Classifications

• • 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
  • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
  • H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D9/00—Chemical paint or ink removers
• • 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
• • 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
  • H01L21/31138—Etching organic layers by chemical means by dry-etching

Definitions

• the present invention relates to the inhibition of titanium corrosion and, in particular, to compounds, compositions and methods used for the inhibition of titanium corrosion.
• Titanium finds application in metallization layers in semiconductor structures. Both the pure element and alloys thereof may be used as barrier layers to prevent electro-migration " - of certain atoms and/or as anti-reflective layers on top of. other metals.
• barrier layers to prevent electro-migration " - of certain atoms and/or as anti-reflective layers on top of. other metals.
• the reduction of interconnect dimensions i.n semiconductor manufacture is leading to the replacement of aluminum by titanium as the metallization layer in semiconductor materials and corrosion and electrolyte etching is a major factor in interconnect deterioration.
• Titanium forms a thin layer of a surface oxide and corrosion inhibition can be associated with retention of this surface layer. Titanium is an amphoteric metal which dissolves (corrodes) readily at both low and high pH. Small amounts of corrosion which occur at neutral pH tend to lower the pH at cathodic sites and increase the pH at anodic sites. Buffering chemicals which ameliorate development of this pH differential can inhibit corrosion. Organic molecules able to complex with the surface oxide layer can • suppress crack formation and can also stabilize the metals .
• Photoresists and other polymeric materials such as polyimides
• Photoresists and other polymeric materials are often subjected to ion implantation, plasma etching, reactive ion etching or ion milling during the fabrication process to define patterns ⁇ in the substrate.
• Oxygen plasma oxidation is also often used for removal of photoresists and other polymeric materials after their use during the semiconductor fabrication process. Such high-energy processes may result in the hardening of the photoresist and the formation of organometallic compounds and other residues on sidewalls of the structures being formed.
• reactive stripper solutions comprising hydroxylamine may be used during the post-metallisation stages for removal of resist residues and deposits left after plasma etch treatments.
• Examples of reactive stripper solutions suitable for these processes are disclosed in the Applicant's US Patents 5 279 771 and 5 334 332.
• hydroxylamine also initiates chemical attack and consequent corrosion of the titanium layer.
• Catechol has previously been added to certain reactive strippers to stabilize the hydroxylamine and it has also been observed that the addition of catechol also has a beneficial activity in inhibiting the corrosion of titanium. Whilst the mode of action of catechol is not known, it is considered that catechol may decrease the surface reactivity either by binding to the solid or by influencing the pH at the interface, or both.
• the present invention provides a composition for removing resist, polymeric material and/or etching residue from a substrate comprising hydroxylamine or a derivative thereof and at least one" .compound having the general formula (I) as shown below:
• R 1 and R 3 are each independently selected from H, OH, C0 2 H, halogen, C x -C 3 alkyl, alkoxy or (CH 2 ) n 0H wherein n is 1, 2 or 3; and R 2 is selected from C 9 -C 16 alkyl, or C 9 -C 16 alkoxy.
• R 2 is selected from C 9 , C 10 , C u or C 12 alkyl, or from C 9 , C 10 , C u or C 12 alkoxy.
• composition according to the present invention is particularly useful as a stripping composition for removing resist material during the manufacture of semiconductor integrated circuits.
• Resist materials which may be removed by the composition of the present invention include positive photoresists comprising, for example, ortho-naphthoquinone diazide sulfonic acid ester or amide sensitizer with novolak-type binders or resins.
• the composition may also be used to remove cured and uncured polymer resists comprising, for example, a polyimide, organometallic polymers formed on a substrate during plasma etching processes, sidewall polymeric materials and metal oxide residues.
• composition according to the present invention may also be used as a cleaning- composition for removing etching residue during the manufacture of semiconductor integrated ' circuits . .,,__.
• suitable substrates include metal substrates comprising titanium and alloys thereof, such as titanium/tungsten, titanium/aluminum, titanium/copper, titanium/tungsten/aluminum, titanium/copper/aluminum, titanium/tungsten/copper and titanium/tungsten/copper/aluminum.
• the substrate may also comprise, for example, a semiconductor wafer having on a surface thereof titanium or an alloy of titanium.
• suitable substrates are well known in the semiconductor industry and include silicon, silicon oxide, silicon nitride, gallium arsenide, and plastics, such as polycarbonate, which have on a surface thereof at least a portion comprising titanium or an alloy thereof.
• the compound having the general formula (I) is preferably selected from one or more of 3,4,5- trihydroxy-nonyl-benzene, 3,4, 5-trihydroxy-decyl- benzene, 3, 4, 5-trihydroxy-undecyl-benzene, 3,4,5- trihydroxy-dodecylnyl-benzene, and 3, 4, 5-trihydroxy- tridecyl-benzene .
• the composition advantageously further comprises a solvent, for example a polar solvent, which is preferable miscible with the hydroxylamine.
• Suitable examples include solvents selected from one or more of an alkanolamine, water, dimethyl sulfoxide, ethylene glycol, ethylene glycol alkyl ether, diethylene glycol alkyl ether (e.g. diethylene glycol butyl ether), triethylene glycol alkyl ether (e.g. triethylene glycol butyl ether) , propylene glycol, propylene glycol alkyl ether, dipropylene glycol alkyl ether (e.g. dipropylene glycol' .ethyl ether), tripropylene glycol alkyl ether, N-substituted pyrrolidone (e.g.
• N- methyl-2-pyrrolidone ethylenediamine.. ethylenetriamine, diethylenetriamine, dimethyl formamide and dimethyl acetamide.
• the most preferred solvent is an alkanolamine. The addition of a solvent strengthens the effectiveness of the composition, particularly when it is used as a stripping composition for removing resist material from a substrate.
• the composition comprises at least 5 wt% hydroxylamine, at least 10 wt% of one or more alkanolamines and from 0.5 to 30 wt% (preferably from 2 to 30 wt%) of one or more compounds having the general formula (I) , with any remaining balance consisting of one or more of the solvents recited above (the most preferable being one or both of water and/or dimethyl sulfoxide) .
• the composition comprises from 10 to 70 wt% hydroxylamine, from 30 to 60 wt% of one or more alkanolamines and from 5 to 15 wt% of one or more compounds having the general formula (I) , with any remaining balance consisting of any of the solvents recited above (the most preferable being one or both of water and/or dimethyl sulfoxide) .
• the hydroxylamine suitable for use in the present invention has the structure NH 2 OH. It may be conveniently provided in the form of a commercially available aqueous solution (about 50 wt%) from Nissin Chemical. Derivatives of hydroxylamine, such as a salt thereof, may also be used.
• Alkanolamines suitable for use in the present invention are preferably miscible with the hydroxylamine and are preferably water-soluble.
• alkanolamines useful in the present invention preferably have relatively high boiling points, preferably 75 °C or- above.
• Suitable alkanolamines are primary, secondary or tertiary amines and are preferably monoamines, dia ines or triamines, and, most preferably, monoamines.
• the alcohol group of the alkanolamines preferably has from 1 to 6 carbon atoms, and can be based on a linear, branched or cyclic alcohol.
• Preferred alkanolamines suitable for use in the composition according to the present invention can be represented by the chemical formula:
• R x and R 2 can each independently be H, CH 3 , CH 3 CH 2 or CH 3 CH 2 OH and R 3 is CH 3 CH 2 OH.
• alkanolamines examples include monoethanolamine, diethanolamine, triethanolamine, tertiarybutyldiethanolamine, isopropanolamine, diisopropanolamine, 2-amino-l-propanol, 3-amino-l- propanol, isobutanolamine, 2- (2-aminoethoxy) ethanol (diglycolamine) , 2- (2-aminoethoxy) p ' ropanol and 1- hydroxy-2-aminobenzene .
• a particularly preferred composition for use as a stripper solution consists of a solvent made up of about 37 wt% hydroxylamine solution (50:50 hydroxylamine: water by weight), about 63 wt% of diglycolamine, and one or more compounds having the general formula (I) as herein described added thereto so as to provide a concentration of about 0.2M.
• the present invention also provides a process for removing resist, polymeric material and/or etching residue from a substrate " ' ⁇ comprising titanium or an alloy thereof, the process comprising contacting the substrate with a composition as hereinbefore described at a temperature and for a time sufficient to remove the resist, polymeric material and/or etching residue from the substrate.
• the temperature is preferably in the range of from 20 to 150°C, more preferably 60 to 70°C, whilst the contact time is preferably in the range of from 2 to
• Suitable substrates have been described above and include, for example, a semiconductor wafer having on a surface thereof titanium or an alloy of titanium.
• the process may further comprise the step of rinsing the substrate with a suitable rinsing composition following substantial removal of the resist, polymeric material and/or etching residue from the substrate.
• a suitable rinsing composition comprises a polar solvent or an aqueous solution having a pH in the range of from 2 to 5.
• Suitable examples of rinsing compositions include isopropyl alcohol, N- methylpyrrolidone, dimethyl sulfoxide, dilute citric • acid and/or dilute, acetic acid.
• the substrate may be rinsed with a rinsing composition as described in the applicant's International Patent Application (WO 98/36045) .
• compositions comprise a monofunctional, difunctional or trifunctional organic acid and a buffering amount of a quarternary a ine, ammonium hydroxide, hydroxylamine, ⁇ hydroxylamine salt, hydrazine or hydrazine salt base.
• the rinsing step may be followed by water rinse, preferably a deionised water rinse, and finally a drying step such as vapour IPA drying.
• the present invention provides a method of inhibiting corrosion of a substrate comprising titanium or an alloy thereof, the method comprising contacting the substrate with one or more compounds selected from those having the general formula (I) as shown below:
• R 1 and R 3 are each independently selected from H, OH, C0 2 H, halogen, C ⁇ alkyl, C ⁇ alkoxy or (CH 2 ) n 0H wherein n is 1, 2 or 3; and R 2 is selected from C 9 -C 16 alkyl, or C 9 -C 16 alkoxy.
• R 2 is selected from C 9 , C 10 , C n or C 12 alkyl, or C 9 , C 10 , C n or C 12 alkoxy.'
• the compound having the general formula (I) may be provided in a composition comprising hydroxylamine or a derivative thereof or it may be provided in a composition comprising a solvent as hereinbefore described.
• the compound having the general formula (I) may preferably be selected from one or more of 3, 4, 5-trihydroxy- nonyl-benzene, 3, 4, 5-trihydroxy-decyl-benzene, 3,4,5- trihydroxy-undecyl-benzene, 3, 4, 5-trihydroxy-dodecyl- benzene, and 3, 4, 5-trih droxy-tridecyl-benzene.
• the compound having the general formula (I) is used in the method according to the present invention as a constituent in compositions comprising hydroxylamine or a derivative thereof and preferably at least one alkanolamine as herein described.
• Suitable substrates have also been described above and include, for example, a semiconductor wafer having on a surface thereof titanium or an alloy of titanium.
• the present invention still further provides for the use of a compound having the general formula (I) as shown below in a stripper or cleaning composition for removing resist, polymeric material and/or etching residue from a substrate, which substrate comprises titanium or an alloy thereof:
• R 1 and R 3 are each independently selected from H, OH, C0 2 H, halogen, C ! -C 3 alkyl, C ⁇ -C ⁇ alkoxy or (CH 2 ) n 0H wherein n is 1, 2 or 3; and R 2 is selected from C 9 -C 16 alkyl, or C 9 -C 16 alkoxy.
• R 2 is selected from C 9 , C 10 , C u or C 12 alkyl, or C 9 , C 10 , C n or C 12 alkoxy.
• the ⁇ compb.und having the general formula (I) is most preferably selected from one or more of 3, 4, 5-trihydroxy-nbnyl-benzene, . 3,4,5- trihydroxy-decyl-benzene, 3, 4, 5-trihydroxy-undecyl- benzene, 3, 4, 5-trihydroxy-dodecyl-benzene, and 3,4,5- trihydroxy-tridecyl-benzene .
• the present invention also provides for the use of a compound having the general formula (I) as shown below as a corrosion inhibitor in a stripper or cleaning composition for removing resist, polymeric material and/or etching residue from a substrate, which substrate comprises titanium or an alloy thereof.
• R 1 and R 3 are each independently selected from H, OH, C0 2 H, halogen, Ci-Cg alkyl, ' C ]. -C 3 alkoxy or (CH 2 ) n 0H wherein n is 1 , 2 or 3 ; and R 2 is selected from C 9 -C 16 alkyl, or C 9 -C 16 alkoxy.
• R 2 is selected from C 9 , C 10 , C u or C 12 alkyl, or C 9 , C 10 , C u or C 12 alkoxy.
• the compound having the general formula (I) is preferably selected from one or more of 3, 4, 5-trihydroxy-nonyl-benzene, 3, 4, 5-trihydroxy- decyl-benzene, 3,4, 5-trihydroxy-undecyl-benzene, 3, 4, 5-trihydroxy-dodecyl-benzene, and 3,4,5- trihydroxy-tridecyl-benzene .
• Suitable substrates include, for example, a semiconductor wafer having on a surface thereof titanium or an alloy of titanium.
• Figure 1 is a plot of titanium film conductance versus time upon exposure to a corrosive solution (hydroxylamine/diglycolamine) and upon exposure to the same corrosive solution containing a corrosion inhibitor (catechol) .
• Figure 2 is a plot of inhibition time versus the molecular weight a series of n-alkyl substituted corrosion inhibitors.
• Titanium coated wafers were obtained from International Wafer Service. 3, , 5-trihydroxy-n-alkyl- benzene compounds were synthesised by the general reaction scheme shown below:
• the thickness of the metal layer is directly related to its conductivity. Therefore the resistance of the film was determined using a 4-point probe (Keither 2010) and the conductivity was taken as a measure of the thickness.
• the corrosive solution used in the tests consisted of 35 wt% aqueous hydroxylamine solution (50:50 hydroxylamine:water) and 60 wt% diglycolamine. Compounds being tested as corrosion inhibitors were added in an amount of 5% w/w. Pieces of silicon wafer coated with 200nm titanium were suspended in the corrosive solution and periodically removed for measuement of the film resistance. In the absence of inhibitor the film conductivity decreased linearly with time as shown in figure 1 (dotted line) . Figure 1 also shows for comparison the change in conductivity when 5% w/w catechol is included in the corrosive solution (solid line) . It can be seen that catechol delays the onset of corrosion.

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• 2000
  • 2000-04-12 GB GBGB0009112.4A patent/GB0009112D0/en not_active Ceased
• 2001
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  • 2001-04-12 JP JP2001574886A patent/JP2003530482A/ja active Pending
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  • 2001-04-12 WO PCT/GB2001/001686 patent/WO2001078129A1/en not_active Ceased
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