Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/42—Stripping or agents therefor
  • G03F7/422—Stripping or agents therefor using liquids only
  • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02041—Cleaning
  • H01L21/02057—Cleaning during device manufacture
  • H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
  • H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
  • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
  • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
  • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
  • H01L21/3105—After-treatment
  • H01L21/311—Etching the insulating layers by chemical or physical means
  • H01L21/31127—Etching organic layers
  • H01L21/31133—Etching organic layers by chemical means
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces
  • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

Definitions

• Resist stripping compositions and methods for manufacturing electrical devices are Resist stripping compositions and methods for manufacturing electrical devices
• the present invention relates to new resist stripping compositions useful for removing patterned resists from substrates, in particular semiconductor substrates, containing copper and low-k or ultra low-k materials.
• the present invention relates to new methods for manufacturing electrical devices, in particular semiconductor integrated circuits (ICs), liquid crystal panels, organic electroluminescent panels, printed circuit boards, micro machines, DNA chips and micro plants, especially ICs, which new methods make use of the new resist stripping compositions.
• ICs semiconductor integrated circuits
• liquid crystal panels organic electroluminescent panels
• printed circuit boards micro machines, DNA chips and micro plants, especially ICs, which new methods make use of the new resist stripping compositions.
• Resists such as deep UV photo resists or electron beam resists are used in the microlithographic technique for producing a wide range of electrical devices, e.g. semiconductor integrated circuits (ICs), liquid crystal panels, organic electroluminescent panels, printed circuit boards, micro machines, DNA chips and micro plants, in particular ICs with LSI (large-scale integration) or VLSI (very-large-scale integration).
• ICs semiconductor integrated circuits
• liquid crystal panels organic electroluminescent panels
• printed circuit boards e.g. semiconductor integrated circuits (ICs), liquid crystal panels, organic electroluminescent panels, printed circuit boards, micro machines, DNA chips and micro plants, in particular ICs with LSI (large-scale integration) or VLSI (very-large-scale integration).
• LSI large-scale integration
• VLSI very-large-scale integration
• a process is used in which a copper multi-layer wiring is formed without etching copper by using a dual damascene process.
• various kinds of dual damascene processes have been proposed.
• One example thereof comprises the formation of a copper layer and the formation of a low-k layer (e.g., SiOC layer) on top of the copper layer followed by the formation of a resist layer as the uppermost layer.
• a metal nitride layer e.g., TiN layer
• BARC barrier anti-reflective layer
• the resist layer is selectively exposed to electromagnetic radiation or electron beams and developed to form a resist pattern ("first photo resist pattern").
• first photo resist pattern a resist pattern
• the low-k or ultra low-k layer is partly dry-etched by way of a fluorine containing plasma.
• the joint use of a metal nitride layer in this process step is customarily designated as "hard mask technique”.
• the first resist pattern is stripped away by an oxygen plasma ashing treatment. This way, wiring trenches are formed.
• second resist pattern another resist pattern
• the remaining low-k or ultra low-k layer is again partly etched away by using the second photo resist pattern as a mask pattern, thereby forming the via holes which communicate with the wiring trenches and the copper interconnect wiring of the level below.
• the second photo resist pattern is also stripped away by oxygen plasma ashing treatment.
• the wiring trenches and via holes are then filled with copper preferably by electroplating, thereby creating multilayer copper wiring conductors.
• the substrate for use in these processes may optionally be provided with a barrier layer (e.g., SiN layer or SiC layer) as an etch-stop layer between the copper layer and the low-k layer.
• a barrier layer e.g., SiN layer or SiC layer
• via holes and trenches are formed, and then, while the barrier layer exposed out on the substrate is kept as such or after the barrier layer has been removed, the photo resist is stripped away and, thereafter, the via holes and the wiring trenches are filled with copper.
• silicon deposition may readily occur, resulting from the low-k layer during the etching treatment and the oxygen plasma ashing treatment for forming the via holes on the trenches, and this may form silicon deposits around the opening of the trenches.
• a deposition that results from the resists may also occur. If these deposits are not completely removed, they can significantly decrease the yield in semiconductor production. Accordingly, oxygen plasma ashing treatment has been used for the removal of the resist patterns and etching residues in conventional patterning for metal wiring.
• ultra-micropatterning technology a material having a lower dielectric constant, i.e. an ultra low-k material, must be used for the insulating low-k layer.
• the American patent application US 2003/0148624 A1 discloses a resist stripping composition for removing ashed and non-ashed resists, the said compositions containing quaternary ammonium hydroxides such as tetramethylammonium hydroxide (TMAH), and organic solvents such as ethanolamine, 1-amino-2-propanol, aminoethoxyethanol, 1- methylaminoethanol, dimethyl sulfoxide, N-methylpyrrolidone, diethyleneglycol monomethyl ether, or diethylenglycol monobutyl ether.
• TMAH tetramethylammonium hydroxide
• the examples specifically disclose a resist stripping composition consisting of 5% by weight ethanolamine, 50% by weight dimethyl sulfoxide, 5% by weight propylene glycol, 0.05% by weight TMAH, 39.55% by weight of water, and 1 ppm or lower of dissolved oxygen, and a resist stripping composition consisting of 28% by weight 1-amino-2-propanol, 62% by weight N- methylpyrrolidone, 1 % by weight TMAH, 9% by weight water, and 1 ppm of dissolved oxygen.
• These prior art resist stripping compositions are used in the process wherein the resists have to be pre-cleaned with a particular cleaning composition containing 1 % by weight or more of hydrogen peroxide and ammonia or ammonium ion.
• Ethanolamine, isopropanolamine, 2-(2-aminoethylamino)ethanol, N-methylethanolamine, N-ethylethanolamine, dicyclohexylamine, and TMAH may be used as the base not containing a metal.
• the complete (A)-component is preferably used in an amount of from 0.01 to 1 % by weight, based on the weight of the resist stripping composition.
• the base not containing a metal can be used in an amount of from 0.1 to 20% by weight, based on the weight of the resist stripping composition.
• Diethyleneglycol monoethyl ether, diethyleneglycol monobutyl ether, N-methylpyrrolidone, and dimethyl sulfoxide can be used as the water-soluble organic solvents (B).
• the international patent application WO 2004/100245 A1 discloses a resist stripping composition
• a resist stripping composition comprising hbSiF ⁇ and/or HBF 4 , preferably in an amount of from 0.001 to 5% by weight of the composition, an organic solvent, preferably in an amount of from 50 to 89% by weight of the composition, optionally an amine, preferably in an amount of less than 1.5% by weight of the composition, a corrosion inhibitor, preferably in an amount of 0.001 to 10% by weight of the composition, and water as the balance.
• N- methylpyrrolidone, diethyleneglycol monomethyl ether, or diethyleneglycol monobutyl ether can be used as the organic solvent.
• Isopropanolamine, 2-(2- aminoethylamino)ethanol, 2-(2-aminoethoxy)ethanol, and ethanolamine can be used as the optional amine.
• TMAH is only used in a so-called high water embodiment which is substantially free of organic solvents.
• a resist stripping comprising a quaternary ammonium hydroxide such as TMAH, preferably an amount of from 1 to 20% by weight of the composition, water, preferably in an amount of from 5 to 60% by weight of the composition, a water-soluble organic solvent, such as dimethyl sulfoxide, N-methylpyrrolidone, diethyleneglycol monomethyl ether, diethyleneglycol monobutyl ether, and a water-soluble amine, such as ethanolamine, isopropanolamine, diethylenetriamine, 2-(2-aminoethoxy)ethanol, or N- methylethanolamine, preferably in an amount of from 10 to 50% by weight of the composition.
• TMAH quaternary ammonium hydroxide
• water preferably in an amount of from 5 to 60% by weight of the composition
• a water-soluble organic solvent such as dimethyl sulfoxide, N-methylpyrrolidone, diethyleneglycol monomethyl ether, diethyleneglycol monobutyl ether
• dilute aqueous resist stripping compositions comprising, for example, from 0.02 to 0.18% by weight of the composition of an ammonium fluoride, from 20 to 40% by weight of the composition of water, from 59 to 85% by weight of the composition of an amide and an ether solvent such as diethyleneglycol monoethyl ether diethyleneglycol monobutyl ether and N-methylpyrrolidone, from 0.2 to 5% by weight of an acid, from 0.2 to 5% by weight of an alkanolamine such as ethanolamine, isopropanolamine, N-methylethanolamine, or 2-(2-aminoethylamino)ethanol, and from 0.2 to 5% by weight of the composition of a quaternary ammonium compound such as TMAH.
• These prior art resist stripping compositions can be used for removing ashed and non- ashed resists.
• a resist stripping composition comprising a quaternary ammonium hydroxide such as TMAH, preferably in an amount of from 1 to 30% by weight of the composition, water, preferably in an amount of from 15 to 94% by weight of the composition, an organic polar solvent such as N-methylpyrrolidone, dimethyl sulfoxide, 3-amino-1-propanol and ethanolamine, or mixtures thereof, preferably in an amount of from 25 to 85% by weight, and hydroxyl amine or a hydroxyl amine derivative, preferably in an amount of from 2 to 12% by weight of the composition.
• TMAH quaternary ammonium hydroxide
• water preferably in an amount of from 15 to 94% by weight of the composition
• an organic polar solvent such as N-methylpyrrolidone, dimethyl sulfoxide, 3-amino-1-propanol and ethanolamine, or mixtures thereof, preferably in an amount of from 25 to 85% by weight, and hydroxyl amine or
• aqueous and nonaqueous resist stripping compositions for removing ashed and non-ashed resists, the said compositions comprising from 0.5 to 15% by weight of the composition of a quaternary ammonium compound such as TMAH or tetrabutylammonium hydroxide (TBAH), an organic solvent such as diethyleneglycol monomethyl ether or diethylene glycol monobutyl ether.
• a quaternary ammonium compound such as TMAH or tetrabutylammonium hydroxide (TBAH)
• organic solvent such as diethyleneglycol monomethyl ether or diethylene glycol monobutyl ether.
• the Example K specifically discloses a resist stripping composition consisting of 65% by weight propyleneglycol methyl ether, 39% by weight propyleneglycol propyl ether, 0.4% by weight water, 0.6% by weight TBAH, 3% by weight p-toluenesulfonic acid, and 1 % by weight ethanolamine.
• the Example L specifically discloses a resist stripping composition being free of water and consisting of 56% by weight propyleneglycol propyl ether, 35.5% by weight propyleneglycol methyl ether, 0.5% by weight TBAH, 6% by weight p- toluenesulfonic acid, and 2% by weight of ethanolamine.
• the Example M specifically discloses a resist stripping composition consisting of 91.5% by weight propyleneglycol methyl ether, 0.2% by weight water, 0.2% by weight TBAH 6% by weight p-toluenesulfonic acid, and 2% by weight ethanolamine.
• a resist stripping composition consisting of 91.5% by weight propyleneglycol methyl ether, 0.2% by weight water, 0.2% by weight TBAH 6% by weight p-toluenesulfonic acid, and 2% by weight ethanolamine.
• E, F, J, N, O, A5 P and S, TMAH is used in higher amounts ranging from 2.5% by weight to 5.5% by weight.
• both PGME and PGPE should mean propyleneglycol methyl ether.
• PGPE really means propyleneglycol propyl ether.
• the American patent application US 2008/0280452 A1 discloses a resist stripping composition for non-ashed resists having a high water content and comprising a quaternary ammonium hydroxide such as TMAH, TBAH or methyltripropylammonium hydroxide (MTPAH) preferably in an amount of from 1 to 20% by weight of the composition, a water-soluble organic solvent such as dimethyl sulfoxide and N- methylpyrrolidone, and a water-soluble amine such as ethanolamine, N- methylethanolamine and 2-(2-aminoethoxy)ethanol, preferably in an amount of from 10 to 15% by weight of the composition.
• Table 2 discloses resist stripping compositions e.g.
• TMAH 50% by weight dimethyl sulfoxide
• stripping solution G 40% by weight water
• 5% by weight TBAH 30% by weight N- methylpyrrolidone
• 30% by weight dimethyl sulfoxide 30% by weight dimethyl sulfoxide
• 25% by weight water stripping solution J
• 5% by weight MTPAH 30% by weight dimethyl sulfoxide, 15% by weight N- methylpyrrolidone, 20% by weight water and 30% by weight 2-(2-aminoethoxy)ethanol.
• a pretreatment with ozone water and/or aqueous hydrogen peroxide is mandatory.
• the prior art resist stripping composition exhibit various drawbacks and disadvantages.
• the resist stripping compositions containing N-methylpyrrolidone prompt concerns over environment, health and safety (EHS).
• compositions having a high water content and/or a high quaternary ammonium hydroxide content can damage the low-k and, in particular, the ultra low-k materials used in the modern IC technology. Due to the complexing and chelating power of hydroxyl amine and hydroxyl amine derivatives, the compositions containing these compounds can cause corrosion of copper vias and interconnects. Both effects can lead to a partial or a complete failure of the IC.
• the removal rate for resists, post-etch residues (PER) and barrier anti-reflective layers (BARC) of resist stripping compositions having a high content of organic solvents strongly depends on the concentration of the quaternary ammonium hydroxides. This strong dependence on the concentration renders the optimization of the compositions difficult and complex. In particular, if high concentrations are required in order to achieve high removal rates, the aforementioned disadvantageous effects are again obtained.
• the known resist stripping compositions exhibit different removal rates for unchanged resists on the one hand and the PER and the BARC on the other hand.
• the PER and the BARC are much more difficult to remove than the unchanged resists. This is because the PER are having a chemical nature different from the resists and because the BARC are customarily highly cross-linked materials which are not easy to dissolve or to disperse.
• the prior art resist stripping compositions may satisfactorily remove the resists but exhibit unsatisfactory removal rates as far as the etch residues, which have a complex composition and, inter alia, contain Teflon-like materials and titanium and/or silicon containing materials, are concerned.
• photoresists are employed for patterning through silicon vias (TSV) and also for plating and bumping (3D Stacked Integrated Circuit, 3D-SIC; 3D Wafer Level Packaging, 3D-WLP).
• TSV through silicon vias
• 3D-SIC 3D Wafer Level Packaging
• plasma damaged photoresist i.e., post etch residues, PER
• PER post etch residues
• the patterning of TSV and the micro-bumping is often done on thinned silicon wafers which are bonded on carriers.
• the resist stripping compositions must also be compatible with the glue material.
• the new resist stripping compositions should no longer exhibit the disadvantageous effects associated with a high water content and/or a high quaternary ammonium hydroxide content and should no longer damage the low-k and, in particular, the ultra low- k materials used in the modern IC technology.
• the new resist stripping compositions should no longer contain hydroxyl amine and hydroxyl amine derivatives so that the risk of the corrosion of copper vias and interconnects is minimized or, ideally, completely avoided.
• the removal rate for resists, post-etch residues (PER) and barrier anti-reflective layers (BARC) of the new resist stripping compositions having a high content of organic solvents should no longer depend on the concentration of the quaternary ammonium hydroxides. This way, the optimization and the adaption of the new compositions to changing manufacturing parameters should be rendered simple, straightforward and efficient, so that high concentrations are no longer required in order to achieve high removal rates.
• the new resist stripping compositions should exhibit the same or essentially the same removal rates for the unchanged resists on the one hand and the PER and the BARC on the other hand, so that the different chemical nature of the PER and the BARC offers no longer an obstacle for their efficient removal.
• the new resist stripping compositions should not only excellently remove the resists but also exhibit excellent removal rates as far as the PER, which have a complex composition and contain Teflon-like materials and titanium and/or silicon containing materials, are concerned.
• the new methods of manufacturing electrical devices should no longer require a pre-treatment step before the removal step.
• the use of ozone water and/or aqueous hydrogen peroxide should be completely dispensed with so that the concerns over EHS associated therewith no longer exist and the damage of the low-k and ultra-low-k materials by these strongly oxidizing solutions can be avoided completely.
• the new methods of manufacture should yield electrical devices which are completely or essentially free from defects, exhibit an excellent functionality and have a long service life.
• the new resist stripping compositions should be capable of being most advantageously used in 3D technologies for the manufacture of 3D architectures, in particular, in the field of patterning through silicon vias (TSV) and also for plating and bumping (3D Stacked Integrated Circuit, 3D-SIC; 3D Wafer Level Packaging, 3D-WLP). In these applications, they should be capable of removing positive-tone and negative-tone photoresists and PER in the same most advantageous manner without damaging blanket wafers surfaces, patterned wafer structures and the glue material bonding thinned silicon wafers on carriers.
• TSV through silicon vias
• 3D-WLP 3D Wafer Level Packaging
• the novel liquid composition has been found, the said composition being free from N-alkylpyrrolidones and hydroxyl amine and hydroxyl amine derivatives, having a dynamic shear viscosity at 50 0 C of from 1 to 10 mPas as measured by rotational viscometry and comprising based on the complete weight of the composition,
• composition or compositions of the invention are designated as "composition or compositions of the invention" as the case may be.
• novel method for preparing a liquid composition being free from N- alkylpyrrolidones and hydroxyl amine and hydroxyl amine derivatives, the said method comprising the steps of
• the novel method for preparing a liquid composition being free from N- alkylpyrrolidone and hydroxyl amine and hydroxyl amine derivatives is referred to as the "method of preparation of the invention".
• the novel method for manufacturing electrical devices has been found, the said method comprising the steps of
• At least one resist stripping composition being free from N- alkylpyrrolidones and hydroxyl amine and hydroxyl amine derivatives and having a dynamic shear viscosity at 50 0 C of from 1 to 10 mPas as measured by rotational viscometry and comprising, based on the complete weight of the composition,
• liquid composition for removing negative-tone and positive- tone photoresists and post etch residues in the manufacture of 3D Stacked Integrated Circuits and 3D Wafer Level Packagings by way of patterning Through Silicon Vias and/or by plating and bumping
• said liquid composition being free from N- alkylpyrrolidones and hydroxyl amine and hydroxyl amine derivatives, having a dynamic shear viscosity at 50 0 C of from 1 to 10 mPas as measured by rotational viscometry and comprising based on the complete weight of the composition,
• compositions of the invention no longer contained N-alkylpyrrolidone, in particular, N-methylpyrrolidone, so that the environmental, health and safety (EHS) problems associated therewith were no longer present.
• EHS environmental, health and safety
• compositions of the invention no longer exhibited the disadvantageous effects associated with a high water content and/or a high quaternary ammonium hydroxide content and no longer damaged the low-k and, in particular, the ultra low-k materials used in the modern IC technology.
• compositions of the invention no longer contained hydroxyl amine and hydroxyl amine derivatives so that the risk of the corrosion of copper vias and interconnects was considerably minimized or, in many cases, completely avoided.
• the removal rate for resists, post-etch residues (PER) and barrier anti-reflective layers (BARC) of the compositions of the invention no longer depended on the concentration of the quaternary ammonium hydroxides.
• PER post-etch residues
• BARC barrier anti-reflective layers
• compositions of the invention exhibited the same or essentially the same removal rates for the unchanged resists on the one hand and the PER and the BARC on the other hand, so that the different chemical nature of the PER and the BARC offered no longer an obstacle for their efficient removal.
• the method of preparation of the invention could be carried out in a simple, economical, safe and excellently reproducible way without causing ESH-problems and did not require any particular and special facilities and safety measures. It yielded liquid compositions, in particular compositions of the invention, which had excellent applicational and property profiles
• the manufacturing method of the invention for electrical devices in particular semiconductor integrated circuits (ICs), liquid crystal panels, organic electroluminescent panels and printed circuit boards, micro machines, DNA chips and micro plants, especially ICs, no longer required a pre-treatment step before the removal step.
• ICs semiconductor integrated circuits
• the use of ozone water and/or aqueous hydrogen peroxide could be completely dispensed with so that the concerns over EHS associated therewith no longer existed and the damage of the low-k and ultra-low-k materials by these strongly oxidizing solutions could be avoided completely.
• the manufacturing method of the invention yielded electrical devices which were completely or essentially free from defects, exhibited excellent functionalities and had a long service life.
• compositions of the invention were most particularly suited for the use of the invention in 3D technologies for the manufacture of 3D architectures, in particular, in the field of patterning through silicon vias (TSV) and also for plating and bumping (3D Stacked Integrated Circuit, 3D-SIC; 3D Wafer Level Packaging, 3D-WLP).
• TSV through silicon vias
• 3D-SIC 3D Wafer Level Packaging
• 3D-WLP 3D Wafer Level Packaging
• the present invention is directed to a liquid composition which is free from N-alkylpyrrolidones, in particular N-methylpyrrolidone and N-ethylpyrrolidone, as well as hydroxyl amine and hydroxyl amine derivatives, in particular hydroxyl amine derivatives as disclosed in the American patent applications US 2005/0266683 A1 , page 4, paragraphs [0046] to [0050], and US 2005/0263743 A1 , page 4, paragraph [0057] to page 5, paragraph [0063].
• N-alkylpyrrolidones in particular N-methylpyrrolidone and N-ethylpyrrolidone
• hydroxyl amine and hydroxyl amine derivatives in particular hydroxyl amine derivatives as disclosed in the American patent applications US 2005/0266683 A1 , page 4, paragraphs [0046] to [0050], and US 2005/0263743 A1 , page 4, paragraph [0057] to page 5, paragraph [0063].
• the characteristic "liquid” means that the composition of the invention is liquid at least at room temperature (i.e. 23°C), preferably at least at 0 0 C and most preferably at least at -10 0 C.
• the characteristic "free from” means that the relevant compounds cannot be detected in the composition of the invention with the known state-of-the-art analytical methods for qualitatively and/or quantitatively detecting N-alkylpyrrolidones hydroxyl amine and hydroxyl amine derivatives, e.g., gas chromatography and/or mass spectrometry.
• the composition of the invention exhibits a dynamic shear viscosity at 50 0 C as measured by rotational viscometry of from 1 to 10 mPas, preferably 2 to 8 mPas, more preferably 1.5 to 7 mPas and most preferably 2 to 6 mPas.
• the composition of the invention also exhibits a dynamic shear viscosity at 23°C as measured by rotational viscometry of from 2 to 20 mPas, more preferably 3 to 16 mPas and most preferably 3 to 14 mPas.
• composition of the invention can be a dispersion, i.e. an emulsion or a suspension, or a homogeneous composition, wherein all the ingredients are molecularly dispersed.
• composition of the invention is a homogeneous, molecularly dispersed composition.
• the polar organic solvent (A) is selected from the group consisting of solvents which exhibit in the presence of dissolved tetramethylammonium hydroxide (B) in an amount of from 0.06 to 4% by weight, based on the complete weight of the respective test solution (AB), at 50 0 C a constant removal rate for a 30 nm thick polymeric barrier anti-reflective layer containing deep UV absorbing chromophoric groups.
• the characteristic "constant" means that, in the given range, the removal rate is completely or virtually independent from the concentration of the tetramethylammonium hydroxide (B).
• test solutions solutions (AB) are stirred during the tests at a constant rotational speed, more preferably at 50 to 200 rpm, even more preferably at 75 to 125 rpm and most preferably at 100 rpm.
• the semiconductor wafer pieces carrying the barrier anti-reflective layers are removed from the test solutions (AB), rinsed with a polar organic solvent, preferably isopropanol, and, thereafter, with deionized water and dried with a dry non- reactive gas, preferably nitrogen.
• a polar organic solvent preferably isopropanol
• deionized water preferably deionized water
• a dry non- reactive gas preferably nitrogen.
• the rinsing and drying steps are carried out at moderate temperatures, preferably at temperatures of from 23 to 50 0 C.
• FTIR Fast Fourier Transformation IR-Spectroscopy
• the barrier anti-reflective layers should still be present, their thickness is measured by way of known and customary methods for measuring the thickness of thin layers.
• transmission FTIR and/or interferometry is or are used to this end.
• the barrier anti-reflective layers are completely removed during the exposure to the test solutions (AB).
• any known polymeric anti-reflective coating compositions as for example, described in the American patent US 5,919,599, column 3, line 40 to column 16, line 36 and column 17, line 25 to column 18, line 25 in conjunction with the Figure 1 , can be used for preparing the polymeric barrier anti-reflective layers containing deep UV chromophoric groups.
• the selective tests guarantee that the organic polar solvents (A) are selected such that the compositions of the invention are even more so capable of completely removing the patterned resists and the post-etch residues together with the barrier anti-reflective layers, most preferably within 180 s without or essentially without redeposition.
• the polar organic solvent (A) is selected from the group consisting of aliphatic polyamines comprising at least two primary amino groups, aliphatic alkanolamines having at least one carbon chain of at least 3 carbon atoms between one primary amino group and one hydroxyl group, aliphatic sulfoxides, and N-substituted imidazoles.
• the solvent (A) is selected from the group consisting of diethylenetriamine (boiling point 207 0 C, flashpoint 102°C), N-methyl imidazole (boiling point 198°C, flashpoint 92°C), 3-amino-1-propanol (boiling point 187°C, flashpoint 101 0 C),
• the composition of the invention comprises, based on the complete weight of the composition, of from 0.05 to ⁇ 0.5% by weight, preferably of from 0.06 to ⁇ 0.5% by weight of at least one quaternary ammonium hydroxide.
• the quaternary ammonium hydroxide (B) is selected from the group consisting of tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, benzyltrimethylammonium, and (2-hydroxyethyl)ammonium hydroxide, in particular tetramethylammonium hydroxide.
• composition of the invention comprises, based on the complete weight of the composition of the invention, ⁇ 5% by weight, preferably ⁇ 4% by weight, more preferably ⁇ 3% by weight and most preferably ⁇ 2% by weight of water.
• the water content can also be so low as to be undetectable by known and customary methods for the qualitative and quantitative detection of water.
• composition of the invention can also contain at least one additional component selected from the group consisting of polar organic solvents (D) different from the solvents (A), corrosion inhibitors (E), chelating agents (F) , fluoride salts (G), and surfactants (H).
• D polar organic solvents
• E corrosion inhibitors
• F chelating agents
• F fluoride salts
• H surfactants
• the polar organic solvent (D) is selected from the group of solvents exhibiting, in the presence of from 0.06 to 4% by weight of dissolved tetramethylammonium hydroxide (B), the weight percentages being based on the complete weight of the test solution (DB), a removal rate at 50 0 C for a 30 nm thick polymeric barrier anti-reflective layer containing deep UV absorbing chromophoric groups which increases with increasing concentration of tetramethylammonium hydroxide (B).
• test solutions (DB) can contain, based on the complete weight of the test solution, up to 16% by weight of water (C).
• the removal rates of the test solutions (DB) are determined in the same way as described above for the test solutions (AB).
• the removal rates of the test solutions (DB) are 0 nm to 100 nm under the conditions set out above at a concentration of 1 % by weight of tetramethylammonium hydroxide (B), based on the complete weight of the test solution (DB).
• the polar organic solvents (D) are having a boiling point at atmospheric pressure above 100 0 C, more preferably above 120 0 C and most preferably above 150°C.
• the polar organic solvents (D) are having a flashpoint as measured in a closed cup up 50 0 C, more preferably above 55°C and most preferably above 60°C.
• the polar organic solvent (D) is selected from the group consisting of alkanol amines, alkylene glycol monoalkyl ethers, N-substituted piperidines, N-substituted cyclic ureas and N-substituted imidazoles, particularly, ethanolamine (boiling point 172°C, flashpoint 85°C), N-methylethanolamine (boiling point 160 0 C, flashpoint 72°C), N- ethylethanolamine (boiling point 168°C, flashpoint 78°C), isopropanolamine (boiling point 159°C, flashpoint 71 0 C), 2-(2-aminoethylamino)ethanol (boiling point 243°C, flashpoint 144°C), 2-(2-aminoethoxy)ethanol (boiling point 223 to 242°C, flashpoint 127°C), diethyleneglycol monoethyl ether (bo
• the copper corrosion inhibitors (E) may be used in broadly varying amounts. Preferably, they are used in the customary and effective amounts disclosed in the above-mentioned prior art.
• any known chelating agent (F) can be used in the composition of the invention.
• the chelating agent (F) is selected from the group of copper chelating agents (F), in particular, from the group of copper chelating agents (F) described in, for example, in the American patent applications
• such copper chelating agents (F) are also used as the copper corrosion inhibitors (E).
• the copper chelating agents (F) may be used in broadly varying amounts. Preferably, they are used in the customary and effective amounts disclosed in the above-mentioned prior art.
• any known fluoride salt (G) may be used in the compositions of the intervention.
• the fluoride salt (G) is selected from the group of salts of hydrofluoric acid and a base not containing a metal, as described in the American patent application US 2004/0106531 A1 , page 3, paragraphs [0035] to [0041].
• the fluoride salts (G) may be used in broadly varying amounts. Preferably, they are used in the customary and effective amounts disclosed in the cited prior art, in particular, in paragraph [0041].
• any known surfactant (H) may be used in the composition of the invention.
• compositions of the invention can be prepared in various ways. Preferably, they are prepared according to the method of production of the invention. It is an advantage of the present invention that the method of production of the invention can also be used for preparing other compositions than the compositions of the invention.
• At least one polar organic solvent (A) is selected as described hereinbefore.
• At least one additional component selected from the group consisting of polar organic solvents (D) different from the solvents (A), corrosion inhibitors (E), chelating agents (F) , fluoride salts (G), and surfactants (H) described hereinbefore can be added in the first process step or in a separate process step preferably in the preferred amounts disclosed in the cited prior art. It is essential for the method of production of the invention that the above-mentioned ingredients are mixed together in the absence of the N-alkylpyrrolidones, hydroxyl amine and hydroxyl amine derivatives as described above.
• the shear viscosity at 50 0 C of the mixture resulting from the second process step is adjusted to 1 to 10 mPas, preferably 2 to 8 mPas, more preferably 1.5 to 7 mPas and most preferably preferably 2 to 6 mPas.
• the process step can be carried out as a separate step or can be integrated into each of the other process steps of the method of production of the invention.
• the latter can be accomplished by carefully selecting the ingredients for the second process step such that the resulting mixture already exhibits the required dynamic viscosity.
• the composition of the invention also exhibits a dynamic shear viscosity at 23°C as measured by rotational viscometry of from 2 to 20 mPas, more preferably 3 to 16 mPas and most preferably 3 to 14 mPas.
• Customary and standard mixing processes and mixing apparatuses such as agitated vessels, in-line dissolvers, high shear impellers, ultrasonic mixers, homogenizer nozzles or counterflow mixers, can be used for carrying out the mixing of the ingredients of the compositions, in particular of the compositions of the invention.
• compositions of the invention can be used for various purposes. In particular, they are used in the manufacturing method of the invention.
• Suitable low-k or ultra-low-k materials and suitable methods of preparing the insulating dielectric layers are described in, for example, the American patent applications US 2005/0176259 A1 , page 2, paragraphs [0025] to [0027], US 2005/0014667 A1 , page 1 , paragraph [0003], US 2005/0266683 A1 , page 1 , paragraph [0003] and page 2, paragraph [0024] or US 2008/0280452 A1 , paragraphs [0024] to [0026] or in the American patent US 7,250,391 B2, column 1 , lines 49 to 54.
• Suitable substrates are particularly semiconductor substrates customarily used for the manufacture of ICs such as silicon wafers.
• a positive or negative resist layer is applied on top of the insulating dielectric layer.
• Suitable materials and methods for preparing positive and negative resist layers are described in, for example, the American patent US 7,250,391 B2, column 1 , lines 55 to 60 or in the American patent applications US 2005/0176259 A1 , page 2, paragraphs [0029] and [0030], US 2006/0016785 A1 , page 3, paragraphs [0025] to [0027] or US 2008/0280452 A1 , paragraphs [0027] to [0029] and page 5, paragraph [0062].
• the resist layer is selectivity exposed to electromagnetic radiation or corpuscular radiation.
• the resist layer can also be directly exposed to corpuscular radiation, preferably, to electron beams.
• the resist pattern can be further baked (post-exposure baking).
• the selectively exposed resist layer is developed with a developer, preferably an aqueous alkaline solution as described in, for example, the American patent application US 2008/0280452 A1 , page 5, paragraph [0062], to yield the resist pattern.
• post-etch residues are generated, which must be removed in the course of the BEOL (back-end of the line) process of manufacturing electrical devices.
• These post-etch residues can have varying compositions comprising Teflon-like materials and titanium and/or silicon containing materials.
• At least one polar organic solvent (A) is selected as described hereinbefore.
• the at least one selected polar organic solvent (A) is used for preparing at least one composition of the invention as the resist stripping composition as described hereinbefore.
• the at least one resist stripping composition prepared in accordance with the seventh process step is used for removing the resist pattern and the post-etch residues by an all-wet process.
• the eighth process step is carried out at temperatures of from 0 to 70 0 C, more preferably 10 to 65°C and most preferably 50 to 60 0 C. It is one of the major advantages of the manufacturing method of the invention that, due to the use of the resist stripping composition of the invention, an ashing step, in particular, an ashing step using an oxygen containing plasma, or a pre-cleaning step, in particular, a precleaning step using ozone water or hydrogen peroxide, can be dispensed with. Moreover, no or only very little redeposition of hardened resist particles and/or post-etch residues can be observed.
• the wire trenches and via holes are filled with at least one material having a low electrical resistivity.
• copper and copper alloys most preferably copper, is used for this purpose.
• known copper electroplating solutions and electroplating methods as, for example, described in the American patent application US 2006/0213780 A1 can be employed.
• a barrier anti-reflective layer as, for example, described in the American patent US 5,919,599 can be interposed between the resist layer and the insulating dielectric layer. Additionally, the barrier anti-reflective layer can also be interposed between the hard mask layer and the resist layer. In both cases, the barrier anti-reflective layer is selectively etched in the fifth process step using the resist pattern resulting from the fourth process step as the mask.
• the resulting surface can be polished by chemical mechanical polishing (CMP) employing methods and equipment well-known in the art of manufacturing electrical devices such as ICs.
• CMP chemical mechanical polishing
• the electrical devices prepared in accordance with the manufacturing method of the invention have an excellent functionality and a very long service life.
• compositions of the invention are that, due to the high a boiling points of the organic polar solvents (A) and the optional organic polar solvents (D) used, they all exhibit a low vapor pressure at medium temperatures, in particular, in the temperature range of from room temperature up to 100 0 C. Moreover, due to the high flashpoints of the organic polar solvents (A) and the optional organic polar solvents (D) used, all the compositions of the invention are not readily flammable and not easily ignitable. Last but not least, the organic polar solvents (A) and the optional organic polar solvents (D) are not critical in terms of ESH. Therefore, this equally applies to compositions of the invention they are contained in. Consequently, the compositions of the invention can be prepared, stored, handled, used and disposed of without causing ESH problems.
• composition of the invention is that it is particularly suitable for the use of the invention.
• the composition of the invention is used for removing positive-tone and negative-tone resists as well as PER from blanket wafers and patterned wafers customarily used for the manufacture of 3D IC architectures which are also referred to as 3D-SIC and 3D-WLP.
• the interconnects are manufactured by way of TSV, plating and/or bumping, in particular micro-bumping (cf. imec, Scientific Report 2008, Advanced Packaging and Interconnect, 3D Interconnect and Packaging, 3D Stacked IC (3D-SIC), 3D-WLP: Micro-Bumping).
• the composition of the invention is applied to the photoresists and PER to be removed from blanket and patterned wafers by known and customary methods and equipment. After the removal of the photoresists, the wafers are rinsed and dried.
• the success of the removal step i.e., the complete absence of the photoresists ad PER, can be confirmed by optical, scanning electron microscopy (X-SEM), atomic force microscopy (AFM) and Fourier transform infrared (FTIR) spectroscopy inspection.
• X-SEM scanning electron microscopy
• AFM atomic force microscopy
• FTIR Fourier transform infrared
• the composition of the invention is capable of removing positive-tone and negative-tone photoresists and PER from the blanket and patterned wafers fast and completely without damaging the fine structures of the patterned wafers or the glue materials present.
• test solutions of tetramethylammonium hydroxide (TMAH) (B) in each of the solvents (S) listed in the Table 1 were prepared.
• Each series of test solutions (SB) consisted of seven solutions having TMAH concentrations of 0.06, 0.1 , 0.2, 0.5, 1.0, 2.0 and 4.0% by weight, the weight percentages being based on the complete weight of the respective test solution (SB), by adding the appropriate amounts of an aqueous solution containing 25% by weight TMAH.
• a coated piece of the silicon semiconductor wafer was exposed in a beaker at 50 0 C for 180 s to a test solution (SB) which was stirred with 100 rpm. Thereafter, the coated piece of the silicon semiconductor wafer was removed from the test solution (SB), rinsed with isopropanol and then with deionized water and dried at 50 0 C with a stream of dry nitrogen. After cooling down to room temperature, it was investigated by transmission FTIR and interferometry whether and, if yes, in what thickness the cross-linked polymeric barrier anti-reflective layer was still present.
• an untreated ultra low-k layer was annealed at 150 0 C for 120 minutes as the reference point. If at all, the annealing caused only very minimal changes of the thickness and of the refractive index.
• test solutions (SB) containing ⁇ 0.5% by weight TMAH exhibited an etching rate below 1 nm/minute, whereas the test solutions (SB) containing more 1 % by weight, 2% by weight and 4% by weight of TMAH exhibited much higher etching rates.
• compositions containing the polar organic solvents (A) selected in accordance with the Example 1 and quaternary ammonium hydroxides, in particular TMAH, in low concentrations are most particularly well suited and can be most advantageously used as resists stripping compositions for the removal of patterned photoresists, polymeric barrier anti-reflective layers and post-etch residues in the back-and-of the line (BEOL) copper damascene process for the manufacture of ICs with VLI and VLSI without damaging the ultra-low-k materials or etching the copper surfaces.
• the coated silicon semiconductor wafers were selectively irradiated with 194 nm deep UV radiation through test masks having various apertures with dimensions below 100 nm, thereby solubilizing the exposed areas of the negative resist. Thereafter, the masks were removed and the irradiated resists layers were developed with an aqueous sodium hydroxide solution to yield the desired resist patterns.
• Resist stripping compositions were prepared by mixing the ingredients in the desired amounts and homogenizing the resulting mixtures. The ingredients and their amounts are compiled in the Table 3. The percentages are given in percent by weight, based on the complete weight of the respective resists stripping composition.
• the step heights of the patterned hard masks equalled exactly their original thickness, demonstrating that the resist stripping compositions had completely removed the patterned resists, the patterned barrier anti-reflective layers and post-etch residues without attacking the ultra low-k layers.
• the patterned hard masks reproduced exactly the structure of the test masks. No defects, deformations, irregular sidewalls, residues or redeposited materials could be observed which even more so underlined that the resist stripping compositions exhibited an excellent cleaning power combined with an excellent compatibility.
• compositions Containing the Polar Organic Solvents (A) and TMAH in Low Concentrations for Stripping Positive-Tone and Negative-Tone Photoresists and Post- Etch Residues and the Compatibility of the Compositions with Glue Materials Bonding Thinned Silicon Wafers on Carriers
• compositions 3.1 to 3.5 of the Example 3 were used for carrying out the Exampled 4.

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