KR20200059326A - Acidic semi-aqueous fluoride activated anti-relective coating cleaners with superior substrate compatibilities and exceptional bath stability - Google Patents

Abstract

Provided herein are novel acidic fluoride activated cleaning chemicals with highly effective ARC removal, cleaning ability, and superior compatibility with a wide variety of materials. In the present invention, ARC removal, PR stripping, etching / ashing residue cleaning and CMP residue removal in FEOL, BEOL and FPD applications, while providing undesired surface modification and excellent substrate compatibility, pH stability, and bath stability. Compositions are provided that provide.

Description

ACIDIC SEMI-AQUEOUS FLUORIDE ACTIVATED ANTI-RELECTIVE COATING CLEANERS WITH SUPERIOR SUBSTRATE COMPATIBILITIES AND EXCEPTIONAL BATH STABILITY} with superior substrate compatibility and exceptional bath stability

The present invention relates to microelectronic cleaning compositions, and their use in microelectronic device cleaning methods, particularly for removal of antireflective coatings (ARCs) and residual cleaning compositions with greater substrate and metallization compatibility.

New strips with the ability to strip or clean both front end of the line (FEOL) and back end of the line (BEOL) due to recent advances in micro- and nano-electronic device production. Ping and cleaning compositions became necessary. It has been found that the cleaning compositions typically used so far are not suitable as new materials used in microelectronic or nanoelectronic platform production. The previously used stripping or cleaning composition is too aggressive and / or is not sufficiently selective. Among the newly used materials used to produce newer microelectronic or nanoelectronic devices such as the above are low-k (<3) and high-k (> 20) and porous dielectrics, copper metallization, fluoropolymer antireflective coatings. (ARC), special hard masks such as those consisting of Ti and TiN, strained wafers of Si / Ge or Ge, and materials such as metal capping layers such as those of CoWP and CoWB. These new materials present new and difficult difficulties for device manufacturers.

For example, cleaning Cu / low-k structures not only requires good cleaning ability, but also requires a solution with exceptional substrate compatibility. Many process technologies developed for traditional or conventional semiconductor devices containing Al / SiO ₂ or Al (Cu) / SiO ₂ structures cannot be applied to Cu / low-k and high-k structures. Similarly, vice versa, many Cu / low-k strippers are not suitable for Al metallisations unless significant control is made.

Manufacturing processes of Cu / low-k and / or high-k structures often produce uniquely cured photoresist layers, tough plasma etching and / or ashing residues. Even highly aggressive reagents such as HF acid, hydroxylamine and strong alkaline solutions often fail to provide suitable cleaning with acceptable substrate compatibility.

Fluoride or HF based aqueous solutions have been used extensively as traditional FEOL and BEOL etchants and cleaning agents. Often, these types of cleaning agents are developed as oxide etchants or ashing residue removers. For example, diluted HF (dHF) solutions and buffered oxide etch (consisting of BOE, HF / NH ₄ F / H ₂ O) are effective oxide (silicon oxide) removers and limited residue cleaners, but are generally photoresist It is not effective for stripping.

Several organic solvent-based or semi-aqueous solutions containing fluoride or HF have also been used in many BEOL applications. However, most of these products are still weak for multi-purpose applications such as removal of plasma cured photoresist and ARC. They may also be overly aggressive in some cases, not sufficiently selective, or new conductive types of materials, such as low-k and high-k and porous dielectrics, copper metallization, fluoropolymer antireflective coatings (ARC) New, highly demanding substrate commercial use for advanced FEOL and BEOL applications using special hard metal gates such as those of Ti and TiN, strained wafers of Si / Ge or Ge, and metal capping layers such as those of CoWP and CoWB The gender and selectivity requirements cannot be met. Accordingly, there is a need for new and improved stripping or cleaning compositions for multi-purpose applications in connection with such new materials used on newer microelectronic and nanoelectronic devices.

To create increasingly smaller microprocessors, memory cells and other semiconductor devices, one of the key strategies is to build multi-gate transistors. In addition to conventional planar multi-gate transistors, non-planar double gates (eg FinFET), or tree-gates have been developed. Frequently, high-k materials and metal gates are also used in this advanced technology (eg, 14 nm node). The list of materials / substrates is extensive: Al, Cu, W, Ti, TiN, TaN, Nb, RuO ₂ , Mo, LaOx, AlOx, HfSiON, COSi ₂ , WSi ₂ , SiN, SiON, TEOS, PolySi, SiGe , Ge, and combinations thereof and / or adducts. Control of the thickness of various, often ultra-thin metal gates (MG), work function metals (WF), and high-k (HK) is important. There are great difficulties associated with introducing cleaning chemicals with a wide range of very high compatibility and enabling (high cleaning ability for various PRs and residues) for ultra-thin films (e.g. 10 Angstrom WF films) do. For example, an etch rate as low as 1 Angstrom of TiN may be too high and unusable in some cases. Current or traditional wet cleaning chemicals can no longer meet this kind of compatibility requirements. There is a need for novel enabling cleaning chemicals with superior substrate compatibility that can selectively clean photoresists, antireflective coatings (ARCs), residual WF metals, and various plasma etching or ashing residues.

Fluoride-activated (based) cleaning chemicals generally work much more effectively under acidic pH conditions. However, acidic fluoride chemicals, especially HF-containing detergents, have the drawback of being a large limitation of metallization and incompatibility with many substrates. For example, an etch rate of 200: 1 DHF at 25 ° C: Al,> 550 / min, TEOS,> 30 / min; 200: 1 DHF at 35 ° C, Al,> 2,000 / min, TEOS,> 140 / min. Even highly diluted 600: 1 DHF at 35 ° C. was Al,> 750 / min. Other fluoride-based detergents containing fluoride salts are also severely limited in cleaning ability or substrate compatibility: at neutral or basic pH, the cleaning ability is generally fairly weak, limited only to selected types of residues that can be cleaned. Will be; At acidic pH, ammonium fluoride containing detergents often have poor copper compatibility; Alkylammonium fluoride-containing cleaners generally have poor aluminum compatibility. In addition, most fluoride-based cleaners exhibit poor compatibility with a variety of important microelectronic materials, such as TEOS, SiN and low-k.

Antireflective coating (ARC) materials are increasingly used in the fabrication of advanced microelectronic devices. One popular ARC is a silicon-containing floor antireflective coating (SiBARC). However, ARC removers based on fluoride activated chemicals are often important metallizations (e.g. Al, Cu, W, Ti, TiN, TaN) and substrates (e.g. TEOS, SiN, high-k, low There is a drawback of severe selectivity problems between providing limited etch damage to -k) and efficient SiBARC removal. Some acidic fluoride cleaning chemicals have shown improvement by providing better compatibility. However, none of them could exhibit a level of compatibility that meets the highly demanded requirements in advanced technology nodes in semiconductors such as 16 nm or less. In special but important applications, optimizing the Al ₂ O ₃ thickness without damaging the Al metallization provides obvious and significant performance. In addition, the need for special cleaning, such as the selective removal of "Al oxide-like", "Ti oxide-like" residues or etched / ashed antireflective coatings, combined with very sparse compatibility, poses great technical difficulties. None of the known chemicals simultaneously met all these difficulties / needs.

Diluted hydrofluoric acid (DHF) is a unique and effective cleaning agent for a wide range of microelectronic applications. However, advanced FEOL and BEOL cleaning requires a much more diverse substrate and metallization compatibility than DHF. In addition, other abilities such as PR (photoresist) stripping are also very beneficial. Therefore, new cleaning chemicals are needed.

Fluoride-based detergents have been widely used in the past for a variety of cleaning needs, but their use has been ruled out in many new applications due to the use of new materials, alloys and composites with different sensitivities. Fluoride containing formulations are well known, for example, to etch silicon oxide at acidic pH, and are commonly used as silicon oxide etchants. A well-known example is an HF-based silicon oxide etchant, such as a buffered oxide etchant (BOE), which includes various ratios of aqueous solutions of HF and NH ₄ F. However, the selectivity of ARC or SiBARC removal for its TEOS is generally very poor. In many previous disclosures, slightly acidic pH (pH> 6), neutral or preferably alkaline pH conditions are used to suppress such compatibility problems. However, the ARC / SiBARC removal ability and cleaning ability are greatly reduced under such pH conditions. One example is U.S. Patent 7,399,365 B2. It is taught to use a preferred pH range of 6.5 to 8.

Related technologies include attempts to address the above problems, including providing a source of fluoride as the active species without distinction. For example, U.S. Pat.No. 6,777,380 includes detergents having a source of fluoride such as hydrofluoric acid, ammonium fluoride, tetramethylammonium fluoride, ammonium bifluoride. However, these examples do not provide the broad compatibility needed for current applications, or also the enhancement of selectivity required.

Accordingly, there is a need for an acidic ARC remover / cleaner that has a desirable pH range of 5 or less and provides high cleaning ability of ARC / SiBARC etching. In addition, cleaning compositions capable of achieving broad compatibility and high selectivity for many important metallization and substrates, including high compatibility / low etch rates for Al, Cu, W, Ti, TiN, TaN, TEOS This is necessary.

Accordingly, provided herein are novel acid fluoride activated cleaning chemicals with highly effective ARC removal, cleaning ability, and superior compatibility with a wide variety of materials. In the present invention, ARC removal, PR stripping, etching / ashing residue cleaning and CMP residue removal in FEOL, BEOL and FPD applications, while providing undesired surface modification and excellent substrate compatibility, pH stability, and bath stability. Compositions are provided that provide.

Provided herein are cleaning compositions for microelectronic applications. The cleaning composition comprises about 0.05% to about 5.0% by weight of a non-fluoride compound, about 0.01% to about 5% by weight of a pH-stabilizing compatibility enhancer, about 5% to about 90% by weight of organic solvent, and about 5% to about 90% water.

In another embodiment, the cleaning composition comprises from about 0.05% to about 1.0% by weight of a non-fluoride compound, from about 0.05% to about 3% by weight of a pH-stabilizing compatibility enhancer, from about 10% to about 70% by weight Organic solvent, and about 10% to about 50% of water.

In another embodiment, the cleaning composition comprises from about 0.1% to about 0.5% by weight of a non-fluoride compound, from about 0.1% to about 1.0% by weight of a pH-stabilizing compatibility enhancer, from about 20% to about 60% by weight Organic solvent, and about 20% to about 40% of water.

In another embodiment, the cleaning composition has a pH of 5.5 or less. In an embodiment, the cleaning composition has a pH of 5.0 or less, and in another embodiment, the composition has a pH of 4.5 or less.

In another embodiment, the cleaning composition further comprises a cosolvent selected from alcohols, alcohol-ethers, and ethers. In an embodiment, the non-fluoride compound can be selected from the group of ammonium bifluoride, alkylammonium bifluoride, potassium bifluoride, and alkali metal nonfluoride. In an embodiment, the non-fluoride compound is selected from any of many commercially available non-fluoride compounds known in the art.

In an embodiment, the pH-stabilizing compatibility enhancer is a variegated acid, or salt thereof. In an embodiment, the pH-stabilizing compatible enhancer is citric acid, monobasic ammonium citrate, dibasic ammonium citrate, tribasic ammonium citrate, phosphoric acid, monobasic ammonium phosphate, dibasic ammonium phosphate, tribasic ammonium phosphate, ascorbic acid , Monobasic ammonium ascorbate, dibasic ammonium ascorbate, and mixtures thereof.

In an embodiment, the organic solvent of the cleaning composition is a sulfide or amide. In another embodiment, the organic solvent is dimethyl sulfoxide, N-methyl pyrrolidone (NMP), N-ethyl pyrrolidone (NEP), N- (2-hydroxyethyl) -2-pyrrolidone (HEP) ), Dimethyl 2-piperidone (DMPD), dimethyl acetamide, formamide, and mixtures thereof.

In another embodiment, the cleaning composition of the present invention further comprises at least another source of fluoride. In embodiments, at least another source of fluoride is a fluoride salt. In another embodiment, the cleaning composition further comprises a corrosion control agent. In embodiments, the corrosion control agent is selected from the group of commercially available control agents known in the art. In another embodiment, the cleaning composition further comprises a surfactant. Surfactants can be selected from the group of commercially available surfactants known in the art.

In another embodiment, the invention provides a microelectronic material from about 0.05% to about 5.0% by weight of a non-fluoride compound, from about 0.01% to about 5% by weight of a pH-stabilizing compatibility enhancer, from about 5% by weight To a cleaning composition comprising from about 90% to about 90% by weight organic solvent, and from about 5% to about 90% water.

For a better understanding of the present invention along with other and additional objects and advantages, reference may be made to the following detailed description in conjunction with the accompanying examples, and the scope of the invention will be referred to in the appended claims. The following detailed description is not intended to limit the scope of the invention by the advantages described above.

The present invention solves the difficult difficulty of using acid fluoride-based chemicals as an antireflective coating (ARC) remover, while simultaneously providing broad superior metallization and substrate compatibility. It can also be considered as a superior diluted hydrofluoric acid (DHF) replacement. This can provide important cleaning for many other advanced line front (FEOL) and line back (BEOL) applications. In addition, the present invention provides an enabling wet scrubbing solution for a wide range of stringent compatibility requirements that are highly required for the fabrication of high-k / multigate and high-k / metal gate devices of less than 28 nm technology.

Current cleaning techniques rarely exhibit such tight control or compatibility (low etch rates) for a broad and long list of metallization and substrate materials. For special applications, the present invention provides a unique one-step optimization of aluminum oxide thickness that is important for performance enhancement.

Acid semi-aqueous composition comprises at least (A) 1 primary fluoride-non-fluoride compound as the activator ^{_{(HF 2 -), (B}} ) multiple pK "pH- stabilization compatibility enhancer" having _a value, (C) " Enhancement of metal compatibility "organic solvents, and (D) water.

The pH (10% diluted aqueous) should be 5.5 or less, more preferably 5.0 or less, most preferably 4.5 or less. Optional components include other fluoride salts, amines, corrosion control agents and corrosion inhibiting co-solvents. The pH-stabilizing compatible enhancer can be selected from citric acid, phosphoric acid, citrate and phosphate. The organic solvent is selected from sulfides, amides, alcohols and ethers. The composition has the ability to remove the cured silicon-containing ARC material and has a wide range of compatibility including Al, Cu, W, TiN, SiN, TaN, and the like. Preferably, they also exhibit acceptable compatibility with TEOS, low-k and high-k materials in selected applications.

As used herein, “non-fluoride compound” or “non-fluoride” refers to a compound having two fluorine atoms. In some embodiments, the non-fluoride compound further comprises a hydrogen atom and is present in salt form. Bifluorides are also known as difluorohydrogenide, and difluorohydrogenate, or hydrogen (difluoride). They can also be represented as inorganic anions having the formula HF ₂ ⁻ . In some cases, the group to hydro-fluoro carbonate anion, such as a non-fluoride (-HF ^-) may absorb a proton by recombinant:

Due to the capture of such protons (H ⁺ ), non-fluorides have basic properties. Its conjugate acid is the reactive intermediate μ-fluoro-fluorodihydrogen (H ₂ F ₂ ), which subsequently dissociates to become hydrogen fluoride. In solution, most non-fluoride ions dissociate.

Because non-fluorides can be basic, the compositions of the present invention use a pH-compatible enhancer to maintain acidic properties in the composition. The term "pH-stabilizing compatible enhancer" as used herein refers to any compound capable of adjusting the pH of the solution to an operable level, most particularly to a pH of 5.5 or less.

As used herein, "organic solvent" refers to a substance capable of dissolving or dispersing one or more other substances whose properties are non-metallic. Organic solvents typically used in liquid form are typically hydrocarbons or related substances. Organic solvents usually have a low boiling point and can be easily evaporated or removed by distillation, leaving dissolved material. Therefore, the solvent should not react chemically with the dissolved compound and must be inert. Among various suitable organic solvents are alcohols, polyhydroxy alcohols such as glycerol, glycols, glycol ethers, alkyl-pyrrolidinones such as N-methylpyrrolidinone (NMP), 1-hydroxyalkyl-2-pyrrolidinones such as 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP), dimethylformamide (DMF), dimethylacetamide (DMAc), sulfolane or dimethylsulfoxide (DMSO). These solvents can be added to reduce the corrosion rate of the aluminum or aluminum alloy and limit the aggressiveness of the cleaning composition, if further aluminum and / or aluminum-alloy corrosion inhibition is desired. Preferred water-soluble organic solvents are polyhydroxy alcohols, such as glycerol, N-methylpyrrolidinone and / or 1-hydroxyalkyl-2-pyrrolidinone, such as 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP). These organic solvents are in an amount of 0% to about 50% by weight, preferably about 5% to about 50% by weight, more preferably about 10% to about 50% by weight, based on the weight of the composition. Can be used in the amount of

These compositions use a non-fluoride, metallized and dielectric compatibility enhancing matrix in a preferred format. They offer exceptional selectivity and compatibility and unique ARC removal capability. They can also be used to clean advanced FEOL and BEOL microelectronic and nanoelectronic structures including sensitive Al, Cu, high-k and low-k, porous low-k substrates. They are capable of removing anti-reflective coatings (ARC), stripping of photoresists, and removal of etch / ash residues.

The chemical compositions described above can be formulated as highly non-aqueous to semi-aqueous solutions or slurries. They include removal of deposited polymers, stripping of ARC and photoresist, cleaning of residues from organic, organometallic and inorganic compounds due to plasma processes, cleaning of residues from planarization processes such as chemical mechanical polishing, and planarization slurries / Can be used in applications as additives in liquids.

Many fluoride-based cleaners have been developed, which cater to a variety of cleaning needs for past and current technologies. However, in new microelectronic applications, often existing and new materials, alloys and composites are currently used in the same device design and manufacture. Therefore, the cleaning solution must be highly compatible with many substrates. For example, the cleaning agent may need to be compatible with Al, Cu, W, TiN, SiN, TaN and TEOS all at the same time. The permissible losses can be limited to 10 kPa or less during processing. For certain line shear (FEOL) applications, some allowable material losses can be 1-2 kPa or less. Thus, previously developed chemicals that were permitted by existing technical requirements and could be considered "compatibility" are no longer permitted by future technical requirements. Its use can lead to serious reliability problems or adverse performance problems. The invention described herein solves all the above difficulties with novel innovative designs and chemicals.

As previously mentioned, neutral or alkaline pH fluoride based chemicals generally have poor cleaning abilities. At acidic pH, the present invention provides the use of non-fluoride as the primary fluoride species, unlike the state of the art associated with most fluoride-based detergents.

By using non-fluoride, the present invention provides superiority over all other fluorides, which are difficult to develop or formulate. The non-fluoride compositions of the present invention provide broad compatibility with a wide range of metallization materials and substrates. HF based cleaners are generally not Al compatible. Ammonium fluoride based cleaning agents have a high Cu etch rate. Alkylammonium fluoride based detergents cause serious Al corrosion problems.

Upon removal or addition of protons, non-fluoride based chemicals can be adjusted to provide optimal HF concentration in a specially designed solvent matrix through the equilibrium proposed below:

In this composition, non-fluoride is used as the primary fluoride species. In an embodiment, the non-fluoride is a single fluoride species in the composition. Many other patents can only broadly include and use any HF or fluoride species as the primary species. This practice often leads to serious compatibility problems. Therefore, these patents do not provide any useful teaching. The present invention specifies that the pH (10% diluted aqueous) should be 5.5 or less, more preferably 5.0 or less, and most preferably 4.5 or less. The present invention may contain other fluoride species (eg fluoride salt or HF), but should be used as one of the small amounts of co-additives.

Additionally, the compositions of the present invention include the use of pH-stabilizing compatibility and selectivity enhancers with multiple pK _a values. We have discovered and established the surprising effect of selected compounds with multiple pK _a values in providing unexpected compatibility enhancements for several important substrates such as SiN, Al. In comparative examples, these unique enhancer-free compositions could not meet the frivolous compatibility requirements; Its use can lead to serious or adverse performance problems. The pH stability of many fluoride-based detergents (eg NH ₄ F-based) is known to have poor pH stability. Using the unique enhancer of the present invention helps provide excellent pH stability and extended bath life.

Buffering ability over a wide range of pH. The present invention has improved buffering ability, minimizing the effect of acid / base added / facing to the detergent. It has been described in the present invention that the selection of a particular compound should have multiple pK _a values. They are multiplicity acids and salts thereof, such as citric acid, monobasic ammonium citrate, dibasic ammonium citrate, tribasic ammonium citrate, phosphoric acid, monobasic ammonium phosphate, dibasic ammonium phosphate, tribasic ammonium phosphate, ascorbic acid, Monobasic ammonium ascorbate, dibasic ammonium ascorbate.

The acid dissociation constant K _a (also known as the acidity constant, or acid-ionization constant) is a quantitative measure of the strength of the acid in solution. It is an equilibrium constant for a chemical reaction known as dissociation in relation to the acid-base reaction. The higher the K _a value, the more the molecules in the solution dissociate and the stronger the acid. The equilibrium of acid harry can be symbolically expressed as:

Here, HA is A ^- is a general acid to be dissociated by being divided into (known as the conjugate base of the acid) and proton H ⁺ (the case of aqueous solutions, is present as the hydronium ion, for example a proton solvated).

The dissociation constant is expressed as the quotient of the normal equilibrium concentration (mol / L), [HA ], - and it is represented by [H ^+] [A]:

Due to the large number of digits occupied by the K _a value, the logarithmic scale of the acid dissociation constant is actually more commonly used. The log constant pK _a (equivalent to -log ₁₀ K _a ) is also sometimes referred to as the acid dissociation constant:

The higher the pK _a value, the smaller the degree of dissociation at any given pH (ie, the weaker the acid). Weak acids have pK _a values in the approximate range of -2 to 12 in water, for example. Acids with pK _a values less than about -2 are called strong acids. The strong acid dissociates to an extent that the concentration of the non-dissociated acid becomes almost undetectable in the aqueous solution. However, the pK _a value for strong acids can be estimated by extrapolation or by theoretical means from measurements in non-aqueous solvents with lower dissociation constants, such as acetonitrile and dimethylsulfoxide.

Only organic solvent matrices of choice can be used to meet a wide range of and sparse metallization and substrate compatibility requirements. Surprisingly, a significant solvent effect was found. In a preferred embodiment, the “enhancement of metal compatibility” organic solvents include sulfides and amides, which are present as primary solvents. They also provide higher PR stripping capabilities. Additionally, alcohols, alcohol-ethers and ethers can also be used, which are preferably used as small amounts of cosolvents.

In another embodiment, water is the solvent. The solvent matrix can be a semi-aqueous system. In an embodiment, the water content is 5% or less. In another embodiment, the water content is at least 20% by weight. Compared to moisture-free and low moisture cleaners, the combination of a semi-aqueous solvent matrix and fluoride often leads to serious metal compatibility problems. The present inventors have solved the above difficulties with the novel use of selected fluoride species, unique compatibility enhancers and compatibility enhancing organic solvents.

The compositions of the present invention also provide novel selectivity between i) ARC and substrate, or ii) ARC and metallization. The chemicals disclosed herein are without significant etch / damage of the substrate (eg, silicon oxide, TEOS or silicon nitride) or etch / damage of metals (eg, Al, Cu, W, Ti, TiN, TaN) , Silicon-containing bottom antireflective coating (SiBARC), such as can provide selective etching / removal of DUO 248 material from Honeywell.

It is known that fluorides of acidic pH have higher reactivity and cleaning ability. However, it also attacks silicon-based materials, such as TEOS. Frequently, it even etches more durable silicon-based materials, such as silicon nitride, at lower etch rates than TEOS. For advanced applications, even lower SiN etch rates, such as 5-10 kPa / min, are often unacceptable. The present invention provides novel etch selectivity between silicon based ARC and other silicon based substrates.

It is also known that acid fluoride based chemicals, especially HF containing formulations, cannot have a wide range of compatibility with a wide variety of metallizations simultaneously. The present invention provides unique broad compatibility with metals (eg Al, Cu, W, Ti, TiN, TaN) and substrates (eg TEOS, SiN, high-k, low-k). to provide. Some acidic fluoride cleaning chemicals have shown improvement by providing better compatibility. However, none of the prior art could exhibit a level of compatibility that meets the highly demanding requirements in advanced technology nodes in semiconductors such as 16 nm or less.

The composition of the present invention may also contain any suitable water-soluble zwitterionic, non-ionic, cationic or anionic surfactant. The addition of a surfactant will reduce the surface tension of the formulation and improve the wetting of the surface to be cleaned to improve the cleaning action of the composition. Surfactants can also be added to reduce the aluminum corrosion rate when further aluminum corrosion inhibition is desired.

Zwitterionic surfactants useful in the compositions of the present invention include betaines and sulfobetaines, such as alkyl betaines, amidoalkyl betaines, alkyl sulfobetaines, and amidoalkyl sulfobetaines; Aminocarboxylic acid derivatives such as amphoglycinate, amphopropionate, amphodiglycinate, and amphodipropionate; Iminoic acid, such as alkoxyalkyl iminoic acid or alkoxyalkyl iminoic acid; Amine oxides, such as alkyl amine oxides and alkylamido alkylamine oxides; Fluoroalkyl sulfonates and fluorinated alkyl zwitterionic materials; And mixtures thereof.

Preferably, zwitterionic surfactants are cocoamidopropyl betaine, cocoamidopropyl dimethyl betaine, cocoamidopropyl hydroxy sultaine, capryloampodipropionate, cocoamidodipropionate, cocoamphoprop Cypionate, cocoamphohydroxyethyl propionate, isodecyloxypropylimino dipropionic acid, laurylimino dipropionate, cocoamidopropylamine oxide and cocoamine oxide and fluorinated alkyl zwitterionic materials . Non-ionic surfactants useful in the compositions of the present invention include acetylenic diols, ethoxylated acetylenic diols, fluorinated alkyl alkoxylates, fluorinated alkyl esters, fluorinated polyoxyethylene alkanols, aliphatic acid esters of polyhydric alcohols, Polyoxyethylene monoalkyl ethers, polyoxyethylene diols, siloxane type surfactants, and alkylene glycol monoalkyl ethers. Preferably, the non-ionic surfactant is an acetylene-based diol or ethoxylated acetylene-based diol. Anionic surfactants useful in the compositions of the present invention include carboxylates, N-acylsarcosinates, sulfonates, sulfates, and mono and diesters of orthophosphoric acid, such as decyl phosphate. Preferably, the anionic surfactant is a metal-free surfactant. Cationic surfactants useful in the compositions of the present invention include amine ethoxylates, dialkyldimethylammonium salts, dialkylmorpholinium salts, alkylbenzyldimethylammonium salts, alkyltrimethylammonium salts, and alkylpyridinium salts. Preferably, the cationic surfactant is a halogen-free surfactant. Examples of particularly suitable surfactants are 3,5-dimethyl-1-hexyn-3-ol (sulfinol-61), ethoxylated 2,4,7,9-tetramethyl-5-decine-4,7-diol ( Sulfinol-465), polytetrafluoroethylene cethoxypropylbetaine (Zonyl FSK), zonyl FSH, Triton X-100, i.e. octylphenoxypolyethoxyethanol, and the like. . The surfactant will generally be present in an amount of 0 to about 5 wt%, preferably 0.001 to about 3 wt%, by weight of the composition.

Example

The invention is further illustrated, but is not limited by the following representative examples, which are intended to illustrate the invention and should not be regarded as limiting.

Ingredients presented in weight percent

Additionally, the following examples also include the ingredients listed below:

Example 7 0.2 wt% MTES

Example 11 0.2% by weight polydimethylsiloxane

Example 12 0.5% by weight polydimethylsiloxane

Example 14 0.2% by weight polydimethylsiloxane

Example 16 0.2 wt% 5 MBZT

Example 18 59.25% by weight N- (2-hydroxyethyl) -2-pyrrolidone (HEP)

Example 19 59.15% by weight N- (2-hydroxyethyl) -2-pyrrolidone (HEP)

The following table illustrates the properties of the compositions of the present invention as exemplified through the examples listed above.

Table I

ARC removers with a wide range of metallization compatible etch rates are in Angstroms / minute

Table II

Cleaning chemicals with superior compatibility

( High potential for cleaning critical for high-k / multigate / metal gate technology below 20 nm )

CDO low-k: k values in the range 2.4-2.5

Table III

Bath life study showing excellent pH and etch rate stability

Table IV

Bath life study showing excellent pH and etch rate stability

Table V

Bath life study showing excellent pH and etch rate stability

Table VI

Table VII-Additional Examples

Ingredients presented in weight percent

In the tests, Examples 30-35 were performed similarly to the other examples in all categories shown in Tables II-VI. Accordingly, although it is described herein that what is considered to be a preferred embodiment of the present invention, those skilled in the art can make changes and modifications to it without departing from the spirit of the present invention, and all such changes and modifications It will be appreciated that it is intended to be claimed as falling within the true scope of the invention.

Claims (1)

0.05% to 5.0% by weight of ammonium bifluoride, 0.01% to 5% by weight of a pH-stabilizing compatible enhancer, 5% to 90% by weight of organic solvent, 5% to 90% of water, and cosolvent A use for microelectronic application of a cleaning composition comprising, wherein the pH is 5.5 or less, the pH-stabilizing compatibility enhancer is a polyhydric acid, or a salt thereof, and the co-solvent is a combination of ethylene glycol and diethylene glycol.