WO2014087925A1 - 半導体素子用洗浄液及びそれを用いた洗浄方法 - Google Patents
半導体素子用洗浄液及びそれを用いた洗浄方法 Download PDFInfo
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- WO2014087925A1 WO2014087925A1 PCT/JP2013/082130 JP2013082130W WO2014087925A1 WO 2014087925 A1 WO2014087925 A1 WO 2014087925A1 JP 2013082130 W JP2013082130 W JP 2013082130W WO 2014087925 A1 WO2014087925 A1 WO 2014087925A1
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- Prior art keywords
- mass
- cleaning
- insulating film
- hydroxide
- cleaning liquid
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- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 11
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 10
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- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 5
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- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 5
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Classifications
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- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
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- 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
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- 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
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- 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
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- 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
- C11D7/36—Organic compounds containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/20—Other heavy metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
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- 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
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- H—ELECTRICITY
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- 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
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0332—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their composition, e.g. multilayer masks, materials
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- H—ELECTRICITY
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- 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
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
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- 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
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- 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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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- 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
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- 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
- H01L21/76838—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 conductors
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
- H01L21/76883—Post-treatment or after-treatment of the conductive material
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- 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
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- 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
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- H01L21/31144—Etching the insulating layers by chemical or physical means using masks
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- 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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32139—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer using masks
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- 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
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- 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
- H01L23/5329—Insulating materials
- H01L23/53295—Stacked insulating layers
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- 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 cleaning agent used in a manufacturing process of a semiconductor integrated circuit and a cleaning method using the same.
- the present invention has a barrier insulating film, a low dielectric constant interlayer insulating film, a hard mask, an organosiloxane thin film, on a substrate having a barrier metal, a copper wiring or a copper alloy wiring, and a low dielectric constant interlayer insulating film, Then, the photoresist is selectively exposed and developed to form a photoresist pattern, and then using the photoresist pattern as a mask, the organosiloxane thin film, hard mask, low dielectric constant Cleaning the semiconductor element that has been subjected to the dry etching treatment on the interlayer insulating film and the barrier insulating film, and suppressing the damage of the low dielectric constant interlayer insulating film, the copper wiring, the barrier metal, and the barrier insulating film, the organosiloxane system Cleaning solution for removing thin film, hard mask, dry
- a conductive thin film such as a metal film, which is a conductive wiring material, or an interlayer insulating film for the purpose of insulating between conductive thin films is usually formed on an element such as a silicon wafer.
- a photoresist is uniformly coated on the surface to provide a photosensitive layer, which is subjected to selective exposure and development to form a desired resist pattern.
- a desired pattern is formed on the thin film by subjecting the interlayer insulating film to a dry etching process using the resist pattern as a mask.
- a series of steps is generally taken to completely remove the resist pattern and the residue generated by the dry etching process (hereinafter referred to as “dry etching residue”) by ashing using oxygen plasma or a cleaning solution.
- the conductive wiring material is changed from aluminum to copper having a lower electric resistance, and accordingly, the interlayer insulating film is changed from a silicon oxide film to a low dielectric constant interlayer insulating film (a film having a relative dielectric constant smaller than 3).
- the transition to “low dielectric constant interlayer insulating film”) is progressing.
- copper is made of a metal such as tantalum or tantalum nitride (hereinafter referred to as “barrier metal”) and an insulating film such as silicon nitride or silicon carbide (hereinafter referred to as “ Covered with a “barrier insulating film”.
- barrier metal a metal such as tantalum or tantalum nitride
- insulating film such as silicon nitride or silicon carbide
- the gap between the photoresist and the interlayer insulation film is filled with a gap such as irregularities or grooves in the underlying element, the function of absorbing the radiation reflected from the element, and the shape of the interlayer insulation film during dry etching.
- a film having a function of maintaining and facilitating precision microfabrication has been used.
- organosiloxane-based thin film An example of such a film is an organosiloxane thin film containing a light absorbing compound (hereinafter referred to as “organosiloxane-based thin film”).
- organosiloxane-based thin film When a pattern of 0.2 ⁇ m or less is formed, the pattern aspect ratio (ratio of resist film thickness divided by resist line width) becomes too large for a resist with a film thickness of 1 ⁇ m, causing problems such as pattern collapse. ing.
- a Ti-based or Si-based film hereinafter referred to as “hard mask”) is inserted between the pattern film to be actually formed and the resist film, and once the resist pattern is dry etched using the hard mask.
- a hard mask method in which a pattern is transferred to a film to be actually formed by dry etching using the hard mask as an etching mask. This method can change the gas used when etching the hard mask and the gas used when actually etching the film to be formed.
- the selectivity with respect to the resist is taken and the actual film is etched.
- a gas having a selection ratio with respect to the hard mask can be selected, so that there is an advantage that a pattern can be formed with a thin resist.
- the low dielectric constant interlayer insulating film present under the organosiloxane thin film may be damaged by exposure to oxygen plasma.
- the low dielectric constant interlayer insulating film around the via portion is damaged, resulting in remarkable electrical characteristics.
- the dry etching residue adheres to the wafer, and at the same time, the dry etching residue must be removed.
- fluorocarbon-based gas is generally used in dry etching, so that the dry etching residue contains fluorine.
- fluorine is mixed into the cleaning liquid in the process of removing the dry etching residue. Fluorine seriously damages the low dielectric constant interlayer insulating film and copper especially when the pH becomes acidic.
- the pH of the cleaning solution is not acidic, when the semiconductor element is cleaned using the cleaning solution after removing the dry etching residue, serious damage may be observed on the low dielectric constant interlayer insulating film and copper. It was.
- Titanium or titanium nitride may be used as a hard mask.
- titanium is mixed into the cleaning liquid.
- a cleaning solution containing oxygen peroxide if titanium is mixed, the decomposition of hydrogen peroxide is accelerated and the storage stability of the cleaning solution deteriorates. Therefore, there is a method for suppressing the decomposition of hydrogen peroxide by titanium mixed in the cleaning solution. It has been demanded.
- Patent Document 1 proposes a semiconductor element cleaning method using a cleaning liquid containing hydrogen peroxide, aminopolymethylene phosphones, potassium hydroxide and water.
- Patent Document 2 discloses a processing solution for a wiring board containing a hydrogen peroxide, a quaternary ammonium hydroxide and a tungsten anticorrosive, and having a pH of 7 or more and 10 or less, wherein the tungsten anticorrosive is a quaternary ammonium and
- a cleaning liquid characterized in that it is at least one member selected from the group consisting of salts thereof, quaternary pyridinium and salts thereof, quaternary bipyridinium and salts thereof, and quaternary imidazolium and salts thereof.
- Patent Document 3 proposes a titanium nitride removing liquid containing 10 to 40% by mass of hydrogen peroxide and tetraalkylammonium hydroxide and having a pH of 6.0 to 8.2 at 25 ° C. .
- Patent Document 4 proposes a semiconductor device cleaning agent containing an oxidizing agent, a metal etching agent, and a surfactant and having a pH of 10 to 14.
- Patent Document 5 proposes a polyester produced using a titanium complex compound as a main catalyst, and mentions hydroxy polyvalent carboxylic acid and / or nitrogen-containing polyvalent carboxylic acid as a chelating agent for the titanium complex compound. .
- Patent Documents 1 to 5 if the hard mask, organosiloxane thin film, photoresist, and dry etching residue cannot be removed sufficiently, or if acid is mixed in the cleaning solution, damage to copper is sufficiently suppressed. Had the problem of not being able to. Furthermore, there is a problem that hydrogen peroxide is greatly decomposed when titanium is mixed in the cleaning liquid (see Comparative Examples 1 to 5 described later).
- the present invention provides an organosiloxane thin film, a hard mask, a dry etching residue, and a photoresist while suppressing damage to a low dielectric constant interlayer insulating film, copper wiring, barrier metal, and barrier insulating film.
- the present invention provides a cleaning liquid to be removed and a cleaning method using the same. Furthermore, the present invention provides a cleaning solution that suppresses damage to copper wiring even when an acid is added to the cleaning solution, and does not cause significant hydrogen peroxide decomposition even when titanium is added to the cleaning solution, and a cleaning method using the same. This is the issue.
- the present invention includes the following aspects. ⁇ 1> On a substrate having a barrier metal, a copper wiring or a copper alloy wiring, and a low dielectric constant interlayer insulating film, a barrier insulating film, a low dielectric constant interlayer insulating film, a hard mask, an organosiloxane thin film, and a photoresist Then, the photoresist is subjected to selective exposure and development to form a photoresist pattern, and then using the photoresist pattern as a mask, the organosiloxane thin film, hard mask, low dielectric constant interlayer insulation
- the quaternary ammonium hydroxide is at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide.
- the aminopolymethylenephosphonic acid is selected from the group consisting of aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and 1,2-propylenediaminetetra (methylenephosphonic acid).
- a substrate having a barrier metal, a copper wiring or a copper alloy wiring, and a low dielectric constant interlayer insulating film, a barrier insulating film, a low dielectric constant interlayer insulating film, a hard mask, an organosiloxane thin film, and a photoresist Then, the photoresist is selectively exposed and developed to form a photoresist pattern, and then the organosiloxane thin film, hard mask, and low dielectric constant interlayer insulating film are formed using the photoresist pattern as a mask.
- the quaternary ammonium hydroxide is at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide.
- the aminopolymethylenephosphonic acid is selected from the group consisting of aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and 1,2-propylenediaminetetra (methylenephosphonic acid).
- the hard mask, the organosiloxane thin film, the dry etching residue, and the photoresist are removed while suppressing damage to the low dielectric constant interlayer insulating film, the copper wiring, the barrier metal, and the barrier insulating film.
- a cleaning liquid and a cleaning method using the same can be provided.
- a cleaning method can be provided, and high-precision and high-quality semiconductor elements can be manufactured with high yield.
- FIG. 1 is a schematic cross-sectional view of a semiconductor device including a barrier metal, copper wiring or copper alloy wiring, barrier insulating film, low dielectric constant interlayer insulating film, hard mask, organosiloxane thin film, dry etching residue, and photoresist. .
- the cleaning liquid of the present invention contains 10 to 30% by mass of hydrogen peroxide, 0.005 to 10% by mass of quaternary ammonium hydroxide, 0.005 to 5% by mass of potassium hydroxide, and 0% of aminopolymethylene phosphonic acid. 0.0005 to 0.005 mass% and water.
- each component will be described in detail.
- the concentration range of hydrogen peroxide used in the present invention is 10 to 30% by mass, preferably 13 to 25% by mass, and particularly preferably 15 to 20% by mass.
- the content is 10 to 30% by mass, the hard mask, organosiloxane thin film, dry etching residue and photoresist can be effectively removed.
- quaternary ammonium hydroxide used in the present invention include, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide. Can be mentioned. These quaternary ammonium hydroxides can be blended alone or in combination of two or more.
- the concentration range of the quaternary ammonium hydroxide used in the present invention is 0.005 to 10% by mass, preferably 0.01 to 8% by mass, and particularly preferably 0.05 to 5% by mass.
- the hard mask, organosiloxane thin film, dry etching residue, and photoresist are effectively removed while suppressing damage to the low dielectric constant interlayer insulating film and the copper wiring. Even when an acid is added to the cleaning solution, damage to the copper wiring is suppressed, and even when titanium is added to the cleaning solution, no significant hydrogen peroxide decomposition occurs.
- the concentration range of potassium hydroxide used in the present invention is 0.005 to 5% by mass, preferably 0.01 to 3% by mass, and particularly preferably 0.02 to 1% by mass.
- the hard mask, organosiloxane thin film, dry etching residue and photoresist are effectively removed while suppressing damage to the low dielectric constant interlayer insulating film and the copper wiring. be able to.
- aminopolymethylenephosphonic acid used in the present invention examples include, for example, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), 1,2-propylenediaminetetra (methylene Phosphonic acid) and the like. These aminopolymethylene phosphonic acids can be blended alone or in combination of two or more.
- the concentration range of the aminopolymethylene phosphonic acid used in the present invention is 0.000005 to 0.005 mass%, preferably 0.00001 to 0.003 mass%, particularly preferably 0.0001 to 0.005 mass%. 0.003 mass%. If it is within the range of 0.000005 to 0.005 mass%, damage to the copper wiring can be suppressed.
- a particularly preferred combination is 15 to 20% by mass of hydrogen peroxide, 0.01 to 8% by mass of quaternary ammonium hydroxide, 0.02 to 1% by mass of potassium hydroxide, Contains 0.00001 to 0.003% by mass of methylenephosphonic acid.
- the sodium concentration as an impurity contained in the cleaning liquid of the present invention is preferably 0.1 ppm or less as a mass, more preferably 0.05 ppm or less, and further preferably 0.03 ppm or less.
- sodium is an unavoidable impurity in the potassium hydroxide, about 0.001 ppm is actually contained in the cleaning composition. If more than 0.1 ppm of sodium is contained, the properties of the manufactured semiconductor may be deteriorated.
- titanium nitride or titanium can be used as a hard mask using the cleaning liquid of the present invention.
- the cleaning liquid of the present invention may be blended with additives conventionally used in semiconductor cleaning liquids as long as the object of the present invention is not impaired.
- a surfactant, an antifoaming agent, etc. can be added as an additive.
- the temperature at which the cleaning liquid of the present invention is used is in the range of 20 to 80 ° C., preferably 25 to 70 ° C., and may be appropriately selected depending on the etching conditions and the semiconductor substrate used.
- ultrasonic waves can be used in combination as necessary.
- the time for using the cleaning solution of the present invention is in the range of 0.3 to 20 minutes, preferably 0.5 to 10 minutes, and may be appropriately selected depending on the etching conditions and the semiconductor substrate used.
- an organic solvent such as alcohol can be used, but rinsing with water is sufficient.
- a semiconductor element and a display element to which the present invention can be applied include substrate materials such as silicon, amorphous silicon, polysilicon, and glass; insulating materials such as silicon oxide, silicon nitride, silicon carbide, and derivatives thereof; tantalum, tantalum nitride, Barrier materials such as ruthenium and ruthenium oxide; wiring materials such as copper and copper alloys; compound semiconductors such as gallium-arsenic, gallium-phosphorus, indium-phosphorus, indium-gallium-arsenic, indium-aluminum-arsenic; chromium oxide, etc. Including oxide semiconductors.
- hydroxysilsesquioxane (HSQ) -based or methylsilsesquioxane (MSQ) -based OCD® (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.), carbon-doped silicon oxide (SiOC) Black Black Diamond (trade name, manufactured by Applied Materials), Aurora (trade name, manufactured by ASM International), Coral (trade name, manufactured by Novellus Systems), Inorganic Orion (trade name, manufactured by Trikon Tenclogies) used.
- the low dielectric constant interlayer insulating film is not limited to these.
- tantalum, tantalum nitride, ruthenium, manganese, magnesium, cobalt and oxides thereof are used as barrier metals.
- the barrier metal is not limited to these.
- barrier insulating film silicon nitride, silicon carbide, or silicon nitride carbide is used as the barrier insulating film.
- the barrier insulating film is not limited to these.
- ⁇ Material removal state and damage evaluation method and evaluation equipment> The removal state of the material and the evaluation of damage were performed by SEM observation.
- SEM apparatus an ultra-high resolution field emission scanning electron microscope SU9000 manufactured by Hitachi High-Technologies Corporation was used.
- the cleaning liquid to which the acid was added was prepared by mixing the cleaning liquid with a 10% by mass hydrofluoric acid aqueous solution in a mass ratio of 100: 2.
- a semiconductor element having a copper wiring was immersed in a cleaning solution to which hydrofluoric acid was added at a predetermined temperature and for a predetermined time, and copper damage was observed by SEM.
- Removal state of titanium hard mask 5 A The hard mask was completely removed. B: The hard mask was almost removed. C: The hard mask was not removed. A and B were set to pass. V. Damage to copper 2 A: No change was observed in copper compared to before washing. B: Some roughness was observed on the copper surface. C: A large hole was seen in copper. A and B were set to pass. VI. Damage to Low Dielectric Interlayer Insulating Film 4 A: No change was observed in the low dielectric constant interlayer insulating film compared to before cleaning. B: The low dielectric constant interlayer insulating film was slightly recessed. C: The low dielectric constant interlayer insulating film was greatly recessed. A and B were set to pass. VII.
- Examples 1 to 22 In the test, a semiconductor element having a cross section of a wiring structure as shown in FIG. 1 was used. In order to remove the hard mask 5, the organosiloxane thin film 6, the dry etching residue 8 and the photoresist 7 which are TiN, they are immersed in the cleaning liquid shown in Table 1 at the temperature and time shown in Table 2, and then ultrapure water Rinse by and drying by dry nitrogen gas injection. By observing the cleaned semiconductor element with SEM, the hard mask 5, the organosiloxane thin film 6, the dry etching residue 8 and the photoresist 7 are removed, and the copper 2 and the barrier metal 1 are tantalum (Ta) / nitrided.
- the hard mask 5, the organosiloxane thin film 6, the dry etching residue 8 and the photoresist 7 could not be removed. Damage was observed in the low dielectric constant interlayer insulating film 4 and the copper 2. Damage was observed in copper 2 when using a cleaning solution to which an acid was added. When titanium was added to the cleaning solution, the decomposition of hydrogen peroxide was small.
- the cleaning liquids described in Patent Documents 1 to 5 are hard masks, organosiloxane thin films, dry etching residues and photo resists while suppressing damage to the barrier metal, the low dielectric constant interlayer insulating film, and the copper wiring.
- a cleaning solution for removing the resist it was found that the cleaning solution was insufficient, copper wiring was damaged, and the cleaning solution was poor in stability (Table 4).
- 3F, 3G, 3H, and 3I cleaning solutions can remove hard masks, organosiloxane thin films, dry etching residues, and photoresists while suppressing damage to the low dielectric constant interlayer insulating film and copper wiring. Insufficient, or when acid was added, copper wiring was damaged, or the stability of hydrogen peroxide by adding titanium was insufficient (Table 4).
- Barrier metal 2 Copper or copper alloy wiring 3: Barrier insulating film 4: Low dielectric constant interlayer insulating film 5: Hard mask 6: Organosiloxane thin film 7: Altered photoresist 8: Dry etching residue
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Abstract
Description
本発明は、上記従来における問題に鑑み、低誘電率層間絶縁膜、銅配線、バリアメタル、及びバリア絶縁膜のダメージを抑制しつつ、オルガノシロキサン系薄膜、ハードマスク、ドライエッチング残渣およびフォトレジストを除去する洗浄液及びそれを用いた洗浄方法を提供することを課題とする。更に、本発明は、洗浄液に酸を添加した場合でも銅配線のダメージを抑制し、洗浄液にチタンを添加した場合でも大きな過酸化水素の分解を起こさない洗浄液及びそれを用いた洗浄方法を提供することを課題とする。
<1> バリアメタルと、銅配線あるいは銅合金配線と、低誘電率層間絶縁膜とを有する基板上に、バリア絶縁膜、低誘電率層間絶縁膜、ハードマスク、オルガノシロキサン系薄膜、及びフォトレジストを順に積層した後、該フォトレジストに選択的露光及び現像処理を施し、フォトレジストパターンを形成し、次いで、このフォトレジストパターンをマスクとして、前記オルガノシロキサン系薄膜、ハードマスク、低誘電率層間絶縁膜およびバリア絶縁膜にドライエッチング処理を施した半導体素子を洗浄して、前記オルガノシロキサン系薄膜、ハードマスク、ドライエッチング残渣およびフォトレジストを除去する洗浄液であって、過酸化水素を10~30質量%、4級アンモニウム水酸化物を0.005~10質量%、水酸化カリウムを0.005~5質量%、アミノポリメチレンホスホン酸を0.000005~0.005質量%および水を含む洗浄液である。
<2> 前記ハードマスクが窒化チタンまたはチタンを含有する上記<1>記載の洗浄液である。
<3> 前記4級アンモニウム水酸化物が、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラプロピルアンモニウム、水酸化テトラブチルアンモニウム及び水酸化ベンジルトリメチルアンモニウムからなる群より選ばれる少なくとも1種以上である上記<1>または<2>記載の洗浄液である。
<4> 前記アミノポリメチレンホスホン酸が、アミノトリ(メチレンホスホン酸)、エチレンジアミンテトラ(メチレンホスホン酸)、ジエチレントリアミンペンタ(メチレンホスホン酸)および1,2-プロピレンジアミンテトラ(メチレンホスホン酸)からなる群より選ばれる少なくとも1種以上である上記<1>~<3>のいずれかに記載の洗浄液である。
<5> ナトリウム濃度が0.1ppm以下である上記<1>~<4>のいずれかに記載の洗浄液である。
<6> バリアメタルと、銅配線あるいは銅合金配線と、低誘電率層間絶縁膜とを有する基板上に、バリア絶縁膜、低誘電率層間絶縁膜、ハードマスク、オルガノシロキサン系薄膜、及びフォトレジストを積層した後、該フォトレジストに選択的露光及び現像処理を施し、フォトレジストパターンを形成し、次いで、このフォトレジストパターンをマスクとして、前記オルガノシロキサン系薄膜、ハードマスク、低誘電率層間絶縁膜およびバリア絶縁膜にドライエッチング処理を施した半導体素子に、過酸化水素を10~30質量%、4級アンモニウム水酸化物を0.005~10質量%、水酸化カリウムを0.005~5質量%、アミノポリメチレンホスホン酸を0.000005~0.005質量%および水を含む洗浄液を用いて、前記ハードマスク、オルガノシロキサン系薄膜、ドライエッチング残渣およびフォトレジストを除去することを特徴とする半導体素子の洗浄方法である。
<7> 前記ハードマスクが窒化チタンまたはチタンを含有する上記<6>記載の洗浄方法である。
<8> 前記4級アンモニウム水酸化物が、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラプロピルアンモニウム、水酸化テトラブチルアンモニウム及び水酸化ベンジルトリメチルアンモニウムからなる群より選ばれる少なくとも1種以上である上記<6>または<7>記載の洗浄方法である。
<9> 前記アミノポリメチレンホスホン酸が、アミノトリ(メチレンホスホン酸)、エチレンジアミンテトラ(メチレンホスホン酸)、ジエチレントリアミンペンタ(メチレンホスホン酸)および1,2-プロピレンジアミンテトラ(メチレンホスホン酸)からなる群より選ばれる少なくとも1種以上である上記<6>~<8>のいずれかに記載の洗浄方法である。
<10> ナトリウム含有量が0.1ppm以下である上記<6>~<9>のいずれかに記載の洗浄方法である。
本発明の洗浄液は、過酸化水素を10~30質量%、4級アンモニウム水酸化物を0.005~10質量%、水酸化カリウムを0.005~5質量%、アミノポリメチレンホスホン酸を0.000005~0.005質量%および水を含む。以下、各成分について詳細に説明する。
例えば、添加剤として、界面活性剤、消泡剤等を添加することができる。
本発明の洗浄液を使用する時間は0.3~20分、好ましくは0.5~10分の範囲であり、エッチングの条件や使用される半導体基体により適宜選択すればよい。
本発明の洗浄液を使用した後のリンス液としては、アルコールのような有機溶剤を使用することもできるが、水でリンスするだけでも十分である。
材質の除去状態とダメージの評価はSEM観察にて行った。SEM装置は、株式会社日立ハイテクノロジーズ社製、超高分解能電界放出形走査電子顕微鏡SU9000を用いた。
酸を添加した洗浄液は、洗浄液に10質量%フッ酸水溶液を質量で100:2の割合で混合して調製した。フッ酸を添加した洗浄液に、銅配線を有する半導体素子を所定の温度と所定の時間、浸漬し、銅のダメージをSEM観察した。
洗浄液とチタン粉末を質量で100:0.005の割合で混合した組成物を60℃の恒温水槽で4時間加熱した。加熱前後の過酸化水素濃度を電位差滴定法(過マンガン酸カリウム使用)で測定し、組成物の過酸化水素分解率を以下の計算式により算出した。
過酸化水素分解率%=100-100×(加熱後洗浄液重量×加熱後過酸化水素濃度)/(加熱前洗浄液重量×加熱前過酸化水素濃度)
I.オルガノシロキサン系薄膜6の除去状態
A:オルガノシロキサン系薄膜が完全に除去された。
B:オルガノシロキサン系薄膜がほとんど除去された。
C:オルガノシロキサン系薄膜が除去されなかった。
A、Bを合格とした。
II.ドライエッチング残渣8の除去状態
A:ドライエッチング残渣が完全に除去された。
B:ドライエッチング残渣がほとんど除去された。
C:ドライエッチング残渣が除去されなかった。
A、Bを合格とした。
III.変質フォトレジスト7の除去状態
A:フォトレジストが完全に除去された。
B:フォトレジストがほとんど除去された。
C:フォトレジストが除去されなかった。
A、Bを合格とした。
IV.チタン系ハードマスク5の除去状態
A:ハードマスクが完全に除去された。
B:ハードマスクがほとんど除去された。
C:ハードマスクが除去されなかった。
A、Bを合格とした。
V.銅2のダメージ
A:洗浄前と比べて銅に変化が見られなかった。
B:銅表面に少し荒れが見られた。
C:銅に大きな穴が見られた。
A、Bを合格とした。
VI.低誘電率層間絶縁膜4のダメージ
A:洗浄前と比べて低誘電率層間絶縁膜に変化が見られなかった。
B:低誘電率層間絶縁膜がわずかにくぼんでいた。
C:低誘電率層間絶縁膜が大きくくぼんでいた。
A、Bを合格とした。
VII.酸を添加した洗浄液で洗浄した場合の銅2のダメージ
A:洗浄前と比べて銅に変化が見られなかった。
B:銅表面に少し荒れが見られた。
C:銅に大きな穴が見られた。
A、Bを合格とした。
VIII.チタンを添加した洗浄液の過酸化水素の安定性
A:過酸化水素分解率が20%未満であった。
B:過酸化水素分解率が20~30%であった。
C:過酸化水素分解率が30%より大きかった。
-:加熱前から過酸化水素を含んでいないため、評価をしなかった。
A、Bを合格とした。
試験には、図1に示したような配線構造の断面を有する半導体素子を使用した。TiNであるハードマスク5、オルガノシロキサン系薄膜6、ドライエッチング残渣8およびフォトレジスト7を除去するため、表1に記した洗浄液に表2に示した温度、時間で浸漬し、その後、超純水によるリンス、乾燥窒素ガス噴射による乾燥を行った。洗浄後の半導体素子をSEMで観察することにより、ハードマスク5、オルガノシロキサン系薄膜6、ドライエッチング残渣8およびフォトレジスト7の除去状態と、銅2、バリアメタル1であるタンタル(Ta)/窒化タンタル(TaN)、バリア絶縁膜3である炭化シリコン、及び低誘電率層間絶縁膜4である炭素ドープ酸化シリコンのダメージを判断した。また、表1に記した洗浄液に酸を添加した洗浄液でも表2に示した温度、時間で浸漬し、その後、超純水によるリンス、乾燥窒素ガス噴射による乾燥を行い、洗浄後の半導体素子をSEMで観察することにより、銅のダメージを観察した。さらに、洗浄液にチタンを添加した場合の過酸化水素の安定性も調べた。
特許文献1記載の、過酸化水素15質量%、水酸化カリウム0.02質量%、1,2-プロピレンジアミンテトラ(メチレンホスホン酸)0.0005質量%、及び水84.9795質量%を含む水溶液(表3の洗浄液3A)を用い、図1に示した半導体素子を洗浄した。表4に洗浄条件と評価結果を示した。ハードマスク5、オルガノシロキサン系薄膜6、ドライエッチング残渣8およびフォトレジスト7は除去できた。低誘電率層間絶縁膜4および銅2にダメージは観察されなかった。しかし、酸を添加した洗浄液を用いた場合は銅2にダメージが観察され、洗浄液にチタンを添加した場合には過酸化水素の分解が大きかった。
特許文献2記載の、過酸化水素15質量%、水酸化ベンジルトリメチルアンモニウム 0.45質量%、ベンザルコニウムクロリド0.01質量%、及び水84.54質量%を含む水溶液(表3の洗浄液3B)を用い、図1に示した半導体素子を洗浄した。表4に洗浄条件と評価結果を示した。ハードマスク5は除去できたが、オルガノシロキサン系薄膜6、ドライエッチング残渣8およびフォトレジスト7を除去することができなかった。低誘電率層間絶縁膜4および銅2にダメージは観察されなかった。酸を添加した洗浄液を用いた場合でも銅2にダメージは観察されなかった。洗浄液にチタンを添加した場合でも過酸化水素の分解は小さかった。
特許文献3記載の、過酸化水素28.4質量%、水酸化テトラメチルアンモニウム1.7質量%、エチレンジアミン四酢酸1.4質量%、及び水68.5質量%を含む水溶液(表3の洗浄液3C)を用い、図1に示した半導体素子を洗浄した。表4に洗浄条件と評価結果を示した。ハードマスク5は除去できたが、オルガノシロキサン系薄膜6、ドライエッチング残渣8およびフォトレジスト7を除去できなかった。低誘電率層間絶縁膜4のダメージは観察されなかったが、銅2にダメージが観察された。さらに、酸を添加した洗浄液を用いた場合は銅2にダメージが観察され、洗浄液にチタンを添加した場合には過酸化水素の分解が大きかった。
特許文献4記載の、過酸化水素0.2質量%、水酸化テトラメチルアンモニウム0.4質量%、水酸化カリウム0.1質量%、オルト過ヨウ素酸0.2質量%、ジエチレントリアミン0.02質量%、エマルゲンA-90 0.1質量%、セチルトリメチルアンモニウムクロライド0.01質量%、ラウリルピリジニウムクロリド0.05質量%、トリメチルフッ化アンモニウム0.5質量%、及び水98.42質量%を含む水溶液(表3の洗浄液3D)を用い、図1に示した半導体素子を洗浄した。表4に洗浄条件と評価結果を示した。ハードマスク5、オルガノシロキサン系薄膜6、ドライエッチング残渣8およびフォトレジスト7を除去できなかった。低誘電率層間絶縁膜4と銅2にダメージが観察された。酸を添加した洗浄液を用いた場合、銅2にダメージが観察された。洗浄液にチタンを添加した場合、過酸化水素の分解は小さかった。
4級アンモニウム水酸化物の代わりに、特許文献5記載のチタンと錯体化合物を形成するキレート剤であるヒドロキシ多価カルボン酸を、過酸化水素、水酸化カリウム、アミノポリメチレンホスホン酸および水に添加した洗浄液(表3の洗浄液3E)を用い、図1に示した半導体素子を洗浄した。表4に洗浄条件と評価結果を示した。ハードマスク5、オルガノシロキサン系薄膜6、ドライエッチング残渣8およびフォトレジスト7はほとんど除去された。低誘電率層間絶縁膜4のダメージは観察されなかったが、銅2にダメージが観察された。酸を添加した洗浄液を用いた場合、銅2にダメージが観察された。洗浄液にチタンを添加した場合、過酸化水素の分解はそれほど大きくなかった。よって、ヒドロキシ多価カルボン酸は、過酸化水素、水酸化カリウム、アミノポリメチレンホスホン酸および水と組み合わせる洗浄液に酸を添加した場合でも銅配線にダメージを与えた。
過酸化水素17質量%、水酸化テトラメチルアンモニウム0.5質量%、水酸化カリウム0.2質量%、及び水82.3質量%を含む水溶液(表3の洗浄液3F)を用い、図1に示した半導体素子を洗浄した。表4に洗浄条件と評価結果を示した。ハードマスク5、オルガノシロキサン系薄膜6、ドライエッチング残渣8およびフォトレジスト7は除去できた。低誘電率層間絶縁膜4および銅2のダメージは観察されなかった。酸を添加した洗浄液を用いた場合でも銅2にダメージは観察されなかった。しかし、洗浄液にチタンを添加した場合、過酸化水素の分解が大きかった。
過酸化水素17質量%、水酸化テトラメチルアンモニウム0.5質量%、ジエチレントリアミンペンタ(メチレンホスホン酸)0.0005質量%、及び水82.4995質量%を含む水溶液(表3の洗浄液3G)を用い、図1に示した半導体素子を洗浄した。表4に洗浄条件と評価結果を示した。ハードマスク5は除去できたが、オルガノシロキサン系薄膜6、ドライエッチング残渣8およびフォトレジスト7は除去できなかった。
過酸化水素17質量%、水酸化カリウム 0.2質量%、ジエチレントリアミンペンタ(メチレンホスホン酸) 0.0005質量%、及び水82.7995質量%を含む水溶液(表3の洗浄液3H)を用い、図1に示した半導体素子を洗浄した。表4に洗浄条件と評価結果を示した。ハードマスク5、オルガノシロキサン系薄膜6、ドライエッチング残渣8およびフォトレジスト7は除去できた。低誘電率層間絶縁膜4および銅2にダメージは観察されなかった。しかし、酸を添加した洗浄液を用いた場合は銅2にダメージが観察され、洗浄液にチタンを添加した場合には過酸化水素の分解が大きかった。
水酸化テトラメチルアンモニウム0.5質量%、水酸化カリウム0.2質量%、ジエチレントリアミンペンタ(メチレンホスホン酸) 0.0005質量%、及び水99.2995質量%を含む水溶液(表3の洗浄液3I)を用い、図1に示した半導体素子を洗浄した。表4に洗浄条件と評価結果を示した。ハードマスク5、オルガノシロキサン系薄膜6、ドライエッチング残渣8およびフォトレジスト7は除去できなかった。低誘電率層間絶縁膜4および銅2にダメージが観察された。
過酸化水素17質量%、水酸化カリウム0.2質量%、1,3-プロパンジアミン0.1質量%、ジエチレントリアミンペンタ(メチレンホスホン酸)0.0005質量%、及び水82.6995質量%を含む水溶液(表3の洗浄液3J)を用い、図1に示した半導体素子を洗浄した。表4に洗浄条件と評価結果を示した。ハードマスク5、オルガノシロキサン系薄膜6、ドライエッチング残渣8およびフォトレジスト7は除去できた。低誘電率層間絶縁膜4にはダメージは観察されなかったが、銅2にダメージが観察された。酸を添加した洗浄液を用いた場合は銅2にダメージが観察され、洗浄液にチタンを添加した場合には過酸化水素の分解が大きかった。
過酸化水素17質量%、水酸化カリウム0.2質量%、アンモニア0.04質量%、ジエチレントリアミンペンタ(メチレンホスホン酸)0.0005質量%、及び水82.7595質量%を含む水溶液(表3の洗浄液3K)を用い、図1に示した半導体素子を洗浄した。表4に洗浄条件と評価結果を示した。ハードマスク5、オルガノシロキサン系薄膜6、ドライエッチング残渣8およびフォトレジスト7は除去できた。低誘電率層間絶縁膜4にはダメージは観察されなかったが、銅2にダメージが観察された。酸を添加した洗浄液を用いた場合は銅2にダメージが観察され、洗浄液にチタンを添加した場合には過酸化水素の分解が大きかった。
過酸化水素17質量%、水酸化カリウム0.2質量%、2-(メチルアミノ)エタノール0.2質量%、ジエチレントリアミンペンタ(メチレンホスホン酸)0.0005質量%、及び水82.5995質量%を含む水溶液(表3の洗浄液3L)を用い、図1に示した半導体素子を洗浄した。表4に洗浄条件と評価結果を示した。ハードマスク5、オルガノシロキサン系薄膜6、ドライエッチング残渣8およびフォトレジスト7は除去できた。低誘電率層間絶縁膜4にはダメージは観察されなかったが、銅2にダメージが観察された。酸を添加した洗浄液を用いた場合は銅2にダメージが観察され、洗浄液にチタンを添加した場合には過酸化水素の分解が大きかった。
2:銅あるいは銅合金配線
3:バリア絶縁膜
4:低誘電率層間絶縁膜
5:ハードマスク
6:オルガノシロキサン系薄膜
7:変質フォトレジスト
8:ドライエッチング残渣
Claims (10)
- バリアメタルと、銅配線あるいは銅合金配線と、低誘電率層間絶縁膜とを有する基板上に、バリア絶縁膜、低誘電率層間絶縁膜、ハードマスク、オルガノシロキサン系薄膜、及びフォトレジストを順に積層した後、該フォトレジストに選択的露光及び現像処理を施し、フォトレジストパターンを形成し、次いで、このフォトレジストパターンをマスクとして、前記オルガノシロキサン系薄膜、ハードマスク、低誘電率層間絶縁膜およびバリア絶縁膜にドライエッチング処理を施した半導体素子を洗浄して、前記オルガノシロキサン系薄膜、ハードマスク、ドライエッチング残渣およびフォトレジストを除去する洗浄液であって、過酸化水素を10~30質量%、4級アンモニウム水酸化物を0.005~10質量%、水酸化カリウムを0.005~5質量%、アミノポリメチレンホスホン酸を0.000005~0.005質量%および水を含む洗浄液。
- 前記ハードマスクが窒化チタンまたはチタンを含有する請求項1記載の洗浄液。
- 前記4級アンモニウム水酸化物が、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラプロピルアンモニウム、水酸化テトラブチルアンモニウム及び水酸化ベンジルトリメチルアンモニウムからなる群より選ばれる少なくとも1種以上である請求項1または2記載の洗浄液。
- 前記アミノポリメチレンホスホン酸が、アミノトリ(メチレンホスホン酸)、エチレンジアミンテトラ(メチレンホスホン酸)、ジエチレントリアミンペンタ(メチレンホスホン酸)および1,2-プロピレンジアミンテトラ(メチレンホスホン酸)からなる群より選ばれる少なくとも1種以上である請求項1~3のいずれかに記載の洗浄液。
- ナトリウム濃度が0.1ppm以下である請求項1~4のいずれかに記載の洗浄液。
- バリアメタルと、銅配線あるいは銅合金配線と、低誘電率層間絶縁膜とを有する基板上に、バリア絶縁膜、低誘電率層間絶縁膜、ハードマスク、オルガノシロキサン系薄膜、及びフォトレジストを積層した後、該フォトレジストに選択的露光及び現像処理を施し、フォトレジストパターンを形成し、次いで、このフォトレジストパターンをマスクとして、前記オルガノシロキサン系薄膜、ハードマスク、低誘電率層間絶縁膜およびバリア絶縁膜にドライエッチング処理を施した半導体素子に、過酸化水素を10~30質量%、4級アンモニウム水酸化物を0.005~10質量%、水酸化カリウムを0.005~5質量%、アミノポリメチレンホスホン酸を0.000005~0.005質量%および水を含む洗浄液を用いて、前記ハードマスク、オルガノシロキサン系薄膜、ドライエッチング残渣およびフォトレジストを除去することを特徴とする半導体素子の洗浄方法。
- 前記ハードマスクが窒化チタンまたはチタンを含有する請求項6記載の洗浄方法。
- 前記4級アンモニウム水酸化物が、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラプロピルアンモニウム、水酸化テトラブチルアンモニウム及び水酸化ベンジルトリメチルアンモニウムからなる群より選ばれる少なくとも1種以上である請求項6または7記載の洗浄方法。
- 前記アミノポリメチレンホスホン酸が、アミノトリ(メチレンホスホン酸)、エチレンジアミンテトラ(メチレンホスホン酸)、ジエチレントリアミンペンタ(メチレンホスホン酸)および1,2-プロピレンジアミンテトラ(メチレンホスホン酸)からなる群より選ばれる少なくとも1種以上である請求項6~8のいずれかに記載の洗浄方法。
- ナトリウム含有量が0.1ppm以下である請求項6~9のいずれかに記載の洗浄方法。
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