KR20180124830A - Acidic semi-aqueous fluoride activated antireflective coating cleaners with superior substrate compatibility and exceptional bath stability - Google Patents

Abstract

The present invention thereby provides novel acidic fluoride activated cleaning chemistries with highly effective ARC removal, cleaning capabilities, and superior compatibility with a wide variety of materials. The present invention provides ARC removal, PR stripping, etch / ashing residue cleaning and CMP residue removal in FEOL, BEOL and FPD applications, with no undesirable surface deformation and excellent substrate compatibility, pH stability, ≪ / RTI > is disclosed.

Description

Acidic semi-aqueous fluoride activated antireflective coating cleaners with superior substrate compatibility and exceptional bath stability

The present invention relates to microelectronic cleaning compositions and their use for anti-reflective coating (ARC) removal and residual cleaning compositions in microelectronic device cleaning methods of these cleaning compositions, especially with larger substrate and metallization compatibility.

Recent advances in the production of micro- and nano-electronic devices have created new strips with stripping or cleaning capabilities both in the front end of the line (FEOL) and in the back end of the line (BEOL) Ping and cleaning compositions have become necessary. It has been found that the cleaning compositions typically used so far are not suitable as novel materials used in the production of microelectronic or nanoelectronic platforms. Previously used stripping or cleaning compositions are either too aggressive and / or not sufficiently selective. Among the newly used materials used to produce such newer microelectronic or nanoelectronic devices are low-k (<3) and high-k (> 20) and porous dielectrics, copper metal oxides, fluoropolymer anti- (ARC), special hard masks such as those composed of Ti and TiN, strained wafers of Si / Ge or Ge, and metal capping layers such as those of CoWP and CoWB. These new materials present new and difficult difficulties for device manufacturers.

For example, cleaning of a Cu / low-k structure not only requires good cleaning capability, but also requires a solution with outstanding substrate compatibility. Many process technologies developed for conventional or conventional semiconductor devices containing Al / SiO ₂ or Al (Cu) / SiO ₂ structures can not be applied to Cu / low-k and high-k structures. In the opposite case, too, many Cu / low-k strippers are not suitable for Al metal oxides unless significant control is achieved.

The fabrication process for Cu / low-k and / or high-k structures often yields uniquely cured photoresist layers, tough plasma etching and / or ashing residues. Even highly aggressive reagents such as HF acid, hydroxylamine, and strongly alkaline solutions often fail to provide adequate cleaning with acceptable substrate compatibility.

Fluoride or HF based aqueous solutions have been widely used as traditional FEOL and BEOL etchants and cleaning agents. Often, these types of detergents are developed as oxide etchants or ashing residue removers. For example, the dilute HF (dHF) solution and a buffered oxide etch (comprising the _{BOE, HF / NH 4 F /} H 2 O) is but an effective oxide (silicon oxide) removing agent is limited residue cleaner, typically a 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 plasma curing photoresists and removal of ARCs. They may also be over-aggressive, not sufficiently selective, or new challenging types of materials such as low-k and high-k and porous dielectrics, copper metal oxides, fluoropolymer antireflective coatings (ARC) , A new and highly demanded substrate 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 CoWP and CoWB Sex and selectivity requirements. Thus, there is a need for new, improved stripping or cleaning compositions for versatile 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 fabricate multi-gate transistors. In addition to conventional planar multi-gate transistors, non-planar double gates (e.g., FinFET), or tri-gates have been developed. Often, high-k materials and metal gates are also used in this advanced technology (e.g., a 14 nm node). Lists of material / substrate is extensive: Al, Cu, W, Ti , TiN, TaN, Nb, RuO 2, Mo, LaOx, AlOx, HfSiON, COSi 2, WSi 2, SiN, SiON, TEOS, poly-Si, SiGe , Ge, and combinations thereof and / or additives. The thickness control of various, often ultra-thin metal gate (MG), work function metal (WF), and high-k (HK) is important. There is a great difficulty associated with introducing cleaning chemicals with a very wide range of very high miscibility and enabling (high cleaning ability for various PRs and residues) for ultra thin films (for example, 10 angstrom WF films) do. For example, an etch rate as low as 1 angstrom of TiN may be too high to be usable in some cases. Current or traditional wet cleaning chemicals can no longer meet the same kind of compatibility requirements. There is a need for a novel enabling cleansing chemical that has superior substrate compatibility that can selectively clean photoresist, antireflective coating (ARC), residual WF metal, and various plasma etch or ashing residues.

Fluoride activated (based) cleaning chemicals generally work much more effectively under acidic pH conditions. However, acidic fluoride chemicals, especially HF-containing cleaners, have the drawback of a large limitation of metallisation and incompatibility with various substrates. For example, an etch rate of 200: 1 DHF at 25 캜: Al, > 550 / min, TEOS, > 30 / min; 200: 1 DHF, Al, > 2,000 / min, TEOS, > 140 / min. At 35 ° C, even highly diluted 600: 1 DHF is Al,> 750 / min. Other fluoride based cleaners 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 and is limited to only selected types of residues that can be cleaned ; At acidic pH, ammonium fluoride containing detergents often have poor copper compatibility; Alkylammonium fluoride containing detergents 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 coatings (ARC) materials are increasingly being 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 used to remove significant metal oxides (e.g. Al, Cu, W, Ti, TiN, TaN) and substrates (e.g., TEOS, SiN, -k &lt; / RTI &gt; and the provision of efficient SiBARC removal. Some acid fluoride cleaning chemicals have shown improvement by providing better compatibility. However, none of them could represent a level of compatibility meeting the highly required requirements in advanced technology nodes in semiconductors such as 16 nm or less. In a specific but important application, optimizing the Al ₂ O ₃ thickness without damaging Al metal oxides provides clear and critical performance. In addition, the need for special cleaning, such as selective removal of "Al oxide-like", "Ti oxide-like" residues, or etched / ashed antireflective coatings, along with highly salubious compatibility, presents a major technical difficulty. None of the known chemicals simultaneously satisfied all of these difficulties / needs.

Diluted hydrofluoric acid (DHF) is a unique and effective detergent in a wide range of microelectronic applications. However, advanced FEOL and BEOL cleaning require much more versatile substrate and metal cargo compatibility than DHF. In addition, other capabilities such as PR (photoresist) stripping are also very beneficial. Therefore, new cleaning chemicals are needed.

Fluoride-based cleaners have been widely used in the past for various cleaning needs, but their use in many new applications has been ruled out due to the use of new materials, alloys and composites with different sensitivities. Fluoride-containing formulations are well known, for example, for etching silicon oxide at acidic pH, and are typically used as silicon oxide etchants. Well known example is the HF- based silicon oxide etchant, such as buffered oxide etchant (BOE), which comprises an aqueous solution of the various non-HF and NH ₄ F. However, the selectivity of ARC or SiBARC removal to its TEOS is generally very poor. Many prior disclosures use weakly acidic pH (pH > 6), neutral or preferably alkaline pH conditions to inhibit such compatibility problems. However, the ARC / SiBARC removal ability and the cleaning ability are greatly reduced at the above-mentioned pH conditions. One example is United States Patent 7,399, 365 B2. It is taught that the preferred pH range of 6.5 to 8 is used.

Related art includes attempts to solve the problem, including providing the fluoride source as an activated species indiscriminately. For example, U.S. Patent No. 6,777,380 includes a detergent having a fluoride source such as hydrofluoric acid, ammonium fluoride, tetramethylammonium fluoride, ammonium bifluoride, and the like. However, these examples do not provide the broad compatibility required for current applications, or also the necessary selectivity enhancement.

Thus, there is a need for an acidic ARC remover / detergent that provides a high cleaning capacity of the ARC / SiBARC etch with a preferred pH range of 5 or less. In addition, cleaning compositions capable of achieving high compatibility / low etch rates for Al, Cu, W, Ti, TiN, TaN, and TEOS, Is required.

Accordingly, there is provided herein a novel acidic fluoride activated cleaning chemistry having a highly effective ARC removal, cleaning capability, and superior compatibility with a wide variety of materials. The present invention provides ARC removal, PR stripping, etch / ashing residue cleaning and CMP residue removal in FEOL, BEOL and FPD applications, with no undesirable surface deformation and excellent substrate compatibility, pH stability, &Lt; / RTI &gt; is disclosed.

A cleaning composition for microelectronic applications is provided herein. The cleaning composition comprises about 0.05 wt.% To about 5.0 wt.% Of a non-fluoride compound, from about 0.01 wt.% To about 5 wt.% Of a pH-stabilizing compatibilizer, from about 5 wt.% To about 90 wt.% Of an organic solvent, 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 compatible enhancer, from about 10% to about 70% Of an organic solvent, and from about 10% to about 50% 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 compatible enhancer, from about 20% Of an organic solvent, and from about 20% to about 40% water.

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

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

In an embodiment, the pH-stabilizing compatible enhancer is a variant acid, or a salt thereof. In an embodiment, the pH-stabilizing compatible enhancer is selected from the group consisting of 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 an amide. In another embodiment, the organic solvent is selected from the group consisting of dimethylsulfoxide, N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N- (2- hydroxyethyl) ), Dimethyl 2-piperidone (DMPD), dimethylacetamide, formamide, and mixtures thereof.

In another embodiment, the cleaning composition of the present invention further comprises at least another fluoride source. In an embodiment, at least another fluoride source is a fluoride salt. In another embodiment, the cleaning composition further comprises a corrosion inhibitor. 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 may be selected from the group of commercially available surfactants known in the art.

In another embodiment, the present invention provides a method of making a microelectronic device comprising applying a microelectronic material at a level of from about 0.05% to about 5.0% by weight of a non-fluoride compound, from about 0.01% to about 5% To about 90% by weight of an organic solvent, and from about 5% to about 90% of water.

For a better understanding of the present invention, together with other and further objects and advantages, reference may be had to the following description, taken in conjunction with the accompanying drawings, in which the scope of the present invention will be described in conjunction with 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 difficulties of using acidic fluoride-based chemicals as antireflective coatings (ARC) removers, providing a wide range of superior metallizations and substrate compatibility at the same time. It can also be regarded as a superior dilute hydrofluoric acid (DHF) alternative. This can provide significant cleaning in many other advanced line shear (FEOL) and line back end (BEOL) applications. In addition, the present invention provides an enabling wet cleaning solution for highly demanding wide and stringent compatibility requirements for fabrication of high-k / multi-gate and high-k / metal gate devices of technology less than 28 nm.

Current cleaning techniques rarely exhibit such stringent control or compatibility (low etch rate) for wider and longer series of metal cargo and substrate materials. For special applications, the present invention provides a unique one-step optimization of the aluminum oxide thickness, which is important for performance enhancement.

The acidic semi-aqueous composition comprises at least (A) a non-fluoride compound (HF ₂ ^- ) as the primary fluoride-activator, (B) a "pH-stabilizing compatible enhancer" with multiple pK _a values, Metal compatibility improver " organic solvent, and (D) water.

The pH (10% diluted aqueous) should be below 5.5, more preferably below 5.0 and most preferably below 4.5. Optional components include other fluoride salts, amines, corrosion inhibitors and corrosion inhibiting co-solvents. The pH-stabilizing compatibility 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 broad 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. Bifluoride is also known as difluorohydrogenide, and difluorohydrogenate, or hydrogen (difluoride). They may 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 proton (H ⁺ ), the non-fluoride has basic characteristics. His mate acid reactive intermediate with μ- fluoro-Fluoro Lodi hydrogen (H ₂ F _2), which is dissociated and subsequently becomes a fluorine hydrocarbon. In solution, most non-fluoride ions dissociate.

Since the non-fluoride may be basic, the compositions of the present invention use a pH-compatible enhancer to maintain the acidic nature of the composition. The term " pH-stabilizing compatible enhancer " as used herein refers to any compound that is capable of adjusting the pH of the solution to an operable level, most particularly a pH of less than or equal to 5.5.

&Quot; Organic solvent " as used herein refers to a material that is capable of dissolving or dispersing one or more other materials whose properties are non-metal. Organic solvents, typically used in liquid form, are typically hydrocarbons or related materials. The organic solvent usually has a low boiling point, can easily be evaporated or can be removed by distillation, leaving a dissolved substance. Therefore, the solvent should not chemically react with the dissolved compound and should be inert. Suitable organic solvents include alcohols, polyhydroxy alcohols such as glycerol, glycols, glycol ethers, alkyl-pyrrolidinones such as N-methylpyrrolidinone (NMP), 1-hydroxyalkyl- There can be mentioned 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP), dimethylformamide (DMF), dimethylacetamide (DMAc), sulfolane or dimethylsulfoxide (DMSO). These solvents may be added to reduce the corrosion rate of metals, especially aluminum and / or aluminum-alloy corrosion inhibition when aluminum or aluminum alloy corrosion inhibition is desired and to limit the aggressiveness of the cleaning composition. Preferred water-soluble organic solvents are polyhydric alcohols such as glycerol, N-methylpyrrolidinone and / or 1-hydroxyalkyl-2-pyrrolidinone, such as 1- (2-hydroxyethyl) (HEP). Such an organic solvent is present in an amount of from 0% to about 50% by weight, preferably from about 5% to about 50% by weight, more preferably from about 10% to about 50% by weight, , &Lt; / RTI &gt;

These compositions use non-fluoride, metalloid and dielectric compatibility enhancing matrices in the preferred format. They offer exceptional selectivity and commercial and unique ARC removal capabilities. They can also be used to clean advanced FEOL and BEOL microelectronics and nanoelectronic structures, including sensitive Al, Cu, high-k and low-k, porous low-k substrates. They are capable of removing antireflective coatings (ARC), stripping photoresist, and removing etching / ashing residues.

Such chemical compositions may be formulated as highly non-aqueous to semi-aqueous solutions or slurries. They include removal of the deposited polymer, stripping of the ARC and photoresist, cleaning of residues from organic, organometallic and inorganic compounds due to the plasma process, cleaning of residues from planarization processes such as chemical mechanical polishing, / As an additive in liquids.

Many fluoride-based cleaners have been developed, which are suitable for a variety of cleaning needs for past and current technologies. However, in new microelectronic applications, often conventional 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 detergent may need to be compatible with both Al, Cu, W, TiN, SiN, TaN, and TEOS simultaneously. Acceptable losses can be limited to less than 10 A during the process. For certain line shear (FEOL) applications, some acceptable material losses may be 1-2 A or less. Thus, previously developed chemicals that were acceptable to existing technical requirements and could be considered " compatible " are no longer allowed in 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, fluoride-based chemicals at neutral or alkaline pH are generally poorly washable. At acidic pH, the present invention provides for the use of non-fluoride as the primary fluoride species, unlike the state of the art associated with most fluoride-based cleaners.

By using non-fluorides, the present invention provides superiority over all other fluorides, which is 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 cleaners have a high Cu etch rate. Alkylammonium fluoride-based cleaners cause severe Al corrosion problems.

With the removal or addition of protons, the non-fluoride based chemistry can be adjusted to provide the optimum HF concentration among the specifically designed solvent matrices through the following proposed equilibrium:

In this composition, the non-fluoride is used as the primary fluoride species. In an embodiment, the non-fluoride is the only fluoride species in the composition. Many other patents are broader and include any HF or fluoride species as only a primary species. Such practices often lead to serious compatibility problems. Thus, these patents do not provide any useful teaching. The present invention specifies that the pH (10% diluted aqueous) should be less than 5.5, more preferably less than 5.0, and most preferably less than 4.5. The present invention may contain other fluoride species (e.g., fluoride salts or HF), but should be used as one of the small amount of co-additives.

In addition, the compositions of the present invention include the use of pH-stabilizing compatible and selective enhancers with multiple pK _a values. The present inventors have discovered and established a surprising effect of selected compounds having multiple pK _a values in providing unexpected compatibility enhancements to a number of important substrates such as SiN, Al. In a comparative example, compositions without these specific enhancers can not meet salt tolerance requirements; Its use can lead to serious or unfavorable performance problems. The pH stability of many fluoride-based cleaners (e.g., NH ₄ F-based) is known to have poor pH stability. Use of a unique enhancer of the present invention is helpful in providing excellent pH stability and prolonged bath life.

Buffer capacity over a wide pH range. The present invention has an improved buffering capacity, which minimizes the effect of the acid or base added to / encountered in the cleaning agent. It is described in the present invention that the selection of a particular compound should have multiple pK _a values. They are selected from the group consisting of a variety of substances and their salts 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 acidity constant, or acid-ionization constant) is a quantitative measure of the strength of acid in solution. This is the equilibrium constant for the chemical reaction known as dissociation in relation to the acid-base reaction. The larger the K _a value, the more molecules dissociate in solution and the stronger the acid. The equilibrium of the acid dissociation can be symbolically expressed as:

Where HA is a generic acid dissociated by partitioning into A ^- (known as the conjugate base of an acid) and proton H ⁺ (in the case of an aqueous solution, as a hydronium ion, for example as solvated protons).

The dissociation constant is usually expressed as a share of the equilibrium concentration (mol / L) and is denoted as [HA], [A ^- ] and [H ⁺ ]:

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

The larger the pK _a value, the smaller the degree of dissociation at any given pH (i.e., the acid becomes weaker). The weak acid has a pK _a value in the approximate range of, for example, -2 to 12 in water. An acid with _a pK _a value of less than about -2 is called a strong acid. The strong acid is dissociated to such an extent that the concentration of the non-dissociated acid is almost completely undetectable in the aqueous solution. However, the pK _a value for strong acids can be estimated by extrapolation from the measurements in non-aqueous solvents with smaller dissociation constants, such as acetonitrile and dimethylsulfoxide, or by theoretical means.

Only selected organic solvent matrices can be used to meet broad and salty metal and substrate compatibility requirements. A surprisingly significant solvent effect was found. In a preferred embodiment, the " metal compatibility enhancing " organic solvent comprises sulfides and amides, which are present as primary solvents. They also provide higher PR stripping capability. Additionally, alcohols, alcohol-ethers and ethers may be used, which are preferably used as minor cosolvents.

In another embodiment, water is a solvent. The solvent matrix may 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 water-free and low-moisture cleaners, the combination of semi-aqueous solvent matrix and fluoride frequently results in serious metal compatibility problems. The inventors have solved the above difficulties with the novel use of selected fluoride species, unique compatible 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 metalloids. The chemicals disclosed herein can be used to remove significant etch / damage to a substrate (e.g., silicon oxide, TEOS, or silicon nitride) or etch / damage of a metal oxide (e.g., Al, Cu, W, Ti, TiN, TaN) , A silicon-containing bottom anti-reflective coating (SiBARC), such as Honeywell, to provide selective etching / removal of DUO 248 material.

Fluorides at acidic pH are known to have higher reactivity and cleaning capabilities. However, it also attacks silicon-based materials such as TEOS. Often, it even etches even more durable silicon-based materials, such as silicon nitride, at a lower etch rate than TEOS. In the case of advanced applications, even lower SiN etch rates such as 5-10 A / 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 acidic fluoride-based chemicals, especially HF-containing formulations, can not have broad compatibility with a wide variety of metal oxides at the same time. The present invention has the unique broad compatibility with metallizations (e.g. Al, Cu, W, Ti, TiN, TaN) and substrates (e.g. TEOS, SiN, high- to provide. Some acid fluoride cleaning chemicals have shown improvement by providing better compatibility. However, none of the prior art has been able to demonstrate a level of compatibility that meets the highly required requirements at advanced technology nodes in semiconductors such as 16 nm or less.

The compositions 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 may also be added to reduce the aluminum corrosion rate if further aluminum corrosion inhibition is desired.

Zwitterionic surfactants useful in compositions of the present invention include betaines and sulphobetaines such as alkyl betaines, amido alkyl betaines, alkyl sulphobetaines and amido alkyl sulphobetaines; Aminocarboxylic acid derivatives such as amphoglycinate, amphopropionate, amphodiglycinate, and amphodipropionate; Iminoic acid, such as alkoxyalkyl imino acid or alkoxy alkyl imino acid; Amine oxides such as alkylamine oxides and alkylamidoalkylamine oxides; Fluoroalkylsulfonates and fluorinated alkyl amphoteric materials; And mixtures thereof.

Preferably, the amphoteric surfactant is selected from the group consisting of cocoamidopropyl betaine, cocoamidopropyl dimethyl betaine, cocoamidopropyl hydroxysultaine, capryloamphodipropionate, cocoamidopropyl ketone, Aminopropionic acid, lauryl iminodipropionate, cocoamidopropylamine oxide, and cocoamine oxide and fluorinated alkyls, both of which are ionic substances . Nonionic surfactants useful in compositions of the present invention include, but are not limited to, 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 acetylenic diol or an ethoxylated acetylenic diol. Anionic surfactants useful in the compositions of the present invention include carboxylates, N-acyl sarcosinates, sulfonates, sulfates, and mono and diesters of orthophosphates such as decyl phosphate. Preferably, the anionic surfactant is a metal-free surfactant. Cationic surfactants useful in 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- Zolyl FSK), Zonyl FSH, Triton X-100, i.e., octylphenoxy polyethoxy ethanol, and the like, and the like . Surfactants will generally be present in an amount of from 0 to about 5 wt%, preferably from 0.001 to about 3 wt%, based on the weight of the composition.

Example

The present invention is further illustrated by the following non-limiting examples, which are intended to be illustrative of the present invention and should not be construed as being limited thereto.

Ingredients presented as weight percentages

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

Example 7 0.2 wt% MTES

Example 11 0.2 wt% polydimethylsiloxane

Example 12 0.5% by weight polydimethylsiloxane

Example 14 0.2 wt% polydimethylsiloxane

Example 16 0.2 wt% 5MBZT

Example 18 59.25 wt% 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 illustrated by the above listed Examples.

Table I

An ARC remover with a wide metal content compatible etch rate is in Angstroms / min.

Table II

Highly compatible cleaning chemicals

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

CDO low-k: k values range from 2.4 to 2.5

Table III

Bass life study showing excellent pH and etch rate stability

Table IV

Bass life study showing excellent pH and etch rate stability

Table V

Bass life study showing excellent pH and etch rate stability

TABLE VI

Table VII - Additional Examples

Ingredients presented as weight percentages

In the tests, Examples 30-35 were performed similarly to the other examples in all categories shown in Tables II-VI. Accordingly, while the present invention has been described in connection with what is presently considered to be the preferred embodiment of the invention, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art without departing from the spirit of the invention And are intended to be claimed as falling within the true scope of the present invention.

Claims (19)

From about 0.05 wt.% To about 5.0 wt.% Of a non-fluoride compound, from about 0.01 wt.% To about 5 wt.% Of a pH-stabilizing compatibilizer, from about 5 wt.% To about 90 wt.% Of an organic solvent, A cleaning composition for microelectronic applications, comprising about 90% water. The composition of claim 1, further comprising 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 compatible enhancer, from about 10% , And from about 10% to about 50% water. The composition of claim 1, further comprising 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 compatible enhancer, from about 20% , And from about 20% to about 40% water. The cleaning composition of claim 1, wherein the pH of the cleaning composition is no greater than 5.5. The cleaning composition of claim 1, wherein the pH of the cleaning composition is 5.0 or less. The cleaning composition of claim 1, wherein the cleaning composition has a pH of 4.5 or less. The cleaning composition of claim 1, further comprising a co-solvent selected from an alcohol, an alcohol-ether, and an ether. 8. The cleaning composition of claim 7, wherein the co-solvent is ethylene glycol, diethylene glycol, or a combination thereof. The cleaning composition of claim 1, wherein the non-fluoride compound is selected from the group consisting of ammonium bifluoride, alkylammonium bifluoride, potassium bifluoride, and alkali metal bifluoride. 10. The cleaning composition of claim 9, wherein the non-fluoride compound is ammonium non-fluoride. The cleaning composition of claim 1, wherein the pH-stabilizing compatible enhancer is a versatile acid, or a salt thereof. 3. The composition of claim 1 wherein the pH-stabilizing compatible enhancer is selected from the group consisting of citric acid, monobasic ammonium citrate, dibasic ammonium citrate, tribasic ammonium citrate, phosphoric acid, monobasic ammonium phosphate, dibasic ammonium phosphate, Wherein the cleaning composition is selected from the group of ascorbic acid, monobasic ammonium ascorbate, dibasic ammonium ascorbate, aminotrimethylenephosphonic acid, and mixtures thereof. The cleaning composition according to claim 1, wherein the organic solvent is sulfide or amide. 14. The method of claim 13, wherein the organic solvent is selected from the group consisting of dimethylsulfoxide, N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N- (2-hydroxyethyl) HEP), N- (2-hydroxyethyl) morpholine, dimethyl 2-piperidone (DMPD), dimethylacetamide, formamide, and mixtures thereof. The cleaning composition of claim 1, further comprising another fluoride source. 16. The cleaning composition of claim 15, wherein said another fluoride source is a fluoride salt. The cleaning composition of claim 1, further comprising a corrosion inhibitor. The cleaning composition of claim 1, further comprising a surfactant. 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 compatible enhancer, from about 5% to about 90% Contacting the cleaning composition with a cleaning composition comprising from about 5% to about 90% water.