KR20070090199A - Selective removal chemistries for semiconductor applications, methods of production and uses thereof - Google Patents

Abstract

Removal chemistry solutions are described herein that include at least one low H2O content fluorine-based constituent and at least one solvent or solvent mixture. Removal chemistry solutions also include: hydrogen fluoride gas, and at least one solvent or solvent mixture. Methods are described herein for producing removal chemistry solutions that include providing at least one gaseous low H2O content fluorine-based constituent, providing at least one solvent or solvent mixture, and bubbling the at least one low H2O content fluorine-based constituent into the at least one solvent or solvent mixture to form the removal chemistry solution. Methods for producing removal chemistry solutions are also described that include: providing at least one low H2O content fluorine-based constituent, providing at least one solvent or solvent mixture, and blending the at least one low H2O content fluorine-based constituent into the at least one solvent or solvent mixture to form the removal chemistry solution. Additional methods of forming a removal chemistry solution include: providing at least one gaseous anhydrous fluorine-based constituent, providing at least one solvent or solvent mixture, and bubbling the at least one anhydrous fluorine-based constituent into the at least one solvent or solvent mixture to form the solution. Also, methods of forming a removal chemistry solution, as described herein include: providing hydrogen fluoride gas, providing at least one solvent or solvent mixture, and bubbling the hydrogen fluoride gas into the at least one solvent or solvent mixture to form the solution.

Description

Selective removal chemicals for semiconductor applications and methods of producing and using them {SELECTIVE REMOVAL CHEMISTRIES FOR SEMICONDUCTOR APPLICATIONS, METHODS OF PRODUCTION AND USES THEREOF}

The present invention relates to selective removal chemicals for semiconductors, electronics and related fields.

In order to meet the requirements for faster performance, the characteristic dimensions of integrated circuit devices continue to shrink. The manufacture of devices with smaller sizes introduces new challenges in many of the processes commonly used in semiconductor fabrication. Dual damascene patterning and via first trench last (VFTL) copper dual damascene patterning through low dielectric constant (less than about 3) or super dielectric constant (less than about 2) materials Is one of. Two examples of dual damascene patterning and structure are described in US Patent Publications 20040152296 and 20040150012, assigned to Texas Instruments. In the fabrication of microelectromechanical systems (MEMS) devices, each continuous or patterned layer, even if left intact, can cause harmful residues that can cause destruction and ultimate failure of any component comprising the layer. It includes. Thus, it is necessary to effectively and completely remove harmful residues generated during the manufacture of semiconductors, MEMS and other electronic devices. In addition, if more than one layer needs to be etched, the etch pattern should be precise and the removal chemical solution used should be selective to the layer being etched. 1A-1C of the prior art show ash residues in via clean (prior art FIG. 1A), trench clean (prior art FIG. 1B) and etch stop clean (prior art FIG. 1C) applications. have. In the prior art, FIG. 1A shows a layered material 100 that includes a polymer sidewall 110 and an ash residue 120. Prior Art FIG. 1B shows a layer forming material 200 comprising a polymer sidewall 21, ash residue 200, via fence 230 and via fill 240. As shown in FIG. Via fence 230 and / or via fill 240 may or may not be present depending on the type of integration. Prior Art FIG. 1C illustrates a layered material 300 comprising a polymer sidewall 310, ash residue 320, via fence 330 and CuO _x and / or CuF _x residue 350. Prior art FIGS. 2A-2C show etch residues including sidewall polymers, antireflective coatings, and other residues in via clean (FIG. 2A), trench clean (FIG. 2B), and etch stop clean (FIG. 2C). Prior Art FIG. 2A illustrates a layered material 400 that includes a polymer sidewall 410, a photoresist layer 420, and an antireflective coating layer 430. Prior Art FIG. 2B illustrates a layer comprising a polymer sidewall 510, an antireflective coating 520, a via fill 525, a via fence 530 and a photoresist layer 540 that may or may not be present depending on the type of integration. The formation material 500 is shown. Via fence 230 and / or via fill 240 may or may not be present depending on the type of integration. Prior Art FIG. 2C shows a layered material 600 that includes a polymer sidewall 610, a via fence 630 and CuO _x and / or CuF _x residue 650. Prior Art FIG. 3 shows a layer forming material 700 comprising UV exposed and developed photoresist 750, BARC (Bottom Anti-Reflective Coating) 710, where it is organic or inorganic. Possible BARCs should be removed without affecting the critical dimensions.

Techniques for removing bulk residues by selective chemical etching and in some cases by selective chemical cleaning are important steps in the manufacture of many semiconductor and electronic devices, including the devices described above. The purpose of successful selective etching and selective cleaning steps is to remove residues without removing or damaging the required parts. In some cases, "removal" of unwanted materials or residues reacts these unwanted materials with solutions or compounds to convert these unwanted materials into materials that do not have a harmful or negative effect on electronic or semiconductor products or components. Includes sikim.

Various semiconductor and electronics materials include different chemicals that must be considered when proceeding with the removal chemistry, and in some cases these semiconductor and electronics materials are modified to increase removal selectivity, such as etching selectivity or cleaning selectivity. do. If the chemistry of the removal layer cannot be modified to improve the removal selectivity, the removal chemical solution should be developed to react specifically with the removal chemical. However, as noted above, because in many instances the chemical to remove the removal layer or layers will also remove or weaken the surrounding or adjacent layers, the chemical properties of the removal material must be evaluated and considered, as well as the peripheral and / or Or the chemical properties of adjacent layers should be considered.

Some purposes to be treated in the selective removal chemical solution are: a) the solution composition must be adjustable to be a selective etching solution and / or a selective cleaning solution; b) the solution must be effective in a low H ₂ O content environment or anhydrous environment; c) be capable of selectively removing harmful substances and compositions from the surface without removing layers and substances that are critical for product success; d) Efficiently etch and / or clean at the center of the wiper or surface and at the edge of the wiper or surface.

EP 887,323 teaches an etching and cleaning solution comprising hydrofluoric acid and ammonium fluoride in propylene carbonate. These etching solutions are specifically designed to etch silicate glass and silicon dioxide. Based on the disclosed chemical composition, this composition of the components appears to be selective for silicate glass and silicon dioxide. JP 9235619 and US Pat. No. 5,476,816 use similar solutions replacing propylene carbonate with ethylene glycol to remove the insulating coating. JP 10189722 uses a solution similar to JP 9235619 except that water is added and the solution is used to clean the oxides from the surface. JP 8222628 and US Pat. No. 3,979,241 use etching solutions of ammonium fluoride and ethylene glycol to remove insulating coatings, and JP 1125831 combines these materials in different concentrations to remove silicon-based compounds. I'm using. US 6,090,721 and 5,939,336 combine ammonium fluoride, propylene glycol and water to etch metal containing etch residues from silicon containing substrates. US Pat. No. 5,478,436 uses ammonium fluoride and ethylene glycol to remove metal-based contaminants from the silicon surface. Many of these solutions can be adjusted to be chemical solutions for selective removal; Can be effective in low H ₂ O content or in anhydrous environments; Efficiently etched and / or cleaned at the center of the wiper or surface and at the edge of the wiper or surface, but without substantially etching and / or removing the silicon-based compounds and / or metal-based layers and compounds required of these compounds There is no compound that can selectively remove harmful substances from the surface.

Therefore, there is a need to form a chemical solution for selective removal that can meet one or more of the following requirements: to any sacrificial layer and / or modified sacrificial layer to enhance the production of layered materials, electronic components and semiconductor components. The optional solution can be adjusted to a) be an optional etching solution and / or optional cleaning solution; b) can be effective in both aqueous and non-aqueous environments; c) may contain one or more low H ₂ O content and / or anhydrous components; d) can be anhydrous or have a low H ₂ O content; e) can be effectively etched and / or cleaned at the center of the wiper and at the edge of the wiper, and at the same time the polymer composition from the surface without significantly or significantly etching the silicon-based compound or the metal-based layer and compound Can be selectively etched; f) be able to effectively etch and / or clean surfaces.

Summary of the Invention

Described herein are removal chemical solutions comprising at least one low H ₂ O content fluorine-based component and at least one solvent or solvent mixture. The removal chemical solution also includes a hydrogen fluoride gas, one or more solvents or a mixture of solvents.

Providing one or more gaseous low H ₂ O content fluorine-based constructs, providing one or more solvents or solvent mixtures, and injecting one or more low H ₂ O content fluorine-based constructs into one or more solvents or solvent mixtures for removal Described herein is a method of producing a removal chemical solution comprising forming a chemical solution.

In addition, one or more low H ₂ O content fluorine-based constructs are provided, one or more solvents or solvent mixtures are provided, and the one or more low H ₂ O content fluorine-based constructs is formulated into one or more solvents or solvent mixtures for removal. A method for producing a removal chemical solution has been described, including forming a chemical solution.

Additional methods of forming the removal chemical solution provide one or more gaseous anhydrous fluorine-based constituents, provide one or more solvents or solvent mixtures, and inject one or more anhydrous fluorine-based constituents into one or more solvents or solvent mixtures Thereby forming a solution. In addition, a method of forming a removal chemical solution as described herein provides a hydrogen fluoride gas, provides one or more solvents or solvent mixtures, and injects the hydrogen fluoride gas into one or more solvents or solvent mixtures to form a solution. It includes.

Brief description of the drawings

Prior Art FIGS. 1A-1C show ash residues in via clean (FIG. 1A), trench clean (FIG. 1B) and etch clean (FIG. 1C) applications.

Prior Art FIGS. 2A-2C show ash residues in via clean (FIG. 2A), trench clean (FIG. 2B) and etch stop clean (FIG. 2C) applications.

Prior Art FIG. 3 shows a layer forming material comprising an organic BARC (bottom antireflective coating) to be removed without affecting critical dimensions.

details

To achieve the above object, removal chemical solutions have been developed that meet one or more of the following requirements: selective to any sacrificial layer and / or modified sacrificial layer to enhance the production of layered materials, electronic components and semiconductor components. The solution may be adjusted to be a) an optional etching solution and / or an optional cleaning solution; b) can be effective in both aqueous and non-aqueous environments; c) may contain one or more low H ₂ O content and / or anhydrous components; d) can be anhydrous or have a low H ₂ O content; e) can be effectively etched and / or cleaned at the center of the wiper and at the edge of the wiper, while at the same time polymer from the surface without significantly or significantly etching the silicon-based compound or the metal-based layer and compound The composition can be selectively etched; f) be able to effectively etch and / or clean surfaces.

The removal chemical solution described herein includes one or more low H ₂ O content fluorine-based constructs, and one or more solvents or solvent mixtures. As described above, the removal chemical solution may be used as an optional etching solution and / or an optional cleaning solution, depending on the application and composition used.

Methods of forming and using these removal chemical solutions are also contemplated and described herein. Such methods include providing a composition of a removal chemical formulation, combining the composition to form a formulation, and applying the formulation to a surface or substrate. In some embodiments, the formulation may be produced in situ (on the direct surface) or formed just prior to application to the surface. In particular, one or more gaseous low H ₂ O content fluorine-based constructs are provided, one or more solvents or solvent mixtures are provided, and one or more low H ₂ O content fluorine-based constructs is injected into one or more solvents or solvent mixtures Described herein are methods for producing a removal chemical solution, including forming a removal chemical solution.

The removal chemical solution may be in an aqueous or non-aqueous environment. As used herein, the term "environment" refers to an environment in a solution containing one or more low H ₂ O content fluorine-based constituents and one or more solvents or solvent mixtures. The term "environment" does not mean the environment surrounding the solution, such as the environment of a laboratory or building. For example, a nonaqueous environment means that the solution is nonaqueous and does not represent the total humidity level in the air of a laboratory or building.

The removal chemical solution under consideration includes one or more low H ₂ O content fluorine-based constructs. The expression “low H ₂ O content” as used herein means that the construct comprises less than about 10 volume percent water. In some embodiments, the one or more low H ₂ O content fluorine-based constructs comprises less than about 5 volume percent water. In other embodiments, the one or more low H ₂ O content fluorine-based constructs comprises less than about 2.5 volume percent water. In yet another embodiment, the one or more low H ₂ O content fluorine-based constructs comprises less than about 1 volume percent water. In some embodiments, the one or more low H ₂ O content fluorine-based constituents comprises less than about 0.5 volume percent water. In other embodiments, the at least one low H ₂ O content fluorine-based construct is an anhydrous construct.

These components are low H ₂ O content of the fluorine-Any suitable, which method comprises one of the substrate components more solvents or formulated in a solvent mixture-based composition inject gas in at least one solvent or solvent mixture or a lower H ₂ O content of the fluorine-containing It can be added by the method. In one contemplated embodiment, anhydrous hydrogen fluoride gas is injected into the required solvent or mixture of solvents. The low H ₂ O content and / or introduction of the anhydrous fluorine-based constituents into one or more solvents or solvent mixtures allows the user to control the water content of the final etch and / or cleaning solution and is also excellent for semiconductor and electronic component applications. Provide etching and / or cleaning properties.

The low H ₂ O content fluorine-based construct may be present in the solution in an amount of less than about 70% by weight. In some embodiments, the low H ₂ O content fluorine-based construct is present in the solution in an amount of about 0.005% to about 70% by weight. In other embodiments, the low H ₂ O content fluorine-based construct is present in the solution in an amount from about 0.005% to about 45% by weight. In other embodiments, the low H ₂ O content fluorine-based construct is present in the solution in an amount from about 0.005% to about 20% by weight. In some embodiments, the low H ₂ O content fluorine-based construct is present in the solution in an amount of about 0.005% to about 5% by weight.

The low H ₂ O content fluorine-based constituents may be any suitable fluorine source such as hydrogen fluoride, ammonium fluoride, tetramethylammonium fluoride, tetrabutylammonium fluoride, tetraethylammonium fluoride, benzyltrimethylammonium fluoride, pyridine hydrogen fluoride , Ammonium bifluoride or combinations thereof.

Low H ₂ O content fluorine-containing construct is added to one or more solvents or solvent mixtures. Solvents contemplated include any pure organic molecule or mixtures thereof that may be volatilized at a predetermined temperature, such as a critical temperature, or may facilitate the design goals or requirements described above. The solvent may also include any pure polar and nonpolar compounds or mixtures thereof. As used herein, the term “pure” means a component having a constant composition. Pure water, for example, consists of H ₂ O alone. As used herein, the term "mixture" means a component that is not pure, including saline. As used herein, the term "polar" refers to a property of a molecule or compound that results in unequal charge, partial charge, or spontaneous charge distribution at or along a point of the molecule or compound. As used herein, the term "non-polar" means a characteristic of a molecule or compound that produces the same charge, partial charge or spontaneous charge distribution at or along a point of the molecule or compound. Those skilled in the chemical and etching solutions art will appreciate that the solvent is nonpolar and the solvent is inherently polar.

Solvents or solvent mixtures (including two or more solvents) include solvents considered to be hydrocarbon-based solvents. Hydrocarbon solvents are solvents comprising carbon and hydrogen. Most hydrocarbon solvents are nonpolar; It should be understood that there are some hydrocarbon solvents that can be considered polar. Hydrocarbons are generally classified into three classes: aliphatic, cyclic, and aromatic. Aliphatic hydrocarbon solvents may include straight chain compounds and compounds that are branched and possibly crosslinked, but aliphatic hydrocarbons do not consider cyclic hydrocarbons. Cyclic hydrocarbon solvents are solvents containing three or more carbon atoms arranged in a ring structure of properties similar to aliphatic hydrocarbons. Aromatic hydrocarbon solvents are solvents which generally comprise three or more unsaturated bonds having a single ring or multiple rings bonded by a common bond and / or multiple rings fused together. Hydrocarbon solvents contemplated are toluene, xylene, p-xylene, m-xylene, mesitylene, solvent naphtha H, solvent naphtha A, alkanes such as pentane, hexane, isohexane, heptane, nonane, octane, dodecane, 2- Methylbutane, hexadecane, tridecane, pentadecane, cyclopentane, 2,2,4-trimethylpentane, petroleum ether, halogenated hydrocarbons such as chlorinated hydrocarbons, nitrated hydrocarbons, benzene, 1,2-dimethylbenzene , 1,2,4-trimethylbenzene, mineral spirits, kerosine, isobutylbenzene, methylnaphthalene, ethyltoluene, ligroine. Particularly contemplated solvents include, but are not limited to, pentane, hexane, heptane, cyclohexane, benzene, toluene, xylene and mixtures or combinations thereof.

The solvent or solvent mixture may include solvents that are not considered part of the hydrocarbon solvent compound system, such as ketones such as acetone, diethyl ketone, methyl ethyl ketone and the like, alcohols, esters, ethers and amines. Other contemplated solvents include propylene carbonate, butylene carbonate, ethylene carbonate, gamma-butyrolacetone, propylene glycol, ethyl lactate, propylene glycol monomethyl ether acetate or combinations thereof. In other contemplated embodiments, the solvent or solvent mixture may comprise a combination of any of the solvents mentioned herein.

The one or more solvents or solvent mixtures may be solvents containing nitrogen, phosphorus, sulfur atoms or combinations thereof such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, pyridine or combinations thereof Can be. Etching and cleaning solutions contemplated in the present invention may utilize miscible solvent constituents.

The solvent and solvent mixture may be present in the solution in an amount of less than about 99.5 weight percent. In some embodiments, the solvent or solvent mixture may be present in the solution in an amount of about 30% to about 99.5% by weight.

The solvent used herein includes any suitable impurity, such as less than about 1 ppm, less than about 100 ppb, less than about 10 ppb, less than about 1 ppb, less than about 100 ppt, less than about 10 ppt, and in some cases less than about 1 ppt. can do. These solvents may be purchased with a purity that is suitable for use in the application contemplated, or further purified to remove additional impurities and reach less than about 10 ppb, less than about 1 ppb, less than about 100 ppt, or more preferably in the field of etching and cleaning. It may be required to lower it to the level at which it will be done.

As noted above, contemplated methods for producing the removal chemical solution provide one or more gaseous low H ₂ O content fluorine-based constructs, provide one or more solvents or solvent mixtures, and one or more low H ₂ O Content Injecting a fluorine-based constituent into one or more solvents or solvent mixtures to form a removal chemical solution. Other contemplated methods provide one or more low H ₂ O content fluorine-based constructs, provide one or more solvents or solvent mixtures, and incorporate one or more low H ₂ O content fluorine-based constructs into one or more solvents or solvent mixtures. Formulating into a chemical solution for removal.

One or more low H ₂ O content fluorine-based compositions, one or more solvents or solvent mixtures, and / or other ingredients / additives referred to herein include a) one or more low H ₂ O content fluorine-based compositions, one or more Purchase at least a portion of the solvent or solvent mixture and / or any other component / additive from the supplier; b) preparing at least a portion of one or more low H ₂ O content fluorine-based constituents, one or more solvents or solvent mixtures and / or any other constituents / additives referred to herein using chemicals provided by another source or Produce; c) preparing or producing at least a portion of the one or more low H ₂ O content fluorine-based constituents, one or more solvents or solvent mixtures and / or any other constituents / additives mentioned above using the chemicals produced or supplied. It may be provided by any suitable method including.

Once the construct is provided, one or more low H ₂ O content fluorine-based constructs are added to one or more solvents or solvent mixtures to form a removal chemical solution. In one contemplated embodiment, HF _(g) is injected into one or more solvents or solvent mixtures until the desired wt% concentration is achieved, which _is the saturation point of HF _{(g) in} the solvent (s). It may include. Alternatively, hydrogen fluoride gas may be injected into the first solvent, followed by other solvents or solvent mixtures may be dissolved in the first solvent after HF _(g) addition.

Additional components may be added to one or more solvents or solvent mixtures, one or more low H ₂ O content fluorine-based constituents and / or the initial resulting removal chemical solution. For example, it may be desirable to dissolve into a solvent component that is a nitrogen-containing species that includes a chelator or NH ₃ . Some of these components are solids, such as amine chelators (eg, hexamethylenetetramine, EDTA) at ambient conditions, and with these components, unique amine-HF adducts are formed during anhydrous hydrogen fluoride gas addition. Water may also be a preferred additional component in the solution under consideration. As an additional component, it is contemplated that water is present in the solution described herein in a weight ratio to hydrogen fluoride of less than 9:10.

Chelating agents such as organic acids (acetic acid, citric acid, oxalic acid, tartaric acid, malic acid, maleic acid, lactic acid), amines (hexamethylenetetramine, triethanolamine, nitrilotriacetic acid, tris (2-pyridylmethyl) amine, EDTA), Phosphonates such as diamyl amylphosphonate, bis (2-chloroethyl) methyl phosphonate, dibutyl butylphosphonate, diethyl benzylphosphonate, nitrilotris (methylene) triphosphonic acid, hydride Hydroxyethylidenediphosphonic acid, sulfonic acids such as 3- (N-tris [hydroxymethyl] methylamine) -2-hydroxypropanesulfonic acid, 3 ([1,1-dimethyl-2-hydroxyethyl ) Amine] -2-hydroxypropanesulfonic acid or combinations thereof may also be added to one or more solvents or solvent mixtures, one or more low H ₂ O content fluorine-based constituents and / or the initial resulting removal chemical solution. have. The chelator is dissolved directly in the first solvent or solvent mixture before or after the addition of a low H ₂ O content fluorine-based constituent (eg HF (g)), or the chelator has low solubility in the first solvent or solvent mixture. If so, it may first be dissolved in a suitable co-solvent before addition to the first solvent or solvent mixture. In some embodiments, the chelating agent includes a metal containing chelating agent. As contemplated herein, one or more chelating agents may be present in the solution in an amount of less than about 20% by weight. In some embodiments, one or more chelating agents may be present in the solution in an amount from about 0.001% to about 20% by weight.

Oxidizing agents such as hydrogen peroxide (aqueous), ozone (injected), urea hydrogen peroxide, benzoyl peroxide, peroxyacetic acid (and halogenated peroxyacetic acid), peroxybenzoic acid, and other organic peroxides are also one or more solvents or solvents. To the mixture, one or more low H ₂ O content fluorine-based constituents and / or the initial resulting removal chemical solution. The oxidant is dissolved directly in the first solvent or solvent mixture before or after the addition of a low H ₂ O content fluorine-based constituent (eg, HF (g)), or if the oxidant has low solubility in the first solvent or solvent mixture. It may first be dissolved in a suitable co-solvent prior to addition to one solvent or solvent mixture. It is contemplated that some of the oxidants may be anhydrous. As contemplated herein, one or more oxidants may be present in the solution in an amount of less than about 20% by weight. In some embodiments, one or more oxidants may be present in the solution in an amount from about 0.001% to about 20% by weight.

Surfactants may be added to one or more solvents or solvent mixtures, one or more low H ₂ O content fluorine-based constituents, and / or initially generated removal chemical solutions to lower the surface tension. As used herein, the term “surfactant” refers to any compound that reduces the surface tension when dissolved in water or a water solution, reduces the interfacial tension between two liquids, or reduces the interfacial tension between a liquid and a solid. it means. Surfactants contemplated may include one or more anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants or combinations thereof. The surfactant is dissolved directly in the first solvent or solvent mixture before or after the addition of a low H ₂ O content fluorine-based constituent (eg HF (g)), or the surfactant has low solubility in the first solvent or solvent mixture. If so, it may first be dissolved in a suitable co-solvent before addition to the first solvent or solvent mixture. Surfactants contemplated are sulfonates such as dodecylbenzene sulfonate, tetrapropylenebenzene sulfonate, dodecylbenzene sulfonate, fluorinated surfactants such as Fluorad FC-93, and L-18691 (3M) Fluorinated nonionic surfactants such as FC-4430 (3M), FC-4432 (3M), and L-18242 (3M), quaternary amines such as dodecyltrimethylammonium bromide or cetyltrimethylammonium bromide, alkyl phenoxy Polyethylene oxide alcohols, alkyl phenoxy polyglycidol, acetyllinic alcohols, polyglycol ethers such as Tergitol TMN-6 (Dow) and Tergitol minifoam 2x (Dow), polyoxy Ethylene fatty ethers such as Brij-30 (Aldrich), Brij-35 (Aldrich), Brij-58 (Aldrich), Brij-72 (Aldrich), Brij-76 (Aldrich), Brij-78 (Aldrich), Brij- 98 (Aldrich), and Brij-700 (Aldrich), Betaine (betaine), Sulfobetaine, such as, It may include a core not shown propyl betaine, and synthetic phospholipids, e.g., di-octanoyl phosphatidyl choline and lecithin, and combinations thereof. As contemplated herein, one or more surfactants may be present in the solution in an amount of about 5% by weight. In some embodiments, one or more surfactants may be present in the solution in an amount from about 0.001% to about 5% by weight.

Additional low H ₂ O content fluorine sources such as ammonium fluoride, hydrogen fluoride, tetramethylammonium fluoride, tetrabutylammonium fluoride, tetraethylammonium fluoride, benzyltrimethylammonium fluoride, pyridine hydrogen fluoride, ammonium bifluoride or combinations thereof Ingredients capable of providing may also be added to one or more solvents or solvent mixtures, one or more low H ₂ O content fluorine-based constituents, and / or initially generated removal chemical solutions. Additional sources of fluoride are dissolved directly in the first solvent or solvent mixture before or after the addition of a low H ₂ O content fluorine-based constituent (eg HF (g)), or the surfactant is low in the first solvent or solvent mixture. If solubilized, it may first be dissolved in a suitable co-solvent prior to addition to the first solvent or solvent mixture. As contemplated herein, one or more H ₂ O content fluoride sources may be present in the solution in an amount of less than about 20% by weight. In some embodiments, one or more anhydrous fluoride sources may be present in the solution in an amount from about 0.001% to about 20% by weight.

As noted above, if one or more low H ₂ O content fluorine-based constituents and one or more solvent or solvent mixture components are provided, they are combined to form a solution, where the solution constituents comprise any adjacent and / or corresponding layers. For example, a concentration suitable for etching and / or cleaning of the sacrificial layer, the changed sacrificial layer, and / or a combination pattern of both from the surface without significantly reacting with the dielectric layer, the hard mask layer, the metal layer, and the like. Although the removal chemical solution contemplated by the present invention is conventionally formulated for a particular application, the disclosures described herein, including the stated purpose, are to those skilled in the art of etching solutions for the electronics and semiconductor fields. If understood, it is contemplated that conventional blending processes do not require excessive experimentation.

The removal chemical solution may be applied to the semiconductor wiper (which may be before or after printing) after photoresist deposition for wiper regeneration purposes, or may be a single wiper or batch process tool for a period between about 15 seconds and about 90 minutes. After etching / plasma treatment (during post-etching / after ash residue removal). The processing temperature may be about 20 ° C to about 80 ° C. The wiper may be once immersed in the solution and fixed or immersed several times for a certain time, may be cleaned by the solution, or the solution may be applied in the form of a methodical pattern, or may be masked by the solution and then cleaned.

The removal chemical solution may also be fixed at a particular temperature that optimizes the removal ability of the solution or the temperature may vary depending on the wiper or surface. The term "to be changed" in relation to temperature means that the solution temperature changes during the processing of the wiper, or that it may vary with the wiper depending on the range of residues to be removed. In some contemplated embodiments, the temperature of the removal chemical solution is fixed below about 80 ° C. In other contemplated embodiments, the temperature of the removal chemical solution is fixed at a temperature of less than about 50 ° C. In still other embodiments, the temperature of the removal chemical solution is fixed at about 30 ° C.

In a single wiper tool, the removal chemical solution can also be applied as a puddle on the stationary phase wiper, which then rotates at a set speed. Alternatively, the removal chemical solution may be applied as a spray to the rotating wiper, where the dispensing takes place only at the center of the wiper, the dispensing head moves from the center of the wiper to the edge, or a number of fixed dispensing heads are centered on the wiper Evenly at the edges. For batch processing, the wiper is immersed in a tank of removal chemical solution and disturbed with shaking, ultrasonic / megasonic and / or air injection.

The sample may be pretreated before application of the removal chemical solution. Pretreatment may include applying liquid or vapor to the wiper surface to improve wetting when a removal chemical solution is applied. Pretreatment also includes applying liquid or vapor to the wiper surface to chemically modify the surface to increase / selective the efficiency of the removal chemical solution. Devices for some of these processes can be found at the following website: http://www.sez.com/SEZ+Internet/HeaderNavigation/Products/SingleWaferTools/SE Z + 203 / main 203.htm, http: / /www.amat.com/products/oasis clean.html, and http://www.tel.com/eng/products/spe/csuwz.htm.

Wiper and layering materials contemplated herein include wiper and layering materials contemplated for use or in use in semiconductor or electronic product applications, such as dual damascene structures, and include at least one material layer. Surfaces contemplated in the present invention may include any suitable substantially solid material, such as a substrate, wiper or other suitable surface. Particularly preferred substrate layers may comprise films, organic polymers, inorganic polymers, glass, ceramics, plastics, metals or coated metals, or composite materials. The surface and / or substrate layers include one or more layers, and in some cases include multiple layers. In other embodiments, the substrate includes materials common to the packaging circuit board industry as well as the integrated circuit industry, such as silicon, copper, glass, and other polymers. Suitable surfaces contemplated in the present invention may also include other preformed layered stacks, other layered parts, or all other parts. Examples of these may be where the dielectric material and the CVD barrier layer are first placed into a layered stack, which layer subsequently refers to the "surface" of the spun-on layered part.

One or more layers may be coupled to a surface or substrate forming a multilayer stack. As used herein, the term "to be coupled" means that the surface and layer or two layers are physically bonded to each other or that the cohesion, covalent and ionic bond, and non-bonding forces between two portions of a material or part, such as Van der Waals ), Which means that physical attraction exists, including static electricity, klong, hydrogen bonding, and / or magnetic attraction. Further, as used herein, the term to be coupled means to include the situation in which the surface and the layer or two layers are directly bonded to each other, but this term also refers to the situation in which the surface and the layer or multiple layers are indirectly coupled to each other. Such as when there is an adhesion promoting layer between the surface and the layer or another layer together between the surface and the layer or multiple layers.

Contemplated dielectric and low dielectric materials that can be used in wiper and layered materials are inorganic-based compounds, such as commonly assigned US Pat. No. 6,143,855 and US Serial No. 10/078919, filed Feb. 19, 2002. Silicon-based compounds disclosed in US Pat. (Eg, Honeywell NANOGLASS® and HOSP® products), gallium-based compounds, germanium-based compounds, arsenic-based compounds, boron-based compounds or combinations thereof and organic-based compounds such as poly Ethers, polyarylene ethers disclosed in commonly assigned US Pat. No. 6,124,421 (eg, from Honeywell FLARE ™), polyimides, polyesters and co-assigned WO01 / 78110 and WO 01/08308 (eg, Honeywell Adamantane-based or cage-based compounds as described in GX-3 ™). Dielectric and low-k materials can be spin coated on the surface, dip coated, spray coated, rolled on the surface, dropped on the surface, and / or spreaded on the surface. by spreading).

Examples of silicone-based compounds include siloxane compounds such as methylsiloxane, methylsilsesquioxane, phenylsiloxane, phenylsilsesquioxane, methylphenylsiloxane, methylphenylsilsesquioxane, silazane polymers, silicate polymers and mixtures thereof do. The silazane polymers contemplated are perhydrosilazanes with a "transparent" polymer backbone to which chromophores can be bound. Examples of siloxane polymers and block polymers are _{hydrosiloxane} polymers of the general formula (H _{0 -1.0} SiO _{1 .5-2.0} ) _x (where x is _greater than about 4), general formula (HSiO _1.5 ) _x (where , x is greater than about 4). Also included are copolymers of hydroxysilsesquioxane and alkoxyhydridosiloxanes or hydroxyhydridosiloxanes. Spin-on glass materials additionally general formula _{(H 0-1.0 Si0 1.5-2.0) n (} R 0-1.0 Si0 1.5-2.0) m organo Hydra Ido siloxane polymer and a general formula _{(HSiO 1 .5) n} (RSiO _{0.5 1)} a organo Hydra Ido silsesquioxane polymer of _m, where, m is more than 0 (zero), and the sum of n and m, and is greater than about 4, R is alkyl or aryl. Some useful organohydridosiloxane polymers have a sum of n and m of about 4 to about 5000 when R is a C ₁ -C ₂₀ alkyl group or a C ₆ -C ₁₂ aryl group. Organohydridosiloxane and organohydridosilsesquioxane polymers mean alternatively spin-on polymers. Some specific examples include alkyl hydridosiloxanes such as methyl hydrido siloxane, ethyl hydrido siloxane, propyl hydrido siloxane, t-butyl hydrido siloxane, phenyl hydrido siloxane; And alkylhydridosilsesquioxanes such as methylhydridosilsesquioxane, ethyl hydridosilsesquioxane, propylhydridosilsesquioxane, t-butylhydridosilsesquioxane, phenylhydridodoses Quoxane, and combinations thereof. Some contemplated spin-on materials are described in the following granted patents and pending patent applications, which are hereby incorporated by reference in their entirety: (PCT / USOO / 15772, filed June 8, 2000; US application Serial no. 09/330248, filed June 10, 1999; US application serial no. 09/491166, filed June 10, 1999; US 6,365,765, issued April 2, 2002; US 6,268,457, Granted July 31, 2001; US Application Serial No. 10/001143, filed November 10, 2001 US Application Serial No. 09/491166, filed January 26, 2000; PCT / USOO / 00523 , Filed Jan. 7, 1999; US 6,177,199, issued January 23, 2001; US 6,358,559, issued March 19, 2002; US 6,218,020, issued April 17, 2001; US 6,361,820, 2002 Granted March 26, 2011; US 6,218,497, April 17, 2001; US 6,359,099, March 19, 2002; US 6,143,855, 7 November 2000; and US Application Serial No. 09 / 611528, filed March 20, 1998).

Solutions of organohydridosiloxane and organosiloxane resins can be used in a variety of electronic devices, micro-electronic devices, especially electronic devices and semiconductor components, including semiconductor integrated circuits and hardmask layers, dielectric layers, etch stop layers, and investment etch stop layers. It can be used to form cage siloxane polymer films useful for the manufacture of layer forming materials. These organohydridosiloxane resin layers can be used for layering materials and devices, such as adamantane-based compounds, diamantane-based compounds, silicon-core compounds, organic dielectrics, and nanoporous materials. It can be combined very well with the dielectric. Compounds that can be substantially compatible with the organohydridosiloxane resin layer contemplated herein are described in PCT application PCT / USOl / 32569, filed Oct. 17, 2001, which is hereby incorporated by reference in its entirety; PCT Application PCT / USOl / 50812, filed December 31, 2001; US Application Serial No. 09/538276; US Application Serial No. 09/544504; US Application Serial No. 09/587851; US Patent No. 6,214,746; US Patent No. 6,171,687; US Patent No. 6,172,128; US Patent No. 6,156,812, filed US application Ser. No. 60/350187, filed Jan. 15, 2002; And US 60/347195, filed Jan. 8, 2002.

Nanoporous silica dielectric films having a dielectric constant of about 1.5 to about 4 may also be one or more layers. Nanoporous silica compounds contemplated herein are described in US Pat. No. 6,022,812; 6,037,275; 6,037,275; 6,042,994; 6,042,994; 6,048,804; 6,048,804; No. 6,090,448; 6,126,733; 6,126,733; No. 6,140,254; 6,204,202; 6,204,202; 6,208,041; 6,208,041; Compounds found in US Pat. Nos. 6,318,124 and 6,319,855. The form of such a film is prepared as a silicon-based precursor, or aged or condensed in the presence of water and heated sufficiently to substantially remove all porogen or form voids in the film. The silicon-based precursor composition comprises a monomer or prepolymer having the general formula R _x -Si-L _y , wherein R is independently selected from alkyl groups, aryl groups, hydrogen and combinations thereof, L is a negatively charged residue, For example, alkoxy, carboxy, amino, amido, halide, isocyanate, and combinations thereof, x is an integer from 0 to about 2, and y is an integer from about 2 to about 4. Other nanoporous compounds and methods are described in US Pat. No. 6,156,812, which is incorporated herein by reference in its entirety; No. 6,171,687; No. 6,172,128; No. 6,214,746; No. 6,313,185; 6,380,347; 6,380,347; And 6,380,270.

Cage molecules or compounds as described in detail herein may also be groups that are bonded to the polymer backbone to form nanoporous materials, where the cage compounds form one form of voids (within molecules), and Or crosslinking at least a portion of the backbone with another backbone may form another type of void (between molecules). Additional cage molecules, cage compounds and modifications of these molecules and compounds are described in detail in PCT / USO1 / 32569, filed October 18, 2001, which is hereby incorporated by reference in its entirety.

Contemplated antireflective and adsorptive coating materials for ultraviolet light etching include one or more inorganic-based compounds or inorganic materials, one or more absorbent compounds, and in some cases, one or more material modifiers, such as filed November 12, 2002. PCT Application PCT / US02 / 36327; The modifiers described in PCT / US03 / 36354, filed November 12, 2003, and US application serial number 10/717028, filed November 18, 2003. One or more material modifiers may provide a coating material that improves the photoetchability, roughness and / or physical properties of the resulting film, for example, by improving etch selectivity and / or stripping selectivity or by minimizing fill vias. It can include any compound or composition that can be varied. One or more material modifiers include one or more porogens, one or more leveling agents, one or more high boiling solvents, one or more densifying agents, one or more catalysts, one or more incorporating inorganic-based materials and / or compounds Or more pH adjusting agents, one or more capping agents, one or more alternative solvents, one or more adhesion promoters, such as resin-based materials, and / or combinations thereof.

The sacrificial compositions and materials may be prepared or formed in a continuous layer of material, in a pattern, in discrete form, or in a combination thereof. As used herein, the term “discontinuous form” means that the composition or material is not made in a continuous layer and is not made in a pattern. Compositions or materials in discontinuous form are prepared or formed in a form with a more random or flat pattern appearance.

Other contemplated layers are welding pastes, polymer weldments, and other weld-based formulations and materials, such as Honeywell International Inc., which is hereby incorporated by reference in its entirety. Welding materials, coating compositions and other related materials, including those described in the patents issued and pending applications: US Patent Application Serial Nos. 09/851103, 60/357754, 60/372525 , 60/396294, and 09/543628; And PCT pending application number PCT / US02 / 14613, and all related continuations, divisions, partial continuations, and foreign applications.

An electronic-based product may be "final" in that it is ready for use by industry or other consumers. Examples of final consumer products are televisions, computers, telephones, pagers, palm-type organizers, portable radios, car stereos, and remote controls. Also contemplated are keyboards usefully employed in "middle" products such as circuit boards, chip packaging, and end products.

The electronic product may also include prototype components at any stage of development, from conceptual models to final scale-up / mock-up. The prototype may or may not contain all substantial parts intended for the final product, and the prototype may have any component composed of composite materials to negate their initial effects on other components during initial testing.

As used herein, "electronic component" means any device or portion thereof that can be used in a circuit to obtain any required electrical field. Electronic components contemplated by the present invention can be classified in many different ways, including classification into active components and passive components. Active components are electronic components capable of any mechanical action, such as amplification, vibration, or signal conditioning, which generally requires a power source for operation. Examples are dipole transistors, field-effect transistors, and integrated circuits. Passive components are electronic components that are static in operation, i.e., electronic components that are generally incapable of amplification or vibration, and which typically do not require power for their characteristic operation. Examples are conventional resistors, capacitors, inductors, diodes, rectifiers and fuses.

Electronic components contemplated in the present invention may also be classified as conductors, semiconductors, or insulators. In the present invention, a conductor is a component that allows charge carriers (eg, electrons) to move easily between atoms, such as in current. Examples of conductor components are circuit traces and vias including metals. An inductor is a component whose action is substantially related to the ability of a material that is extremely resistant to conduction of current, for example, the material used to electrically separate other components, and a semiconductor is an electrical current inherently resisting between conductors and insulators. It is a part that has a function that is substantially related to the ability of the material to conduct it. Examples of semiconductor components are transistors, some lasers, rectifiers, thyristors, and photosensors.

Electronic components contemplated by the present invention may also be classified as a power source or a power consumption. Power supply components are typically used to power other components and include batteries, capacitors, coils, and fuel cells. As used herein, the term "battery" means a device that produces an amount of power available through a chemical reaction. Similarly rechargeable or secondary batteries are devices that store the amount of electrical energy available through chemical reactions. Power consumption components include resistors, transistors, ICs, sensors, and the like.

Still other electronic components contemplated by the present invention may also be classified as discrete or integrated components. Discrete components are devices that provide one particular electronic property concentrated at a location in a circuit. Such examples are resistors, capacitors, diodes and transistors. Integrated components are combinations of components that can provide multiple electrical properties at one location in a circuit. Such an example is an IC, ie an integrated circuit in which multiple components and connection traces are combined to perform multiple or complex actions such as logic.

Example

Example 1

To measure the etch rate of various combinations of anhydrous hydrogen fluoride, propylene carbonate and acetic acid on a blanket film of material common to semiconductor / memory device applications are tested and described as follows.

Procedure: Anhydrous etchant was used as a source of anhydrous HF. A solution of 10% by volume HF in acetic acid, 5% by volume HF in acetic acid, 2.5% by volume HF in acetic acid, and 1.25% by volume HF in acetic acid was prepared in a 500 ml HDPE bottle by the following method.

The resulting propylene carbonate / HF / acetic acid solution was then prepared using the resulting HF / acetic acid solution.

Anhydrous mixtures of hydrogen fluoride, propylene carbonate and acetic acid-etching data

The following solutions were prepared for use as comparisons:

Etching Process:

About 2 cm x 2 cm films of the following materials: Thermal Oxide (TOx), TEOS and CVD OSG (k-2.7) had a film thickness measured by n + k. The sample was then clamped and placed in a solution fixed at 21.5 ° C. using a temperature bath. The reaction was carried out for 10 minutes. The sample was then removed from the solution and placed in a water beaker to quench the reaction. Wafer samples were completely dried with CDA, and post-treatment film measurements were performed using n + k.

The results of the experiments using these solutions are as follows:

OSG film was peeled off

Example 2

The etch rate of the anhydrous mixture of propylene carbonate and hydrogen fluoride pyridine, the mixture of N-methyl-2-pyrrolidone / acetic acid / HF, ethyl lactate / acetic acid / HF is measured and described as follows.

Purpose: To measure the etch rate of various mixtures of solvent and HF.

Procedure: The solution was quantified into a 250 ml beaker and mixed. The amounts of ingredients are as follows:

Etching Process:

About 2 cm x 2 cm films of the following materials: Thermal Oxide (TOx), TEOS and CVD OSG (k-2.7) had a film thickness measured by n + k. The sample was then clamped and placed in a solution fixed at 21.5 ° C. using a temperature bath. The reaction was carried out for 10 minutes. The sample was then removed from the solution and placed in a water beaker to quench the reaction. Wafer samples were completely dried with CDA, and post-treatment film measurements were performed using n + k.

The results of the experiments using these solutions are as follows:

Example 3

The etching rate of SiN / Cu and the removal of CuO by the anhydrous PC / HF / HOAc mixture are measured and described below.

Purpose: To test the effect of various compositions of PC / HF / HOAc on SiN, Cu and CuO blanket films.

Procedure: About 0.25%, about 0.5%, about 1% and about 2% by volume of HF in a 3.5: 1 PC: HOAc solution was prepared as described in Example 1. CuO films were formed by oxidizing a 2 cm x 2 cm Cu blanket film on a hot plate of about 6 heating settings. Samples were inspected every 30 seconds until the film was visually removed by immersing the CuO sample in a HF / PC / HOAc solution in a temperature controlled bath. Etch rates of SiN and Cu were performed as described above.

Experimental results using these solutions are as follows:

Example 4

The etch rate of the anhydrous propylene carbonate-hydrogen fluoride mixture of various semiconductor materials is measured and described below.

Purpose: To measure the etching rates of different concentrations of anhydrous hydrogen fluoride in propylene carbonate solutions on thin film materials commonly used in IC manufacturing. Materials tested include TEOS, thermal oxides (TOx), OSG (k = about 2.7), Si ₃ N ₄ and HSQ.

Procedure: The concentration tested was supplied using anhydrous propylene carbonate-hydrogen fluoride (PC-HF) solution with 5.11 wt.% HF as a stock solution. The diluted PC-HF solution is as follows:

2 cm x 2 cm gupons / wipers of TEOS, OSG, HSQ, Thermal Oxide (TOx) and Si ₃ N ₄ have pre-measured film thickness using the Filmetrics F2O Thin Film Measurement System (n + k) . Sample coupons were soaked in each solution containing the stock solution for 10 minutes. The sample was then washed with DI water and dried with CDA. Sample coupons were measured again using the Peel Matrix F20.

The results of experiments using these solutions are as follows:

Accordingly, certain embodiments and applications of selective etching and cleaning solutions for semiconductors and electronic products, the preparation and use of these solutions are disclosed herein. However, it will be apparent to those skilled in the art that many more changes are possible without departing from the concept of the invention in addition to those described above. Accordingly, the subject matter of the invention is not limited except as by the spirit disclosed. Further, in view of the disclosure, all terms are intended to encompass the broadest possible ways consistent with the concept, and in particular, the terms "comprising" and "comprising" are considered to refer to an element, part or step in a non-exclusive manner. To indicate that the referenced element, part, or step is present with, used with, or combined with other elements, parts, or steps not expressly referenced.

Claims (115)

A removal chemical solution comprising at least one low H ₂ O content fluorine-based construct, and at least one solvent or solvent mixture. The removal chemical solution of claim 1, wherein the at least one low H ₂ O content fluorine-based constituent comprises anhydrous hydrogen fluoride or hydrogen fluoride pyridine. The removal chemical solution of claim 1, wherein the low H ₂ O content fluorine-based construct is present in the etching solution in an amount of less than about 70% by weight. 4. The chemical solution of claim 3 wherein the low H ₂ O content fluorine-based constituent is present in an amount from about 0.005% to about 70% by weight. The removal chemical solution of claim 4 wherein the low H ₂ O content fluorine-based constituent is present in an amount from about 0.005% to about 45% by weight. The chemical solution of claim 5 wherein the low H ₂ O content fluorine-based constituent is present in an amount from about 0.005% to about 20% by weight. The removal chemical solution of claim 6, wherein the low H ₂ O content fluorine-based constituent is present in an amount from about 0.005% to about 5% by weight. 3. The chemical solution of claim 2 wherein the low H ₂ O content fluorine-based constituent comprises hydrogen fluoride gas. The removal chemical solution of claim 1, wherein the low H ₂ O content fluorine-based constituent comprises less than about 10 volume percent water. 10. The removal chemical solution of claim 9 wherein the low H ₂ O content fluorine-based constituent comprises less than about 5 volume percent water. The chemical solution of claim 10 wherein the low H ₂ O content fluorine-based constituent comprises less than about 2.5 volume percent water. 12. The removal chemical solution of claim 11 wherein the low H ₂ O content fluorine-based constituent comprises less than about 1 volume percent water. 13. The removal chemical solution of claim 12 wherein the low H ₂ O content fluorine-based constituent is anhydrous. 3. The chemical solution of claim 2 wherein hydrogen fluoride pyridine is added to at least one solvent or solvent mixture in a 3: 1 molar ratio of hydrogen fluoride: pyridine or 9: 1 molar ratio of hydrogen fluoride: pyridine. The method of claim 1, wherein the one or more solvents or solvent mixtures are propylene carbonate, butylene carbonate, ethylene carbonate, gamma-butyrolactone, N-methyl-2-pyrrolidone, propylene glycol, ethylene glycol A chemical solution for removal comprising ethyl lactate, N, N-dimethylacetamide, propylene glycol monomethyl ether acetate, dimethyl sulfoxide, pyridine or combinations thereof. The removal chemical solution of claim 1, wherein the one or more solvents or solvent mixtures are present in the removal chemical solution in an amount of less than about 99.5% by weight. The removal chemical solution of claim 16, wherein the one or more solvents or solvent mixtures are present in the etching solution in an amount from about 30% to about 99.5% by weight. The removal chemical solution of claim 1, further comprising one or more additional ingredients. 19. The chemical solution of claim 18, wherein the one or more additional ingredients comprise one or more oxidants. The chemical solution of claim 19 wherein the oxidant comprises hydrogen peroxide, urea hydrogen peroxide, benzoyl peroxide, peroxybenzoic acid, peroxyacetic acid, halogenated peroxyacetic acid, organic peroxide, ozone and combinations thereof. 20. The chemical solution of claim 19 wherein the at least one oxidant comprises an anhydrous oxidant. 20. The removal chemical solution of claim 19 wherein at least one oxidant is present in the solution in an amount of less than about 20% by weight. 23. The chemical solution of claim 22 wherein the one or more oxidants are present in the solution in an amount from about 0.001% to about 20% by weight. 19. The chemical solution of claim 18, wherein the at least one additional constituent comprises a low H ₂ O content fluoride source. The method of claim 24 wherein the low H ₂ O content fluoride source is ammonium fluoride, tetramethylammonium fluoride, tetrabutylammonium fluoride, hydrogen fluoride, tetraethylammonium fluoride, benzyltrimethylammonium fluoride, ammonium bifluoride And a chemical solution for removal comprising a combination thereof. The chemical solution of claim 25, wherein the low H ₂ O content fluoride source is present in the solution in an amount of less than about 20% by weight. 27. The removal chemical solution of claim 26, wherein the low H ₂ O content fluoride source is present in the solution in an amount from about 0.001% to about 20% by weight. 19. The removal chemical solution of claim 18 wherein at least one additional component is a surfactant. 29. The chemical solution of claim 28, wherein the surfactant comprises an anionic surfactant, cationic surfactant, nonionic surfactant, amphoteric surfactant or combinations thereof. The chemical solution of claim 29, wherein the anionic surfactant comprises a sulfonate compound, a fluorinated anionic surfactant, or a combination thereof. 31. The chemical solution of claim 30 wherein the sulfonate compound comprises dodecylbenzene sulfonate, tetrapropylenebenzene sulfonate, dodecylbenzene sulfonate or combinations thereof. 31. The chemical solution of claim 30, wherein the fluorinated anionic surfactant comprises Fluorad FC-93. 30. The chemical solution of claim 29, wherein the cationic surfactant comprises a quaternary amine. 34. The chemical solution of claim 33 wherein the quaternary amine comprises dodecyltrimethylammonium bromide or cetyltrimethyl ammonium bromide or combinations thereof. 30. The chemical solution of claim 29, wherein the nonionic surfactant comprises alkyl phenoxy polyethylene oxide alcohols, alkyl phenoxy polyglycidol, and acetylinic alcohols or combinations thereof. 30. The chemical solution of claim 29, wherein the amphoteric surfactant comprises betaine, sulfobetaine, synthetic phospholipids, or a combination thereof. 37. The chemical solution of claim 36 wherein the sulfobetaine comprises cocoamidopropyl betaine. 37. The chemical solution of claim 36, wherein the synthetic phospholipid comprises dioctanoylphosphatidylcholine, lecithin or a combination thereof. The chemical solution of claim 28 wherein the surfactant is present in the solution in an amount of less than about 5% by weight. The removal chemical solution of claim 39 wherein the surfactant is present in the solution in an amount from about 0.001% to about 5% by weight. 19. The chemical solution of claim 18, wherein the additional component comprises one or more chelating agents. 42. The chemical solution of claim 41 wherein the one or more chelating agents is present in the solution in an amount of less than about 20% by weight. 43. The chemical solution of claim 42 wherein the one or more chelating agents is present in the solution in an amount from about 0.001% to about 20% by weight. 42. The chemical solution of claim 41 wherein the chelating agent comprises an organic acid, amine, phosphonate, sulfonic acid or combinations thereof. 45. The chemical solution of claim 44 wherein the organic acid comprises acetic acid, citric acid, lactic acid, oxalic acid, tartaric acid, maleic acid or combinations thereof. 45. The chemical solution of claim 44, wherein the amine comprises hexamethylenetetramine, EDTA, triethanolamine, nitrilotriacetic acid, tris (2-pyridylmethyl) amine, or a combination thereof. The method of claim 44 wherein the phosphonate is diamyl amylphosphonate, bis (2-chloroethyl) methyl phosphonate, dibutyl butylphosphonate, diethyl benzylphosphonate, nitrilotris (methylene) tri A removal chemical solution comprising phosphonic acid and hydroxyethylidenediphosphonic acid or a combination thereof. 45. The method of claim 44, wherein the sulfonic acid is 3- (N-tris [hydroxymethyl] methylamine) -2-hydroxypropanesulfonic acid and 3 ([1,1-dimethyl-2-hydroxyethyl) amine] -2 A removal chemical solution comprising hydroxypropanesulfonic acid or a combination thereof. 19. The removal chemistry solution of claim 18 wherein the additional constituents comprise water. 50. The removal chemical solution of Claim 49 wherein water is present in the solution in a weight ratio to less than 9:10 hydrogen fluoride. The removal chemical solution of claim 1, wherein the solution is an etching solution. The chemical solution for removal of claim 1 wherein the solution is a cleaning solution. The method of claim 1, wherein the at least one low H ₂ O content fluorine-based constituent comprises hydrogen fluoride gas and the at least one solvent or solvent mixture is propylene carbonate, ethylene carbonate, butylene carbonate, propylene glycol , Chemical solution for removal comprising ethylene glycol or combinations thereof. 19. The method of claim 18, wherein the one or more low H ₂ O content fluorine-based constructs comprise hydrogen fluoride gas; At least one solvent or solvent mixture comprises propylene carbonate, ethylene carbonate, butylene carbonate, propylene glycol, ethylene glycol or combinations thereof; A removal chemical solution wherein the additional constituents comprise ozone, hydrogen peroxide or a combination thereof. 19. The method of claim 18, wherein the one or more low H ₂ O content fluorine-based constructs comprise hydrogen fluoride gas; At least one solvent or solvent mixture comprises propylene carbonate, ethylene carbonate, butylene carbonate, propylene glycol, ethylene glycol or combinations thereof; A removal chemical solution wherein the additional constituents comprise one or more chelating agents. Providing one or more low H ₂ O content fluorine-based constituents, providing one or more solvents or solvent mixtures, and combining one or more low H ₂ O content fluorine-based constituents into one or more solvents or solvent mixtures for removal A method of forming a chemical solution for removal comprising forming a. 57. The method of claim 56, wherein the one or more additional ingredients are provided, the one or more additional ingredients are combined into one or more second solvents or solvent mixtures to form a constituent-solvent mixture, and the constituent-solvent mixture into the removal chemical solution. Further comprising formulating. 59. The method of claim 57, wherein the at least one low H ₂ O content fluorine-based constituent comprises anhydrous hydrogen fluoride, gaseous hydrogen fluoride, or hydrogen fluoride pyridine. The method of claim 56, wherein the low H ₂ O content fluorine-based construct is present in the solution in an amount of less than about 70 weight percent. 60. The method of claim 59, wherein the low H ₂ O content fluorine-based construct is present in an amount from about 0.005% to about 70% by weight. 61. The method of claim 60, wherein the low H ₂ O content fluorine-based construct is present in an amount from about 0.005% to about 45% by weight. The method of claim 61, wherein the low H ₂ O content fluorine-based construct is present in an amount from about 0.005% to about 20% by weight. 63. The method of claim 62, wherein the low H ₂ O content fluorine-based construct is present in an amount from about 0.005% to about 5% by weight. 59. The method of claim 56, wherein the low H ₂ O content fluorine-based constituent comprises less than about 10 volume percent water. 65. The method of claim 64, wherein the low H ₂ O content fluorine-based construct comprises less than about 5 volume percent water. 66. The method of claim 65, wherein the low H ₂ O content fluorine-based construct comprises less than about 2.5 volume percent water. 67. The method of claim 66, wherein the low H ₂ O content fluorine-based constituent comprises less than about 1 volume percent water. 68. The method of claim 67, wherein the low H ₂ O content fluorine-based construct is anhydrous. 59. The method of claim 58, wherein the hydrogen fluoride pyridine is added to one or more solvents or solvent mixtures in a 3: 1 molar ratio of hydrogen fluoride: pyridine or 9: 1 molar ratio of hydrogen fluoride: pyridine. 59. The method of claim 56, wherein the one or more solvents or solvent mixtures are propylene carbonate, butylene carbonate, ethylene carbonate, gamma-butyrolactone, N-methyl-2-pyrrolidone, propylene glycol, ethylene glycol , Ethyl lactate, N, N-dimethylacetamide, propylene glycol monomethyl ether acetate, dimethyl sulfoxide, pyridine or combinations thereof. The method of claim 70, wherein the one or more solvents or solvent mixtures are present in the solution in an amount of less than about 99.5 weight percent. The method of claim 71, wherein the one or more solvents or solvent mixtures are present in the etching solution in an amount from about 30% to about 99.5% by weight. 57. The method of claim 56, further comprising one or more additional constructs. 74. The method of claim 73, wherein the one or more additional constructs comprises one or more oxidants. 75. The method of claim 74, wherein the oxidant comprises hydrogen peroxide, urea hydrogen peroxide, benzoyl peroxide, peroxybenzoic acid, peroxyacetic acid, halogenated peroxyacetic acid, organic peroxide, ozone and combinations thereof. 75. The method of claim 74, wherein the at least one oxidant comprises an anhydrous oxidant. 75. The method of claim 74, wherein the one or more oxidants are present in the solution in an amount of less than about 20% by weight. 78. The method of claim 77, wherein the at least one oxidant is present in the solution in an amount from about 0.001% to about 20% by weight. 74. The method of claim 73, wherein the one or more additional ingredients comprises a low H ₂ O content fluoride source. 80. The method of claim 79 wherein the low H ₂ O content fluoride source is ammonium fluoride, tetramethylammonium fluoride, tetrabutylammonium fluoride, hydrogen fluoride, tetraethylammonium fluoride, benzyltrimethylammonium fluoride, ammonium bifluoride And combinations thereof. 81. The method of claim 80, wherein the low H ₂ O content fluoride source is present in the solution in an amount of less than about 20 weight percent. 82. The method of claim 81, wherein the low H ₂ O content fluoride source is present in the solution in an amount of about 0.001% to about 20% by weight. 74. The method of claim 73, wherein the one or more additional ingredients comprises a surfactant. 84. The method of claim 83, wherein the surfactant comprises an anionic surfactant, cationic surfactant, nonionic surfactant, amphoteric surfactant or combinations thereof. 85. The method of claim 84, wherein the anionic surfactant comprises a sulfonate compound, a fluorinated anionic surfactant, or a combination thereof. 86. The method of claim 85, wherein the sulfonate compound comprises dodecylbenzene sulfonate, tetrapropylenebenzene sulfonate, dodecylbenzene sulfonate, or a combination thereof. 86. The method of claim 85, wherein the fluorinated anionic surfactant comprises Fluorad FC-93. 85. The method of claim 84, wherein the cationic surfactant comprises quaternary amines. 89. The method of claim 88, wherein the quaternary amine comprises dodecyltrimethylammonium bromide or cetyltrimethyl ammonium bromide or combinations thereof. 85. The method of claim 84, wherein the nonionic surfactant comprises alkyl phenoxy polyethylene oxide alcohols, alkyl phenoxy polyglycidol, and acetylinic alcohols or combinations thereof. 85. The method of claim 84, wherein the amphoteric surfactant comprises betaine, sulfobetaine, synthetic phospholipids, or a combination thereof. 92. The method of claim 91, wherein the sulfobetaine comprises cocoamidopropyl betaine. 92. The method of claim 91, wherein the synthetic phospholipids comprise dioctanoylphosphatidylcholine, lecithin or combinations thereof. The method of claim 84, wherein the surfactant is present in the solution in an amount of less than about 5 weight percent. 95. The method of claim 94, wherein the surfactant is present in the solution in an amount of about 0.001% to about 5% by weight. 74. The method of claim 73, wherein the additional construct comprises one or more chelating agents. 97. The method of claim 96, wherein the one or more chelating agents is present in the solution in an amount of less than about 20% by weight. 98. The method of claim 97, wherein the one or more chelating agents is present in the solution in an amount of about 0.001% to about 20% by weight. 97. The method of claim 96, wherein the chelating agent comprises an organic acid, amine, phosphonate, sulfonic acid or combinations thereof. 110. The method of claim 99, wherein the organic acid comprises acetic acid, citric acid, lactic acid, oxalic acid, tartaric acid, maleic acid or combinations thereof. 105. The method of claim 99, wherein the amine comprises hexamethylenetetramine, EDTA, triethanolamine, nitrilotriacetic acid, tris (2-pyridylmethyl) amine, or a combination thereof. 103. The method of claim 99, wherein the phosphonate is diamyl amylphosphonate, bis (2-chloroethyl) methyl phosphonate, dibutyl butylphosphonate, diethyl benzylphosphonate, nitrilotris (methylene) tri Phosphonic acid and hydroxyethylidenediphosphonic acid or combinations thereof. 110. The method of claim 99, wherein the sulfonic acid is 3- (N-tris [hydroxymethyl] methylamine) -2-hydroxypropanesulfonic acid and 3 ([1,1-dimethyl-2-hydroxyethyl) amine] -2 -Hydroxypropanesulfonic acid or combinations thereof. 74. The method of claim 73, wherein the additional component comprises water. 107. The method of claim 104, wherein water is present in the etching solution in a weight ratio to hydrogen fluoride of less than 9:10. An etching solution prepared by the method of claim 56. A cleaning solution prepared by the method of claim 56. 59. The method of claim 58, wherein the at least one low H ₂ O content fluorine-based constituent comprises hydrogen fluoride gas and the at least one solvent or solvent mixture is propylene carbonate, ethylene carbonate, butylene carbonate, propylene glycol , Ethylene glycol or combinations thereof. 74. The method of claim 73, wherein the at least one low H ₂ O content fluorine-based construct comprises hydrogen fluoride gas; At least one solvent or solvent mixture comprises propylene carbonate, ethylene carbonate, butylene carbonate, propylene glycol, ethylene glycol or combinations thereof; Wherein the additional component comprises ozone, hydrogen peroxide or a combination thereof. 74. The method of claim 73, wherein the at least one low H ₂ O content fluorine-based construct comprises hydrogen fluoride gas; At least one solvent or solvent mixture comprises propylene carbonate, ethylene carbonate, butylene carbonate, propylene glycol, ethylene glycol or combinations thereof; Wherein the additional constituent comprises one or more chelating agents. For removal, including providing one or more gaseous anhydrous fluorine-based constituents, providing one or more solvents or solvent mixtures, and injecting the one or more anhydrous fluorine-based constituents into one or more solvents or solvent mixtures to form a solution. How to form a chemical solution. Further includes that incorporated into the at least one solvent or solvent mixture described composition-of claim 111, wherein the one or more additional low H ₂ O content of fluorine of - providing a substrate structure, and one or more additional low H ₂ O content of the fluorine of How to. 118. The method of claim 112, wherein the one or more additional ingredients are provided, the one or more additional ingredients are combined with one or more second solvents or solvent mixtures to form a constituent-solvent mixture, and the constituent-solvent mixture is combined into solution. How to further include. Providing hydrogen fluoride gas, Providing one or more solvents or solvent mixtures, A method of forming a removal chemical solution, comprising injecting hydrogen fluoride gas into one or more solvents or solvent mixtures to form a solution. A removal chemical solution comprising hydrogen fluoride gas and one or more solvents or mixtures of solvents.

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