WO2005053004A1 - Selective removal chemistries for sacrificial layers methods of production and uses thereof - Google Patents

Abstract

Etching solutions described herein include a) at least one fluorine-based constituent, b) at least one acid constituent, such as a strong acid in some cases, and c) a suitable solvent constituent, wherein the etching solution selectively etches at least one sacrificial layer from a surface or layered component. Methods are described herein for producing an etching solution that include: a) providing at least one fluorine-based constituent; b) providing a solvent constituent; c) providing an acid constituent; d) blending the fluorine-based constituent, the acid constituent and the compatible solvent constituent to form a solution, wherein the etching solution selectively etches at least one sacrificial layer from a surface or layered component. Other described methods of forming an etching solution include: a) providing a hydrogen fluoride constituent; b) providing a hydrochloric acid constituent; c) providing a propylene carbonate constituent; d) blending the constituents to form a solution, wherein the etching solution selectively etches at least one sacrificial layer from a surface or layered component.

Description

SELECTIVE REMOVAL CHEMISTRIES FOR SACRIFICIAL LAYERS, METHODS OF PRODUCTION AND USES THEREOF

This PCT Application claims priority to US Provisional Application Serial No.: 60/523624 filed on November 19, 2003, which is incorporated herein in its entirety by reference.

FIELD OF THE SUBJECT MATTER

The field of the subject matter is selective etch chemistries and cleaning chemistries for semiconductor, electronic and related applications.

BACKGROUND To meet the requirements for faster performance, the characteristic dimensions of features of integrated circuit devices have continued to be decreased. Manufacturing of devices with smaller feature sizes introduces new challenges in many of the processes conventionally used in semiconductor fabrication. Dual damascene patterning and via first trench last (VFTL) copper dual damascene patterning through a low dielectric constant (less than about 3) material or ultra low dielectric constant (less than about 2) material is one of these manufacturing methods and can be very difficult. In the manufacture of MEMS (microelectromechanical systems) devices, each continuous or patterned layer comprises deleterious residues that, if left even partially intact, will contribute to the breakdown and ultimately the failure of any component that comprises that layer. Therefore, it is imperative that any deleterious residues produced during the manufacture of semiconductor, MEMS and other electronic devices be removed effectively and completely. Prior Art Figures 1A-1C show ash residues in a via clean (Prior Art Figure 1A), a trench clean (Prior Art Figure IB) and an etch stop clean (Prior Art Figure 1C) application. In Prior Art Figure 1A, shows a layered material 100 that comprises a polymer sidewall 110 and ash residues 120. Prior Art Figure IB shows a layered material 200 that comprises a polymer sidewall 210, ash residues 220, a via fence 230 and a via fill 240. The via fence 230 and/or via fill 240 may or may not be present depending on the integration scheme. Prior Art Figure 1C shows a layered material 300 that comprises a polymer sidewall 310, ash residues 320, a via fence 330 and CuO_x and/or CuF_x residues 350. Prior Art Figures 2A-2C show etch residues, including sidewall polymers, antireflective coatings and other residues, in a via clean (Figure 2A), a trench clean (Figure 2B) and an etch stop clean (Figure 2C) application, hi Prior Art Figure 2A, shows a layered material 400 that comprises a polymer sidewall 410, a photoresist layer 420 and an antireflective coating layer 430. Prior Art Figure 2B shows a layered material 500 that comprises a polymer sidewall 510, antireflective coating 520, a via fill 525, a via fence 530, which may or may not be present depending on the integration scheme, and a photoresist 540. The via fence 230 and/or via fill 240 may or may not be present depending on the integration scheme. Prior Art Figure 2C shows a layered material 600 that comprises a polymer sidewall 610, a via fence 630 and CuO_x and/or CuF_x residues 650. Prior art Figure 3 shows a layered material 700 that comprises a UV exposed and developed photoresist 705, a BARC (Bottom Anti-Reflective Coating) 710, wherein the BARC, which may be organic or inorganic, needs to be removed without impacting critical dimensions. The technique of bulk residue removal by means of a selective chemical etching and in some cases selective chemical cleaning is a key step in the manufacture of many semiconductor and electronic devices, including those mentioned. The goal in successful selective etching and selective cleaning steps is to remove the residue without removing or compromising the desirable components. Each class of semiconductor and electronic materials comprise different chemistries that should be considering when developing the removal chemistry and in several cases, these semiconductor and electronic materials have also been modified to increase etch or removal selectivity. If the chemistry of the sacrificial layer cannot be modified in order to improve the etch or removal selectivity, then etching and removal solutions should be developed to specifically react with the chemistry of the sacrificial material. However as mentioned, not only does the chemistry of the sacrificial material need to be evaluated and considered, but also the chemistry of the surrounding and/or adjacent layers should be considered, because in many instances, the chemistry that will remove the sacrificial layer or layers will also remove or weaken the surrounding or adjacent layers. Several of the goals that have yet to be addressed in a selective etching solution and a selective cleaning solution are the following: a) the solution constituents should be able to be tailored to be both a selective etching solution and a selective cleaning solution; b) the solution should be effective in an anhydrous environment and in an aqueous environment; c) should be able to selectively remove deleterious materials and compositions from a surface without removing the layers and materials that are crucial to product success; and d) can both etch and clean effectively at the center of the wafer or surface and at the edge of the wafer or surface. European Patent No. 887,323 teaches an etching and cleaning solution that comprises hydrofluoric acid and ammonium fluoride in propylene carbonate. This etching solution is specifically designed to etch silicate glass and silicon dioxide. Based on the chemistry disclosed, it appears that this combination of constituents is selective to silicate glass and silicon dioxide. JP 9235619 and US Issued Patent 5,476,816 uses a similar solution replacing propylene carbonate with ethylene glycol in order to remove insulating coatings. JP 10189722 uses a similar solution as JP 9235619 except water is also added and the solution is used to clean oxides from a surface. ^' JP 8222628 and US Issued Patent 3,979,241 use an etching solution of ammonium fluoride and ethylene glycol to remove insulating coatings, and JP 1125831 uses this same blend at a different concentration to remove silicon-based compounds. US Issued Patents 6,090,721 and 5,939,336 blends ammonium fluoride, propylene glycol and water to etch metal-containing etch residues from silicon containing substrates. US Issued Patent 5,478,436 uses ammonium fluoride and ethylene glycol to remove metal-based contaminants from a silicon surface. Although many of these solutions can be tailored to be a selective removal solution; can be effective in anhydrous environments; and can both etch and clean effectively at the center of the wafer or surface and at the edge of the wafer or surface, none of these compounds can selectively remove deleterious materials from a surface without etching and/or removing necessary silicon-based compounds and/or metal-based layers and compounds. Therefore, it would be desirable to form a selective etching solution and a selective cleaning solution that can do at least one of the following: a) the solution constituents should be able to be tailored to be both a selective etching solution and a selective cleaning solution; b) the solution should be effective in both aqueous and anhydrous environments; c) can both etch and clean effectively at the center of the wafer and at the edge of the wafer and at the same time can selectively etch polymeric compositions from a surface without etching silicon-based compounds or metal-based layers and compounds; and d) can both etch and clean effectively surfaces, wherein the solutions are selective to any sacrificial layer and/or modified sacrificial layer in order to advance the production of layered materials, electronic components and semiconductor components.

SUMMARY OF THE SUBJECT MATTER Etching solutions described herein include a) at least one fluorine-based constituent, b) at least one acid constituent, such as a strong acid in some cases, and c) a suitable solvent constituent, wherein the etching solution selectively etches at least one sacrificial layer from a surface or layered component. Methods are described herein for producing an etching solution that include: a) providing at least one fluorine-based constituent; b) providing a solvent constituent; c) providing an acid constituent; d) blending the fluorine-based constituent, the acid constituent and the compatible solvent constituent to form a solution, wherein the etching solution selectively etches at least one sacrificial layer from a surface or layered component. Other described methods of forming an etching solution include: a) providing a hydrogen fluoride constituent; b) providing a hydrochloric acid constituent; c) providing a propylene carbonate constituent; d) blending the constituents to form a solution, wherein the etching solution selectively etches at least one sacrificial layer from a surface or layered component.

BRIEF DESCRIPTION OF THE FIGURES

Prior Art Figures 1A-1C show ash residues in a via clean (Figure 1A), a trench clean (Figure IB) and an etch stop clean (Figure 1C) application.

Prior Art Figures 2A-2C show etch residues in a via clean (Figure 2A), a trench clean (Figure 2B) and an etch stop clean (Figure 2C) application.

Prior art Figure 3 shows a layered material that comprises an organic BARC (Bottom Anti- Reflective Coating), wherein the organic BARC needs to be removed without impacting critical dimensions.

Figure 4 show etch rate results for a contemplated etching solution. Figure 5 show etch rate results for a contemplated etching solution.

DETAILED DESCRIPTION In order to achieve the goals previously described, a selective etching solution and a selective cleaning solution has been developed that can do at least one of the following: a) the solution constituents can be tailored to be both a selective etching solution and a selective cleaning solution; b) the solution is effective in both aqueous and non-aqueous environments; c) the solution can both etch and clean effectively at the center of the wafer and at the edge of the wafer and at the same time can selectively etch polymeric compositions from a surface without etching silicon-based compounds or metal-based layers and compounds; and d) can both etch and clean effectively surfaces, wherein the solutions are selective to any sacrificial layer and/or modified sacrificial layer in order to advance the production of layered materials, electronic components and semiconductor components. Etching solutions described herein include a) at least one fluorine-based constituent, b) at least one acid constituent, such as a strong acid in some cases, and c) a suitable solvent constituent, wherein the etching solution selectively etches at least one sacrificial layer from a surface or layered component. As used herein, the phrase "selectively etches" means that the etching solution comprises constituents that are at a suitable concentration such as to etch at least one sacrificial layer from a surface or layered component while still remaining selective towards adjacent and/or corresponding permanent layers, such as dielectric layers, hardmask layers, conductive layers and combinations thereof. The etching solutions contemplated herein can be custom blended for specific applications; however, it is contemplated that the process of custom blending does not require undue experimentation once the disclosure herein, including the stated goals, is understood by one of ordinary skill in the art of etching solutions for electronic and semiconductor applications. . Methods for producing an etching solution include: a) providing at least one fluorine- based constituent; b) providing a solvent constituent; c) providing an acid constituent; d) blending the fluorine-based constituent, the acid constituent and the compatible solvent constituent to form a solution, wherein the etching solution selectively etches at least one sacrificial layer from a surface or layered component. Other contemplated methods of forming an etching solution include: a) providing a hydrogen fluoride constituent; b) providing a hydrochloric acid constituent; c) providing a propylene carbonate constituent; d) blending the constituents to form a solution, wherein the etching solution selectively etches at least one sacrificial layer from a surface or layered component. In general, these methods of forming and uses of these selective etch and cleaning chemistries include providing the constituents of the selective etch chemistry formulation, blending the constituents to form the formulation and applying the formulation to a surface or substrate. In some embodiments, the formulation may be produced in situ (directly on the surface) or may be formed before application to the surface. The etching solution may be in either an aqueous or non-aqueous environment. As used herein, the term "environment" means that environment in the solution containing the fluorine-based salt and/or the non-polar or compatible solvent. The term "environment" does not mean the environment surrounding the solution, such as the environment present in the lab or in the building. For example, a non-aqueous environment means that the solution is non- aqueous and does not refer to the overall humidity level of the air in the lab or building. The etching solutions contemplated herein utilize at least one fluorine-based compound as one of the constituents of the solutions. Fluorine-based compounds may comprise any suitable fluorine-based compound, such as hydrogen fluoride, fluorine-based salts, such as quaternary ammonium compounds like tetraalkylammonium fluoride compounds, such as tetramethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride and tetraethylarnmonium fluoride, and other fluorine-based salts, such as ammonium fluoride. Ammonium salts are also contemplated, such as those having the formula (R1)(R2)(R3)(R4)NF, where Rl, R2, R3 and R4 may be the same or different and may comprise hydrogen or alkyl groups, including straight-chain and branched alkyl groups. The fluorine-based constituent contemplated herein is present in solution at less than about 10 weight percent relative to the strong acid constituent and the solvent constituent. In some embodiments, the fluorine-based constituent contemplated herein is present in solution at less than about 5 weight percent relative to the strong acid constituent and the solvent constituent. In other embodiments, the fluorine-based constituent contemplated herein is present in solution at less than about 1 weight percent relative to the strong acid constituent and the solvent constituent. In yet other embodiments, the fluorine-based constituent contemplated herein is present in solution at less than about 0.5 weight percent relative to the strong acid constituent and the solvent constituent, hi additional embodiments, the fluorine- based constituent contemplated herein is present in solution at less than about 0.1 weight percent relative to the strong acid constituent and the solvent constituent. Contemplated etching solutions comprise an acid constituent in conjunction with the fluorine-based constituent. Acids contemplated herein may comprise any single weak acid, combination of weak acids, strong acid, combination of strong acids or combinations thereof as long as the acid constituent does not detrimentally interfere with any metal layers and/or conductive layers, hi some embodiments, the acid constituent may comprise hydrochloric acid. The acid constituent contemplated herein is present in solution at less than about 5 weight percent relative to the fluorine-based constituent and the solvent constituent. In some embodiments, the acid constituent contemplated herein is present in solution at less than about 2 weight percent relative to the fluorine-based constituent and the solvent constituent. In other embodiments, the acid constituent contemplated herein is present in solution at less than about 1 weight percent relative to the fluorine-based constituent and the solvent constituent. In yet other embodiments, the acid constituent contemplated herein is present in solution at less than about 0.1 weight percent relative to the fluorine-based constituent and the solvent constituent. In additional embodiments, the acid constituent contemplated herein is present in solution at less than about 0.05 weight percent relative to the fluorine-based constituent and the solvent constituent. Both the etching and the cleaning solutions contemplated herein - also utilize a compatible solvent constituent. Contemplated solvents include any suitable pure or mixture of organic molecules that are volatilized at a desired temperature, such as the critical temperature, or that can facilitate any of the above-mentioned design goals or needs. The solvent may also comprise any suitable pure or mixture of polar and non-polar compounds. As used herein, the term "pure" means that component that has a constant composition. For example, pure water is composed solely of H₂O. As used herein, the term "mixture" means that component that is not pure, including salt water. As used herein, the term "polar" means that characteristic of a molecule or compound that creates a substantial unequal charge, partial charge or spontaneous charge distribution at one point of or along the molecule or compound. As used herein, the term "non-polar" means that characteristic of a molecule or compound that creates a substantially equal charge, partial charge or spontaneous charge distribution at one point of or along the molecule or compound. It should be understood that those compounds included under the definition of "non-polar" are those compounds that are both clearly non-polar or slightly polar. One of ordinary skill in the art of chemistry and etching solutions will know which solvents are non-polar/slightly polar and which solvents are clearly polar in nature. It is also contemplated that the solvents used herein may comprise any suitable impurity level, such as less than about 1 ppm, less than about 100 ppb, less than about 10 ppb and in some cases, less than about 1 ppb. These solvents may be purchased having impurity levels that are appropriate for use in these contemplated applications or may need to be further purified to remove additional impurities and to reach the less than about 10 ppb and less than about 1 ppb levels that are becoming more desirable in the art of etching and cleaning. In some contemplated embodiments, the solvent or solvent mixture (comprising at least two solvents) comprises those solvents that are considered part of the hydrocarbon family of solvents. Hydrocarbon solvents are those solvents that comprise carbon and hydrogen. It should be understood that a majority of hydrocarbon solvents are non-polar; however, there are a few hydrocarbon solvents that could be considered polar. Hydrocarbon solvents are generally broken down into three classes: aliphatic, cyclic and aromatic. Aliphatic hydrocarbon solvents may comprise both straight-chain compounds and compounds that are branched and possibly crosslinked, however, aliphatic hydrocarbon solvents are not considered cyclic. Cyclic hydrocarbon solvents are those solvents that comprise at least three carbon atoms oriented in a ring structure with properties similar to aliphatic hydrocarbon solvents. Aromatic hydrocarbon solvents are those solvents that comprise generally three or more unsaturated bonds with a single ring or multiple rings attached by a common bond and/or multiple rings fused together. Contemplated hydrocarbon solvents include 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 ethers, 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. i other contemplated embodiments, the solvent or solvent mixture may comprise those solvents that are not considered part of the hydrocarbon solvent family of compounds, such as ketones, such as acetone, diethyl ketone, methyl ethyl ketone and the like, alcohols, esters, carbonate-based compounds, such as propylene carbonate and the like, ethers and amines. Contemplated solvents may also comprise nitrogen, phosphorus, sulfur or a combination thereof. In yet other contemplated embodiments, the solvent or solvent mixture may comprise a combination of any of the solvents mentioned herein. In yet other contemplated embodiments, the solvent or solvent mixture may comprise butylene carbonate, ethylene carbonate, gamma-butyrolactone, N-methyl-2-pyrrolidone, propylene glycol, ethylene glycol, ethyl lactate, N,N-dimethylactamide, propylene glycol monomethyl ether acetate, dimethyl sulfoxide, pyridine or a combination thereof A method of forming an etching solution contemplated herein comprises a) providing at least one fluorine-based constituent; b) providing a solvent constituent; c) providing an acid constituent; d) blending the fluorine-based constituent, the acid constituent and the compatible solvent constituent to form a solution, wherein the solution constituents are at a suitable concentration to etch sacrificial layers, modified sacrificial layers and/or patterns from a surface without reacting with adjacent and/or corresponding layers and/or patterns. Another contemplated method of forming an etching solution comprises a) providing a hydrogen fluoride constituent; b) providing a hydrochloric acid constituent; c) providing a propylene carbonate constituent; d) blending the constituents to form a solution, wherein the solution constituents are at a suitable concentration sacrificial layers, modified sacrificial layers and/or patterns from a surface without reacting with adjacent and/or corresponding layers and/or patterns. The fluorine-based constituent, the acid constituent and/or the solvent constituent may be provided by any suitable method, including a) buying at least some of the fluorine-based constituent, the acid constituent and/or the solvent constituent from a supplier; b) preparing or producing at least some of the fluorine-based constituent, the acid constituent and/or the solvent constituent in house using chemicals provided by another source and/or c) preparing or producing at least some of the fluorine-based constituent, the acid constituent and/or the solvent constituent in house using chemicals also produced or provided in house or at the location. Once the at least one fluorine-based constituent, the acid constituent and/or the solvent constituent are provided, they are blended to form a solution, wherein the solution constituents are at a suitable concentration to etch sacrificial layers, modified sacrificial layers and/or patterns of both of these compositions from a surface without reacting any adjacent and/or corresponding layers, such as dielectric layers, hard mask layers, metal layers, etc. Blending the constituents may be achieved by utilizing any suitable method or methods known in the art, such as mixing and then stirring the constituents. Another method of blending the constituents may be to synthesize one of the components or constituents directly into the solution. For example, at least one of the fluorine-based constituents could be synthesized directly in the solvent. More specifically, TMAF can be made or purchased initially or can be made in situ by reacting tetramethylammonium hydroxide (TMAH) with HF. Once the etching solutions are formed, a coated wafer or surface may be placed in the path of the solution for etching. It should be understood that the etching solutions will at least etch in part the sacrificial layer, the modified sacrificial layer and/or the sacrificial patterns from the surface, substrate or wafer. In some contemplated embodiments, the etching solutions will etch the entire the sacrificial layer, the modified sacrificial layer and/or the sacrificial patterns from the surface, substrate or wafer. The wafer may be dipped into solution once and held for a particular time period or dipped multiple times, may be rinsed by the solution, may have the solution applied , in a methodical patterned form, may be masked and then rinsed by the solution, etc. " In contemplated embodiments where the wafer or substrate is dipped into solution and held for a particular time period, the time period is greater than about 5 minutes. In some contemplated embodiments where the wafer or substrate is dipped into solution and held for a particular time period, the time period is greater than about 10 minutes. In other contemplated embodiments where the wafer or substrate is dipped into solution and held for a particular time period, the time period is greater than about 15 minutes. In yet other contemplated embodiments where the wafer or substrate is dipped into solution and held for a particular time period, the time period is greater than about 20 minutes. The solution may be sprayed onto a spinning wafer for a particular time period or sprayed multiple times. In contemplated embodiments where the solution is sprayed onto a spinning wafer for a particular time period, the time period is greater than about 20 seconds. In some contemplated embodiments where the solution is sprayed onto a spinning wafer for a particular time period, the time period is greater than about 1 minute. In other contemplated embodiments where the solution is sprayed onto a spinning wafer for a particular time period, the time period is greater than about 3 minutes. In yet other contemplated embodiments where the solution is sprayed onto a spinning wafer for a particular time period, the time period is greater than about 10 minutes. In other contemplated embodiments where the solution is sprayed onto a spinning wafer for a particular time period, the time period is greater than about 30 minutes. For example, the cleaning/etching solution may be applied to a semiconductor wafer post photoresist deposition (may be pre or post lithography) for wafer rework purposes, or after plasma treatment (for post etch/post ash residue removal) in either a single wafer or batch processing tool for a period of time between about 15 seconds and about 10 minutes. Processing temperature may be from about 10°C up to about 80°C. The wafer may be dipped into solution once and held for a particular time period or dipped multiple times, may be rinsed by the solution, may have the solution applied in a methodical patterned form, may be masked and then rinsed by the solution, etc. The etching solution may also be held at a particular temperature which optimizes the etching abilities of the solution or may be varied with respect to temperature depending on the wafer or surface to be cleaned. The term "varied" is used herein with respect to temperature to mean that the solution temperature may be varied while the wafer is being processed or may be varied from wafer to wafer depending on the extent of residue that needs to be etched. In some contemplated embodiments, the temperature of the etching solution is held at less than about 30°C. In other contemplated embodiments, the temperature of the etching solution is held at less than about 25°C. In yet other contemplated embodiments, the temperature of the etching solution is held at about 22°C. At least one layer may be coupled to the surface or substrate creating a multilayered stack. As used herein, the term "coupled" means that the surface and layer or two layers are physically attached to one another or there's a physical attraction between two parts of matter or components, including bond forces such as covalent and ionic bonding, and non-bond forces such as Van der Waals, electrostatic, coulombic, hydrogen bonding and/or magnetic attraction. Also, as used herein, the term coupled is meant to encompass a situation where the surface and layer or two layers are directly attached to one another, but the term is also meant to encompass the situation where the surface and the layer or plurality of layers are coupled to one another indirectly - such as the case where there's an adhesion promoter layer between the surface and layer or where there's another layer altogether between the surface and layer or plurality of layers. Contemplated dielectric and low dielectric materials that may be used on wafers and layered materials comprise inorganic-based compounds, such as silicon-based disclosed in commonly assigned US Patent 6,143,855 and pending US Serial No. 10/078919 filed February 19, 2002; (for example Honeywell NANOGLASS® and HOSP® products), gallium-based, germanium-based, arsenic-based, boron-based compounds or combinations thereof, and organic-based compounds, such as polyethers, polyarylene ethers disclosed in commonly assigned US Patent 6,124,421 (such as Honeywell FLARE™ product), polyimides, polyesters and adamantane-based or cage-based compounds disclosed in commonly assigned WO 01/78110 and WO 01/08308 (such as Honeywell GX-3™ product). The dielectric and low dielectric materials may be applied by spin coating the material on to the surface, dip coating, spray coating, rolling the material on to the surface, dripping the material on to the surface, and/or spreading the material on to the surface.

Examples of silicon-based compounds comprise siloxane compounds, such as methylsiloxane, methylsilsesquioxane, phenylsiloxane, phenylsilsesquioxane, methylphenylsiloxane, methylphenylsilsesquioxane, silazane polymers, silicate polymers and mixtures thereof. A contemplated silazane polymer is perhydrosilazane, which has a "transparent" polymer backbone where chromophores can be attached. Examples of siloxane polymers and blockpolymers include hydrogensiloxane polymers of the general formula (Ho-ι.oSiOι.5,2.o)_x and hydrogensilsesquioxane polymers, which have the formula (HSiOι.₅)_x, where x is greater than about four. Also included are copolymers of hydrogensilsesquioxane and an alkoxyhydridosiloxane or hydroxyhydridosiloxane. Spin-on glass materials additionally include organohydridosiloxane polymers of the general formula (Ho-ι.oSiO₁.5-2.o)n(Ro-ι.oSiO₁.5-2.o)mj and organohydridosilsesquioxane polymers of the general formula (HSiOι_.5)_n(RSiOι_.5)_m, where m is greater than zero and the sum of n and m is greater than about four and R is alkyl or aryl. Some useful organohydridosiloxane polymers have the sum of n and m from about four to about 5000 where R is a Cι-C₂₀ alkyl group or a C₆-C₁₂ aryl group. The organohydridosiloxane and organohydridosilsesquioxane polymers are alternatively denoted spin-on-polymers. Some specific examples include alkylhydridosiloxanes, such as methylhydridosiloxanes, ethylhydridosiloxanes, propylhydridosiloxanes, t-butylhydridosiloxanes, phenylhydridosiloxanes; and alkylhydridosilsesquioxanes, such as methylhydridosilsesquioxanes, ethylhydridosilsesquioxanes, propylhydridosilsesquioxanes, t-butylhydridosilsequioxanes, phenylhydridosilsesquioxanes, and combinations thereof. Several of the contemplated spin- on materials are described in the following issued patents and pending applications, which are herein incorporated by reference in their entirety: (PCT/US00/15772 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 on April 2, 2002; US 6,268,457 issued on July 31, 2001; US Application Serial No. 10/001143 filed November 10, 2001; US Application Serial No. 09/491166 filed January 26, 2000; PCT/US00/00523 filed January 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 issued March 26, 2002; US 6,218,497 issued April 17, 2001; US 6,359,099 issued March 19, 2002; US 6,143,855 issued November 7, 2000; and US Application Serial No. 09/611528 filed March 20, 1998).

Solutions of organohydridosiloxane and organo siloxane resins can be utilized for forming caged siloxane polymer films that are useful in the fabrication of a variety of electronic devices, micro-electronic devices, particularly semiconductor integrated circuits and various layered materials for electronic and semiconductor components, including hardmask layers, dielectric layers, etch stop layers and buried etch stop layers. These organohydridosiloxane resin layers are quite compatible with other materials that might be used for layered materials and devices, such as adamantane-based compounds, diamantane- based compounds, silicon-core compounds, organic dielectrics, and nanoporous dielectrics.

Compounds that are considerably compatible with the organohydridosiloxane resin layers contemplated herein are disclosed in PCT Application PCT/US01/32569 filed October 17,

2001; 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 6,214,746; US Patent 6,171,687; US Patent 6,172,128; US Patent 6,156,812, US

Application Serial No. 60/350187 filed January 15, 2002; and US 60/347195 filed January 8,

2002, which are all incorporated herein by reference in their entirety.

Nanoporous silica dielectric films with dielectric constants ranging from about 1.5 to about 4 can be also as at least one of the layers. Nanoporous silica compounds contemplated herein are those compounds found in US Issued Patents: 6,022,812; 6,037,275; 6,042,994; 6,048,804; 6,090,448; 6,126,733; 6,140,254; 6,204,202; 6,208,041; 6,318,124 and 6,319,855. These types of films are laid down as a silicon-based precursor, aged or condensed in the presence of water and heated sufficiently to remove substantially all of the porogen and to form voids in the film. The silicon-based precursor composition comprises monomers or prepolymers that have the formula: R_x-Si-L_y, wherein R is independently selected from alkyl groups, aryl groups, hydrogen and combinations thereof, L is an electronegative moiety, such as alkoxy, carboxy, amino, amido, halide, isocyanato and combinations thereof, x is an integer ranging from 0 to about 2, and y is an integer ranging from about 2 to about 4. Other nanoporous compounds and methods can be found in US Issued Patents 6,156,812; 6,171,687; 6,172,128; 6,214,746; 6,313,185; 6,380,347; and 6,380,270, which are incorporated herein in their entirety.

Cage molecules or compounds, as described in detail herein, can also be groups that are attached to a polymer backbone, and therefore, can form nanoporous materials where the cage compound forms one type of void (intramolecular) and where the crosslinking of at least one part of the backbone with itself or another backbone can form another type of void (intermolecular). Additional cage molecules, cage compounds and variations of these molecules and compounds are described in detail in PCT/US01/32569 filed on October 18, 2001 , which is herein incorporated by reference in its entirety. Contemplated anti-reflective and absorbing coating materials for ultraviolet photolithography may comprise at least one inorganic-based compound or inorganic material, at least one absorbing compound and in some cases, at least one material modification agent, such as those disclosed in PCT Applications PCT/US02/36327 filed on November 12, 2002; PCT/US03/36354 filed on November 12, 2003 and in US Application Serial No. 10/717028 filed on November 18, 2003. The at least one material modification agent may include any compound or composition that can modify the coating material to improve the photolithographic, compatibility and/or physical quality of the resulting film, such as by improving the etch selectivity and/or stripping selectivity or by minimizing the fill bias. The at least one material modification agent may comprise at least one porogen, at least one leveling agent, at least one high-boiling solvent, at least one densifying agent, at least one catalyst, at least one pH tuning agent, at least one capping agent, at least one replacement solvent, at least one adhesion promoter, such as a resin-based material and/or a combination thereof that are incorporated into the inorganic-based material or compound. The sacrificial compositions and materials may be laid down or formed as a continuous layer of material, in a pattern, in a non-continuous form or as a combination thereof. As used herein, the phrase "non-continuous form" means that the composition or material is not laid down in a continuous layer and is also not laid down in a pattern. The composition or material in a non-continuous form is laid down or formed having a more random or non-pattern-like appearance. Other contemplated layers may include solder materials, coating compositions and other related materials, including solder pastes, polymer solders and other solder-based formulations and materials, such as those found in the following Honeywell International Inc.'s issued patents and pending patent applications, which are incoφorated herein in their entirety: US Patent Application Serial Nos. 09/851103, 60/357754, 60/372525, 60/396294, and 09/543628; and PCT Pending Application Serial No.: PCT/US02/14613, and all related continuations, divisionals, continuation-in-parts and foreign applications. Electronic-based products can be "finished" in the sense that they are ready to be used in industry or by other consumers. Examples of finished consumer products are a television, a computer, a cell phone, a pager, a palm-type organizer, a portable radio, a car stereo, and a remote control. Also contemplated are "intermediate" products such as circuit boards, chip packaging, and keyboards that are potentially utilized in finished products. Electronic products may also comprise a prototype component, at any stage of development from conceptual model to final scale-up/mock-up. A prototype may or may not contain all of the actual components intended in a finished product, and a prototype may have some components that are constructed out of composite material in order to negate their initial effects on other components while being initially tested.

As used herein, the term "electronic component" means any device or part that can be used in a circuit to obtain some desired electrical action. Electronic components contemplated herein may be classified in many different ways, including classification into active components and passive components. Active components are electronic components capable of some dynamic function, such as amplification, oscillation, or signal control, which usually requires a power source for its operation. Examples are bipolar transistors, field-effect transistors, and integrated circuits. Passive components are electronic components that are static in operation, i.e., are ordinarily incapable of amplification or oscillation, and usually require no power for their characteristic operation. Examples are conventional resistors, capacitors, inductors, diodes, rectifiers and fuses. Electronic components contemplated herein may also be classified as conductors, semiconductors, or insulators. Here, conductors are components that allow charge carriers (such as electrons) to move with ease among atoms as in an electric current. Examples of conductor components are circuit traces and vias comprising metals. Insulators are components where the function is substantially related to the ability of a material to be extremely resistant to conduction of current, such as a material employed to electrically separate other components, while semiconductors are components having a function that is substantially related to the ability of a material to conduct current with a natural resistivity between conductors and insulators. Examples of semiconductor components are transistors, diodes, some lasers, rectifiers, thyristors and photosensors. Electronic components contemplated herein may also be classified as power sources or power consumers. Power source 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 usable amounts of electrical power through chemical reactions. Similarly, rechargeable or secondary batteries are devices that store usable amounts of electrical energy through chemical reactions. Power consuming components include resistors, transistors, ICs, sensors, and the like.

Still further, electronic components contemplated herein may also be classified as discreet or integrated. Discreet components are devices that offer one particular electrical property concentrated at one place in a circuit. Examples are resistors, capacitors, diodes, and transistors. Integrated components are combinations of components that can provide multiple electrical properties at one place in a circuit. Examples are ICs, i.e., integrated circuits in which multiple components and connecting traces are combined to perform multiple or complex functions such as logic. EXAMPLES

EXAMPLE 1

Tables 1-3 show etch rate results using a contemplated etching solution to etch an antireflective coating (ARC) and/or absorbing composition, such as those contemplated herein. Table 1 shows etch rates for several ARCs, Table 2 shows etch rates for several dielectric materials and Table 3 shows overall etch selectivity.

EXAMPLE 2

Figures 4-5 show etch rate results (as a function of concentration and in some cases as a function of concentration and bake temperature of the anti-reflective coating) using contemplated etching solutions to etch a DUO layer, which is another anti-reflective coating and/or absorbing composition.

Thus, specific embodiments and applications of etching solutions that are selective to sacrificial materials and modified sacrificial materials, these solutions manufacture and uses thereof have been disclosed. It should be apparent, however, to those skilled in the art that many more modifications besides those already described are possible without departing from the inventive concepts herein. The inventive subject matter, therefore, is not to be restricted except in the spirit of the disclosure. Moreover, in interpreting the disclosure, all terms should be interpreted in the broadest possible manner consistent with the context. In particular, the terms "comprises" and "comprising" should be inteφreted as referring to elements, components, or steps in a non-exclusive manner, indicating that the referenced elements, components, or steps may be present, or utilized, or combined with other elements, components, or steps that are not expressly referenced.

Claims

CLAIMSI claim:

1. An etching solution, comprising: at least one fluorine-based constituent, at least one acid constituent; and a solvent constituent, wherein the etching solution selectively etches at least one sacrificial layer from a surface or layered component.

2. The etching solution of claim 1, wherein the at least one fluorine-based constituent comprises hydrogen fluoride, fluorine-based salts or a combination thereof.

3. The etching solution of claim 2, wherein hydrogen fluoride comprises anhydrous hydrogen fluoride or aqueous hydrogen fluoride.

4. The etching solution of claim 2, wherein the fluorine-based salts comprise quaternary ammonium compounds, ammonium fluoride or combinations thereof.

5. The etching solution of claim 4, wherein the quaternary ammonium compounds comprise tetramethylammonium fluoride, tefrapropylammonium fluoride, tetrabutylammonium fluoride, tefraethylammonium fluoride and combinations thereof.

6. The etching solution of claim 1, wherein the at least one acid constituent comprises a weak acid, a strong acid or combinations thereof.

7. The etching solution of claim 6, wherein the at least one acid constituent comprises hydrochloric acid.

8. The etching solution of claim 1, wherein the at least one acid constituent is present in the etching solution at less than about 2 weight percent relative to the at least one fluorine-based constituent and the solvent constituent.

9. The etching solution of claim 8, wherein the at least one acid constituent is present in the etching solution at less than about 1 weight percent relative to the at least one fluorine-based constituent and the solvent constituent.

10. The etclung solution of claim 9, wherein the at least one acid constituent is present in the etching solution at less than about 0.1 weight percent relative to the at least one fluorine-based constituent and the solvent constituent.

11. The etching solution of claim 10, wherein the at least one acid constituent is present in the etching solution at less than about 0.05 weight percent relative to the at least one fluorine-based constituent and the solvent constituent.

12. The etching solution of claim 1, wherein the solvent constituent comprises at least one hydrocarbon solvent.

13. The etching solution of claim 1, wherein the solvent constituent comprises propylene carbonate, butylene carbonate, ethylene carbonate, gamma- butyrolactone, N-methyl- 2-pyriOlidone, propylene glycol, ethylene glycol, ethyl lactate, N,N-dimethylactamide, propylene glycol monomethyl . ether acetate, dimethyl sulfoxide, pyridine or a combination thereof.

14. A method of forming an etching solution, comprising: providing at least one fluorine-based constituent; providing a solvent constituent; providing an acid constituent; and blending the fluorine-based constituent, the acid constituent and the compatible solvent constituent to form a solution, wherein the etching solution selectively etches at least one sacrificial layer from a surface or layered component.

15. The method of claim 14, wherein the at least one fluorine-based constituent comprises hydrogen fluoride, fluorine-based salts or a combination thereof.

16. The method of claim 15, wherein hydrogen fluoride comprises anhydrous hydrogen fluoride or aqueous hydrogen fluoride.

17. The method of claim 15, wherein the fluorine-based salts comprise quaternary ammonium compounds, ammonium fluoride or combinations thereof.

18. The method of claim 17, wherein the quaternary ammonium compounds comprise teframemylammonium fluoride, tetrapropylammomum fluoride, tetrabutylammonium fluoride, tetraetliylammonium fluoride and combinations thereof.

19. The method of claim 14, wherein the at least one acid constituent comprises a weak acid, a strong acid or combinations thereof.

20. ' The method of claim 19, wherein the at least one acid constituent comprises hydrochloric acid.

21. The method of claim 20, wherein the at least one acid constituent is present in the etching solution at less than about 2 weight percent relative to the at least one fluorine- based constituent and the solvent constituent.

22. The method of claim 20, wherein the at least one acid constituent is present in the etching solution at less than about 1 weight percent relative to the at least one fluorine- based constituent and the solvent constituent.

23. The method of claim 22, wherein the at least one acid constituent is present in the etching solution at less than about 0.1 weight percent relative to the at least one fluorine-based constituent and the solvent constituent.

24. The method of claim 23, wherein the at least one acid constituent is present in the etching solution at less than about 0.05 weight percent relative to the at least one fluorine-based constituent and the solvent constituent.

25. The method of claim 14, wherein the solvent constituent comprises at least one hydrocarbon solvent.

26.. The method of claim 14, wherein the solvent constituent comprises propylene carbonate, butylene carbonate, ethylene carbonate, gamma- butyrolactone, N-methyl- 2-pyrrolidone, propylene glycol, ethylene glycol, ethyl lactate, N,N-dimethylactamide, propylene glycol monomethyl ether acetate, dimethyl sulfoxide, pyridine or a combination thereof.

27. A method of forming an etching solution, comprising: providing a hydrogen fluoride constituent; providing a hydrochloric acid constituent; providing a propylene carbonate constituent; and blending the constituents to form a solution, wherein the etching solution selectively etches at least one sacrificial layer from a surface or layered component.