaction mixture was heated at 40 °C for 24 hours. The cooled reaction mixture was filtered and the solvent was removed in vacuo to give surfactant 3 as a pale yellow solid in quantitative yield. - H NMR(500 MHz, DMSO) δ 0.09 (s, 27H), 0.38 - 0.42 (m, 2H), 1.23 - 1.26 (m, 2H), 1.37 - 1.40 (m, 2H), 1.52 - 1.55 (m, 2H), 1.65 - 1.69 (m, 2H),2.08 (t, J = 7.4 Hz, 2H),2.99 (dd, J = 13, 6.9 Hz, 2H), 3.04 (s, 9H), ), 3.24 – 3.33 (m, 2H).

[0240] The pure product is soluble in water and has surfactant properties. The halogen anion can be obtained directly from the N-alkylation reaction, and other desired counter anions can be obtained by anion exchange.

[0241] Substrate

[0242] Concentration

[0243] The critical micelle concentration (CMC) of surfactant 3 was determined. Based on the variation of surface tension with concentration in water, the CMC was measured to be approximately 1.6 mmol. The plateau value of the minimum surface tension achievable by this surfactant was approximately 20 mN / m, indicating outstanding interfacial activity of this surfactant. These results are plotted as surface tension vs concentration in Teflon as follows.

[0244] The dynamic surface tension of surfactant 3 was determined using a bubble pressure tensiometer that measures the variation of surface tension of the newly created air-water interface with time. 10×CMC A graph showing the results as surface tension vs time is presented and indicates that surfactant 3 completely saturates the interface in less than 500 ms, making it unusually fast in interfacial adsorption.

[0245] In addition to the ability of surfactant 3 to lower interfacial and surface tensions, formulations containing only the surfactant have excellent wetting properties. For example, hydrophobic substrates such as polyethylene and polypropylene exhibit total surface wetting with a contact angle of 0°. On oleophobic and hydrophobic substrates such as Teflon, the measured contact angle was extremely low, at 10.5° (Table 2).

[0246] Table 2

[0247] Polyethylene <![CDATA[CA of surfactant 3( o )]]> 10×CMC <![CDATA[CA of water ( o )]]> Polypropylene 10.5 10×CMC 119 Nylon 0 10×CMC 91.5 Polyethylene Terephthalate 0 10×CMC 93.3 Example 3a: 0 Synthesis of 6 - ((3 - (1,1,1,5,5,5 - hexamethyl - 3 - ((trimethylsilyl)oxy)trisiloxan - 3 - yl)propyl)amino) - N,N - dimethyl - 6 - oxohexane - 1 - amine oxide (Surfactant 4) 50 Example 3b: 0 Determination of the Physical Properties of Surfactant 4 65.3

[0248] Figure 4

[0249] Figure 5 Substrate

[0250]

[0251] In a 100 mL round-bottom flask, surfactant 1 (1.00 g, 2.02 mmol, 1 equivalent) was added to distilled water (80 mL), followed by 50% hydrogen peroxide (1.15 mL, 20.2 mmol, 10 equivalents). The reaction mixture was refluxed for 12 h and then concentrated in vacuo. The residue was washed three times with acetone to obtain surfactant 4 in 99% yield. 11H NMR (500 MHz, DMSO) δ 0.09 (s, 27H), 0.38 - 0.44 (m, 2H), 1.21 - 1.25 (m, 2H), 1.35 - 1.42 (m, 2H), 1.50 - 1.55 (m, 2H), 1.71 - 1.75 (m, 2H), 2.05 - 2.08 (m, 2H), 2.97 - 3.00 (m, 2H), 3.01 (s, 9H), 3.11 – 3.14 (m, 2H).

[0252] Concentration

[0253] Teflon

[0254] The critical micelle concentration (CMC) of surfactant 4 was determined. From the variation of surface tension with concentration in water, the CMC was found to be approximately 0.49 mmol. The plateau value of the minimum surface tension achievable with this surfactant was approximately 20 mN / m, indicating outstanding interfacial activity. These results are plotted as surface tension vs concentration in 10×CMC .

[0255] The dynamic surface tension of surfactant 4 was measured using a bubble pressure tensiometer. Polyethylene A graph showing the results as surface tension vs time is presented and indicates that surfactant 4 completely saturates newly formed air - water interfaces within one second or less, making it very fast in interfacial adsorption.

[0256] In addition to the ability of surfactant 4 to lower interfacial and surface tensions, formulations containing surfactant 4 at concentrations of only 1 - 100×CMC have excellent wetting properties. For example, a solution of surfactant 4 at a concentration of 10×CMC in water shows a contact angle of 0° on hydrophobic substrates such as polyethylene and polypropylene, and a contact angle of 10.6° on oleophobic and hydrophobic substrates such as Teflon. These contact angles are extremely low compared to the contact angles of water on the same substrates (Table 3).

[0257] Table 3

[0258] 10×CMC <![CDATA[CA of surfactant 4( o )]]> Polypropylene <![CDATA[CA of water( o )]]> 10×CMC 10.6 Nylon 119 10×CMC 0 Polyethylene Terephthalate 91.5 10×CMC 0 Example 4a: 93.3 Synthesis of 4 - ((6 - ((3 - (1,1,1,5,5,5 - hexamethyl - 3 - ((trimethylsilyl)oxy)trisiloxan - 3 - yl)propyl)amino) - 6 - oxohexyl)dimethylammonio)butane - 1 - sulfonate (Surfactant 5) 0 Example 4b: 50 Determination of the Physical Properties of Surfactant 5 0 Figure 6 65.3

[0259] Figure 7

[0260] Substrate Concentration )

[0261]

[0262] In a 100 mL round-bottom flask, surfactant 1 (1.00 g, 2.02 mmol, 1 eq) was added to ethyl acetate (EtOAc) (30 mL), followed by the addition of 1,2-butanesultone (0.27 mL, 2.2 mmol, 1.1 eq). The reaction mixture was refluxed for 12 h, and then the solvent was removed. The resulting white waxy solid was washed with acetone to obtain surfactant 5 in 50% yield. 1 H NMR (500 MHz, DMSO) δ 0.10 (s, 27H), 0.38 - 0.46 (m, 2H), 1.23 - 1.27(m, 2H), 1.37 - 1.68 (m, 10H), 1.73 - 1.78 (m, 2H), 2.45 - 2.48 (m, 2H), 2.97 - 3.01(m, 8H), 3.18 - 3.21 (m, 2H), 3.23 - 3.27 (m, 2H).

[0263] Teflon

[0264] 10×CMC

[0265] The critical micelle concentration (CMC) of surfactant 5 was measured. Based on the variation of surface tension with concentration in water, the CMC was determined to be approximately 0.39 mmol. The plateau value of the minimum surface tension achievable by this surfactant was approximately 21 mN / m, indicating that the surfactant has outstanding interfacial activity. These results are plotted as surface tension vs concentration in Polyethylene .

[0266] The dynamic surface tension of surfactant 5 was determined using a bubble pressure tensiometer. 10×CMC A graph showing the results as surface tension vs time is presented and indicates that surfactant 5 completely saturates the newly formed air-water interface within one second or less, making it very fast in interfacial adsorption.

[0267] Finally, a solution of surfactant 5 at a concentration of 10×CMC in water exhibited a contact angle of 0° on hydrophobic substrates such as polyethylene and polypropylene, and a contact angle of 10.2° on oil-repellent and hydrophobic substrates such as Teflon. These contact angles are extremely low compared to the contact angles of water on the same substrates (Table 4).

[0268] Table 4

[0269] Polypropylene <![CDATA[CA of surfactant 5( o )]]> 10×CMC <![CDATA[CA of water( o )]]> Polyethylene Terephthalate 10.2 10×CMC 119 Nylon 0 10×CMC 91.5 Polyethylene - HD 0 10×CMC 93.3 Example 5: 0 Formulation for Prefabricating Agent 65.3 Component 0 Function 50 Weight % 0 Surfactant 93.6

[0270] Wetting Agent

[0271] Oxalic Acid

[0272] In this embodiment, a formulation for a pre-texturing agent is provided. The components of the formulation are shown in Table 5 below.

[0273] Table 5

[0274] Cleaning Agent Water Example 6: Formulation for Etching Agent Component 0.01-30 Function Weight % 0.1-30 Hydrofluoric Acid 60-99.89

[0275] Etching Agent

[0276] Surfactant

[0277] In this embodiment, a formulation used as an etchant is provided. The formulation is shown in Table 6 below.

[0278] Table 6

[0279] Emulsifying Agent Nitric Acid Oxidizing Agent Oxalic Acid Complexing Agent 0.1-5 Water Example 7: 0.0001-1 Formulation for Photoresist Stripper Component 0.01-0.5 ​ ​ 0.1-10 ​ 83.5-99.9

[0280] ​

[0281] ​

[0282] In this embodiment, a formulation used as a photoresist stripper is provided. The formulation is shown in Table 7 below.

[0283] Table 7

[0284] ​ Function Weight % Alkanolamine Stripping agent 5-15 Sulfone Solvent 35-55 Glycol ether Solvent 35-55 Surfactant Detergent 0.05-0.5

[0285] Aspect

[0286] Aspect 1 is a formulation for a pre-texturing agent, comprising: at least one surfactant of formula I,

[0287]

[0288] wherein R 1 and R 2 may be the same or different and each comprises at least one group selected from C 1 -C 6 alkyl groups, and optionally the C 1 -C 6 alkyl group may contain one or more oxygen, nitrogen or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain may optionally be substituted by one or more substituents selected from hydroxy, amino, amido, sulfonyl, sulfonate, carbonyl, carboxy and carboxylate; n is an integer from 1 to 12; the terminal nitrogen is optionally further substituted by R 3 wherein R 3 is selected from hydrogen, oxygen, hydroxy and C 1 -C 6An alkyl group; an optional counterion associated with the compound, which, if present, is selected from chloride, bromide, and iodide ions; and at least one of one or more solvents and one or more antifoaming agents.

[0289] Aspect 2 is a formulation for a pre-texturing agent, comprising: at least one surfactant of formula I,

[0290]

[0291] wherein R 1 and R 2 may be the same or different and comprise at least one group selected from C 1 -C 6 alkyl groups, optionally the C 1 -C 6 alkyl group may contain one or more oxygen, nitrogen, or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain may optionally be substituted by one or more substituents selected from hydroxyl, amino, amide, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1 to 12; the terminal nitrogen is optionally further substituted by R 3 wherein R 3 is selected from hydrogen, oxygen, hydroxyl, and C 1 -C 6 alkyl groups; an optional counterion associated with the compound, which, if present, is selected from chloride, bromide, and iodide ions; and one or more solvents.

[0292] Aspect 3 is the formulation of aspect 1 or aspect 2, further comprising one or more acids.

[0293] Aspect 4 is the formulation of any one of aspects 1 - 3, further comprising one or more bases.

[0294] Aspect 5 is the formulation of any one of aspects 1 - 4, further comprising one or more chelating agents.

[0295] Aspect 6 is a formulation for a pre-texturing agent, comprising: at least one surfactant of formula I,

[0296]

[0297] wherein R 1 and R 2 may be the same or different and comprise at least one group selected from C 1 -C 6 alkyl groups, optionally the C 1 -C 6The alkyl group may contain one or more oxygen, nitrogen or sulfur atoms or a group containing at least one of these atoms, and the alkyl chain may optionally be substituted by one or more substituents selected from hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl and carboxylate; n is an integer from 1 to 12; the terminal nitrogen is optionally further substituted by R 3 substituted, where R 3 is selected from hydrogen, oxygen, hydroxyl and C 1 -C 6 alkyl; an optional counterion associated with the compound, which if present is selected from chloride, bromide and iodide; and one or more defoamers.

[0298] Aspect 7 is a formulation according to aspect 6, further comprising one or more acids.

[0299] Aspect 8 is a formulation according to aspect 6 or aspect 7, further comprising one or more bases.

[0300] Aspect 9 is a formulation according to any one of aspects 6-8, further comprising one or more chelating agents.

[0301] Aspect 10 is a formulation according to any one of aspects 6-9, further comprising one or more solvents.

[0302] Aspect 11 is a formulation for an etchant, comprising: at least one surfactant of formula I,

[0303]

[0304] where R 1 and R 2 may be the same or different and contain at least one group selected from C 1 -C 6 alkyl, optionally the C 1 -C 6 alkyl group may contain one or more oxygen, nitrogen or sulfur atoms or a group containing at least one of these atoms, and the alkyl chain may optionally be substituted by one or more substituents selected from hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl and carboxylate; n is an integer from 1 to 12; the terminal nitrogen is optionally further substituted by R 3 substituted, where R 3 is selected from hydrogen, oxygen, hydroxyl and C 1 -C 6 alkyl; an optional counterion associated with the compound, which if present is selected from chloride, bromide and iodide; and hydrofluoric acid (HF).

[0305] Aspect 12 is a formulation according to aspect 11, further comprising one or more oxidizing agents.

[0306] Aspect 13 is a formulation of Aspect 11 or Aspect 12, further comprising one or more complexing agents.

[0307] Aspect 14 is a formulation for a photoresist stripping formulation, comprising: at least one surfactant of Formula I,

[0308]

[0309] wherein R 1 and R 2 may be the same or different and comprise at least one group selected from C 1 -C 6 alkyl, optionally the C 1 -C 6 alkyl may contain one or more oxygen, nitrogen or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain may optionally be substituted by one or more substituents selected from hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl and carboxylate; n is an integer from 1 to 12; the terminal nitrogen is optionally further substituted by R 3 wherein R 3 is selected from hydrogen, oxygen, hydroxyl and C 1 -C 6 alkyl; an optional counterion associated with the compound, which if present is selected from chloride, bromide and iodide; and an alkanolamine.

[0310] Aspect 15 is a formulation of Aspect 14, further comprising sulfoxide.

[0311] Aspect 16 is a formulation of Aspect 15, further comprising sulfone.

[0312] Aspect 17 is a formulation of any one of Aspects 14 - 16, further comprising a glycol ether.

Claims

1. A formulation for a pre-texturing agent, comprising: At least one surfactant of formula I, wherein R 1 and R 2 may be the same or different and each contains at least one group selected from C 1 -C 6 alkyl groups, and optionally the C 1 -C 6 alkyl group may contain one or more oxygen, nitrogen or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain may optionally be substituted by one or more substituents selected from hydroxy, amino, amido, sulfonyl, sulfonate, carbonyl, carboxy and carboxylate; n is an integer from 1 to 12; The terminal nitrogen is optionally further substituted by R 3 wherein R 3 is selected from hydrogen, oxygen, hydroxyl, and C 1 -C 6 alkyl; Optional counterions associated with the surfactant, which if present are selected from chloride, bromide, and iodide ions; and At least one of one or more solvents and one or more defoamers.

2. The formulation according to claim 1, further comprising one or more acids.

3. The formulation according to claim 1, further comprising one or more bases.

4. The formulation according to claim 1, further comprising one or more chelating agents.

5. A formulation for an etchant, comprising: At least one surfactant of formula I, wherein R 1 and R 2 may be the same or different and each contains at least one group selected from C 1 -C 6 alkyl groups, and optionally the C 1 -C 6 alkyl group may contain one or more oxygen, nitrogen or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain may optionally be substituted by one or more substituents selected from hydroxy, amino, amido, sulfonyl, sulfonate, carbonyl, carboxy and carboxylate; n is an integer from 1 to 12; The terminal nitrogen is optionally further substituted by R 3 wherein R 3 is selected from hydrogen, oxygen, hydroxyl and C 1 -C 6 alkyl; Optional counterions associated with the surfactant, which if present are selected from chloride, bromide, and iodide ions; and Hydrofluoric acid (HF).

6. The formulation according to claim 5, further comprising one or more oxidizing agents.

7. The formulation according to claim 5, further comprising one or more complexing agents.

8. A formulation for a photoresist stripping formulation, comprising: At least one surfactant of formula I, wherein R 1 and R 2 may be the same or different and each contains at least one group selected from C 1 -C 6 alkyl groups, and optionally the C 1 -C 6 alkyl group may contain one or more oxygen, nitrogen or sulfur atoms or groups containing at least one of these atoms, and the alkyl chain may optionally be substituted by one or more substituents selected from hydroxy, amino, amido, sulfonyl, sulfonate, carbonyl, carboxy and carboxylate; n is an integer from 1 to 12; The terminal nitrogen is optionally further substituted by R 3 wherein R 3 is selected from hydrogen, oxygen, hydroxyl, and C 1 -C 6 alkyl; Optional counterions associated with the surfactant, which if present are selected from chloride, bromide, and iodide ions; and Alkanolamine.

9. The formulation according to claim 8, further comprising sulfoxide.

10. The formulation according to claim 8, further comprising sulfone.

11. The formulation according to claim 8, further comprising glycol ether.

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