WO2008023753A1 - Solution pour éliminer un résidu après un procédé de traitement par voie sèche de semi-conducteur et procédé d'élimination du résidu utilisant celle-ci - Google Patents

Solution pour éliminer un résidu après un procédé de traitement par voie sèche de semi-conducteur et procédé d'élimination du résidu utilisant celle-ci Download PDF

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Publication number
WO2008023753A1
WO2008023753A1 PCT/JP2007/066336 JP2007066336W WO2008023753A1 WO 2008023753 A1 WO2008023753 A1 WO 2008023753A1 JP 2007066336 W JP2007066336 W JP 2007066336W WO 2008023753 A1 WO2008023753 A1 WO 2008023753A1
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acid
residue
solution according
film
removing solution
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PCT/JP2007/066336
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English (en)
Japanese (ja)
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Shingo Nakamura
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Daikin Industries, Ltd.
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Priority to JP2008530947A priority Critical patent/JP4766114B2/ja
Publication of WO2008023753A1 publication Critical patent/WO2008023753A1/fr

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    • 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
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
    • 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
    • G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
    • H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
    • H01L21/76814—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics post-treatment or after-treatment, e.g. cleaning or removal of oxides on underlying conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
    • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
    • H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
    • H01L23/53204—Conductive materials
    • H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
    • H01L23/53228—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being copper
    • H01L23/53238—Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a chemical solution for removing residues formed during dry etching and / or ashing (ashing) in a semiconductor device manufacturing process, and a semiconductor device that removes these residues using the chemical solution It relates to the manufacturing method. In particular, it relates to residue removal solutions used in the manufacture of Cu / Low-k multilayer wiring structures.
  • semiconductor devices having an Al / SiO multilayer wiring structure that uses A1 or A1 alloy as a wiring material and a SiO film as an interlayer insulating film have been mainly manufactured.
  • low-k film low dielectric constant film
  • Many semiconductor devices with Cu / Low-k multi-layer wiring structure using these are manufactured.
  • Cu / Low-k multilayer wiring structures are processed by a method called damascene.
  • a trench (trench) or hole (via hole) is processed in an interlayer insulating film substrate, and a wiring material such as Cu is embedded in the additional portion to form a wiring structure.
  • trenches and via holes for wiring are continuously formed on an interlayer insulating film substrate made of a low-k film or the like, and then a wiring material such as Cu is embedded.
  • a via hole is formed first, followed by a via first process in which a trench for wiring is formed.
  • a trench for wiring is first formed, and then a trench for forming a via hole is formed.
  • a via hole is formed in an interlayer insulating film substrate by dry etching, and then a filling agent is buried and planarized. Then, lithography for forming the trench is performed and dry etching is performed. Thereafter, the resist and the filling agent that are no longer needed are removed from the substrate on which the trenches and via holes are formed by ashing or the like. [0006] However, even after this process, unnecessary substances that cannot be completely removed (hereinafter referred to as "residues after the dry process”) remain on the substrate.
  • Cu which is a wiring material
  • a low-k film of an interlayer insulating film may be damaged by a dry process using plasma such as dry etching or ashing.
  • plasma such as dry etching or ashing.
  • a Cu oxide film is formed on the surface of the Cu metal wiring.
  • the low-k film is often damaged by the dry process. When washed with a polymer stripping solution, it is easily etched to cause pattern dimension changes. Furthermore, the semiconductor device cleaning apparatus is changing from a batch type apparatus to a single wafer type apparatus. For this reason, it has become difficult to completely remove the residue after the drive process, which adheres strongly to the Cu / Low-k structure, in a short time by the conventional method using a stripping solution. In addition, although corrosion of the Cu butter due to cleaning is not observed, cracks are often generated along the grain boundaries on the Cu surface when observed in detail. These small Cu surface cracks are likely to adversely affect the performance of force devices. In addition, the growth of Cu oxide film due to exposure of the wafers processed after the cleaning process to the atmosphere also causes device failures.
  • the present invention can suppress cracks on the Cu surface without damaging the Cu and low-k films, and can remove residues after the dry process in a short time.
  • the purpose is to provide a chemical solution. It is another object of the present invention to provide a semiconductor device manufacturing method using the same.
  • Patent Document 1 JP-A-11 316464
  • Patent Document 2 Japanese Patent Laid-Open No. 2004-94203
  • Patent Document 3 Japanese Patent Laid-Open No. 2005-347587
  • Patent Document 4 Japanese Unexamined Patent Publication No. 2006-11297
  • the inventor uses an aqueous solution containing a strong acid capable of forming a complex or chelate with Cu, a polycarboxylic acid salt, and water as basic compositions without damaging the Cu and low-k films. ⁇ Suppresses cracks on the Cu surface and removes residues after the dry process that adheres strongly in a short time. I found that I can leave. Based on this knowledge, further studies have been made and the present invention has been completed.
  • the present invention provides the following removal solution for residues present in a semiconductor substrate after dry etching and / or ashing, and a method for manufacturing a semiconductor device using the residue removal solution.
  • Item 1 A solution for removing residues present on a semiconductor substrate after dry etching and / or ashing, comprising a strong acid capable of forming a complex or chelate with Cu, a polycarboxylate, and water. Residue removing liquid.
  • Item 2 The residue removing solution according to Item 1, which is a Bronsted acid having a strong acidity S capable of forming a complex or chelate with Cu and a pKa at 25 ° C of 3 or less.
  • Item 3 Strong acidity capable of forming a complex or chelate with Cu. At least one selected from the group consisting of trifluoroacetic acid, hydrobromic acid, perchloric acid, sulfuric acid, oxalic acid, malonic acid, and citrate. Item 3. A residue removal solution according to item 1 or 2.
  • Item 4 Polycarboxylic acid salt: oxalic acid, malonic acid, succinic acid, gnoretaric acid, adipic acid
  • Item 5 The concentration of the strong acid capable of forming a complex or chelate with Cu in the residue removing solution is 0.;! To 5% by weight, and the concentration of the polycarboxylate is 0.;! To 20% by weight.
  • the residue removing solution according to any one of Items 4 to 4;
  • Item 6 The residue removing solution according to any one of Items 1 to 5, wherein the pH is 4 to 6.5.
  • Item 7 The residue removing solution according to any one of Items 5 to 5, further containing an organic compound.
  • Item 8. The organic compound is at least one selected from the group consisting of polycarbonyls, hydroxyketones, esters, C3 or higher alcohols, C3 or higher aldehydes, polyethers, and sulfones.
  • Item 8. A residue removal solution according to Item 7.
  • Item 9 The residue removing solution according to Item 7 or 8, wherein the pH is 4 to 7.
  • Item 10 The concentration of the strong acid capable of forming a complex or chelate with Cu in the residue removing solution is 0. Item 7-9, which is 5% by weight, the concentration of polycarboxylate is 0.;! ⁇ 20% by weight, and the concentration of organic compound is 0.5-60% by weight. Residue removal solution.
  • Item 11 The residue removing solution according to any one of Items 10 to 10, further containing a fluorine compound.
  • Item 12 The compound power according to Item 11, which is hydrogen fluoride or fluoride salt of ammonia, hydroxylamine, primary, secondary or tertiary amine, quaternary ammonium or polyamine. Residue removal solution.
  • Item 13 The residue removing solution according to any one of Items 1 to 12, further comprising a Cu crack inhibitor and / or a Cu antioxidant.
  • Item 14 A method for removing residues present on a semiconductor substrate after dry etching and / or ashing, wherein the semiconductor substrate after dry etching and / or ashing is selected from the items 1 to 13; A method for removing residues, comprising contacting with a residue removing solution.
  • Item 15 The residue removing method according to Item 14, which is a semiconductor substrate having Cu as a wiring material and having a low dielectric constant film (Low-k film) as an interlayer insulating material.
  • a method for manufacturing a semiconductor device comprising: (1) dry etching and / or etching a semiconductor substrate having Cu as a wiring material and having a low dielectric constant film (Low-k film) as an interlayer insulating material.
  • a manufacturing method comprising: a step of ashing; and (2) bringing the semiconductor substrate treated in (1) above into contact with the residue removing solution according to any one of Items;!
  • the residue removing solution of the present invention is characterized by containing, as basic compositions, a strong acid capable of forming a complex or chelate with Cu (hereinafter also referred to as “strong acid”), a polycarboxylate, and water. Furthermore, by adding organic compounds, surfactants, fluorine compounds, crack inhibitors, antioxidants, etc., it is possible to add more excellent functions.
  • the target of the residue removing solution of the present invention is mainly a Cu oxide film and a residue after the dry process.
  • Cu oxide film As the Cu oxide film, Cu oxide formed during dry etching and / or ashing, or when the metal is naturally oxidized when exposed to the atmosphere due to movement between processes, etc.
  • the natural oxide film of Cu that has been made is listed. These compositions, CuO, is rich Cu 2 0, Cu (OH) and the like.
  • Residues after the dry pro-process are Cu oxide films on the Cu surface of the Cu / Low-k multilayer wiring structure and / or dry on the wafer formed using Cu as the conductive metal. It consists of a modified Cu material containing Cu oxide formed by etching and / or ashing. This residue adheres mainly to the Cu wiring on which the pattern is formed, to the side wall of the pattern formed with an interlayer insulating film such as a low-k film, and to the surface of the interlayer insulating film substrate.
  • the residue formed on Cu is an altered residue composed of a mixture of Cu oxide and its Cu oxidized and / or fluorinated by dry etching and / or ashing. The residue has a high electrical resistance and forms an insulating layer close to Cu oxide.
  • Residue adhering to the side wall of the pattern formed by the interlayer insulating film such as low-k film is dry etching of stopper film such as SiN, low-k film, filling agent, etc. Sputtered by, and may contain Si or organic matter. Residues on the surface of the interlayer insulating film substrate can be removed by dry etching in addition to organic substances such as resists, anti-reflective films and filling agents that could not be removed by ashing, and residues in processes using inorganic masks. It can be inferred that it contains some Si and Cu alterations coming from the bottom of the holes and trenches.
  • the interlayer insulating film mainly means a low-k film (low dielectric constant film), but also includes, for example, a silicon oxide film (FSG film) containing fluorine. .
  • Ratio of interlayer insulation film The dielectric constant is usually greater than 1 and about 4 or less, preferably about 3 or less, more preferably about 2.8 or less, and even more preferably about 2.6 or less.
  • Low-k films are mainly produced by coating or plasma CVD.
  • LKD series (trade name, manufactured by JSR), HSG series (trade name, manufactured by Hitachi Chemical), Nanoglass (trade name, manufactured by Honeywell), IPS (trade name) , Catalyst Chemicals), ZM (trade name, Dow Corning), XLK (trade name, Dow Coming), FOx (trade name, Dow Corning), Orion (trade name, Tricon), NCS (Trade name, manufactured by Catalyst Kasei), SiLK (trade name, manufactured by Dow Coming), etc.
  • inorganic SOG film HSG: hydrogenated silsesquioxane film
  • organic SOG film MSQ film: methyl silsesquioxane film
  • poly Coating film organic polymer film) containing allyl ether as the main component
  • Black Diamond (trade name, manufactured by Applied Materials), Coral (trade name, manufactured by Novellus), Aurora (trade name, manufactured by ASM)
  • the resist includes, but is not limited to, KrF (krypton F), ArF, F resist and the like.
  • the embedding agent is an organic compound that also functions as an antireflection film.
  • a strong acid capable of forming a complex or chelate with Cu is a Bronsted acid having a pKa at 25 ° C of 3 or less (preferably 2 or less, more preferably 0 to 2), and a hydrogen ion H + And a structure (part) that forms a chelate or complex with Cu, and has the function of removing residues after the dry process.
  • Examples monochrome mouth acid, dichloroacetic acid, trichloroacetic port acetate, a - black port butyrate, beta black port butyrate, gamma black port butyrate, Monofuruoro acetate, Jifuruoro acetate, halogen-containing carboxylic acids such as Torifuruoro acetate, Examples thereof include inorganic acids such as hydrobromic acid, perchloric acid and sulfuric acid, and polycarboxylic acids such as oxalic acid, malonic acid, tartaric acid and citrate.
  • oxalic acid, malonic acid, citrate, and trifluoroacetic acid are preferred, with oxalic acid, malonic acid, citrate, trifluoroacetic acid, hydrobromic acid, and perchloric acid being preferred.
  • the concentration of the strong acid in the residue removing solution can be appropriately selected according to the amount and quality of the residue after the dry process to be removed.
  • the concentration of the strong acid is generally about 0.;! To 10% by weight, preferably 0.;! To 5% by weight, and more preferably 0.;! To 3% by weight. These The lower the concentration, the more the residue after the dry process is removed, and the higher the concentration, the easier the removal of the residue. 5% by weight or less is desirable from the viewpoint of cost effectiveness.
  • the polycarboxylate has a function of reducing damage to the low-k film, interacting with a strong acid, preventing corrosion of Cu, and removing a residue after a dry process containing Cu.
  • the amine salt of polycarboxylic acid is highly effective in suppressing cracks on the Cu surface.
  • polycarboxylate examples include oxalic acid, malonic acid, succinic acid, dartaric acid, adipic acid, malic acid, tartaric acid, diammonium hydrogen citrate, ammonium dihydrogen citrate, kenic acid, and the like. And salts formed from bases such as ammonia, hydroxylamine, primary, secondary or tertiary amine, quaternary ammonium, and polyamine.
  • bases such as ammonia, hydroxylamine, primary, secondary or tertiary amine, quaternary ammonium, and polyamine.
  • polycarboxylic acids such as malonic acid, diammonium hydrogen citrate, dihydrogen quanate, and kenic acid, and ammonia, primary, secondary or tertiary amines, quaternary ammonia, polyamines, etc.
  • a salt formed from the base examples include oxalic acid, malonic acid, succinic acid, dartaric acid, adipic acid, mal
  • malonic acid ammonium dihydrogen ammonium, ammonium dihydrogen ammonium, or ammonium salt of polycarboxylic acid such as citrate, methylamine salt, ethylamine salt, propylamine salt, butyramine Salt, dimethylamine salt, jetylamine salt, trimethyloleamine salt, triethylamine salt, propanediamine salt, triethylenetetramine salt, tetramethylammonium hydroxide salt, choline salt and the like.
  • polycarboxylic acid such as citrate, methylamine salt, ethylamine salt, propylamine salt, butyramine Salt, dimethylamine salt, jetylamine salt, trimethyloleamine salt, triethylamine salt, propanediamine salt, triethylenetetramine salt, tetramethylammonium hydroxide salt, choline salt and the like.
  • malonic acid ammonium salt methylamine salt, ethylamine salt, tetramethylammonium hydroxide salt or choline salt
  • methylammine salt, ethyllamine salt tetramethylammonium hydroxide hydrogen diammonium citrate salt Or dicholine ammonium salt
  • ammonium salt, methylamine salt, ethylamine salt, tetramethyl hydroxide Ammonium salt or choline salt is most preferred.
  • the polycarboxylate may be used in the form of crystals, or an aqueous solution obtained by mixing and neutralizing the above acid and base in water.
  • concentration of the polycarboxylate in the residue removal solution is generally from 0.;! To 20% by weight, preferably from 0.5 to; 10% by weight, more preferably from! To 5% by weight.
  • the molar ratio of strong acid (strong acid / polycarboxylic acid salt) that can form a salt is preferably about 0.3 to 1, and more preferably 0.35 to 0.8. If this ratio is less than 0.3, Cu will be corroded, and if it exceeds 1, the ability to remove residues after the dry process tends to decrease.
  • An organic compound (particularly a water-soluble organic compound) may be further added to the residue removing solution of the present invention.
  • This organic compound reduces the corrosion of Cu by strong acid, and after the dry process such as the surface residue of the interlayer insulation film substrate that adheres to the sidewall of the pattern formed by the interlayer insulation film such as low-k film The effect of removing the residue is added.
  • organic compounds include hydrophilic or water-soluble neutral organic compounds such as polycarbonyls, hydroxyketones, esters, C3 or higher alcohols, C3 or higher aldehydes, and polyethers. And sulfones are preferred.
  • polycarbonyls examples include 2,3 butanedione, 2,4 pentadione, methylglyoxal, acetylacetone, and the like.
  • 2, 3 butaneji examples include 2, 3 butaneji
  • hydroxyketones include acetoin, acetone alcohol, diacetone alcohol and the like. Of these, acetoin and acetone alcohol are preferred.
  • esters include monocarboxylic acid esters such as methyl acetate, ethyl acetate, methyl propionate, and ethyl propionate; dimethyl oxalate, cetyl oxalate, dimethyl malonate, jetyl malonate, and succinic acid.
  • Polycarboxylic acid esters such as dimethyl; Carbonic acid esters such as dimethyl carbonate and jetyl carbonate; Cyclic esters such as propylene carbonate, ethylene carbonate, and butyrolatatane; Keto acid esters such as methyl acetate acetate and ethyl acetate, methyl lactate, ethyl lactate, Oxyesters such as butyl lactate; Ethylene glycol monomethenoate etherate acetate, Ethylene glycol monomethinoate noate acetate, Ethylene glycol nolemono-n-butinoleethenoate acetate, Diethylene glycol monomethyl acetate Ruasetato, acetate diethylene glycol monomethyl E chill ether, acetic acid diethylene glycol Honoré mono - n - butyl Honoré ether Honoré ethyleneglycidyl Kono registration ⁇ diacetate (ethylene diacetate), propylene glycol monomethyl ether
  • C3 or higher alcohols include monoalcohols having a hydrophobic group such as a long chain (eg, C3-6) alkynole group such as isopropyl alcohol, 1-butanol, tert-butyl alcohol, and isobutyl alcohol; ethylene glycol Diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, poly (propylene glycol), glycerin, 2-amino-2-ethyl-1, 3-propanediol, 2-amino -2-methyl-1,3-propanediol, 1,2-cyclohexanediol, 2,2-dimethyl-1,3-propanediol, 2,5-dimethyleno-2,5-hexanediol, 2, 3-naphthalenediol, 1,2-butanediol, 1,3-butanediol, 1,4
  • Preferable examples include isopropylenoleanolone, 1-butanolenore, isobutinoleanole, diethyleneglycol, dipropylene glycol, triethyleneglycol, tetraethylenedaricol and the like.
  • C3 or higher aldehydes examples include propionaldehyde, butanal, and pen. Tanal and the like can be mentioned.
  • Polyethers include, for example, dimethoxymethane, diethoxymethane, dimethoxyethane, dimethoxypropane, ethylene glyconoresin methinoleatenore, ethyleneglycoleno methinoreino enoenoate, ethylene glycono lesino oleore.
  • Etherenole ethylene glycolenoresi-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol methino ethino ree eno enore, diethylene glycol ole techno eno eno enore, diethylene glycol noreno tere-n-butyl ether, triethylene glycol dimethyl ether, triethylene glycol eno Reethino Remethino Reethenore, Triethylene Glycono Resetino Reethenore, Tetraethylene Glycono Resin Metino Reethenore, Tetraethylene Glycol Bruno Leger Chino les ether Honoré, like polyethylene Chi glycol dimethyl ether.
  • Preferable examples include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol dimethylolate nore, triethyleneglycolino methinoleatenole, tetraethyleneglycol dimethyl ether and the like.
  • sulfones examples include sulfolane and dimethyl sulfone.
  • the concentration of the organic compound in the residue removing solution is generally 60% by weight or less, preferably 0.5 to 60% by weight, more preferably 2 to 40% by weight, particularly preferably 3 to 30% by weight. It is.
  • a fluorine compound may be further added to the residue removing solution, which increases the effect of removing residues adhering to the side wall of the pattern formed by the interlayer insulating film such as the low-k film. It is.
  • This residue is a result of dry etching of a stopper film such as SiN, a low-k film, a filling agent, etc. due to the power of the Cu-modified material, and may contain Si or organic matter! / is there.
  • Si and organic substances are contained in the residue, Cu oxide can be removed without adding a fluorine compound if Cu oxide is the main constituent.
  • interlayer insulation films such as low-k films that have been damaged by plasma during the dry process are easily etched by fluorine compounds and may not be processed as designed. For this reason, it is preferable to add a small amount of a fluorine compound in order to add a higher removal effect when the residue cannot be removed sufficiently or when it remains uncertain whether it has been removed or not.
  • Examples of the fluorine compound include hydrogen fluoride or fluoride salts such as ammonia, hydroxylamine, primary, secondary or tertiary amine, quaternary ammonium or polyamine. It is done. Specifically, hydrogen fluoride, ammonium fluoride, ammonium monohydrogen difluoride, methylamine fluoride, fluorinated tyramine, decylamine fluoride, triethylenetetramine fluoride, tetramethylammonium fluoride and the like are preferable. One or two or more fluorine compounds may be used. As one embodiment of the present invention, for example, an aqueous ammonium fluoride solution or dilute hydrofluoric acid (50% by weight aqueous solution) can be suitably used.
  • the concentration of the fluorine compound in the residue removal solution is appropriately selected according to the type and amount of the interlayer insulating film such as the silicon-containing film and the low-k film and the interlayer insulating film damaged by the dry process. can do.
  • the concentration of the fluorine compound is 5% by weight or less, preferably 0.001 to 5% by weight, and more preferably 0.01 to 3% by weight.
  • the residue removal solution should not contain a fluorine compound or contain a small amount (1 wt% or less). Is preferred. If the concentration is less than 0.001% by weight, the effect of removing residues may be reduced.
  • a surfactant may be further added to the residue removing solution of the present invention. This is because the surfactant increases the wettability with respect to the hydrophobic interlayer insulating film and allows the chemical solution to spread uniformly according to the pattern shape.
  • the type is not particularly limited, such as a cationic system, an anionic system, or a nonionic system.
  • the concentration of surfactant in the residue removal solution is generally 0.00001. -5% by weight, preferably 0.0001-3% by weight. If it is less than 0.00001% by weight, the surface activity effect is small. If it is more than 5% by weight, the effect is not changed.
  • Anti-cracking agent may be further added to the residue removing solution of the present invention.
  • Anti-cracking agents include sulfur-containing compounds with unshared electrons having oxygen with unshared electrons and / or nitrogen with unshared electrons, sulfides, mercabtans, thiocarboxylic acids, thioacetamides, thiourea. And thiadiazoles, tetrazoles, triazines, thiazoles, thiophenes, pyrimidines, purines, thiazolines and thiazolidines. Specifically, the following compounds can be preferably exemplified.
  • Examples of the sulfides include thiodiglycol, 2,2'-thiodiacetic acid, 3,3'-dithiodipropionic acid, and the like.
  • mercaptans examples include mercaptoacetic acid, thiomalic acid, thiolactic acid, 3-mercaptopropionic acid, aminothiophenol, 2-mercaptoethanol, 3-mercapto-1, 2-propanediol, and the like.
  • thiocarboxylic acids examples include thiolacetic acid, 3-acetylethylthio-2-methylpropanoic acid, and the like.
  • Examples of the thioacetamides include thioacetamide.
  • thioureas examples include thiourea, thiocarbohydrazide, guanylthiourea, ethylenethiourea, malonylthiourea, and the like.
  • thiadiazoles examples include 2,5-dimercapto-1,3,4-thiadiazole, 2-thioacetic acid-5-mercapto-1,3,4-thiadiazole, 2,5-dithioacetic acid-1 , 3,4-Chiasia zone.
  • Examples of the tetrazole include 1-methyl-5-mercapto-tetrazole and the like.
  • triazines examples include 2,4,6-trimercapto-S-triazine.
  • thiazoles examples include 4-thiazolecarboxylic acid, 2-aminothiazole and the like.
  • thiophenes examples include 2,5-thiophenedicarboxylic acid and 3-thiophenmalone. Acid, 2-thiophenecarboxylic acid and the like.
  • the pyrimidines include, for example, 2-thiobarbituric acid, 2-thiocytosine, thiouracil.
  • purines examples include 2,5-dithiopurine and 6-mercaptopurine.
  • thiazolines examples include 2-amino-2-thiazoline, 2-thiazoline-2-thiol, and the like.
  • thiazolidines examples include 2,4-thiazolidinedione, 2-thio-4-thiazolidone,
  • Examples include 2-imino-4-thiazolidinone.
  • the anti-cracking agent can be used supplementarily, and its concentration is, for example, 0.0
  • An antioxidant may be further added to the residue removing solution of the present invention.
  • examples of the antioxidant include benzotriazole.
  • the concentration is, for example, 0.00001-3 weight
  • % Preferably 0.0005 to 1% by weight.
  • the ratio of water contained in the residue removing solution of the present invention is usually 40 to 99.5 weight in the residue removing solution.
  • % Preferably about 70 to 99% by weight, and is determined by the force determined according to the amount (concentration) of components other than water.
  • the pH of the removing solution of the present invention is 4-7. If the pH is less than 4, the surface of the low-k film damaged by the dry process is likely to be altered, and if the pH is more than 7, Cu is easily corroded.
  • the pH is preferably 4 to 6.5. The pH is adjusted by the amount of strong acid, polycarboxylate and, if necessary, the organic compound.
  • the concentration of the strong acid is about 0.;! To 5% by weight (preferably 0.3-3 weight
  • the concentration of polycarboxylate is about 0 ⁇ ;! ⁇ 20% by weight (preferably 0 ⁇ 5 ⁇
  • the pH is about 4 to 6.5 (preferably about 4 to 6).
  • the molar ratio of strong acid to polycarbonate is about 0.3 to 1 (preferably about 0.35 to 0.8).
  • the concentration of the strong acid is about 0.; (Preferably about 0.3 to 3% by weight), and the concentration of the polycarboxylate is about 0.5 to 20% by weight (preferably about 0.75 to about 10% by weight).
  • the concentration of is 0.5 to 60% by weight (preferably 2 to 40% by weight, more preferably 3 to 30% by weight).
  • the pH is about 4-7 (preferably about 4-6).
  • the molar ratio of strong acid to polycarboxylate is about 0.3 to 1 (preferably about 0.30 to 0.8).
  • the residue removal method of the present invention mainly removes residues present in a semiconductor substrate after a dry process (dry etching and / or etching) in the formation process of a capacitor structure such as damascene or dual damascene. It is a method of removing. Specifically, the residue present on the semiconductor substrate having a Cu / Low-k multilayer wiring structure after the dry process is removed using the residue removing liquid described above.
  • the present invention also provides a method for manufacturing a semiconductor device.
  • the manufacturing method includes (1) dry etching and / or assembling a semiconductor substrate having Cu as a wiring material and having a low dielectric constant film (Low-k film) as an interlayer insulating material, and (2) The method includes the step of bringing the semiconductor substrate treated in (1) into contact with the residue removing liquid.
  • Low-k film low dielectric constant film
  • an insulating film barrier such as a SiN, SiC, or TaN film is formed on the low-k film as necessary. Etching the film together with the low-k film.
  • the residue removal process is performed by bringing a semiconductor substrate, which is an object to be processed, into contact with a residue removal solution.
  • the method for contacting the residue removing liquid can be appropriately set according to the type and temperature of the residue removing liquid.
  • a contact method for example, a batch type in which a large amount of processing object (wafer) stored in a cassette is immersed in a tank for storing chemical liquid, and cleaning is performed by applying the chemical liquid on the rotated processing object (wafer).
  • Various contact methods such as a single wafer type and a spray type in which a chemical solution is continuously sprayed on a workpiece (wafer) to be cleaned are used.
  • the temperature of the residue removing solution is, for example, about 10 to 60 ° C, preferably about 15 to 40 ° C.
  • the contact time is not particularly limited and can be appropriately selected. For example, 0.5 to 60 minutes Minutes, preferably about 1 to 40 minutes.
  • the wafer may be immersed in a residue removing liquid under stirring as necessary.
  • the speed of stirring is not limited and can be appropriately selected. Unnecessary material is difficult to peel off
  • the object to be treated may be immersed in a residue removal solution and subjected to ultrasonic cleaning! /.
  • the Cu oxide removal method of the present invention can be performed by washing the wafer from which Cu oxide and / or the residue after the dry process have been removed with pure water. This washing process can wash away the residue removal solution.
  • the semiconductor substrate from which the Cu oxide and / or the residue after the dry process has been removed using the residue removing solution of the present invention is a commonly used method such as Cu wiring (for example, a detailed semiconductor) It can be processed into various kinds of semiconductor devices (devices) according to CMP technology, edited by Toshiro Dohi, edited by 2001).
  • the residue removing solution of the present invention suppresses etching of silicon-containing films and low-k films, and can remove strongly adhered residues after dry process and Cu oxide film in a short time without Cu corrosion. In particular, it has the effect of suppressing the slight cracking of the Cu surface that could not be solved by conventional polymer stripping solutions that cause less damage to low-k films.
  • a wafer with a test pattern having a Cu / Low-k dual damascene structure formed by a via-first process was used to investigate the removal of residues and the change in pattern shape after the dry process.
  • the low-k film of Cu / Low-k dual damascene structure is a SiOC film formed by plasma CVD, and the insulating film barrier is a SiN film. Residues after the dry process adhere firmly and are difficult to remove. A large amount of residue is present at the bottom of the via hole, and is slightly observed on the side wall of the via hole and the low-k substrate surface.
  • the wafer with the test pattern was immersed in the chemical solutions shown in Examples and Comparative Examples at 25 ° C for 1 to 3 minutes under stirring (about 600 rpm), rinsed with running ultrapure water, and dried.
  • the residue removal treatment after the dry process was performed.
  • the residue removal state and cross-sectional shape after the dry process were observed with an electron microscope (SEM) for 12 via holes. Furthermore, in order to judge the presence or absence of Cu surface cracks, 60 via holes were observed from above with an electron microscope (SEM). The cross section was also observed with SEM as needed.
  • Table 2 Comparative Examples are shown in Table 4 and Table 6.
  • Tables 3, 5 and 7 show the results of testing using these chemicals.
  • Table 1 shows the test criteria.
  • Examples 1 to 21 are residue removal solutions composed of strong acid and polycarboxylate
  • Examples 22 to 25 are residue removal solutions obtained by adding NH F and organic compounds in addition to strong acid and polycarboxylate. is there.
  • Table 3 shows the results of testing using the chemical solutions of Examples 1 to 25.
  • the polycarboxylic acid salt is a methylolamine salt, an ethylamine salt, a jetylamine salt, a triethylenetetramine salt, a tetramethylammonium hydroxide salt, or a choline salt. Even if is used, the same effect is exhibited.
  • Example 22 in place of propylene glycolenomethenoylethenoate acetate, acetoin, ethylene glycol diacetate (ethylene diacetate), diethylene glycol, triethylene glycol dimethyl ether, methyl acetoacetate, acetic acid The same effect was obtained when diethylene glycol monoethyl ether was used.
  • the oxidation state of Cu was determined by measuring the humidity of a Cu blanket wafer immersed in a chemical solution at 27 ° C.
  • Table 4 shows the component compositions of the residue removal solutions of Comparative Examples 1-9. Comparative Example;! P H of the residue-removing solution of 1-9 was formulated to be about 2.
  • Comparative Examples 1 to 9 all have insufficient Cu crack prevention. In other items in Table 5, those with a rating of C or less indicate poor performance. Therefore, all the chemical solutions shown in Table 4 are not preferred as residue removal solutions.
  • Table 6 shows the component compositions of the residue removal solutions of Comparative Examples 10 to 17;

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Abstract

L'invention concerne une solution pour éliminer le résidu après un procédé de traitement par voie sèche. La solution permet de réguler la formation de minuscules craquelures sur une surface de cuivre sans endommager le cuivre et un film à faible k qui ne peut pas être obtenu par les solutions existantes d'élimination basées sur des polymères. L'invention concerne également l'établissement d'un procédé de production d'un dispositif semi-conducteur utilisant la solution. De manière plus spécifique, l'invention concerne une solution pour éliminer le résidu restant sur un substrat semi-conducteur après gravure à sec et/ou calcination caractérisée par le fait qu'elle comprend un acide fort capable de former un complexe ou un chélate avec Cu, un sel d'acide polycarboxylique et de l'eau ; et un procédé d'élimination de résidu restant sur un substrat semi-conducteur après gravure à sec et/ou calcination utilisant cette solution pour éliminer le résidu.
PCT/JP2007/066336 2006-08-24 2007-08-23 Solution pour éliminer un résidu après un procédé de traitement par voie sèche de semi-conducteur et procédé d'élimination du résidu utilisant celle-ci WO2008023753A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010024093A1 (fr) * 2008-08-25 2010-03-04 ダイキン工業株式会社 Solution pour l’élimination d’un résidu après un traitement à sec d’un semi-conducteur et procédé d’élimination de résidu l’utilisant
JP2013101224A (ja) * 2011-11-08 2013-05-23 Nagase Chemtex Corp レジスト残渣除去組成物
US8669217B2 (en) 2010-03-25 2014-03-11 Fujifilm Corporation Cleaning composition, cleaning process, and process for producing semiconductor device
CN110383426A (zh) * 2017-03-06 2019-10-25 福吉米株式会社 表面处理组合物及其制造方法、以及使用表面处理组合物的表面处理方法及半导体基板的制造方法
US11899369B2 (en) 2016-06-03 2024-02-13 Fujifilm Corporation Treatment liquid, method for washing substrate, and method for removing resist

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JPH11316464A (ja) * 1998-02-27 1999-11-16 Kanto Chem Co Inc フォトレジスト剥離液組成物
JP2005210082A (ja) * 2003-12-24 2005-08-04 Kao Corp 半導体素子洗浄用組成物
JP2006114872A (ja) * 2004-09-15 2006-04-27 Daikin Ind Ltd 銅酸化物を含む銅変質層の除去液及び除去方法
JP2006173180A (ja) * 2004-12-13 2006-06-29 Kao Corp 剥離剤組成物

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JPH11316464A (ja) * 1998-02-27 1999-11-16 Kanto Chem Co Inc フォトレジスト剥離液組成物
JP2005210082A (ja) * 2003-12-24 2005-08-04 Kao Corp 半導体素子洗浄用組成物
JP2006114872A (ja) * 2004-09-15 2006-04-27 Daikin Ind Ltd 銅酸化物を含む銅変質層の除去液及び除去方法
JP2006173180A (ja) * 2004-12-13 2006-06-29 Kao Corp 剥離剤組成物

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010024093A1 (fr) * 2008-08-25 2010-03-04 ダイキン工業株式会社 Solution pour l’élimination d’un résidu après un traitement à sec d’un semi-conducteur et procédé d’élimination de résidu l’utilisant
JP5278434B2 (ja) * 2008-08-25 2013-09-04 ダイキン工業株式会社 半導体ドライプロセス後の残渣除去液及びそれを用いた残渣除去方法
KR101354419B1 (ko) * 2008-08-25 2014-01-22 다이킨 고교 가부시키가이샤 반도체 드라이 프로세스 후의 잔사 제거액 및 그것을 이용한 잔사 제거 방법
US8747564B2 (en) 2008-08-25 2014-06-10 Daikin Industries, Ltd. Solution for removal of residue after semiconductor dry process and residue removal method using same
US8669217B2 (en) 2010-03-25 2014-03-11 Fujifilm Corporation Cleaning composition, cleaning process, and process for producing semiconductor device
US9396926B2 (en) 2010-03-25 2016-07-19 Fujifilm Corporation Cleaning composition, cleaning process, and process for producing semiconductor device
JP2013101224A (ja) * 2011-11-08 2013-05-23 Nagase Chemtex Corp レジスト残渣除去組成物
US11899369B2 (en) 2016-06-03 2024-02-13 Fujifilm Corporation Treatment liquid, method for washing substrate, and method for removing resist
CN110383426A (zh) * 2017-03-06 2019-10-25 福吉米株式会社 表面处理组合物及其制造方法、以及使用表面处理组合物的表面处理方法及半导体基板的制造方法
CN110383426B (zh) * 2017-03-06 2023-05-09 福吉米株式会社 表面处理组合物及其制造方法、以及使用表面处理组合物的表面处理方法及半导体基板的制造方法

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JP4766114B2 (ja) 2011-09-07

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