TW201311869A - Compositions and methods for selectively etching silicon nitride - Google Patents

Abstract

Compositions useful for the selective removal of silicon nitride materials relative to silicon oxide materials from a microelectronic device having same thereon. The removal compositions include at least one alkoxysilane, at least one etchant, at least one oxidizing agent, at least one organic solvent, and water.

Description

Composition and method for selectively etching tantalum nitride

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a composition and method for selectively etching tantalum nitride in the presence of yttrium oxide, and more particularly to an etch other than ruthenium oxide in a multilayer semiconductor wafer structure. Rate and selectivity Effectively and efficiently etch the composition and method of tantalum nitride.

Conventional wet etching techniques for selectively removing tantalum nitride (Si ₃ N ₄ ) utilize a hot (about 145-180 ° C) phosphoric acid (H ₃ PO ₄ ) solution containing water, typically 85%. Phosphoric acid and 15% water (volume ratio). Using fresh hot phosphoric acid, the typical Si ₃ N ₄ :SiO ₂ selectivity is about 40:1. Advantageously, when the nitride layer is removed, hydrated yttrium oxide is formed, which, consistent with the Le Châtelier's principle, inhibits the additional removal of yttrium oxide from the surface of the device; thus the selectivity gradually increases with use. Disadvantages associated with the use of hot phosphoric acid etching include corrosion of metal telluride materials (e.g., gate contact materials), etching of hafnium oxide, and process control due to difficulties associated with maintaining a particular amount of water in the process solution. In addition, hot phosphoric acid single wafer tools are difficult to adopt media, which has become more and more popular among many manufacturers.

Another way to selectively remove tantalum nitride involves the use of a composition comprising hydrofluoric acid, however, such compositions also remove ruthenium oxide. A Si ₁₀ N ₄ :SiO ₂ selectivity of about 10:1 can be achieved by dilution, however, the etch rate of tantalum nitride can be compromised and pressures above ambient must be used. Removing the silicon nitride yet another method comprises the use of dry etching to remove halogenated gaseous material, however, Si ₃ N _4: SiO ₂ selective etching process or even worse than those obtained using the aforementioned wet ratio.

Accordingly, it is an object of the present invention to provide for the selective removal of tantalum nitride material relative to a cerium oxide material while minimizing the removal or corrosion of other existing materials without compromising the etch rate of tantalum nitride. Improve the composition.

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a composition and method for selectively etching tantalum nitride from a germanium containing germanium nitride and germanium oxide device relative to germanium oxide. Other materials (eg, metal halides, etc.) that may be present on the microelectronic device should not be substantially removed or corroded by the compositions.

In one aspect, an etching composition is described, the composition comprising at least one alkoxydecane compound, at least one organic solvent, at least one oxidizing agent, at least one etchant, and water, wherein the etching composition is self-contained with nitrogen The surface of the microelectronic device of the plutonium material at least partially removes the tantalum nitride material.

In another aspect, a method of etching a tantalum nitride material from a surface of a microelectronic device having a tantalum nitride material thereon, the method comprising: the surface comprising at least one alkoxydecane compound, at least one organic The composition of the solvent, the at least one oxidizing agent, the at least one etchant, and the water is contacted, wherein the composition at least partially removes the tantalum nitride material from the surface.

Other aspects, features and specific examples of the invention will be apparent from the appended claims and appended claims.

In general, the present invention relates to the selective removal of a composition of tantalum nitride relative to a cerium oxide material, and is therefore suitable for use as an etchant for at least partially removing a tantalum nitride material from a microelectronic device. Furthermore, the present invention is generally directed to a wet-base method for selectively removing tantalum nitride from a cerium oxide material from a microelectronic device comprising a tantalum nitride and yttria material. Other materials (eg, metal halides, etc.) that may be present on the microelectronic device should not be substantially removed or corroded by the compositions.

For ease of reference, "microelectronic devices" correspond to semiconductor substrates, flat panel displays, phase change memory devices, solar panels, and the like that are fabricated for use in microelectronics, integrated circuits, energy harvesting, or computer chip applications. Solar cell devices, photovoltaic devices, and other products of microelectromechanical systems (MEMS). It should be understood that the terms "microelectronic device", "microelectronic substrate" and "microelectronic device structure" are not meant to be limiting, and include any substrate or structure that will ultimately become a microelectronic device or microelectronic assembly. The microelectronic device can be a patterned, blanket, control, and/or test device.

As used herein, "applying" to a microelectronic device having a tantalum nitride material thereon removes the nitride material from at least partial removal of the tantalum nitride material from the microelectronic device.

As used herein, "tantalum nitride" and "Si ₃ N ₄ " correspond to pure tantalum nitride (Si ₃ N ₄ ) and impure nitrides including hydrogen, carbon and/or oxygen impurities present in the crystal structure. Hey. For the purposes of this description, tantalum nitride is referred to as SiN _x .

As used herein, "at least partially removing a tantalum nitride material" is equivalent to removing at least a portion of the exposed tantalum nitride layer. For example, partially removing the tantalum nitride material includes anisotropically removing the tantalum nitride layer covering/protecting the gate electrode to form a SiN _x sidewall. In addition, the compositions described herein can be used more generally to selectively remove the tantalum nitride material relative to the tantalum oxide layer. In these cases, "selective removal" is defined as the use of the composition described herein, at least 50:1, more preferably at least 75:1, and optimally at least 100:1 for SiN _x :SiO ₂ Sexual removal.

As used herein, "about" means equivalent to ± 5% of the stated value.

As used herein, "cerium oxide" or "SiO ₂ " material is equivalent to a material deposited from a source of cerium oxide precursor, such as TEOS, thermally deposited cerium oxide, or using such as SiLK ^TM , AURORA ^TM , CORAL ^TM , BLACK DIAMOND ^TM commercially or precursors of deposition of carbon doped oxide (CDO). For the purposes of this specification, "yttria" is intended to broadly include SiO ₂ , CDO, decane, and thermal oxides. The yttria or SiO ₂ material corresponds to pure tantalum nitride (SiO ₂ ) and impure yttrium oxide including impurities present in the structure.

It should be understood that some chemical components, when at their lowest energy (ie, steady state), especially when commercially available, naturally include negligible amounts of water. For the purposes of this description, naturally occurring water is not considered to be added water.

The composition preferably has good metal compatibility, for example, a low etch rate on the interconnect metal and/or interconnect metal halide material. Related metals include, but are not limited to, copper, tungsten, cobalt, molybdenum, aluminum, niobium, titanium, and tantalum. Related tellurides include any of the species including Ni, Pt, Co, Ta, Mo, W, and Ti, including, but not limited to, TiSi ₂ , NiSi, CoSi ₂ , NiPtSi, antimony telluride, antimony molybdenum, and antimony Tungsten.

The compositions of the present invention can be embodied as a more complete description of the particular formulations below.

In all such compositions, when a particular component of the composition is discussed with reference to a range of weight percentages including a lower limit of zero, it is apparent that such components may or may not be present in various specific embodiments of the composition, and are present. In the case of such components, it may be present in a concentration as low as 0.001 weight percent based on the total weight of the components in which the components are used.

In one aspect, a composition is described for removing a tantalum nitride material from a surface of a microelectronic device having a tantalum nitride material thereon, the composition comprising at least one alkoxydecane compound. In one embodiment, the composition for removing the tantalum nitride material from the surface of the microelectronic device having the tantalum nitride material thereon comprises, consists of, or consists essentially of: At least one alkoxydecane compound, at least one organic solvent, and at least one etchant. In another embodiment, the composition for removing the tantalum nitride material from the surface of the microelectronic device having the tantalum nitride material thereon comprises, consists of, or consists essentially of the following components : at least one alkoxydecane compound, at least one organic solvent, at least one etchant, and at least one oxidizing agent. In yet another embodiment, the composition for removing the tantalum nitride material from the surface of the microelectronic device having the tantalum nitride material thereon comprises, consists of, or consists essentially of Composition: at least one alkoxydecane compound, at least one organic solvent, at least one etchant, at least one oxidizing agent, and water. When water is present, the amount of water added is preferably no more than about 25% by weight based on the total weight of the composition, preferably no more than 20% by weight based on the total weight of the composition. If yttrium oxide is present during the yttrium nitride removal, the composition may be used to selectively remove the tantalum nitride material relative to the ruthenium oxide layer, wherein the selective removal of SiN _x : SiO ₂ is at least 50:1, Better at least 75:1, and optimally at least 100:1.

Organic solvents encompassed herein include, but are not limited to, glycols such as ethylene glycol, neopentyl glycol, and propylene glycol (PG), dimers, trimers, and tetramers thereof such as dipropylene glycol, diethylene glycol ( PEG) and the like; alcohols such as linear or branched C ₂ -C ₆ alcohols including ethanol, propanol, butanol, pentanol, and hexanol; and glycol ethers such as diethylene glycol monomethyl ether, triethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether , diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether, propylene glycol monoethyl ether, propylene glycol n-propyl ether, dipropylene glycol Propyl ether, tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether (DPGBE), tripropylene glycol n-butyl ether, propylene glycol phenyl ether (phenoxy-2-propanol) and combination. The at least one organic solvent preferably comprises propylene glycol, diethylene glycol, or a combination thereof.

While not wishing to be bound by theory, it is believed that the alkoxydecane acts as an etch rate inhibitor for the cerium oxide material by physical adsorption and/or chemisorption onto the oxide material. This will reduce the oxide etch rate, thereby increasing the selectivity of the composition relative to yttrium oxide for tantalum nitride. The alkoxydecanes encompassed have the general formula SiR ¹ R ² R ³ R ⁴ wherein R ¹ , R ² , R ³ and R ⁴ are identical or different from each other and are selected from the group consisting of hydrogen, linear C _1- C ₆ alkyl (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl), branched C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy (eg, methoxy) Base, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), phenyl, and combinations thereof. It will be apparent to those skilled in the art that as alkoxydecane, at least one of R ¹ , R ² , R ³ or R ⁴ must be a C ₁ -C ₆ alkoxy group. Alkoxy decanes encompassed include trimethoxy decane, triethoxy decane, methyl dimethoxy decane, methyl diethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, Tris-propoxydecane, ethyltrimethoxydecane, dimethylethoxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane, phenyltrimethoxydecane, tetraethoxy Baseline, N-propyltrimethoxydecane, N-propyltriethoxydecane, n-butyltrimethoxydecane, n-butyltriethoxydecane, hexyltrimethoxydecane,hexyltriethoxy Decane, and combinations thereof. The alkoxydecane preferably includes N-propyltrimethoxydecane.

Etchants contemplated include, but are not limited to, hydrofluoric acid, ammonium fluoride, ammonium hydrogen fluoride, hexafluoroantimonic acid, tetrafluoroboric acid, tetrabutylammonium tetrafluoroborate (TBA-BF ₄ ), tetraalkylammonium fluoride ( NR ₄ F), alkyl hydrogen fluoride (NRH ₃ F), dialkyl ammonium hydrogen fluoride (NR ₂ H ₂ F), trialkyl ammonium hydrogen fluoride (NR ₃ HF), trialkyl ammonium trihydrogen fluoride (NR ₃ : 3HF), wherein R may be the same or different from each other and are selected from a linear or branched C ₁ -C ₆ alkyl group (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl) and combinations thereof a group of people. Preferably, the fluoride source comprises ammonium hydrogen fluoride.

Oxidizing agents encompassed herein include, but are not limited to, hydrogen peroxide (H ₂ O ₂ ), FeCl ₃ (hydrated and unhydrated), oxygenated (2KHSO ₅ .KHSO ₄ .K ₂ SO ₄ ), ammonium polyatomic salts (eg, ammonium peroxymonosulfate, ammonium chlorite (NH ₄ ClO ₂ ), ammonium chlorate (NH ₄ ClO ₃ ), ammonium iodate (NH ₄ IO ₃ ), ammonium nitrate (NH ₄ NO ₃ ), Ammonium borate (NH ₄ BO ₃ ), ammonium perchlorate (NH ₄ ClO ₄ ), ammonium periodate (NH ₄ IO ₃ ), ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ), ammonium hypochlorite (NH ₄ ClO)), sodium polyatomic salt (for example, sodium persulfate (Na ₂ S ₂ O ₈ ), sodium hypochlorite (NaClO)), potassium polyatomic salt (for example, potassium iodate (KIO ₃ ), permanganic acid Potassium (KMnO ₄ ), potassium persulfate, nitric acid (HNO ₃ ), potassium persulfate (K ₂ S ₂ O ₈ ), potassium hypochlorite (KClO), tetramethylammonium polyatomic salt (eg, tetramethylammonium chlorite) ((N(CH ₃ ) ₄ )ClO ₂ ), tetramethylammonium chlorate ((N(CH ₃ ) ₄ )ClO ₃ ), tetramethylammonium iodate ((N(CH ₃ ) ₄ )IO ₃ )) Tetramethylammonium borate ((N(CH ₃ ) ₄ )BO ₃ ), tetramethylammonium perchlorate ((N(CH ₃ ) ₄ )ClO ₄ ), tetramethylammonium periodate ((N(CH ₃ ) ₄ ) ) IO _4), tetramethylammonium persulfate _{((N (CH 3) 4} ) S 2 O 8)), multi-tetrabutylammonium Sub salts (e.g., tetrabutylammonium peroxymonosulfate sulfate, peroxy monosulfate, iron nitrate _{(Fe (NO 3) 3)} , urea hydrogen peroxide _{((CO (NH 2) 2} ) H 2 O 2), peracetic acid (CH ₃ (CO)OOH), and combinations thereof. The oxidant can be introduced to the composition at the manufacturer, prior to introduction of the composition to the device wafer, or at the device wafer (ie, in situ). The oxidizing agent comprises a nitrate compound such as nitric acid, ammonium nitrate, or a combination thereof.

In a particularly preferred embodiment, the composition comprises, consists of, or consists essentially of ammonium hydrogen fluoride, propylene glycol, at least one alkoxy decane, nitric acid, and water. In another embodiment, the composition comprises, consists of, or consists essentially of ammonium hydrogen fluoride, propylene glycol, at least one alkoxy decane, ammonium nitrate, and water. In yet another embodiment, the composition comprises, consists of, or consists essentially of ammonium hydrogen fluoride, diethylene glycol, at least one alkoxy decane, nitric acid, and water. In a particularly preferred embodiment, the composition comprises, consists of, or consists essentially of ammonium hydrogen fluoride, propylene glycol, N-propyltrimethoxydecane, nitric acid, and water. In another embodiment, the composition comprises, consists of, or consists essentially of ammonium hydrogen fluoride, propylene glycol, N-propyltrimethoxydecane, ammonium nitrate, and water. In yet another embodiment, the composition comprises, consists of, or consists essentially of ammonium hydrogen fluoride, diethylene glycol, N-propyltrimethoxydecane, nitric acid, and water.

In one embodiment, the composition is substantially free of abrasive materials, such as chemical mechanical polishing materials such as vermiculite, alumina, and other particulate materials for CMP, and is not used under supercritical conditions, ie, the composition does not have Supercritical component. Further, the composition may not form a polymeric or resinous material. As defined herein, "substantially free" is equivalent to less than about 2% by weight, more preferably less than 1% by weight, and most preferably less than 0.1% by weight, based on the total weight of the composition. Further, when water is present, the amount of added water is preferably not more than about 25% by weight based on the total weight of the composition, preferably not more than 20% by weight based on the total weight of the composition.

The compositions of the present invention have a pH in the range of from about 1 to about 7, preferably from about 3 to about 7, and most preferably from about 3 to about 4.

In another embodiment, any of the compositions of the present invention may further comprise a tantalum nitride material residue, wherein the tantalum nitride material residue is suspended and/or dissolved in the removal composition.

In one embodiment, the composition comprises, consists of, or consists essentially of at least one alkoxydecane compound, at least one organic solvent, at least one etchant, at least one oxidizing agent, and water, The following ranges exist based on the total weight of the composition:

It is understood that the general practice is to make a concentrated form of the composition for dilution prior to use. For example, the composition can be fabricated to include at least one alkoxydecane compound, at least one organic solvent, at least one etchant, at least one oxygen The more concentrated form of the agent, and water, is then diluted with at least one organic solvent at the manufacturer, prior to use, and/or during use in the factory. The dilution ratio can range from about 0.1 part diluent to 1 part composition concentrate to about 100 parts diluent: 1 part composition concentrate. When diluted, the compositions of the present invention have a pH in the range of from about 1 to about 7, preferably from about 3 to about 7, and most preferably from about 3 to about 4.

The compositions described herein are readily formulated by simply adding the individual ingredients and mixing to a uniform state. In addition, the composition can be readily formulated as a single package formulation or as a plurality of formulations mixed at or before the point of use, preferably in multiple portions. Multiple servings of multiple formulations may be mixed at the tool or in a mixing zone/range such as a wire mixture or a reservoir upstream of the tool. Portions encompassing multiple formulations may comprise any combination of ingredients/components that form the desired composition when mixed together. The concentration of the individual ingredients can vary widely within a particular multiple of the composition, i.e., more dilute or more concentrated, and when it is apparent that the composition can vary and alternatively comprise any combination of ingredients consistent with the disclosure herein, Composition, or consist essentially of.

Thus, another aspect relates to a kit comprising one or more components present in one or more containers suitable for forming the compositions described herein. Preferably, the kit comprises at least one alkoxydecane compound, at least one organic solvent, at least one etchant, at least one oxidizing agent and water stored in one or more containers for use at the factory and water And / or an additional combination of organic solvents. Alternatively, the kit includes for at least one organic solvent at the factory with water The agent, and/or the at least one oxidizing agent, in combination with at least one alkoxydecane compound, at least one organic solvent, at least one etchant, and water, in one or more containers. Those skilled in the art will recognize that other combinations are covered here. The kit of containers must be suitable for storing and transporting the components of the removal composition, for example, a NOWPak® container (Advanced Technology Materials, Inc., Danbury, Conn., USA). The one or more containers containing the components of the composition preferably include means for fluidly communicating the components of the one or more containers for blending and dispensing. For example, with reference to a NOWPak® container, gas pressure can be applied to the outside of the liner in the one or more containers to cause at least a portion of the contents of the liner to drain, and thus can be blended and dispensed by fluid communication. Alternatively, gas pressure may be applied to the headspace of a conventional pressurizable container, or a pump may be used to achieve fluid communication. Additionally, the system preferably includes a dispensing port for dispensing the blended removal composition to the process tool.

It is preferred to use a polymeric film material that is substantially chemically inert, free of impurities, flexibility, and elasticity, such as high density polyethylene, to make the liner of the one or more containers. The ideal lining material does not require co-extrusion or barrier layers for processing, and does not contain any pigment, UV inhibitor, or process agent that would adversely affect the purity requirements of the components to be placed in the liner. A list of ideal lining materials includes pure (no additives) polyethylene, pure polytetrafluoroethylene (PTFE), polypropylene, polyurethane, polydivinylidene, polyvinyl chloride, polyacetal, polyphenyl A film of ethylene, polyacrylonitrile, polybutene, or the like. Preferred thicknesses of such lining materials range from about 5 mils (0.005 inches) to about 30 mils (0.030 inches). Within the range, for example, a thickness of 20 mils (0.020 inch).

</ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; (APPARATUS AND METHOD FOR MINIMIZING THE GENERATION OF PARTICLES IN ULTRAPURE LIQUIDS)"; US Patent No. 6,698,619, entitled "Recyclable and Recyclable Boiler Bag Fluid Storage and Dispensing Container System (RETURNABLE AND REUSABLE, BAG-IN-DRUM FLUID STORAGE AND DISPENSING CONTAINER SYSTEM); and PCT/US08/63276, filed on May 9, 2008, entitled "SYSTEMS AND METHODS FOR MATERIAL BLENDING AND DISTRIBUTION".

In still another aspect, the present invention is directed to a method of etching a tantalum nitride material from the surface of a microelectronic device having a tantalum nitride material thereon using the compositions described herein. For example, the tantalum nitride material can be removed without substantially damaging the metal and metal telluride interconnect materials. Moreover, the compositions preferably selectively remove the tantalum nitride material relative to the cerium oxide. Thus, in a preferred embodiment, a surface selectively and substantially removed from a surface of a microelectronic device having a yttria material and a tantalum nitride material thereon using the composition described herein is described. The method of the tantalum nitride material. As defined previously, "selective removal" is defined as the use of the compositions described herein, at least 50: 1, more preferably at least 75:1, and optimally at least 100:1 selectivity for SiN _x :SiO ₂ Remove.

In etching applications, the composition is applied to the surface of the microelectronic device having the tantalum nitride material thereon in any suitable manner, for example, by spraying the composition onto the surface of the device, via a device that will include a tantalum nitride material. Soaking (in a static or dynamic volume composition) by contacting the device with another material (eg, a mat, or fiber absorbing applicator member) on which the composition is absorbed, by including a tantalum nitride material The apparatus is in contact with the circulating composition, or by any other suitable means, means or technique by which the composition is removed from contact with the tantalum nitride material. Applications can be used in batch or single wafer devices for dynamic or static cleaning. Advantageously, the compositions described herein are highly efficient and highly selective by virtue of their selectivity for the tantalum nitride material relative to other materials that may be present on the structure of the microelectronic device and exposed to the composition, such as yttrium oxide. The at least partial removal of the tantalum nitride material is achieved in a sexual manner.

When the composition described herein is used to remove the tantalum nitride material from a microelectronic device structure having a tantalum nitride material thereon, the composition and device structure are typically from about 40 ° C to about 150 ° C, preferably about 80. The contact is carried out at a temperature ranging from ° C to about 120 ° C for a period of from about 1 minute to about 200 minutes, preferably from about 5 minutes to about 60 minutes. The contact times and temperatures are illustrative and any other suitable time and temperature conditions for effectively removing the tantalum nitride material from the device structure can be used. Advantageously, when the composition comprises an organic solvent of the amount described herein, the method of etching tantalum nitride can be carried out at a higher temperature, A higher etch rate is tolerated.

In one embodiment, the composition is heated on the line during delivery to the device structure. The composition lifetime increases with on-line heating rather than in the tank itself.

After the desired etching action is achieved, the composition can be easily removed from its previously applied microelectronic device, for example, via a rinse, wash, or other removal step, which may be given by the composition of the present invention. Required and effective in the final application. For example, the device may be deionized water rinsing comprises rinsing solution and / or dried (e.g., spin drying, N _2, steam drying, etc.).

The composition described herein preferably etches the tantalum nitride material selectively with respect to yttria. In one embodiment, the etch rate of tantalum nitride is high (about 90 to about 100 angstroms per minute), while the selectivity of SiN _x : SiO ₂ is moderate (about 80:1 to about 150:1). In another embodiment, the etch rate of tantalum nitride is low (about 20 to about 50 angstroms per minute), while the selectivity of SiN _x : SiO ₂ is high (> 200: 1). In yet another embodiment, the etch rate of tantalum nitride is moderate (about 60 to about 90 angstroms per minute), while the selectivity of SiN _x : SiO ₂ is moderate (about 80:1 to about 150:1). ).

Still another aspect of the invention pertains to improved microelectronic devices and products containing such microelectronic devices made according to the methods described herein.

Yet another aspect relates to a method of making an article comprising a microelectronic device, the method comprising contacting the microelectronic device with the composition for a time sufficient to etch away from a surface of the microelectronic device having the tantalum nitride material thereon a tantalum nitride material, and incorporating the microelectronic device into the article, wherein the removal composition And consisting of, or consisting essentially of, at least one alkoxydecane compound, at least one organic solvent, at least one etchant, at least one oxidizing agent, and water. The composition may further comprise, consist of, or consist essentially of a tantalum nitride material.

Another aspect of the invention relates to a manufactured article comprising the following components, consisting essentially of, or consisting essentially of: a substrate of a microelectronic device; a layer of tantalum nitride on the substrate; And a composition comprising, consisting essentially of, or consisting of at least one alkoxydecane compound, at least one organic solvent, at least one etchant, at least one oxidizing agent, and water.

The features and advantages of the present invention are more fully apparent from the illustrative embodiments set forth herein.

[Example 1]

Five compositions as described in Table 1 below were prepared. The thermal oxide and tantalum nitride samples were each immersed in each composition at 110 ° C for 30 minutes and 10 minutes, and the etching rate of each was measured using an ellipsometer. The results including the selectivity of SiN _x :SiO ₂ are provided in Table 1.

***

Although the present invention has been described with reference to the specific aspects, features, and illustrative embodiments of the present invention, it is understood that the utility of the invention is not limited thereto, but may be extended to and encompass many other variations, modifications, and alternatives. For example, it will be readily apparent to those skilled in the art based on the disclosure herein. Accordingly, the present invention is intended to be broadly construed and construed as the invention

Claims (21)

An etching composition comprising at least one alkoxydecane compound, at least one organic solvent, at least one oxidizing agent, at least one etchant, and water, wherein the etching composition is used for self-contained tantalum nitride material The surface of the electronic device at least partially removes the tantalum nitride material. The etching composition of claim 1, wherein the added amount is less than about 25% by weight based on the total weight of the composition. The etching composition of claim 1, wherein the organic solvent comprises a substance selected from the group consisting of ethylene glycol, neopentyl glycol, propylene glycol (PG), dipropylene glycol, diethylene glycol (PEG) ), ethanol, propanol, butanol, pentanol, hexanol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, B Glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl Ether (DPGME), tripropylene glycol methyl ether, propylene glycol monoethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether ( DPGBE), tripropylene glycol n-butyl ether, propylene glycol phenyl ether (phenoxy-2-propanol), and combinations thereof. The etching composition of claim 1, wherein the at least one organic solvent comprises propylene glycol or diethylene glycol. The etching composition of claim 1, wherein the alkoxydecane has the formula SiR ¹ R ² R ³ R ⁴ , wherein the R ¹ , R ² , R ³ and R ⁴ are the same or different from each other and are The group consisting of hydrogen, a linear C ₁ -C ₆ alkyl group, a branched C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a phenyl group, and combinations thereof is selected, the At least one of R ¹ , R ² , R ³ or R ⁴ is a C ₁ -C ₆ alkoxy group. The etching composition of claim 1, wherein the alkoxydecane comprises a substance selected from the group consisting of trimethoxy decane, triethoxy decane, methyl dimethoxy decane, and Diethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, methyl tripropoxy decane, ethyl trimethoxy decane, dimethyl ethoxy decane, dimethyl dimethyl Oxy decane, dimethyl diethoxy decane, phenyl trimethoxy decane, tetraethoxy decane, N-propyl trimethoxy decane, N-propyl triethoxy decane, n-butyl trimethoxy Alkane, n-butyltriethoxydecane, hexyltrimethoxydecane, hexyltriethoxydecane, and combinations thereof. The etching composition of claim 1, wherein the alkoxydecane comprises N-propyltrimethoxydecane. The etching composition of claim 1, wherein the etchant comprises a substance selected from the group consisting of hydrofluoric acid, ammonium fluoride, ammonium hydrogen fluoride, hexafluoroantimonic acid, tetrafluoroboric acid, and tetrafluorocarbon. Tetrabutylammonium borate (TBA-BF ₄ ), tetraalkylammonium fluoride (NR ₄ F), alkyl hydrogen fluoride (NRH ₃ F), dialkyl ammonium hydrogen fluoride (NR ₂ H ₂ F), trialkyl ammonium hydrogen fluoride (NR ₃ HF), trialkylammonium trihydrogen fluoride (NR ₃ : 3HF), wherein R may be the same or different from each other and is selected from the group consisting of a linear or branched C ₁ -C ₆ alkyl group and combinations thereof. group. An etching composition according to claim 1, wherein the etchant Includes ammonium bifluoride. The etching composition of claim 1, wherein the at least one oxidizing agent comprises a substance selected from the group consisting of hydrogen peroxide, FeCl ₃ , oxone, ammonium peroxymonosulfate, and sub Ammonium chlorate, ammonium chlorate, ammonium iodate, ammonium nitrate, ammonium perborate, ammonium perchlorate, ammonium periodate, ammonium persulfate, ammonium hypochlorite, sodium persulfate, sodium hypochlorite, potassium iodate, permanganese Potassium acid, potassium persulfate, nitric acid, potassium persulfate, potassium hypochlorite, tetramethylammonium chlorite, tetramethylammonium chlorate, tetramethylammonium iodate, tetramethylammonium perborate, tetramethylammonium perchlorate, iodine Tetramethylammonium acid, tetramethylammonium persulfate, tetrabutylammonium peroxymonosulfate, peroxymonosulfuric acid, ferric nitrate, urea hydrogen peroxide, peracetic acid, and combinations thereof. The etching composition of claim 1, wherein the at least one oxidizing agent comprises nitric acid. The composition of claim 1, which comprises a component selected from the group consisting of ammonium hydrogen fluoride, propylene glycol, N-propyltrimethoxydecane, nitric acid, and water; ammonium hydrogen fluoride, propylene glycol, N- Propyltrimethoxydecane, ammonium nitrate, and water; and ammonium hydrogen fluoride, diethylene glycol, N-propyltrimethoxydecane, nitric acid, and water. The composition of claim 1, wherein the pH is in the range of from about 1 to about 7. The composition of claim 1, wherein the pH is in the range of from about 3 to about 7. For example, the composition of the first item of the patent scope, wherein the composition One step contains a residue of tantalum nitride material. A method of etching a tantalum nitride material from a surface of a microelectronic device having a tantalum nitride material thereon, the method comprising contacting the surface with a composition of any one of claims 1 to 15, wherein The composition at least partially removes the tantalum nitride material from the surface. The method of claim 16, wherein the composition selectively removes the tantalum nitride material relative to the cerium oxide material. The method of claim 17, wherein the SiN _x :SiO ₂ removal has a selectivity of at least 50:1. The method of claim 16, wherein the contacting comprises a time in the range of from about 1 minute to about 200 minutes at a temperature in the range of from about 40 °C to about 150 °C. The method of claim 16, wherein the composition is heated on the line during delivery to the device structure. The method of claim 16, wherein the composition is rinsed from the surface after the desired etching action is achieved.