JP4565741B2 - Silicate-containing alkaline composition for microelectronic substrate cleaning - Google Patents

Silicate-containing alkaline composition for microelectronic substrate cleaning Download PDF

Info

Publication number
JP4565741B2
JP4565741B2 JP2000550003A JP2000550003A JP4565741B2 JP 4565741 B2 JP4565741 B2 JP 4565741B2 JP 2000550003 A JP2000550003 A JP 2000550003A JP 2000550003 A JP2000550003 A JP 2000550003A JP 4565741 B2 JP4565741 B2 JP 4565741B2
Authority
JP
Japan
Prior art keywords
wt
solution
water
weight
silicate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP2000550003A
Other languages
Japanese (ja)
Other versions
JP2003526111A (en
Inventor
デイビッド・シー・スキー
Original Assignee
マリンクロッド・ベイカー・インコーポレイテッドMallinckrodt Baker, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US8568198P priority Critical
Priority to US11508499P priority
Priority to US60/085,681 priority
Priority to US60/115,084 priority
Application filed by マリンクロッド・ベイカー・インコーポレイテッドMallinckrodt Baker, Inc. filed Critical マリンクロッド・ベイカー・インコーポレイテッドMallinckrodt Baker, Inc.
Priority to PCT/US1999/010875 priority patent/WO1999060448A1/en
Publication of JP2003526111A publication Critical patent/JP2003526111A/en
Application granted granted Critical
Publication of JP4565741B2 publication Critical patent/JP4565741B2/en
Anticipated expiration legal-status Critical
Application status is Expired - Fee Related legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/044Hydroxides, bases
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/0005Special cleaning and washing methods
    • C11D11/0011Special cleaning and washing methods characterised by the objects to be cleaned
    • C11D11/0023"Hard" surfaces
    • C11D11/0047Electronic devices, e.g. PCBs, semiconductors
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/08Silicates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/36Organic compounds containing phosphorus
    • C11D3/364Organic compounds containing phosphorus containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3947Liquid compositions
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26Processing photosensitive materials; Apparatus therefor
    • G03F7/42Stripping or agents therefor
    • G03F7/422Stripping or agents therefor using liquids only
    • G03F7/425Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041Cleaning
    • H01L21/02057Cleaning during device manufacture
    • H01L21/0206Cleaning during device manufacture during, before or after processing of insulating layers
    • H01L21/02063Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041Cleaning
    • H01L21/02057Cleaning during device manufacture
    • H01L21/02068Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • H01L21/02071Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers

Description

[0001]
Background of the Invention
The present invention relates to a composition useful in the microelectronics industry for cleaning semiconductor wafer substrates. More particularly, the present invention relates to an alkaline stripping composition containing metal ion free silicate that is used to clean wafers having metal wiring and bias by removing metal or organic impurities without damaging the integrated circuit. Or relates to a cleaning composition.
[0002]
Description of prior art
Integrated parts of microelectronic molded products have photoresist applications that transfer images from a mask or reticle to a desired circuit layer. After the desired image transfer is made, the desired structure is formed using an etching method. The most common structure formed in this way is a metal wiring or a bias.
[0003]
This metal wiring is used to make electrical communication between various parts of the integrated circuit in the same mold layer. A bias is a hole that is etched down to the dielectric layer and later filled with a conductive metal. They are used to form electrical connections between different vertical layers of the integrated circuit. The methods used to form metal interconnects and bias generally use a halogen containing gas.
[0004]
After the etching process is complete, the photoresist mass can be removed by either chemical stripper solution or oxygen plasma ashing. The problem is that these etching steps produce very insoluble metal-containing residues that are not removed by conventional chemical stripper solutions. Also, during the ashing process, the metal-containing residue is oxidized and becomes more difficult to remove, particularly in the case of aluminum-based integrated circuits. See "Managing Etch and Implant Residue," Semiconductor Internatonal, August 1997, pages 56-63.
[0005]
An example of such an etching method is the embossing of metal wiring on an integrated circuit. In this method, after applying a photoresist coating to a metal film, drawing is performed through a mask or a reticle, and a pattern of the photoresist coating is selectively exposed. This coating is developed and either exposed or unexposed photoresist is removed depending on the color tone of the photoresist used to form a photoresist on the metal pattern. The remaining photoresist is usually recured at an elevated temperature to remove the solvent and optionally crosslink the polymer matrix. Next, an actual metal etching process is performed. This etching process removes the metal not covered with the photoresist through the action of gas plasma. By removing the metal, the pattern is transferred from the photoresist layer to the metal layer. The remaining photoresist is then removed (“strip”) with an organic stripper solution or oxygen plasma ashing. This ashing method is often followed by a washing step using an organic stripper solution. However, currently available stripper solutions, usually alkaline stripper solutions, leave insoluble metal oxides or other metal-containing residues in the integrated circuit.
[0006]
  Another example of such an etching method is embossing a bias (internal communication hole) on an integrated circuit. In this method, after applying a photoresist coating to a dielectric film, drawing is performed through a mask or a reticle, and a pattern of the photoresist coating is selectively exposed. This coating is developed and either exposed or unexposed photoresist is removed depending on the color tone of the photoresist used to form a photoresist on the metal pattern. The remaining photoresist is usually recured at an elevated temperature to remove the solvent and optionally crosslink the polymer matrix. Next, an actual metal etching process is performed. This etching removes the dielectric not covered with the photoresist through the action of gas plasma. By removing the dielectric, the pattern is transferred from the photoresist layer to the dielectric layer. The remaining photoresist is then removed (“strip”) with an organic stripper solution or oxygen plasma ashing. Typically, the dielectric is etched to the point where the underlying metal layer is exposed. Titanium or titanium nitride anti-reflective ordiffusionThe barrier layer is typically present at the metal / dielectric interface. This boundary layer is usually subjected to etching to expose the underlying metal. The action of etching the titanium or titanium nitride layer is the etching that forms titanium inside the biasResidueFound to be incorporated into. Oxygen plasma ashing oxidizes these bias residues and makes their removal more difficult. Therefore, a titanium residue removal etchant must be added to the stripper solution to allow cleaning of these residues. See "Removal of Titanium Oxide Grown on Titanium Nitride and reduction of Via Contact Resistance Using a Modern Plasma Asher", Mat. Res. Soc. Symp. Proc. Vol. 495, 1998, pages 345-352. Use organic stripper solution after ashingrinseThe process is often performed. However, currently available stripper solutions, usually alkaline stripper solutions, leave insoluble metal oxides and other metal-containing residues on the integrated circuit. There are several commercially available hydroxylamine-based strippers and post ash residue removers with high organic solvent content, but they are not effective for bias or other residues found in metal wiring. They also require high temperatures (typically above 65 ° C.) to clean residues from bias and metal wiring.
[0007]
  When using alkaline strippers on microcircuits containing metal films, especially aluminum, or aluminum or titaniumofWhen used with a combination of such active metals and higher positive metals such as copper or tungsten, ie, metal films containing alloys, a good quality circuit may not always be obtained. Various types of metal corrosion have been observed, such as corrosion whiskers, pitting, and metal wiring notching, due at least in part to the reaction of the metal with the alkaline stripper. Furthermore, Lee et al., Proc. Interface '89, pp. 137-149 shows that very little corrosive action occurs until the water washing step required to remove the organic stripper from the wafer. This corrosion is clearly the result of contact between the metal and the strong alkaline aqueous solution present in the rinse. Aluminum metal corrodes rapidly under such conditions (Ambat et al., Corrosion Science, Vol. 33 (5), p. 684. 1992).
[0008]
Prior methods used to avoid such corrosion problems have used an intermediate rinse step with a non-alkaline organic solvent such as isopropyl alcohol. However, such methods are expensive and are undesirable for safety, chemical hygiene and environmental reasons.
[0009]
The prior art discloses several organic strippers that are used to remove the photoresist mass after the etching process. U.S. Pat. Nos. 4,765,844, 5,102,777, and 5,308,745 disclose photoresist strippers containing various combinations of organic solvents. However, these strippers are not very effective for wafers "ashed" with oxygen plasma as described above. Some photoresist strippers attempt to address this problem by adding additional water and organic corrosion inhibitors such as catechol. Such compositions are described in U.S. Pat. Nos. 5,482,566, 5,279,771, 5,381,807, 5,334,332, 5,709,756, Nos. 5,707,947 and 5,419,779, and WO9800244. In some cases, hydroxylamine, which is also a hydrazine derivative, is added. Due to its toxicity, the use of catechol raises various environmental, safety and hygiene concerns.
[0010]
  The cleaning liquid used for the electric circuit board contains silicate metal as a corrosion inhibitor. Examples of such cleaning liquids are disclosed in SU761976, DD143,920, DD243,921, US5,264,046, US5,234,505, US5,234,506 and 5,393,448. The metal wiring on the circuit board is much larger than that found in integrated circuits, so cleaningRequirements for requirementsIs small. In the case of integrated circuits, metal contamination resulting from the cleaning solution can cause premature device failure even at very low concentrations. Therefore, any of the formulations deliberately added with metals such as the metal silicates listed above will impair the performance and reliability of the integrated circuit device. U.S. Pat. No. 4,659,650 discloses using a sodium metasilicate solution to dissolve a metal lifted mask.
[0011]
  US 5,817,610 and EP 829,768 disclose the use of quaternary ammonium silicate, quaternary ammonium hydroxide and water for use in removing plasma etching residues. In these two disclosures, catechol origimer is preferred over quaternary ammonium silicate as a corrosion inhibitor.TheNo examples of quaternary ammonium silicates used as corrosion inhibitors are shown. US 5,756,973 and EP 828,197 disclose the use of quaternary ammonium silicates, amine compounds, water and optionally organic polar solvents for use as stripping and cleaning compositions. None of the four disclosures listed above disclose the benefits of adding an aminocarboxylic acid buffer or a titanium residue removal accelerator. The four disclosures listed above do not disclose the advantages of adding a titanium residue removal accelerator. The present invention shows that in order to effectively clean the titanium-containing residues found after the plasma etching step in some cases, it is necessary to add a titanium residue removal accelerator. US 5,759,973 and EP 828,197 disclose the use of chelators selected from sugars such as glucose, fructose or sucrose and sugar alcohols such as xylitol, mannitol and sorbitol. Laboratory testing of the formulations of the present invention with addition of fructose or sorbitol resulted in solutions that were not as stable as formulations containing aminocarboxylic acids or that did not contain chelating or buffering agents.
[0012]
Patent application WO9523999 discloses the use of tetramethylammonium silicate and ammonium silicate as corrosion inhibitors in the solution used to remove the resist originating from the circuit board. However, it is said that the advantage of the disclosed formulation is that it does not contain (ethylenedinitrilo) tetraacetic acid (EDTA). In contrast, in the present invention, the use of an optional chelating agent such as EDTA was beneficial.
[0013]
Other uses of the silicate inhibitor include magnetic head cleaner (JP09, 245, 311), laundry detergent (WO9,100,330), metal treatment liquid (DE2,234,842, US3,639,185, US3). 773,670, US 4,351,883, US 4,341,878, EP 743,357, US 4,710,232), rosin flux remover (US 5,549,761) and photoresist (JP 50, 101, 103). It is done.
[0014]
  Both metal ion free silicates such as tetramethylammonium silicate and silicate metals are used as components of photoresist developers (US 4,628,023, JP 63,147,163, US 4,822,722, US 4,931). , 380, RD318,056, RD347,073, EP62,733). Photoresist developer removes modified photoresist embossed areas by exposure before etching and oxygen plasma ashing processUsed forIs done. This leaves a photoresist pattern on the wafer surface that is typically exposed and exposed.YoAndAddition“Curing” by heat to form an etching mask. This mask is used during plasma etching process and oxygen plasma “ashing” processInYokoThisUsually removed after use. The present invention relates to the removal of residues formed during these last two steps, and not to the photoresist development process handled by the patent set forth in this paragraph.
[0015]
A solution of tetramethylammonium hydroxide (TMAH) in silicic acid or solid silicone has been reported to be useful for passivation of aluminum during micromachining ("Aluminum passivation in Saturated TMAHW Solution for IC-Compatible Microstructures and Device Isolation ", Sarrow et al., SPIE Vol. 2879, Proceedings- Micromachining and Microfabrication Process Technology II, The International Society for Optical Engineering, Oct. 14-15, 1996, pp. 242-250). The application of micromachining is outside the scope of the present invention. The solutions in the cited references are about 25% by weight silicate (SiO 22Conversion). This concentration is the concentration used in the examples of the present invention, ie, about 0.01 to about 2.9% by weight silicate (SiO2Remarkably higher). The use of the chelating agent catechol as a silicone etch rate enhancer is also proposed. In the present invention, the increased etch rate of silicone is undesirable because it can damage the silicon dioxide dielectric layer commonly used in integrated circuits, as well as the exposed silicone on the backside of the wafer.
[0016]
The use of quaternary ammonium hydroxide in photoresist strippers is disclosed in US Pat. No. 4,776,892, US Pat. No. 5,563,119, JP093199098 A2, EP578570 A2, WO91117484 A1 and US Pat. No. 4,776,892. The use of chelating agents and complexing agents for sequestering in various detergents is also described in WO 9705228, US 5,466,389, US 5,498,293, EP 812011, US 5,561,105, JP0621 773, JP06250400, JP06250400 and GB1. 573, 206.
[0017]
US Pat. No. 5,466,389 discloses an aqueous alkaline solution containing a cleaning solution for microelectronic substrates containing quaternary ammonium hydroxide and optionally a metal chelator and is effective for a pH range of about 8-10. . In the present invention, a pH higher than 10 is required to achieve the desired residue removal. Furthermore, the silicate has limited water solubility at about pH 10. In laboratory tests, when the pH of the tetramethylammonium silicate solution drops to about 10, the solution becomes “cloudy” as silicic acid precipitates from the solution.
[0018]
US 5,498,293 discloses a method using an aqueous alkaline cleaning solution containing a quaternary ammonium hydroxide and optionally a metal chelating agent useful for cleaning silicon wafers. This cleaning method disclosure is for processing on a substrate prior to the presence of an integrated metal circuit, which is used to substantially eliminate silicon dioxide and for integrated circuit sub-fabricated products. Used before using photoresist. In contrast, the present invention focuses on the cleaning of wafers with existing integrated circuits that are photoresist coated, etched, and oxygen plasma ashed.
[0019]
None of the compositions disclosed in the prior art can effectively remove all organic contaminants and metal-containing residues remaining after a typical corrosion process. Accordingly, there is a need for a stripping composition that cleans semiconductor wafer substrates by removing metal and organic contaminants from such substrates without damaging the integrated circuit. Such compositions should not particularly corrode metal undulations comprising integrated circuits and should avoid costly and detrimental consequences attributed to an intermediate rinse step.
[0020]
Summary of the Invention
Accordingly, it is an object of the present invention to provide a composition useful in the microelectronics industry for cleaning semiconductor wafer substrates.
[0021]
Another object of the present invention is to provide a composition that removes metals and organic contaminants (contaminants) from a semiconductor wafer substrate without compromising the integrated circuit.
[0022]
Another object of the present invention is to provide a composition that avoids the costly and deleterious consequences associated with an intermediate rinse step.
[0023]
It is a further object of the present invention to provide a method for cleaning a semiconductor wafer substrate that removes metal and organic contaminants from such substrates without damaging the integrated circuit, and avoids costly and detrimental consequences attributed to an intermediate rinse step. That is.
[0024]
  These and other objectives are achieved using a novel aqueous composition for stripping or cleaning semiconductor wafer substrates containing one or more metal ion free bases and water soluble metal ion free silicates. . The composition may contain undesirable contaminants and / orThe residueSubstrate surfaceWashKeep in contact with the semiconductor wafer substrate for a sufficient time and temperature to clean.
[0025]
Preferably, the composition comprises from about 0.01% to about 2% by weight of one or more metal ion free bases dissolved in water in an amount sufficient to bring the pH to about 11 or higher.2Conversion) water-soluble metal-free silicate.
[0026]
Any suitable base may be used in the composition of the present invention. Preferably such bases are selected from hydroxides and organic amines, most preferably quaternary ammonium hydroxides and ammonium hydroxides.
[0027]
Any suitable silicate may be used in the composition of the present invention. Preferably, the silicate is selected from quaternary ammonium silicates, most preferably tetramethylammonium silicate.
[0028]
  The composition of the present invention may contain other components such as chelating agents, organic cosolvents, titanium residue removal accelerators and surfactants. Chelating agents are present in amounts up to about 2% by weightThePreferably, the organic co-solvent is present in an amount up to about 20% by weight, the titanium residue removal accelerator is preferably present in an amount up to about 30% by weight, and the surfactant is about 0.00%. It is preferably present in an amount up to 5% by weight.
[0029]
The composition can be used to clean a substrate containing an integrated circuit or can be used to clean a substrate that does not contain an integrated circuit. If an integrated circuit is present, the composition removes contaminants without damaging the integrated circuit.
[0030]
  The method of cleaning a semiconductor wafer substrate of the present invention can remove the composition of the present invention from unwanted contaminants and / orThe residueSubstrate surfaceWashIt must be in contact with the semiconductor wafer substrate for a sufficient time and temperature to clean. The method includes both liquid bath and spray applications. Typically, the substrate is exposed to the composition for a suitable time and at a suitable temperature, rinsed with high purity deionized water and dried.
[0031]
The composition cleans the wafer substrate by removing metal and organic residues. Importantly, this cleaning method does not damage the integrated circuits on the wafer substrate and avoids the costly and detrimental consequences associated with the intermediate rinse steps required by previous methods.
[0032]
Other objects, advantages and novel features of the invention will become apparent from the following detailed description of the invention.
[0033]
Detailed Description of the Invention
The present invention provides a novel aqueous composition for stripping or cleaning a semiconductor wafer substrate comprising one or more metal ion free bases and a water soluble metal ion free silicate. Preferably, the present invention comprises a sufficient amount of one or more alkali metal ion free base components to make a solution of pH about 11 or higher, preferably about pH 11 to about pH 13, and about 0.01% To about 5%, preferably about 0.01% to about 2% by weight (SiO 22An aqueous alkaline stripping or cleaning composition comprising a metal ion-free water-soluble silicate.
[0034]
The composition may also contain a chelating agent in a weight concentration of about 0.01 to about 10%, usually about 0.01% to about 2%. Further optional ingredients include about 0.1% to about 80%, usually about 1% to about 30% by weight aqueous organic solvent, about 1% to about 50%, usually about 1% to about 30%. % By weight of titanium residue removal accelerator, and from about 0.01% to about 1%, preferably from about 0.01% to about 0.5% by weight of a water-soluble surfactant.
[0035]
The composition is an aqueous solution containing a base, silicate, optional ingredients, and water, if present, preferably high purity deionized water.
[0036]
  Any suitable base is included in the composition of the invention.useMay be. Such bases are preferably quaternary ammonium hydroxides, such as tetraalkylammonium hydroxides (usually containing hydroxy and alkoxy containing alkyl groups of 1 to 4 carbon atoms in the alkyl or alkoxy group). Most preferred among these alkaline substances are tetramethylammonium hydroxide and trimethyl-2-hydroxyethylammonium hydroxide (choline). Examples of other quaternary ammonium hydroxides that can be used include trimethyl-3-hydroxypropylammonium hydroxide, trimethyl-3-hydroxybutylammonium hydroxide, trimethyl-4-hydroxybutylammonium hydroxide, triethyl hydroxide- 2-hydroxyethylammonium hydroxide, tripropyl-2-hydroxyethylammonium hydroxide, tributyl-2-hydroxyethylammonium hydroxide, dimethylethyl-2-hydroxyethylammonium hydroxide, dimethyldi (2-hydroxyethyl) ammonium hydroxide, water Monomethyltri (2-hydroxyethyl) ammonium oxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyl-triethyl hydroxide Ammonium monomethyl tripropyl ammonium hydroxide, monomethyl tributylammonium hydroxide, monoethyl trimethyl ammonium hydroxide, monoethyl tributylammonium hydroxide, dimethyl diethylammonium hydroxide, hydroxide dimethyldibutyl ammonium, and mixtures thereof.
[0037]
Other bases that will function in the present invention include ammonium hydroxide, organic amines, especially 2-aminoethanol, 1-amino-2-propanol, 1-amino-3-propanol, 2- (2-aminoethoxy). ) Alkanolamines such as ethanol, 2- (2-aminoethylamino) ethanol, 2- (2-aminoethylamino) ethylamine, and guanidine, 1,3-pentanediamine, 4-aminomethyl-1,8 Others such as octanediamine, aminoethylpiperazine, 4- (3-aminopropyl) morpholine, 1,2-diaminocyclohexane, tri (2-aminoethyl) amine, 2-methyl-1,5-pentanediamine and hydroxylamine These are strong organic bases. Alkaline solutions containing metal ions such as sodium or potassium can also function, but are not preferred because residual metal contamination can occur. Also useful are mixtures of these further alkaline components, in particular ammonium hydroxide and the above mentioned tetraalkylammonium hydroxides.
[0038]
Any suitable metal ion free silicate may be used in the composition of the present invention. Such silicates are preferably quaternary ammonium silicates such as tetraalkylammonium silicates (usually containing hydroxy and alkoxy containing alkyl groups of 1 to 4 carbon atoms in the alkyl or alkoxy groups). The most preferred metal ion free silicate component is tetramethylammonium silicate. Other suitable metal ion free silicate sources for the present invention may be generated in situ by dissolving one or more of the following materials in a highly alkaline detergent. Suitable metal ion free materials useful for producing silicates in detergents include solid silicone wafers, silicic acid, colloidal silica, fumed silica, or any other form of silicone or silica. Silicate metal such as sodium metasilicate may be used, but cannot be encouraged because of the adverse effect of metal contamination on the integrated circuit.
[0039]
The compositions of the present invention may also be formulated with a suitable metal chelating agent to increase the ability to retain the metal in the formulation solution and to enhance dissolution of metal residues on the wafer substrate. Typical examples of chelating agents useful for this purpose include the following organic acids and their isomers and salts: (ethylenedinitrilo) tetraacetic acid (EDTA), butylenediaminetetraacetic acid, cyclohexene-1,2 -Diaminetetraacetic acid (CyDTA), diethylenetriaminepentaacetic acid (DETPA), ethylenediaminetetrapropionic acid, (hydroxyethyl) ethylenediaminetriacetic acid (HEDTA), N, N, N ', N'-ethylenediaminetetra (methylenephosphonic) acid (EDTMP) ), Triethylenetetramine hexaacetic acid (TTHA), 1,3-diamino-2-hydroxypropane-N, N, N ′, N′-tetraacetic acid (DHPTA), methyliminodiacetic acid, propylenediaminetetraacetic acid, nitrotriacetic acid (NTA), citric acid, tartaric acid, gluconic acid, sugar acid Glyceryl acid, oxalic acid, phthalic acid, maleic acid, mandelic acid, malonic acid, lactic acid, salicylic acid, catechol, gallic acid, propyl gallate, pyrogallol, 8-hydroxyquinoline, and cysteine.
[0040]
A preferred chelating agent is an aminocarboxylic acid such as EDTA. This type of chelator has a high affinity for aluminum-containing residues typically found on metal wiring or bias after plasma “ashing”. Furthermore, the pKa value of this type of chelator includes a pKa value of about 12, which improves the performance of the composition of the present invention.
[0041]
The composition of the present invention may also contain one or more suitable water-soluble organic solvents. Suitable various organic solvents include alcohols, polyhydric alcohols, glycols, glycol ethers, N-methylpyrrolidinone (NMP), 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP) and the like. There are alkyl-pyrrolidinones such as 1-hydroxyalkyl-2-pyrrolidinone, dimethylformamide (DMA), dimethylacetamide (DMAc), sulfolane or dimethyl sulfoxide (DMSO). If further aluminum and / or aluminum copper alloy and / or copper corrosion protection is desired, these solvents can be added to reduce the corrosion rate of aluminum and / or aluminum copper alloy and / or copper. Also good. Preferred water-soluble organic solvents include polyhydric alcohols such as glycerol and 1-hydroxyalkyl-2-pyrrolidinones such as 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP).
[0042]
The compositions of the present invention may also include one or more suitable titanium residue removal accelerators. Various suitable titanium residue removal accelerators include hydroxylamine, hydroxylamine salts, peroxides, ozone and fluoride. Preferred titanium residue removal accelerators are hydroxylamine and hydrogen peroxide.
[0043]
  The compositions of the present invention may also include any suitable water soluble amphoteric, nonionic, cationic or anionic surfactant. The addition of a surfactant reduces the surface tension of the formulation and improves the wettability of the surface being cleaned.WashingThe action is improved. If further aluminum corrosion protection is desired, surfactants can be added to reduce the aluminum corrosion rate.
[0044]
Amphoteric surfactants useful in the compositions of the present invention include betaines and sulfobetaines such as alkylbetaines, amidoalkylbetaines, alkylsulfobetaines and amidoalkylsulfobetaines; amphoglynates, amphpropionates, Afocarboxylic acid derivatives such as fodiglycinate and amphodipropionate; iminodiacids such as alkoxyalkyliminodiacids or alkoxyalkyliminodiacids; amine oxides such as alkylamine oxides and alkylamidoalkylamine oxides; fluoro And alkyl sulfonates and fluorinated alkyl amphoteric substances; and mixtures thereof.
[0045]
Preferably, the amphoteric surfactant is cocoamidopropyl betaine, cocoamidopropyl dimethylbetaine, cocoamidopropylhydroxysultain, capryloamphodipropionate, cocoamidodipropionate, cocoamphopropionate, cocoamphohydroxyethyl Propionate, isodecyloxypropyliminodipropionic acid, lauryliminodipropionate, cocoamidopropylamine oxide and cocoamine oxide, and fluorinated alkyl amphoteric substances.
[0046]
Nonionic surfactants useful in the compositions of the present invention include acetyl diols, ethoxylated acetyl diols, fluorinated alkyl alkoxylates, fluorinated alkyl esters, fluorinated polyoxyethylene alkanols, many Examples thereof include fatty acid esters of polyhydric alcohols, polyoxyethylene monoalkyl ethers, polyoxyethylene diols, siloxane surfactants, and alkylene glycol monoalkyl ethers. Preferably, the nonionic surfactant is an acetylenic diol or an ethoxylated acetylenic diol.
[0047]
Anionic surfactants useful in the compositions of the present invention include carboxylates, N-acyl sarcosinates, sulfonates, sulfates, and mono- and diesters of orthophosphoric acid such as decyl phosphate. . Such an anionic surfactant is preferably a metal-free surfactant.
[0048]
Cationic surfactants useful in the compositions of the present invention include amine ethoxylates, dialkyldimethylammonium salts, dialkylmorpholinum salts, alkylbenzyldimethylammonium salts, alkyltrimethylammonium salts, and alkylpyridinium salts. Such a cationic surfactant is preferably a halogen-free surfactant.
[0049]
In a preferred embodiment of the invention, the composition comprises about 0.1 to 2% by weight tetramethylammonium hydroxide (TMAH) and about 0.01 to 1% by weight (SiO 2).2This is an aqueous solution containing tetramethylammonium silicate (TMAS).
[0050]
In another embodiment of the invention, the composition comprises about 0.1 to 2% by weight of tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight of trans- (1,2-cyclohexylene dihydrate. Nitrilo) tetraacetic acid (CyDTA), and about 0.01 to 1% by weight (SiO2This is an aqueous solution containing tetramethylammonium silicate (TMAS).
[0051]
In another embodiment of the invention, the composition comprises about 0.1 to 2% by weight of tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight of trans- (1,2-cyclohexylene dihydrate. Nitrilo) tetraacetic acid (CyDTA), about 0.01 to 1% by weight (SiO2Converted) tetramethylammonium silicate (TMAS), and an aqueous solution containing about 0.5 to 20% by weight of a polyhydroxy compound, preferably glycerol.
[0052]
In another embodiment of the invention, the composition comprises about 0.1 to 2% by weight of tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight of trans- (1,2-cyclohexylene dihydrate. Nitrilo) tetraacetic acid (CyDTA), about 0.01 to 1% by weight (SiO2Converted) tetramethylammonium silicate (TMAS), about 0.5 to 20% by weight of a polyhydroxy compound, and about 0.01 to 0.3% by weight of a nonionic ethoxylated acetyl diol surfactant. It is.
[0053]
In another embodiment of the invention, the composition comprises about 0.1 to 2% by weight of tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight of trans- (1,2-cyclohexylene dihydrate. Nitrilo) tetraacetic acid (CyDTA), about 0.01 to 1% by weight (SiO2Converted) tetramethylammonium silicate (TMAS) and about 0.5 to 20% by weight of alkyl-pyrrolidinone such as 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP), preferably 1- (2-hydroxy An aqueous solution containing ethyl) -2-pyrrolidinone (HEP).
[0054]
  In another embodiment of the invention, the composition comprises about 0.1 to 2% by weight of tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight of trans- (1,2-cyclohexylene dihydrate. Nitrilo) tetraacetic acid (CyDTA), about 0.01 to 1% by weight (SiO2) Tetramethylammonium silicate (TMAS), and about 0.5 to 20% by weight of an alkyl-pyrrolidinone such as 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP), and about 0.01 to 0. 3% by weight of nonionic ethoxylated acetyl diolWorldIt is an aqueous solution containing a surfactant.
[0055]
  Of the present inventionpreferableIn an embodiment, the composition comprises about 0.1 to 10% by weight tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight (SiO 22Conversion) tetramethylammonium silicate (TMAS), and an aqueous solution containing about 1 to 10% by weight of hydrogen peroxide.
[0056]
  Another one of the present inventionpreferableIn an embodiment, the composition comprises about 0.1 to 9 wt% tetramethylammonium hydroxide (TMAH), about 0.01 to 4 wt% (SiO2Conversion) tetramethylammonium silicate (TMAS), and an aqueous solution containing about 1 to 20% by weight of hydroxylamine.
[0057]
In another embodiment of the invention, the composition comprises about 0.1 to 10% by weight of tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight of trans- (1,2-cyclohexylene dihydrate. Nitrilo) tetraacetic acid (CyDTA), about 0.01 to 1% by weight (SiO2Conversion) tetramethylammonium silicate (TMAS), and an aqueous solution containing about 1 to 10% by weight of hydrogen peroxide.
[0058]
In another embodiment of the invention, the composition comprises about 0.1 to 9% by weight of tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight of trans- (1,2-cyclohexylene dihydrate. Nitrilo) tetraacetic acid (CyDTA), about 0.01 to 4% by weight (SiO 2)2Conversion) tetramethylammonium silicate (TMAS), and an aqueous solution containing about 1 to 20% by weight of hydroxylamine.
[0059]
In another embodiment of the invention, the composition comprises about 0.1 to 10% by weight of tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight of trans- (1,2-cyclohexylene dihydrate. Nitrilo) tetraacetic acid (CyDTA), about 0.01 to 1% by weight (SiO2Conversion) tetramethylammonium silicate (TMAS), about 1 to 10% by weight of hydrogen peroxide, and about 0.01 to 0.3% by weight of a nonionic ethoxylated acetyl diol surfactant. .
[0060]
In another embodiment of the invention, the composition comprises about 0.1 to 9% by weight of tetramethylammonium hydroxide (TMAH), about 0.01 to 1% by weight of trans- (1,2-cyclohexylene dihydrate. Nitrilo) tetraacetic acid (CyDTA), about 0.01 to 4% by weight (SiO 2)2Conversion) tetramethylammonium silicate (TMAS), about 1 to 20% by weight hydroxylamine, and about 0.01 to 0.3% by weight nonionic ethoxylated acetyl diol surfactant.
[0061]
In all embodiments, the balance of the composition is water, preferably high purity deionized water.
[0062]
  As shown in the following examples, a composition containing only an alkaline base cannot obtain an effective cleaning effect without corroding the undulations of the aluminum metal integrated circuit. This example also includes (1) silicate buffering (pKa) to prevent aluminum metal integrated circuits from corrosion.2= 11.8) shows the usefulness of adding soluble silicates to highly basic formulations to extend the bath life of these cleaning compositions and (3) to reduce the silicon dioxide dielectric etch rate. Further advantages of the composition of the present invention are as follows. (1) High water content (without intermediate rinsing (such as isopropanol))Immediate(2) Integrated circuit board is supported by preventing the corrosion of the metal after washing by assisting water washing, and only negligible carbon contamination occurs on the substrate surface)TheNon-toxic especially avoiding catechols, volatile organic solvents and organic amines characteristic of prior art compositions used for tripping and washingcomponentWith the use ofYes,Hygiene, safety, environmental and handling risks are low, (3) Titanium-containing residues are removed from integrated circuit boards at low temperaturesAbility to(4) compatibility of these compounding agents with photosensitive low-k dielectric materials used in integrated circuits, (5) compatibility with copper (low etching rate) and (6) the composition of the present invention, Wafer in post chemical mechanical polishing (CMP) operationsubstrateAbility to clean and prevent contamination.
[0063]
  The method of the present invention applies a contaminated substrate to a substrate surface.FromA semiconductor wafer substrate is cleaned by exposure to the composition of the present invention for a time and at a temperature sufficient to clean undesired contaminants. If desired, the substraterinse andThe composition and contaminants are removed and dried to remove excess solvent or rinse agent. The substrate can then be used for the intended purpose.
[0064]
Preferably, the method uses a liquid bath or spray application to expose the substrate to the composition. The liquid bath or spray washing time is generally from 1 minute to 30 minutes, preferably from 5 minutes to 20 minutes. The liquid bath or spray washing temperature is generally 10 ° C to 85 ° C, preferably 20 ° C to 45 ° C.
[0065]
  If necessary,rinseThe time is generally 10 seconds to 5 minutes at room temperature, preferably 30 seconds to 2 minutes at room temperature.Preferably deionized water is used to rinse the substrate.
[0066]
If necessary, drying of the substrate can be achieved by any combination of air evaporation, heating, centrifugation, or pressurized gas. A preferable drying method is to centrifuge for a time until the wafer substrate is dried under a flow of an inert gas such as nitrogen through a filter.
[0067]
  The method of the present invention comprises a semiconductor wafer substrate that has been previously oxygen plasma ashed to remove photoresist lumps, particularly silicone, silicon oxide, silicon nitride, tungsten, tungsten alloy, titanium, titanium alloy, tantalum, tantalum alloy, It is extremely effective for cleaning wafer substrates containing copper, copper alloys, aluminum, or aluminum alloy films. The method is undesirable for metal and organic contaminantsExcludingHowever, it does not cause unacceptable corrosion to the silicone, silicon oxide, silicon nitride, tungsten, tungsten alloy, titanium, titanium alloy, tantalum, tantalum alloy, copper, copper alloy, aluminum, or aluminum alloy film.
[0068]
Example
The following examples illustrate specific embodiments of the invention described herein. It will be apparent to those skilled in the art that various modifications and improvements are possible and are considered to be within the scope of the described invention.
[0069]
Experimental procedure
  The percentages shown in the examples are percentages by weight unless otherwise specified. Aluminum metal corrosion is expressed in terms of both metal loss% and general corrosion index. The general corrosion index given isVery fewSlight, mild, moderate, andStrict. A small amount of ammonium corrosion is considered acceptable,Very few, Or just a little. Mild, moderate orStrictCorrosion was considered unacceptable. The cleaning and corrosion data registrations obtained using a scanning electron microscope (SEM) or field emission scanning electron microscope (FE-SEM) are all of the difference between untreated and treated samples from the same wafer.EyeAccording to sight.
[0070]
Example 1
Aqueous solution “A” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465 (product of Air Products and Chemicals, Inc.) and 0.14% by weight (SiO2% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 12.2. Aqueous solution “B” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Prepared with the activator Surfynol-465 (the remainder of the solution is water), the pH is about 12.7. Aqueous solution “C” is 0.08 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465 and 0.13% by weight (Si02% Conversion) Tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 10.5. Aqueous solution “D” is 0.09 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Prepared with the activator Surfynol-465 (the remainder of the solution is water), the pH is about 9.6. The aqueous solution “E” is 0.1 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic Surfactant Surfynol-465 and 0.010 wt% (Si02% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 11.3. Aqueous solution “F” is 0.08 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic Prepared using the surfactant Surfynol-465 (the remainder of the solution is water), the pH is about 10.9. (A) plating with aluminum copper alloy, then titanium nitride, (b) taking a lithographic pattern using a photoresist material, (c) transferring the pattern using reactive ion etching, (d) oxygen plasma ashing Using wafer # 1 sample with pre-manufactured 1 micron wide undulations and wiring formed with aluminum copper and capped with titanium nitride, while removing the organic photoresist residue by The performance of the solution was evaluated. Wafer samples were removed from each of these solutions at 21-65 ° C. for 5-10 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the sample was observed with a scanning electron microscope (SEM) to determine the degree of cleaning and / or corrosion of the aluminum copper metal relief. The results are shown in Table 1.
[Table 1]
[0071]
According to Table 1, the data show the ability of TMAS to prevent corrosion of aluminum relief associated with exposure to alkaline solutions, and by adding tetramethylammonium silicate to a tetramethylammonium hydroxide based cleaning solution, It shows that undesired integrated circuit corrosion is completely inhibited.
[0072]
Example 2
  The aqueous solution “G” is 2.0 wt% tetramethylammonium hydroxide (TMAH), 0.09 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.06 wt% nonionic interface. Activator Surfynol-465 and 0.13% by weight (Si02% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 13.6. Aqueous solution “H” is 0.09 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465 and 0.14% by weight (Si02% Conversion) prepared by adding tetramethylammonium silicate (TMAS) (the remainder of the solution is water), and the pH is about 10.8. The aqueous solution “M” is 1.8 wt% tetramethylammonium hydroxide (TMAH), 0.09 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.06 wt% nonionic interface. Activator Surfynol-465 and1.3% By weight (Si02% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 13.0. Aqueous solution “N” is 1.9 wt% tetramethylammonium hydroxide (TMAH), 0.09 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.06 wt% nonionic interface Activator Surfynol-465 and 0.86 wt% (Si02% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 13.2. Aqueous solution “O” is 1.9 wt% tetramethylammonium hydroxide (TMAH), 0.09 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.06 wt% nonionic Surfactant Surfynol-465 and 0.70 wt% (Si02% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 13.2. The aqueous solution “P” is 1.9 wt% tetramethylammonium hydroxide (TMAH), 0.09 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.06 wt% nonionic Surfactant Surfynol-465 and 0.54 wt% (Si02% Conversion) prepared by adding tetramethylammonium silicate (TMAS) (the remainder of the solution is water), and the pH is about 13.3. Aqueous solution “Q” is 2.0 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.06 wt% nonionic Surfactant Surfynol-465 and 0.45 wt% (Si02% Conversion) prepared by adding tetramethylammonium silicate (TMAS) (the remainder of the solution is water), and the pH is about 13.3. The aqueous solution “R” is 2.0% by weight tetramethylammonium hydroxide (TMAH), 0.1% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.06% by weight nonionic. Surfactant Surfynol-465 and 0.28 wt% (Si02% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 13.4. The aqueous solution “S” is 2.0% by weight tetramethylammonium hydroxide (TMAH), 0.1% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07% by weight nonionic. Surfactant Surfynol-465 and 0.19 wt% (Si02% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 13.4. The aqueous solution “T” is 0.1 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic Surfactant Surfynol-465 and 0.020 wt% (Si02% Conversion) prepared by adding tetramethylammonium silicate (TMAS) (the remainder of the solution is water), and the pH is about 11.2. The aqueous solution “U” is 0.1 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic Surfactant Surfynol-465 and 0.070 wt% (Si02% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 10.9. (A) plating with aluminum copper alloy, then titanium nitride, (b) taking a lithographic pattern using a photoresist material, (c) transferring the pattern using reactive ion etching, (d) oxygen plasma ashing Using wafer # 1 sample with pre-manufactured 1 micron wide undulations and wiring formed with aluminum copper and capped with titanium nitride, while removing the organic photoresist residue by The performance of the solution was evaluated. The wafer sample was removed from the solution at 21-65 ° C. for 5-20 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the sample was observed with a scanning electron microscope (SEM) to determine the degree of cleaning and / or corrosion of the aluminum copper metal relief. The results are shown in Table 2.
[Table 2]
[0073]
  According to Table 2, the data show that to prevent or attenuate the corrosion of aluminum relief associated with exposure to these alkaline solutions,As it growsThere is a need to increase the concentration of TMASis thereIndicating that the optimum pH range of the solution of the present application is about 11-13.
[0074]
Example 3
Aqueous solution “I” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.06 wt% nonionic interface Activator Surfynol-465, 0.13% by weight (Si02% Conversion) Tetramethylammonium silicate (TMAS) and 5 wt% glycerol were added. The balance of this solution is water. Aqueous solution “J” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.09 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.06 wt% nonionic interface Activator Surfynol-465, 0.13% by weight (Si02% Conversion) Tetramethylammonium silicate (TMAS) and 6 wt% glycerol were added. The balance of this solution is water. Aqueous solution “K” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.09 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.06 wt% nonionic interface Activator Surfynol-465, 0.12% by weight (Si02% Conversion) It was prepared by adding tetramethylammonium silicate (TMAS) and 10% by weight diethylene glycol (DEG). The balance of this solution is water. (A) plating with aluminum copper alloy, then titanium nitride, (b) taking a lithographic pattern using a photoresist material, (c) transferring the pattern using reactive ion etching, (d) oxygen plasma ashing Using wafer # 1 sample with pre-manufactured 1 micron wide undulations and wiring formed with aluminum copper and capped with titanium nitride, while removing the organic photoresist residue by The performance of the solution was evaluated. The wafer sample was removed from the solution at 21-35 ° C. for 5-20 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the sample was observed with a scanning electron microscope (SEM) to determine the degree of cleaning and / or corrosion of the aluminum copper metal relief. The results are shown in Table 3.
[Table 3]
[0075]
According to Table 3, the data show that the addition of a water-soluble organic solvent is advantageous for the ability to prevent or attenuate the corrosion of aluminum undulations associated with exposure to TMA-containing alkaline solutions. It shows that by adding a water-soluble solvent to an object, the cleaning time can be extended without corroding metal wiring existing in the integrated circuit.
[0076]
Example 4
  Aqueous solution “L” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465, 0.14% by weight (Si02% Conversion) Tetramethylammonium silicate (TMAS) and 3% by weight glycerol were added. The balance of this solution is water. Wafer sample # 2 having a width of 1/2 micron for a 1 micron deep hole (bias) through the dielectric material exposing the aluminum copper metal on its substrate is (a) aluminum copper and then titanium nitride. Plating, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, and (d) applying the pattern to the dielectric layer using reactive ion etching (E) Pre-manufactured by removing most of the remaining photoresist by oxygen plasma ashing, while mainly leaving behind inorganic residues. Wafer sample # 3, having a width of 1 micron against a 1 micron deep tapered hole (bias) through the dielectric material exposing the aluminum copper metal on its substrate, is plated with (a) aluminum copper and then titanium nitride. (B) coated with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using photoresist material, and (d) transferring the pattern to the dielectric layer using reactive ion etching And (e) pre-manufactured by removing most of the remaining photoresist by oxygen plasma ashing, while mainly leaving behind inorganic residues. These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 20-21 ° C. for 10 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample was taken and then observed with a scanning electron microscope (SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 4.
[Table 4]
[0077]
According to Table 4, the data show that the addition of a water-soluble organic solvent is advantageous for the ability to prevent or attenuate the corrosion of aluminum undulations associated with exposure to TMA-containing alkaline solutions. It shows that by adding a water-soluble solvent to the object, it is possible to clean the bias without corroding the metal at the base of the bias.
[0078]
Example 5
  (A) plating with aluminum copper alloy, then titanium nitride, (b) taking a lithographic pattern using a photoresist material, (c) transferring the pattern using reactive ion etching, (d) oxygen plasma ashing Wafer # 1 and # 4 samples with 1 micron wide relief and wiring formed with aluminum copper and capped with titanium nitride, pre-manufactured by removing the organic photoresist residues by Each was used to evaluate the performance of the solution. Wafer samples were removed from the solution at 11-65 ° C. for 5-30 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the sample was observed with a scanning electron microscope (SEM) to determine the degree of cleaning and / or corrosion of the aluminum copper metal relief. The results are shown in Tables 5A, 5B and 5C.
[Table 5]
[Table 6]
[Table 7]
[0079]
According to Tables 5A, 5B and 5C, the data show that both formulations have significant processing latitude with or without the addition of a water-soluble organic solvent (Solution “L”) (Solution “A”). Is shown. A comparison of Tables 5B and 5C also shows that the addition of water-soluble organic solvents (solution “L”) reduces the aluminum metal corrosion that occurs with extended process time and high temperatures, further improving processing latitude. Is shown. In Table 5B, where an organic solvent was added to the formulation, the observed corrosion range was only 0-4%, even with a cleaning temperature of 65 ° C. In Table 5C, where no organic solvent was added, 4% or more corrosion was observed with a cleaning time of 10 minutes or more. The data also shows the considerable processing latitude that can be obtained with the compositions of the present invention and that processing tolerance can be further improved by the addition of an optional water-soluble solvent.
[0080]
Example 6
  The aqueous solution “V” was 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.07 wt% nonionic surfactant Surfynol-465 and 0.14 wt% (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water. Aqueous solution “W” is 0.6 wt% tetramethylammonium hydroxide (TMAH), 0.3 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465 and 0.14% by weight (Si02% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water. Aqueous solution “X” is 0.7 wt% tetramethylammonium hydroxide (TMAH), 0.5 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465 and 0.14% by weight (Si02% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water. (A) plating with aluminum copper alloy, then titanium nitride, (b) taking a lithographic pattern using a photoresist material, (c) transferring the pattern using reactive ion etching, (d) oxygen plasma ashing Using a wafer # 4 sample with pre-manufactured 1 micron wide undulations and wiring made of aluminum copper and capped with titanium nitride, while removing organic photoresist residues by The performance of the solution was evaluated. The wafer sample was removed from the solution at 20-21 ° C. for 5 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the sample was observed with a scanning electron microscope (SEM) to determine the degree of cleaning and / or corrosion of the aluminum copper metal relief. The results are shown in Table 6.
[Table 8]
[0081]
According to Table 6, the data show that good stripping performance is obtained over a wide range of CyDTA concentrations. In this way, the amount of chelating agent present can be adjusted to accommodate the sample being washed. More difficult samples may require this desired component to achieve complete washing. The data also indicates that chelating agents are optionally used in the compositions disclosed herein.
[0082]
Example 7
  The aqueous solution “Y” was 0.4 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA) and 0.14 wt% (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water. (A) plating with aluminum copper alloy, then titanium nitride, (b) taking a lithographic pattern using a photoresist material, (c) transferring the pattern using reactive ion etching, (d) oxygen plasma ashing Using a wafer # 4 sample with pre-manufactured 1 micron wide undulations and wiring made of aluminum copper and capped with titanium nitride, while removing organic photoresist residues by The performance of the solution was evaluated. The wafer sample was removed from the solution at 20-21 ° C. for 5 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the sample was observed with a scanning electron microscope (SEM) to determine the degree of cleaning and / or corrosion of the aluminum copper metal relief. The results are shown in Table 7.
[Table 9]
[0083]
According to Table 7, the data indicate that good stripping performance can be obtained for formulations mixed with surfactants to improve substrate wetting, and optionally in the compositions disclosed herein. It shows that a surfactant is used.
[0084]
Example 8
An open tank aging experiment was performed using a standard tank for two different formulations. The first tank was operated at room temperature for 24.75 hours, and the second tank was operated at 45 ° C. for 24.75 hours. (A) plating with aluminum copper alloy, then titanium nitride, (b) taking a lithographic pattern using a photoresist material, (c) transferring the pattern using reactive ion etching, (d) oxygen plasma ashing Using a wafer # 4 sample with pre-manufactured 1 micron wide undulations and wiring made of aluminum copper and capped with titanium nitride, while removing organic photoresist residues by The performance of the solution was evaluated. Wafer samples were placed in this bath for 10 minutes at 20 ° C. or 45 ° C., rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the sample was observed with a scanning electron microscope (SEM) to determine the degree of cleaning and / or corrosion of the aluminum copper metal relief. The results are shown in Table 8.
[Table 10]
[0085]
According to Table 8, the data show the benefits of silicate buffering during long-term open bath aging at room and elevated temperatures. No change in stripping performance occurred during this aging period. The data also shows that the compositions of the present invention are not subject to aging.
[0086]
Example 9
The aqueous solution “A1” was 0.27 wt% tetramethylammonium hydroxide (TMAH) and 0.14 wt% (SiO 22% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “A2” was 0.38 wt% tetramethylammonium hydroxide (TMAH), 0.09 wt% chelating agent (ethylenedinitrilo) tetraacetic acid (EDTA) and 0.14 wt% (SiO 22% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “A3” was 0.39 wt% tetramethylammonium hydroxide (TMAH), 0.10 wt% chelating agent diethylenetriaminepentaacetic acid (DETPA) and 0.14 wt% (SiO 22% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “A4” was 0.40 wt% tetramethylammonium hydroxide (TMAH), 0.10 wt% chelating agent triethylenetetramine hexaacetic acid (TTHA) and 0.14 wt% (SiO 22% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “A5” is 0.40 wt% tetramethylammonium hydroxide (TMAH), 0.10 wt% chelating agent 1,3-diamino-2-hydroxypropane-N, N, N ′, N′-tetraacetic acid It was prepared by adding (DHPTA) and 0.14 wt% (Si02% conversion) tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “A6” contains 0.47 wt% tetramethylammonium hydroxide (TMAH), 0.13 wt% chelator N, N, N ′, N′-ethylenediaminetetra (methylenephosphonic acid) (EDTMP) and 0. 14% by weight (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). Each solution was placed in a 125 ml glass bottle and placed in an oven set at 45 ° C. with the lid loosely closed for 1 hour. A piece of 0.05 mm × 12 mm × 50 mm, 99.8% purity aluminum foil was washed with acetone, dried, and then weighed on an analytical balance. After preheating for 1 hour, each solution was removed from the oven, and then a piece of aluminum foil was placed in the jar and again loosely capped and returned to the oven. After 1 hour at about 45 ° C., the bottle was removed from the oven. The aluminum piece was removed, washed with water, then rinsed with acetone, dried and weighed on an analytical balance. The relative degree of corrosion was determined from the weight loss. The results are shown in Table 9.
[Table 11]
[0087]
  According to Table 9, the data show that adding a chelating agent is useful to increase the aluminum etch rate. To allow removal of metal residues found on the wafer after oxygen plasma ashing in an acceptable stripping temperature and time range, it may be necessary to increase the aluminum etch rate. The data can also be used as desired to obtain the desired aluminum etch rate for the inventive compositions herein.variousConstructionNo kiIt shows that a rate agent is used.
[0088]
Example 10
The aqueous solution “B1” was 0.22% by weight tetramethylammonium hydroxide (TMAH), 0.1% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA) and 0.14% by weight (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “B2” was 0.30 wt% tetramethylammonium hydroxide (TMAH), 0.10 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA) and 0.14 wt% (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “B3” was 0.45% by weight tetramethylammonium hydroxide (TMAH), 0.30% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA) and 0.14% by weight (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.2). The aqueous solution “B4” was 0.59% by weight tetramethylammonium hydroxide (TMAH), 0.50% by weight trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA) and 0.14% by weight (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.1). The aqueous solution “B5” was composed of 1.1 wt% tetramethylammonium hydroxide (TMAH), 1.0 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA) and 0.14 wt% (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “B6” was 4.1% by weight tetramethylammonium hydroxide (TMAH), 4.8% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA) and 0.13% by weight (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). Each solution was placed in a 125 ml polyethylene bottle and placed in an oven set at 45 ° C. with the lid loosely closed for 1 hour. A 0.05 mm x 12 mm x 50 mm, 99.8% pure aluminum foil piece was rinsed with acetone, dried, and then weighed on an analytical balance. After preheating for 1 hour, each solution was removed from the oven, and then a piece of aluminum foil was placed in the jar and again loosely capped and returned to the oven. After 1 hour at about 45 ° C., the bottle was removed from the oven. The aluminum piece was removed, washed with water, then rinsed with acetone, dried and weighed on an analytical balance. The relative degree of corrosion was determined from the weight loss. The results are shown in Table 10.
[Table 12]
[0089]
According to Table 10, the data show that the addition of a chelating agent is useful to increase the aluminum etch rate. To allow removal of metal residues found on the wafer after oxygen plasma ashing in an acceptable stripping temperature and time range, it may be necessary to increase the aluminum etch rate. The aluminum etch rate is directly proportional to the amount of chelating agent used. The data also indicate that chelating agents, optionally added at various concentrations, are used to obtain the desired aluminum etch rate for the inventive compositions herein.
[0090]
Example 11
The aqueous solution “C1” was 0.25 wt% tetramethylammonium hydroxide (TMAH) and 0.14 wt% (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “C2” was 0.36 wt% choline and 0.14 wt% (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “C3” was 0.76 wt% tetrabutylammonium hydroxide (TBAH) and 0.14 wt% (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “C4” was 1.6 wt% methyltriethanolammonium hydroxide (MAH) and 0.14 wt% (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “C5” was 0.36 wt% methyltriethylammonium hydroxide (MTEAH) and 0.14 wt% (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). Each solution was placed in a 125 ml glass bottle and placed in an oven set at 45 ° C. with the lid loosely closed for 1 hour. A 0.05 mm × 12 mm × 50 mm, 99.8% purity aluminum foil piece was rinsed with acetone, dried, and then weighed on an analytical balance. After preheating for 1 hour, each solution was removed from the oven, and then a piece of aluminum foil was placed in the jar and again loosely capped and returned to the oven. After 1 hour at about 45 ° C., the bottle was removed from the oven. The aluminum piece was removed, washed with water, then rinsed with acetone, dried and weighed on an analytical balance. The relative degree of corrosion was determined from the weight loss. The results are shown in Table 11.
[Table 13]
[0091]
  According to Table 11, the data indicate that TMAH may be replaced with various metal ion free bases to increase the aluminum etch rate. To allow removal of metal residues found on the wafer after oxygen plasma ashing in an acceptable stripping temperature and time range, it may be necessary to increase the aluminum etch rate. The data also shows that to obtain the desired aluminum etch rate for the inventive compositions herein,variousConstructionGoldIt indicates that a genus ion-free alkaline component is used.
[0092]
Example 12
The aqueous solution “D1” was prepared by adding 0.14 wt% tetramethylammonium hydroxide (TMAH). The balance of this solution is water (solution pH = 12.3). The aqueous solution “D2” was 0.25 wt% tetramethylammonium hydroxide (TMAH) and 0.14 wt% (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.3). The aqueous solution “D3” was 1.2 wt% tetramethylammonium hydroxide (TMAH) and 1.3 wt% (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.6). The aqueous solution “D4” was 1.8% by weight tetramethylammonium hydroxide (TMAH) and 2.8% by weight (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.6). Each solution was placed in a 125 ml glass bottle and placed in an oven set at 45 ° C. with the lid loosely closed for 1 hour. A 0.05 mm × 12 mm × 50 mm, 99.8% purity aluminum foil piece was rinsed with acetone, dried, and then weighed on an analytical balance. After preheating for 1 hour, each solution was removed from the oven, and then a piece of aluminum foil was placed in the jar and again loosely capped and returned to the oven. After 1 hour at about 45 ° C., the bottle was removed from the oven. The aluminum piece was removed, washed with water, then rinsed with acetone, dried and weighed on an analytical balance. The relative degree of corrosion was determined from the weight loss. The results are shown in Table 12.
[Table 14]
[0093]
According to Table 12, the data show that the addition of silicate to the metal ion free basic solution inhibits the corrosion of aluminum metal and also obtains the desired aluminum etch rate for the inventive compositions herein. This indicates that metal ion-free silicates added in various concentrations are used.
[0094]
Example 13
The aqueous solution “E1” was 0.22 wt% tetramethylammonium hydroxide (TMAH) and 0.14 wt% (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.2). The aqueous solution “E2” was 0.22 wt% tetramethylammonium hydroxide (TMAH), 0.14 wt% (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 2.9 wt% glycerol. The balance of this solution is water (solution pH = 12.1). The aqueous solution “E3” was 0.20 wt% tetramethylammonium hydroxide (TMAH), 0.13 wt% (SiO2% Conversion) Tetramethylammonium silicate (TMAS) and 9.1 wt% triethylene glycol monomethyl ether were added. The balance of this solution is water (solution pH = 12.2). The aqueous solution “E4” was 0.19 wt% tetramethylammonium hydroxide (TMAH), 0.12 wt% (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 13 wt% N-methylpyrrolidinone. The balance of this solution is water (solution pH = 12.2). The aqueous solution “E5” was 0.19 wt% tetramethylammonium hydroxide (TMAH), 0.12 wt% (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 17% by weight diethylene glycol. The balance of this solution is water (solution pH = 12.1). The aqueous solution “E6” was 0.17 wt% tetramethylammonium hydroxide (TMAH), 0.11 wt% (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 23 wt% isopropyl alcohol. The balance of this solution is water (solution pH = 12.7). Each solution was placed in a 125 ml polyethylene bottle and placed in an oven set at 45 ° C. with the lid loosely closed for 1 hour. A 0.05 mm × 12 mm × 50 mm, 99.8% purity aluminum foil piece was rinsed with acetone, dried, and then weighed on an analytical balance. After preheating for 1 hour, each solution was removed from the oven, and then a piece of aluminum foil was placed in the jar and again loosely capped and returned to the oven. After 1 hour at about 45 ° C., the bottle was removed from the oven. The aluminum piece was removed, washed with water, then rinsed with acetone, dried and weighed on an analytical balance. The relative degree of corrosion was determined from the weight loss. The results are shown in Table 13.
[Table 15]
[0095]
According to Table 13, the data show that the addition of a water-soluble organic solvent is useful to slow the aluminum etch rate. To completely avoid aluminum corrosion during the stripping process, it may be necessary to slow the aluminum etch rate. The aluminum etching rate is inversely proportional to the amount of solvent used, regardless of the solvent type. A wide variety of water soluble solvents are shown below. The data also shows that various types of water-soluble organic solvents are optionally used to obtain the desired aluminum etch rate for the inventive compositions herein.
[0096]
Example 14
The aqueous solution “G1” was 0.22 wt% tetramethylammonium hydroxide (TMAH) and 0.14 wt% (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS). The balance of this solution is water (solution pH = 12.2). The aqueous solution “G2” was 0.22 wt% tetramethylammonium hydroxide (TMAH), 0.14 wt% (SiO2% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 0.10 wt% nonionic surfactant Surfynol-465. The balance of this solution is water (solution pH = 12.2). The aqueous solution “G3” was 0.22 wt% tetramethylammonium hydroxide (TMAH), 0.14 wt% (SiO2% Conversion) Tetramethylammonium silicate (TMAS) and 0.10 wt% nonionic surfactant Fluorad FC-170C (product of 3M Industrial Chemicals Division) were added. The balance of this solution is water (solution pH = 12.2). The aqueous solution “G4” was 0.22 wt% tetramethylammonium hydroxide (TMAH), 0.14 wt% (SiO2% Conversion) Tetramethylammonium silicate (TMAS) and 0.042 (effective) wt% amphoteric surfactant Reuteric AM KSF-40 (product of Witco Corporation) was added to prepare. The balance of this solution is water (solution pH = 12.2). The aqueous solution “G5” was 0.22 wt% tetramethylammonium hydroxide (TMAH), 0.14 wt% (SiO2% Conversion) Tetramethylammonium silicate (TMAS) and 0.026 (effective) wt% anionic surfactant Fluorad FC-93 (a product of 3M Industrial Chemicals Division) was prepared. The balance of this solution is water (solution pH = 12.2). The aqueous solution “G6” was 0.22 wt% tetramethylammonium hydroxide (TMAH), 0.14 wt% (SiO2% Conversion) Tetramethylammonium silicate (TMAS) and 0.037 (effective) wt% cationic surfactant Barquat CME-35 (product of Lonza, Inc.) was added. The balance of this solution is water (solution pH = 12.2). Each solution was placed in a 125 ml polyethylene bottle and placed in an oven set at 45 ° C. with the lid loosely closed for 1 hour. A 0.05 mm × 12 mm × 50 mm, 99.8% purity aluminum foil piece was rinsed with acetone, dried, and then weighed on an analytical balance. After preheating for 1 hour, each solution was removed from the oven, and then a piece of aluminum foil was placed in the jar and again loosely capped and returned to the oven. After 1 hour at about 45 ° C., the bottle was removed from the oven. The aluminum piece was removed, washed with water, then rinsed with acetone, dried and weighed on an analytical balance. The relative degree of corrosion was determined from the weight loss. The results are shown in Table 14.
[Table 16]
[0097]
According to Table 14, the data show that the addition of a surfactant is useful to slow the aluminum etch rate. To completely avoid aluminum corrosion during the stripping process, it may be necessary to slow the aluminum etch rate. Useful aluminum etch rate suppression occurs with all four surfactants. This adds to the expected desirable property of improving the wettability of the sample in the presence of a surfactant. The data also indicates that various types of surfactants are optionally used to obtain the desired aluminum etch rate for the inventive compositions herein.
[0098]
Example 15
  Aqueous solution “F1” is 0.20 wt% tetramethylammonium hydroxide (TMAH), 0.11 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA) and 0.07 wt% nonionic interface. Prepared by adding the activator Surfynol-465. The balance of this solution is water (solution pH = 12.3). The aqueous solution “F2” was 0.30% by weight tetramethylammonium hydroxide (TMAH), 0.10% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO2% Conversion) Tetramethylammonium silicate (TMAS) and 0.07 wt% nonionic surfactant Surfynol-465 were added. The balance of this solution is water (solution pH = 12.3). The aqueous solution “F3” was 0.29% by weight tetramethylammonium hydroxide (TMAH), 0.10% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO2% Conversion) Tetramethylammonium silicate (TMAS), 3.0 wt% glycerol and 0.07 wt% nonionic surfactant Surfynol-465 were added. The balance of this solution is water (solution pH = 12.1). Sections from the same Si (100) wafer with about 650 nm thermal oxide were rinsed with acetone, dried, and then measured using a Rudolph FTM interferometer to determine the thermal oxide thickness. Four regions were measured and mapped for follow-up measurements after processing. Each sample was then placed in a bottle and again placed in an oven set at 45 ° C. with the lid loosely closed. After 24 hours at about 45 ° C., the bottle was removed from the oven, a sample was removed, washed with water, then rinsed with acetone, dried and further measured with an interferometer. The relative corrosion degree was determined from the difference in the thickness of the thermal oxide film averaged over the four regions on the sample. The results are shown in Table 15.
[Table 17]
[0099]
  According to Table 15, data accompanies exposure to alkaline solutiontwoIt shows that the addition of silicate is advantageous to prevent or weaken the corrosion of silicon oxide. Typically, the silicon dioxide dielectric is present on the surface of the integrated circuit during metal wiring or bias stripping. Damage to these dielectrics must be avoided. The data also shows that the addition of tetramethylammonium silicate to a tetramethylammonium hydroxide-based cleaning solution typically inhibits unwanted corrosion of dielectric materials present in integrated circuits.
[0100]
Example 16
Organic contaminants remaining after washing were measured using a secondary ion mass spectrometer (SIMS). A silicon wafer sample sputtered with a 0.35 micron film of aluminum-1% copper alloy is treated with a silicate solution “A” and a commercially available post-etch residue remover, EKC-265.TMAlso washed (product of EKC Technology, Inc.). EKC-265TMComprises about 15% to 20% of catechol, hydroxylamine and water, respectively, with the balance being 2- (2-aminoethoxy) ethanol. The wafer sample was placed in solution “A” at 35 ° C. for 5 minutes, then rinsed with deionized water filtered at 0.2 microns for 2 minutes and dried under pressure nitrogen. A second wafer sample is prepared using EKC-265 using the time and temperature recommended by the manufacturer.TMTreated in the same way. A third untreated wafer piece (also from the same silicone wafer) was used as a control. The wafer samples were then analyzed by Dynamic-SIMS using an etch rate of 22.1 Å / sec with a 0.5 second pause. The carbon surface contamination of the three samples was then compared using the carbon-12 atomic power released from the surface. The results are shown in Table 16.
[Table 18]
[0101]
According to Table 16, the data show the advantages of the present invention with respect to providing a surface free of organic contaminants after cleaning, and the use of the composition described herein for integrated circuits with carbon-containing (organic) impurities. Indicates that there is almost no contamination.
[0102]
Example 17
  Aqueous solution “H1” is 0.27 wt% tetramethylammonium hydroxide (TMAH), 0.092 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.062 wt% nonionic interface Activator Surfynol-465, 0.13% by weight (Si02% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 2.7 wt% glycerol. The balance of this solution is water. Aqueous solution “H2” is 0.28 wt% tetramethylammonium hydroxide (TMAH), 0.097 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.065 wt% nonionic interface Activator Surfynol-465, 0.13% by weight (Si02% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 2.9 wt% glycerol. The balance of this solution is water. Aqueous solution “H3” is 0.32 wt% tetramethylammonium hydroxide (TMAH), 0.11 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.075 wt% nonionic interface Activator Surfynol-465, 0.15% by weight (Si02% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 3.3 wt% glycerol. The balance of this solution is water. Aqueous solution “H4” is 0.39 wt% tetramethylammonium hydroxide (TMAH), 0.14 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.091 wt% nonionic interface Activator Surfynol-465, 0.19 wt% (Si02% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 4.0 wt% glycerol. The balance of this solution is water. Aqueous solution “H5” is 0.58 wt% tetramethylammonium hydroxide (TMAH), 0.20 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.14 wt% nonionic interface Activator Surfynol-465, 0.28 wt% (Si02% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 6.0 wt% glycerol. The balance of this solution is water. Aqueous solution “H6” is 1.2 wt% tetramethylammonium hydroxide (TMAH), 0.41 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.27 wt% nonionic interface. Activator Surfynol-465, 0.56% by weight (Si02% Conversion) Tetramethylammonium silicate (TMAS) and 12 wt% glycerol were added. The balance of this solution is water. The aqueous solution “H7” was 5.1 wt% tetramethylammonium hydroxide (TMAH), 1.8 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 2.4 wt% (SiO2% Conversion) Tetramethylammonium silicate (TMAS) and 52 wt% glycerol were added. The balance of this solution is water. (A) plating with aluminum copper alloy, then titanium nitride, (b) taking a lithographic pattern using a photoresist material, (c) transferring the pattern using reactive ion etching, (d) oxygen plasma ashing Wafer # 5 and # 6 samples with 1 micron wide undulations and wiring made of aluminum copper and capped with titanium nitride, previously removed by removing organic photoresist residues, while leaving behind mainly inorganic residues Was used to evaluate the performance of the solution. Wafer samples # 7 and # 8 having a width of 1/2 micron with respect to a 1 micron deep hole (bias) through the dielectric material exposing the aluminum copper metal on its substrate are (a) aluminum copper, then Plating with titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a lithographic pattern of bias using a photoresist material, and (d) patterning using reactive ion etching. Transferred to the dielectric layer and (e) pre-manufactured by removing most of the remaining photoresist by oxygen plasma ashing, while mainly leaving behind inorganic residues. Wafer sample # 9, having a width of 1 micron against a 1 micron deep tapered hole (bias) through the dielectric material exposing the aluminum copper metal on its substrate, is plated with (a) aluminum copper and then titanium nitride. (B) coated with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using photoresist material, and (d) transferring the pattern to the dielectric layer using reactive ion etching And (e) pre-manufactured by removing most of the remaining photoresist by oxygen plasma ashing, while mainly leaving behind inorganic residues. Wafer samples were removed from the solution at 21-45 ° C. for 5-10 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the sample was observed with a scanning electron microscope (SEM) to determine the degree of cleaning and / or corrosion of the aluminum copper metal relief. The results are shown in Tables 17A to 17E.
[Table 19]
[Table 20]
[Table 21]
[Table 22]
[Table 23]
[0103]
According to Tables 17A through 17E, the data was obtained from several different oxygen plasma ashed wafer samples with seven different formulations and no unacceptable aluminum corrosion by varying the pH and concentration of each component. This shows that the residue can be cleaned well.
[0104]
Example 18
  The aqueous solution “H8” was 5.1% by weight tetramethylammonium hydroxide (TMAH), 1.8% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 2.4% by weight (SiO2% Conversion) Tetramethylammonium silicate (TMAS) and 52 wt% dimethyl sulfoxide (DMSO) were added. The balance of this solution is water. Aqueous solution “H9” is 0.58 wt% tetramethylammonium hydroxide (TMAH), 0.20 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.14 wt% nonionic interface Activator Surfynol-465, 0.28 wt% (Si02% Conversion) Prepared by adding tetramethylammonium silicate (TMAS) and 6.0 wt% glycerol. The balance of this solution is water. Aqueous solution “H10” is 0.88 wt% tetramethylammonium hydroxide (TMAH), 0.30 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.20 wt% nonionic interface Activator Surfynol-465, 0.42% by weight (Si02% Conversion) Tetramethylammonium silicate (TMAS) and 9.0 wt% glycerol were added. The balance of this solution is water. Wafer sample # 10, having a width of 1 micron for a 2 micron deep hole (bias) through the dielectric material exposing the photoresist and aluminum copper metal on its substrate, is: (a) aluminum copper, then titanium nitride (B) coated with a silicon oxide dielectric using chemical vapor deposition, (c) a lithographic pattern of bias using a layer of photoresist material about 1 micron thick, and (d) reactive ions. The pattern was transferred to the dielectric layer using etching, and (e) pre-manufactured by removing the solvent by hard baking of the photoresist at high temperature, while leaving behind mainly the organic photoresist layer. Using this sample, the performance of the solution was evaluated as follows. The wafer sample was removed from the solution at 45-65 ° C. for 20-30 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the samples were observed with a scanning electron microscope (SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 18.
[Table 24]
[0105]
According to Table 18, the data demonstrates the ability of the present invention to clean the organic photoresist layer from the semiconductor wafer surface before the sample is oxygen plasma ashed, while preventing or reducing the corrosion of aluminum undulations. Yes.
[0106]
Example 19
The aqueous solution “H11” was 6.2% by weight tetramethylammonium hydroxide (TMAH), 2.1% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 64% by weight glycerol and 2.9%. % By weight (Si02% Conversion) prepared by adding a colloidal silica solution (having a particle size of 20 nm). The balance of this solution is water. The pH of the solution “H11” is about 13.1. (A) plating with aluminum copper alloy, then titanium nitride, (b) taking a lithographic pattern using a photoresist material, (c) transferring the pattern using reactive ion etching, (d) oxygen plasma ashing Wafer samples # 5 and # 6 having 1 micron wide reliefs and wirings formed of aluminum copper and capped with titanium nitride, previously removed by removing organic photoresist residues, while leaving mainly inorganic residues behind Was used. Treatment for each sample was performed at 22-45 ° C. for 5-10 minutes, removed, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, the sample was observed with a scanning electron microscope (SEM) to determine the degree of cleaning and / or corrosion of the aluminum copper metal relief. The results are similar to those obtained for solution “H7” in Example 17, indicating that colloidal silica can be used as a source of silicates free of water-soluble metal ions of the present invention.
[0107]
Example 20
Aqueous solution “L” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465, 0.14% by weight (Si02% Conversion) Tetramethylammonium silicate (TMAS) and 3% by weight glycerol were added. The balance of this solution is water, and this pH is about 12.1. The aqueous solution “Z” was prepared by adding 1.3 wt% tetramethylammonium hydroxide (TMAH), 0.58 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA) The balance is water), and the pH is about 13.0. The aqueous solution “M1” was 1.2 wt% tetramethylammonium hydroxide (TMAH), 0.45 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO2% Conversion) Prepared using tetramethylammonium silicate (TMAS) 18.5% by weight hydroxylamine and 0.07% by weight nonionic surfactant Surfynol-465 (the remainder of the solution is water), the pH is about 12 .1. The aqueous solution “P1” was 2.2% by weight tetramethylammonium hydroxide (TMAH), 0.11% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO2% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 1.6 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 22-65 ° C. for 20 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 19.
[Table 25]
[0108]
According to Table 19, the data show the ability of hydroxylamine or hydrogen peroxide to facilitate the removal of titanium-containing residues at low temperatures.
[0109]
Example 21
The aqueous solution “M2” was 0.67% by weight tetramethylammonium hydroxide (TMAH), 0.46% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO2% Conversion) prepared using tetramethylammonium silicate (TMAS), 1.0 wt% hydroxylamine and 0.07 wt% nonionic surfactant Surfynol-465 (the rest of the solution is water), the pH is about 12.1. The aqueous solution “M3” was 0.94 wt% tetramethylammonium hydroxide (TMAH), 0.45 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.20 wt% (SiO2% Conversion) prepared using tetramethylammonium silicate (TMAS), 5.1 wt% hydroxylamine and 0.1 wt% nonionic surfactant Surfynol-465 (the remainder of the solution is water), and the pH is about 12 .1. The aqueous solution “M4” was 1.1 wt% tetramethylammonium hydroxide (TMAH), 0.46 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.18 wt% (SiO2% Conversion) prepared using tetramethylammonium silicate (TMAS), 10.0 wt% hydroxylamine and 0.09 wt% nonionic surfactant Surfynol-465 (the rest of the solution is water), the pH is about 12.1. The aqueous solution “M5” was 1.3% by weight tetramethylammonium hydroxide (TMAH), 0.42% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO2% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 47.3 wt% hydroxylamine (the remainder of the solution is water), the pH is about 12.1. Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 35 ° C. for 20 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 20.
[Table 26]
[0110]
According to Table 20, the data show the ability of hydroxylamine to facilitate the removal of titanium-containing residues at low temperatures.
[0111]
Example 22
The aqueous solution “M6” was 0.82 wt% tetramethylammonium hydroxide (TMAH), 0.14 wt% (SiO2% Conversion) prepared using tetramethylammonium silicate (TMAS), 18.8 wt% hydroxylamine and 0.07 wt% nonionic surfactant Surfynol-465 (the balance of this solution is water), and this pH is about 12.1. Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 35 ° C. for 20 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 21.
[Table 27]
[0112]
According to Table 21, the data show that good stripping performance is obtained over a range of CyDTA concentrations. Thus, the amount of chelating agent present can be adjusted to accommodate the sample being washed. More difficult samples may require this desired component to achieve complete washing. The data also indicates that chelating agents are optionally used in the compositions disclosed herein.
[0113]
Example 23
The aqueous solution “M7” was 6.0 wt% tetramethylammonium hydroxide (TMAH), 0.35 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 1.2 wt% (SiO2% Conversion) prepared using tetramethylammonium silicate (TMAS), 17.7 wt% hydroxylamine and 0.06 wt% nonionic surfactant Surfynol-465 (the remainder of the solution is water), and the pH is about 13.0. The aqueous solution “M8” was 7.1 wt% tetramethylammonium hydroxide (TMAH), 0.46 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 2.7 wt% (SiO2% Conversion) Prepared using tetramethylammonium silicate (TMAS) and 19.1% by weight hydroxylamine (the remainder of the solution is water), the pH is about 13.0. The aqueous solution “M9” was 8.2 wt% tetramethylammonium hydroxide (TMAH), 0.45 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 4.1 wt% (SiO2% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 19.0 wt% hydroxylamine (the remainder of the solution is water), the pH is 13.0. Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 35 ° C. for 20 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 22.
[Table 28]
[0114]
According to Table 22, the data show the ability of tetramethylammonium silicate to prevent or attenuate corrosion of exposed aluminum on the base of the bias even at very high formulation pH.
[0115]
Example 24
The aqueous solution “M10” was 0.34 wt% tetramethylammonium hydroxide (TMAH), 0.47 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.01 wt% (SiO2% Conversion) prepared using tetramethylammonium silicate (TMAS), 18.6% by weight hydroxylamine and 0.06% by weight nonionic surfactant Surfynol-465 (the remainder of the solution is water), and the pH is about 10.1. Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 20-65 ° C. for 5-30 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 23.
[Table 29]
[0116]
According to Table 23, the data show that high pH, high concentration of tetramethylammonium silicate can be used to inhibit aluminum corrosion. The data also shows that high pH, low working temperature can be used.
[0117]
Example 25
The aqueous solution “P1” was 2.2% by weight tetramethylammonium hydroxide (TMAH), 0.11% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO2% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 1.6 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. The aqueous solution “P2” was 9.7 wt% tetramethylammonium hydroxide (TMAH), 0.11 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO2% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 9.4 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 21-35 ° C. for 20 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 24.
[Table 30]
[0118]
According to Table 24, the data show that a range of hydrogen peroxide concentrations are useful for removing titanium-containing residues in the bias.
[0119]
Example 26
The aqueous solution “P3” was 3.5% by weight tetramethylammonium hydroxide (TMAH), 0.10% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO2% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 1.5 wt% hydrogen peroxide (the remainder of the solution is water), and the pH is about 12.2. The aqueous solution “P4” was 3.9 wt% tetramethylammonium hydroxide (TMAH), 0.096 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.59 wt% (SiO2% Conversion) prepared with tetramethylammonium silicate (TMAS) and 1.4 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 12.2. Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 22 ° C. for 10 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 25.
[Table 31]
[0120]
According to Table 25, the data show that high concentrations of tetramethylammonium silicate can be used to inhibit aluminum corrosion when hydrogen peroxide is present.
[0121]
Example 27
The aqueous solution “P5” was 2.1 wt% tetramethylammonium hydroxide (TMAH), 0.14 wt% (SiO2% Conversion) prepared with tetramethylammonium silicate (TMAS) and 1.5 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. The aqueous solution “P6” was 2.4% by weight tetramethylammonium hydroxide (TMAH), 0.53% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO2% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 1.6 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. The aqueous solution “P7” was 2.9 wt% tetramethylammonium hydroxide (TMAH), 1.4 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO2% Conversion) prepared with tetramethylammonium silicate (TMAS) and 1.5 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 21-23 ° C. for 20 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 26.
[Table 32]
[0122]
According to Table 26, the data indicate that a range of CyDTA concentrations are useful.
[0123]
Example 28
  The aqueous solution “P8” was 0.40 wt% tetramethylammonium hydroxide (TMAH), 0.10 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO2% Conversion) prepared using tetramethylammonium silicate (TMAS) and 19.2 wt% hydrazine (the remainder of the solution is water), the pH is about 12.1. The aqueous solution “P9” was 4.33 wt% tetramethylammonium hydroxide (TMAH), 0.088 wt% trans- (1,2-cyclohexylene dinitrilo) tetraacetic acid (CyDTA), 0.12 wt% (SiO2% Conversion) Prepared using tetramethylammonium silicate (TMAS) and 15.7 wt% formaldehyde (the remainder of the solution is water), the pH is about 12.1. The aqueous solution “P10” was 0.26 wt% tetramethylammonium hydroxide (TMAH), 11.5 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.13 wt% (SiO2% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 16.7 wt% methylamine (the remainder of the solution is water) and the pH is about 12.1. Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 35 ° C. for 20-30 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 27.
[Table 33]
[0124]
According to Table 27, the data show that other small molecules have no effect on titanium residue removal. Like hydroxylamine, hydrazine is a powerful reducing agent. It is not anticipated that hydrazine will be ineffective, and using a silicate-containing formulation, the titanium-containing residue found in wafer sample # 11 can be cleaned from bias, which is unique to hydroxylamine and hydrogen peroxide. It proves that it is a thing.
[0125]
Example 29
  Aqueous solution “L” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Surfactol-465, 0.14% by weight (Si02% Conversion) Tetramethylammonium silicate (TMAS) and 3% by weight glycerol were added. The balance of this solution is water and the pH is about 12.1. The aqueous solution “M1” was 1.2 wt% tetramethylammonium hydroxide (TMAH), 0.45 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO2%) Prepared using tetramethylammonium silicate (TMAS), 18.5 wt% hydroxylamine and 0.07 wt% nonionic surfactant Surfynol-465 (the balance of this solution is water) About 12.1. The aqueous solution “P8” was 0.40 wt% tetramethylammonium hydroxide (TMAH), 0.10 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO2% Conversion) prepared using tetramethylammonium silicate (TMAS) and 19.2 wt% hydrazine (the remainder of the solution is water), the pH is about 12.1. Aqueous solution “S1” was 583 grams deionized water, 7.8 grams tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 8.6 grams tetramethylammonium silicate (TMAS, SiO2As the pH is 12.5. Aqueous solution “S2” was prepared by combining 99.0 grams of solution “S1” with 2.5 grams of β-cyclodextrin (solution pH = 12.1). Aqueous solution “S3” was prepared by combining 99.0 grams of solution “S1” with 2.5 grams of sodium hypophosphite (solution pH = 12.3). Aqueous solution “S4” was prepared by combining 99.0 grams of solution “S1” with 2.5 grams of sodium dithionite (solution pH = 6.7). Aqueous solution “S5” was prepared by combining 99.0 grams of solution “S1” with 2.5 grams of sodium sulfite (solution pH = 12.3). The stock aqueous solution “S5b” is 1,775.2 grams deionized water and 96.0 grams tetramethylammonium hydroxide (TMAH) 25% aqueous solution, 8.8 grams trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid. (CyDTA) and 114.8 grams tetramethylammonium silicate (TMAS, SiO)2As 10.0%). Preservative aqueous solution “S5c” consists of 900 ml deionized water and 300 ml solution “S5”.bIt was prepared by combining. Aqueous solution “S6” was prepared by combining 80.0 grams solution “S5c”, 5.0 grams L-ascorbic acid and 18.2 grams tetramethylammonium hydroxide (TMAH) 25% aqueous solution (solution pH = 12). .3). Aqueous solution “S7” was prepared by combining 80.0 grams of solution “S5c”, 5.0 grams of hydroquinone and 27.1 grams of tetramethylammonium hydroxide (TMAH) 25% aqueous solution (solution pH = 12.4). . Aqueous solution “S8” was prepared by combining 80.0 gram solution “S5c”, 5.0 gram L (+)-cysteine and 29.6 gram tetramethylammonium hydroxide (TMAH) 25% aqueous solution (solution pH). = 12.4). Aqueous solution “S9” was prepared by combining 80.0 grams solution “S5c”, 10.0 grams ammonium persulfate and 32.9 grams tetramethylammonium hydroxide (TMAH) 25% aqueous solution (solution pH = 12.6). ). Aqueous solution “S10” was prepared by combining 80.0 grams of solution “S5c”, 5.0 grams of nitric acid and 10.2 grams of tetramethylammonium hydroxide pentahydrate (TMAH) (solution pH = 12.4). ). Aqueous solution “S11” was prepared by combining 90.0 grams of solution “S5c”, 5.0 grams and 19.2 grams of 25% aqueous solution of tetramethylammonium hydroxide (TMAH) (solution pH = 12.3). Aqueous solution “S12” was 80.0 grams solution “S5c”, 5.0 grams 88% formic acid, 10.0 grams tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 12.7 grams tetramethylammonium hydroxide pentahydrate. (TMAH) was prepared by combining (solution pH = 12.6). Aqueous solution “S13” was prepared by combining 80.0 grams of solution “S5c”, 5.0 grams of sulfuric acid and 17.5 grams of tetramethylammonium hydroxide pentahydrate (TMAH) (solution pH = 12.3). ). Aqueous solution “S14” was prepared by combining 80.0 grams of solution “S5c”, 5.0 grams of phosphoric acid and 20.1 grams of tetramethylammonium hydroxide pentahydrate (TMAH) (solution pH = 12 .3). Aqueous solution “S15” is 80.0 grams solution “S5c”, 6.0 grams oxalic acidtwoPrepared by combining hydrate, 16.0 grams tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 9.3 grams tetramethylammonium hydroxide pentahydrate (TMAH) (solution pH = 12.6). ). Aqueous solution “S16” was prepared by combining 80.0 grams solution “S5c”, 5.0 grams catechol and 16.1 grams tetramethylammonium hydroxide (TMAH) 25% aqueous solution (solution pH = 12.4). . Each solution was placed in a 125 ml polyethylene bottle and placed in an oven set at 45 ° C. with the lid tightly closed and preheated for 1 hour. A 0.025 mm × 13 mm × 50 mm, 99.94% pure titanium foil piece was rinsed with deionized water, acetone, dried, and then weighed on an analytical balance. After preheating for 1 hour, each solution was removed from the oven, and then a piece of titanium foil was placed in a jar, re-capped and returned to the oven. After 24 hours at about 45 ° C., the bottle was removed from the oven. The titanium foil pieces were removed and rinsed with deionized water, then with acetone, dried and weighed on a chemical balance. The relative degree of corrosion was determined from the weight loss. The results are shown in Table 28.
[Table 34]
[0126]
According to Table 28, the data indicate that all of the possible titanium residue removal accelerators tested above (except hydroxyamine) were ineffective at process temperatures as low as 45 ° C. The lack of effectiveness of the hydrazine shown here confirms the FE-SEM results shown in Example 28. The results shown demonstrate that it is peculiar to hydroxylamine to increase the relative titanium etch (removal) rate.
[0127]
Example 30
  The aqueous solution “R1” was 583 grams deionized water, 4.68 grams tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 8.64 grams tetramethylammonium silicate (TMAS, SiO).2As 10.0%) and 0.66 grams trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), which has a pH of 11.3. Aqueous solution “R2” was prepared by combining 99.0 gram solution “R1”, 0.33 gram tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 1.0 gram hydroxylamine 50% aqueous solution (solution pH = 12.0). Aqueous solution “R3” was prepared by combining 99.0 gram solution “R1”, 0.34 gram tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 5.0 gram hydroxylamine 50% aqueous solution (solution pH = 11.9). Aqueous solution “R4” was prepared by combining 99.0 gram solution “R1”, 0.34 gram tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 10.0 gram hydroxylamine 50% aqueous solution (solution pH = 11.6). Aqueous solution “R5” was prepared by combining 99.0 gram solution “R1”, 0.52 gram tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 1.0 gram hydroxylamine 50% aqueous solution (solution pH = 12.2). Aqueous solution “R6” was prepared by combining 99.0 gram solution “R1”, 0.54 gram tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 5.0 gram hydroxylamine 50% aqueous solution (solution pH = 12.0). Aqueous solution “R7” was prepared by combining 99.0 grams of solution “R1”, 0.56 grams of tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 10.2 grams hydroxylamine 50% aqueous solution (solution pH = 11.8). The stock aqueous solution “R8” is 583 grams deionized water, 4.68 grams tetramethylammonium hydroxide (TMAH) 25% aqueous solution and 8.64 grams tetramethylammonium silicate (TMAS, SiO).2As the pH is 12.0. Aqueous solution “R9” was prepared by combining 94.0 grams solution “R8” and 20.0 grams hydroxylamine 50% aqueous solution (solution pH = 11.3). Each solution was placed in a 125 ml polyethylene bottle and placed in an oven set at 45 ° C. with the lid tightly closed and preheated for 1 hour. A 0.025 mm × 13 mm × 50 mm, 99.94% pure titanium foil piece was rinsed with deionized water, acetone, dried, and then weighed on an analytical balance. After preheating for 1 hour, each solution was removed from the oven, and then a piece of titanium foil was placed in a jar, re-capped and returned to the oven. After 24 hours at about 45 ° C., the bottle was removed from the oven. The titanium foil pieces were removed and rinsed with deionized water, then with acetone, dried and weighed on a chemical balance. The relative degree of corrosion was determined from the weight loss. The results are shown in Table 29.
[Table 35]
[0128]
According to Table 29, the data indicate that as the concentration of the titanium residue removal accelerator hydroxylamine increases, the relative titanium foil removal increases. The degree of titanium removal in this test is directly proportional to the effectiveness in cleaning wafer sample # 11.
[0129]
Example 31
The aqueous solution “M1” was 1.2 wt% tetramethylammonium hydroxide (TMAH), 0.45 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO2% Conversion) Prepared using tetramethylammonium silicate (TMAS) 18.5% by weight hydroxylamine and 0.07% by weight nonionic surfactant Surfynol-465 (the remainder of the solution is water), the pH is about 12 .1. The aqueous solution “P1” was 2.2% by weight tetramethylammonium hydroxide (TMAH), 0.11% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO2% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 1.6 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. The commercially available post-etch residue remover used for comparison is EKC-265.TM(Product of EKC Technology, Inc.) and ACT-935TM (product of ACT Inc.). Wafer sample # 11 having a width of 0.3 to 0.5 microns for a 0.5 micron deep hole (bias) through the dielectric layer and titanium nitride layer exposing the aluminum copper metal on its substrate, (A) plating with aluminum copper and then titanium nitride, (b) coating with silicon oxide dielectric using chemical vapor deposition, (c) taking a bias lithographic pattern using a photoresist material, (d) reactivity The pattern was transferred to the dielectric layer using ion etching and (e) the majority of the remaining photoresist was removed by oxygen plasma ashing, while the pre-manufactured (residue Measured by Auger electron microscopic analysis of the transverse cross section). These samples were used to evaluate the performance of the solution. The wafer sample was removed from the solution at 35 ° C. for 20 minutes, rinsed with deionized water, and dried with pressurized nitrogen gas. After drying, a cross section of the sample bias was taken and then observed with a field emission scanning electron microscope (FE-SEM) to determine the degree of undulation cleaning and / or corrosion. The results are shown in Table 30.
[Table 36]
[0130]
According to Table 30, the data show that at a process temperature as low as 35 ° C., the composition of the present invention was effective in removing residues known to contain titanium. This data also shows that the use of the titanium residue removal accelerator hydroxylamine for low temperature cleaning is unique to the compositions of the present invention.
[0131]
Example 32
Aqueous solution “L” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465, 0.14% by weight (Si02% Conversion) Tetramethylammonium silicate (TMAS) and 3% by weight glycerol were added. The balance of this solution is water, and this pH is about 12.1. The aqueous solution “M1” was 1.2 wt% tetramethylammonium hydroxide (TMAH), 0.45 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO2% Conversion) Prepared using tetramethylammonium silicate (TMAS) 18.5% by weight hydroxylamine and 0.07% by weight nonionic surfactant Surfynol-465 (the remainder of the solution is water), the pH is about 12 .1. The aqueous solution “P1” was 2.2% by weight tetramethylammonium hydroxide (TMAH), 0.11% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO2% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 1.6 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. A silicone wafer sample with a cured layer of hydrogen silsesquioxane (HSQ) low-k dielectric was placed in a Fourier transform infrared (FTIR) spectrometer and a reference spectrum was taken. HSQ has Si—H bonds in its structure, which is 2100 cm.-1It is clear that The wafer sample was then processed in one of the above solutions at room temperature (about 22 ° C.) for 10 minutes, rinsed with deionized water and further dried. The sample was then placed in FTIR and a second spectrum was obtained. About 2100cm-1Were used to compare the processed wafer spectra against the reference spectra. For comparison, a commercially available post-etch residue remover, EKC-265TM(Product of EKC Technology, Inc.) was similarly tested (10 minutes) at the manufacturer's recommended temperature of 65 ° C. The results are shown in Table 31.
[Table 37]
[0132]
According to Table 31, the data show that the compositions of the present invention are unique in that they are compatible with photosensitive low-k dielectric materials such as HSQ.
[0133]
Example 33
  Aqueous solution “A” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465 (product of Air Products and Chemicals, Inc.) and 0.14% by weight (SiO2% Conversion) tetramethylammonium silicate (TMAS) is added (the rest of the solution is water) and the pH is about 12.2. Aqueous solution “L” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465, 0.14% by weight (Si02% Conversion) Tetramethylammonium silicate (TMAS) and 3% by weight glycerol were added. The balance of this solution is water, and this pH is about 12.1. The aqueous solution “M1” was 1.2 wt% tetramethylammonium hydroxide (TMAH), 0.45 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO2% Conversion) Prepared using tetramethylammonium silicate (TMAS) 18.5% by weight hydroxylamine and 0.07% by weight nonionic surfactant Surfynol-465 (the remainder of the solution is water), the pH is about 12 .1. The aqueous solution “P1” was 2.2% by weight tetramethylammonium hydroxide (TMAH), 0.11% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO2% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 1.6 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. Storage aqueous solution “T1” is 1.6 wt% tetramethylammonium hydroxide (TMAH), 0.41 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.27 wt% nonionic Surfactant Surfynol-465, 0.56% by weight (Si02% Conversion) Tetramethylammonium silicate (TMAS) and 12 wt% glycerol were added. The balance of the solution is water, and the pH is about 12.5. Aqueous solution “T2” was prepared by diluting 25 ml solution “T1” with 70 ml deionized water and 5 ml glycerol. Aqueous solution “T3” was prepared by diluting 25 ml solution “T1” with 65 ml deionized water and 10 ml glycerol. Aqueous solution “T4” was prepared by diluting 25 ml solution “T1” with 60 ml deionized water and 15 ml glycerol. Aqueous solution “T5” was prepared by diluting 25 ml solution “T1” with 55 ml deionized water and 20 ml glycerol. Aqueous solution “T6” was prepared by diluting 25 ml solution “T1” with 50 ml deionized water and 25 ml glycerol. Aqueous solution “T7” was prepared by diluting 25 ml solution “T1” with 25 ml deionized water and 50 ml glycerol. Aqueous solution “T8” was prepared by diluting 25 ml solution “T1” with 75 ml glycerol. Aqueous solution “T9” was prepared by diluting 25 ml solution “T1” with 70 ml deionized water and 5 ml 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP). Aqueous solution “T10” was prepared by diluting 25 ml solution “T1” with 65 ml deionized water and 10 ml 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP). Aqueous solution “T11” was prepared by diluting 25 ml solution “T1” with 60 ml deionized water and 15 ml 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP). Aqueous solution “T12” was prepared by diluting 25 ml solution “T1” with 55 ml deionized water and 20 ml 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP). Aqueous solution “T13” was prepared by diluting 25 ml solution “T1” with 50 ml deionized water and 25 ml 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP). Aqueous solution “T14” was prepared by diluting 25 ml solution “T1” with 25 ml deionized water and 50 ml 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP). Aqueous solution “T15” was prepared by diluting 25 ml solution “T1” with 75 ml 1- (2-hydroxyethyl) -2-pyrrolidinone (HEP). Each solution was placed in a 125 ml polyethylene bottle, tightly capped and placed in an oven set at 45 ° C, 65 ° C or 85 ° C and preheated for 1 hour or held at room temperature (about 22 ° C). A piece of 0.025 mm × 13 mm × 50 mm pure copper foil was immersed in dilute hydrochloric acid, rinsed with deionized water and acetone, dried, and then weighed on an analytical balance. After preheating for 1 hour, each solution was removed from the oven (if heated), and then a piece of copper foil was placed in a jar and again capped and returned to the oven. After 24 hours at about 22-85 ° C., the bottle was removed from the oven. A piece of copper foil was removed, rinsed with deionized water, then with acetone, dried and weighed on a chemical balance. The degree of corrosion was determined from the weight loss. For comparison, a commercially available post-etch residue remover, EKC-265TM(Product of EKC Technology, Inc.), EKC-270TM(Product of EKC Technology, Inc.), EKC-311TM(Product of EKC Technology, Inc.), ACT-935TM (product of ACT Inc.), ACT NP-937TM(ACT Inc. product) and ACT-941TM (ACT Inc. product) were similarly tested at the manufacturer's recommended temperature of 65 ° C. The results are shown in Table 32.
[Table 38]
[0134]
According to Table 32, the data show that several compositions of the present invention are compatible with copper. The data also shows that the composition M1 of the present invention is superior to a commercially available hydroxylamine-containing post-etch residue remover formulation for use with copper plating. Furthermore, the data show that the addition of the titanium residue removal accelerator hydrogen peroxide reduces the copper corrosion rate.
[0135]
Example 34
Aqueous solution “L” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465, 0.14% by weight (Si02% Conversion) Tetramethylammonium silicate (TMAS) and 3% by weight glycerol were added. The balance of this solution is water, and this pH is about 12.1. In a clean room, the total particles found on a 3 inch silicone wafer with 650 angstroms of thermal oxide were measured using a wafer particle counter (size of 0.1 to 10 microns). The wafer was then chemically mechanically polished (CMP) with an alumina-based polishing slurry and rinsed with deionized water. The wafer was then “brush cleaned” using solution “L” at room temperature (about 22 ° C.), then rinsed with deionized water and spin-dried. The total particle (0.1 to 10 micron size) present on the wafer surface after cleaning was then measured using a wafer particle counter. For comparison, a second wafer using deionized water as a “brush cleaner” after CMP was tested. The results are shown in Table 33.
[Table 39]
[0136]
According to Table 33, the data show that the compositions of the present invention are unique because they remove particulate contaminants that occur after chemical mechanical polishing.
[0137]
Example 35
Aqueous solution “L” is 0.3 wt% tetramethylammonium hydroxide (TMAH), 0.1 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.07 wt% nonionic interface Activator Surfynol-465, 0.14% by weight (Si02% Conversion) Tetramethylammonium silicate (TMAS) and 3% by weight glycerol were added. The balance of this solution is water, and this pH is about 12.1. The aqueous solution “M1” was 1.2 wt% tetramethylammonium hydroxide (TMAH), 0.45 wt% trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14 wt% (SiO2% Conversion) prepared using tetramethylammonium silicate (TMAS), 18.5 wt% hydroxylamine and 0.07 wt% nonionic surfactant Surfynol-465 (the remainder of the solution is water), and the pH is about 12.1. The aqueous solution “P1” was 2.2% by weight tetramethylammonium hydroxide (TMAH), 0.11% by weight trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid (CyDTA), 0.14% by weight (SiO2% Conversion) Prepared with tetramethylammonium silicate (TMAS) and 1.6 wt% hydrogen peroxide (the remainder of the solution is water), the pH is about 11.5. Sections from the same Si (100) wafer with about 650 nm thermal oxide were rinsed with acetone, dried, and further measured with a Rudolph FTM interferometer to determine the thermal oxide thickness. Four ranges were measured and mapped for follow-up measurements after processing. Each sample was then placed in a jar and again loosely capped and placed in an oven pre-set at 45 ° C. or left at room temperature (about 22 ° C.). After 24 hours at about 22 ° C. or about 45 ° C., the bottle was removed from the oven and the sample was removed, washed with water, then rinsed with acetone, dried and measured with an interferometer. The relative etch rate was determined from the difference in the thickness of the thermal oxide film averaged over the four areas on the sample. For comparison, a commercially available post-etch residue remover, EKC-265TM(Product of EKC Technology, Inc.), EKC-270TM(Product of EKC Technology, Inc.), EKC-311TM(Product of EKC Technology, Inc.), ACT-935TM(Product of ACT Inc.), ACT NP-937TM(A product of ACT Inc.) and ACT-941TM(ACT Inc. product) was similarly tested at the manufacturer's recommended temperature of 65 ° C. The results are shown in Table 34.
[Table 40]
* 18 hours test at 65 ℃
[0138]
According to Table 34, the data show that the compositions of the present invention are unique in that they clean unwanted residues from the wafer substrate without undesirable etching of the dielectric layer. These results are consistent with the results shown in Example # 15 for silicate-containing compositions.
[0139]
The examples show 10 surprising and unexpected results related to the present invention. First, it is possible to clean undesirable residues from the wafer surface while preventing undesirable metal corrosion at low working temperatures and short working times. Second, the use of silicate as a buffer, high dilution rate, and unexpectedly high bath stability of the high pH composition (pKa = 11.8). Third, the silicate added to the highly alkaline cleaning agent inhibits undesirable dissolution of the silicon oxide dielectric material present in the integrated circuit. Fourth, because the composition is very aqueous (typically> 80% water), no intermediate rinsing step is required prior to water washing to prevent post-wash corrosion. Fifth, due to the high moisture content of these compositions, the hygiene, safety, and environmental health associated with use and handling compared to typical organic photoresist strippers and post-plasma ash residue removers. The risk of Sixth, the composition of the present invention has been shown to have substantially no carbon residue contamination on the substrate surface after processing compared to a typical post-organic ash residue remover. . Seventh, it has been found that the compositions of the present invention are compatible with photosensitive low-k dielectric materials used in integrated circuits. Eighth, it is possible to remove difficult-to-handle titanium-containing residues at low temperatures. Ninth, it has been found that the composition of the present invention is compatible with copper metal. Tenth, it has been found that the compositions of the present invention are also effective in removing silica and alumina chemical mechanical polishing (CMP) slurry residues from wafer substrates. Silicates are known aluminum corrosion inhibitors, but their ability to inhibit aluminum corrosion and to selectively remove high aluminum and / or titanium content metal-containing photoresist residues is surprising. Yes and unexpected. Silicate buffering during processing, negligible carbon contamination on substrate surface, low dielectric etch, compatibility with photosensitive low-k dielectric materials, compatibility with copper metal, low-handling titanium-containing residues at low temperatures The ability to be removed, the ability to clean silica and alumina chemical mechanical polishing (CMP) slurry residues and the ability to effectively use such high water concentrations were also surprising and unexpected aspects of the present invention.
[0140]
Obviously, many modifications and variations of the present invention are possible in light of the above teachings. Accordingly, it is to be understood that the invention may be practiced otherwise than as specifically described within the scope of the appended claims.

Claims (26)

  1. A composition for stripping or cleaning an integrated circuit substrate containing a titanium residue, comprising :
    (A) one or more metal ion free bases selected from the group consisting of quaternary ammonium hydroxide, ammonium hydroxide and organic amines in an amount sufficient to provide a pH 11 or higher solution;
    (B) a water-soluble metal ion-free silicate selected from the group consisting of 0.01 wt% to 5 wt% ammonium silicate and quaternary ammonium silicate;
    (C) (1) 0.01% to 10% by weight of (ethylenedinitrilo) tetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N, N, N 1, selected from the group consisting of ', N'-tetraacetic acid, N, N, N', N'-ethylenediaminetetra (methylene phosphoric acid), and (1,2-cyclohexylenedinitrilo) -tetraacetic acid or One or more chelating agents, or (2) one or more titanium residue removal accelerators selected from the group consisting of 1 wt% to 50 wt% hydroxylamine, hydroxylamine salt, peroxide, ozone and fluoride At least one component comprising either or both of
    (D) A composition comprising water.
  2.   The composition of claim 1, wherein the metal ion free base is present in an amount sufficient to provide a pH of 11-13.
  3.   The composition of claim 1 further comprising one or more water-soluble auxiliary organic solvents.
  4.   The composition according to claim 3, wherein the concentration of the water-soluble auxiliary organic solvent is 0.1 wt% to 80 wt%.
  5.   5. The composition of claim 4, wherein the water soluble auxiliary organic solvent is selected from the group consisting of 1-hydroxyalkyl-2-pyrrolidinone, alcohols and polyhydroxy compounds.
  6.   The composition of claim 1, further comprising one or more water-soluble surfactants.
  7.   The composition according to claim 6, wherein the concentration of the water-soluble surfactant is 0.01% by weight to 1% by weight.
  8.   The composition of claim 1, wherein the base is selected from the group consisting of choline, tetrabutylammonium hydroxide, tetramethylammonium hydroxide, methyltriethanolammonium hydroxide, and methyltriethylammonium hydroxide.
  9.   The composition according to claim 1, wherein the water-soluble metal ion-free silicate is tetramethylammonium silicate.
  10.   The composition according to claim 1, comprising from 0.1 to 3% by weight of tetramethylammonium hydroxide and from 0.01 to 1% by weight of tetramethylammonium silicate.
  11.   The composition according to claim 10, further comprising 0.01 to 1% by weight of trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid.
  12. A method for cleaning a semiconductor wafer substrate containing a titanium residue ,
    A semiconductor wafer substrate at a time and temperature sufficient to clean undesired contaminants and residues from the substrate surface;
    (A) one or more metal ion free bases selected from the group consisting of quaternary ammonium hydroxide, ammonium hydroxide and organic amines in an amount sufficient to provide a pH 11 or higher solution;
    (B) a water-soluble metal ion-free silicate selected from the group consisting of 0.01 wt% to 5 wt% ammonium silicate and quaternary ammonium silicate;
    (C) (1) 0.01% to 10% by weight of (ethylenedinitrilo) tetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N, N, N 1, selected from the group consisting of ', N'-tetraacetic acid, N, N, N', N'-ethylenediaminetetra (methylene phosphoric acid), and (1,2-cyclohexylenedinitrilo) -tetraacetic acid or One or more chelating agents, or (2) one or more titanium residue removal accelerators selected from the group consisting of 1 wt% to 50 wt% hydroxylamine, hydroxylamine salt, peroxide, ozone and fluoride At least one component comprising either or both of
    (D) A method comprising contacting with a composition comprising water.
  13.   The method of claim 12, wherein the semiconductor wafer substrate is contacted with the composition for 1 to 30 minutes.
  14.   The method of claim 12, wherein the semiconductor wafer substrate is contacted with the composition at a temperature of 10 ° C. to 85 ° C.
  15.   The method of claim 12, further comprising rinsing and drying steps.
  16.   13. The method of claim 12, wherein the composition contains metal ion free base in an amount sufficient to bring the pH to 11-13.
  17.   13. The method of claim 12, further comprising one or more water-soluble auxiliary organic solvents in the composition.
  18.   The process according to claim 17, wherein the concentration of the water-soluble auxiliary organic solvent is from 0.1% to 80% by weight.
  19.   18. The method of claim 17, wherein the water soluble auxiliary organic solvent is selected from the group consisting of 1-hydroxyalkyl-2-pyrrolidinone, alcohols and polyhydroxy compounds.
  20.   13. The method of claim 12, further comprising one or more water soluble surfactants in the composition.
  21.   The method according to claim 20, wherein the concentration of the water-soluble surfactant is 0.01% by weight to 1% by weight.
  22.   13. The method of claim 12, wherein the base in the composition is selected from the group consisting of choline, tetrabutylammonium hydroxide, tetramethylammonium hydroxide, methyltriethanolammonium hydroxide, and methyltriethylammonium hydroxide.
  23.   The method according to claim 12, wherein the water-soluble metal ion-free silicate in the composition is tetramethylammonium silicate.
  24.   The process according to claim 12, wherein the composition comprises 0.1 to 3 wt% tetramethylammonium hydroxide and 0.01 to 1 wt% tetramethylammonium silicate.
  25.   25. The method of claim 24, wherein the composition further comprises 0.01 to 1% by weight of trans- (1,2-cyclohexylenedinitrilo) tetraacetic acid.
  26. (A) one or more metal ion free bases selected from the group consisting of quaternary ammonium hydroxide, ammonium hydroxide and organic amines in an amount sufficient to provide a pH 11 or higher solution;
    (B) a water-soluble metal ion-free silicate selected from the group consisting of 0.01 wt% to 5 wt% ammonium silicate and quaternary ammonium silicate;
    (C) (1) 0.01% to 10% by weight of (ethylenedinitrilo) tetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-hydroxypropane-N, N, N 1, selected from the group consisting of ', N'-tetraacetic acid, N, N, N', N'-ethylenediaminetetra (methylene phosphoric acid), and (1,2-cyclohexylenedinitrilo) -tetraacetic acid or One or more chelating agents, or (2) one or more titanium residue removal accelerators selected from the group consisting of 1 wt% to 50 wt% hydroxylamine, hydroxylamine salt, peroxide, ozone and fluoride At least one component comprising either or both of
    (D) A composition for stripping or cleaning an integrated circuit substrate containing a titanium residue formed by mixing water.
JP2000550003A 1998-05-18 1999-05-17 Silicate-containing alkaline composition for microelectronic substrate cleaning Expired - Fee Related JP4565741B2 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US8568198P true 1998-05-18 1998-05-18
US11508499P true 1999-01-07 1999-01-07
US60/085,681 1999-01-07
US60/115,084 1999-01-07
PCT/US1999/010875 WO1999060448A1 (en) 1998-05-18 1999-05-17 Silicate-containing alkaline compositions for cleaning microelectronic substrates

Publications (2)

Publication Number Publication Date
JP2003526111A JP2003526111A (en) 2003-09-02
JP4565741B2 true JP4565741B2 (en) 2010-10-20

Family

ID=43127099

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2000550003A Expired - Fee Related JP4565741B2 (en) 1998-05-18 1999-05-17 Silicate-containing alkaline composition for microelectronic substrate cleaning

Country Status (1)

Country Link
JP (1) JP4565741B2 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4572466B2 (en) * 2000-12-27 2010-11-04 東ソー株式会社 Resist stripper
MY139607A (en) * 2001-07-09 2009-10-30 Avantor Performance Mat Inc Ammonia-free alkaline microelectronic cleaning compositions with improved substrate compatibility
US7435712B2 (en) * 2004-02-12 2008-10-14 Air Liquide America, L.P. Alkaline chemistry for post-CMP cleaning
MY145938A (en) * 2007-02-14 2012-05-31 Avantor Performance Mat Inc Peroxide activated oxometalate based formulations for removal of etch residue
JP2012255909A (en) * 2011-06-09 2012-12-27 Tosoh Corp Resist stripping agent and stripping method using the same

Also Published As

Publication number Publication date
JP2003526111A (en) 2003-09-02

Similar Documents

Publication Publication Date Title
EP1024965B1 (en) Process for removing residues from a semiconductor substrate
US7402552B2 (en) Non-corrosive cleaning composition for removing plasma etching residues
US6191086B1 (en) Cleaning composition and method for removing residues
US6831048B2 (en) Detergent composition
EP1035446B1 (en) Resist stripping composition and process for stripping resist
US6943142B2 (en) Aqueous stripping and cleaning composition
TWI622639B (en) Metal and dielectric compatible sacrificial anti-reflective coating cleaning and removal composition
EP0886547B1 (en) Cleaning wafer substrates of metal contamination while maintaining wafer smoothness
US8361237B2 (en) Wet clean compositions for CoWP and porous dielectrics
US6916772B2 (en) Sulfoxide pyrolid(in)one alkanolamine cleaner composition
US6825156B2 (en) Semiconductor process residue removal composition and process
US20020037819A1 (en) Stripping composition
US20090099051A1 (en) Aqueous fluoride compositions for cleaning semiconductor devices
DE60128501T2 (en) Composition for removing photoresist
US7888301B2 (en) Resist, barc and gap fill material stripping chemical and method
JP5237300B2 (en) Liquid cleaning agent to remove residues after etching
ES2293340T3 (en) Decapant and cleaning compositions for microelectronica.
US9217929B2 (en) Composition for removing photoresist and/or etching residue from a substrate and use thereof
US9063431B2 (en) Aqueous cleaner for the removal of post-etch residues
EP1091254A2 (en) Resist stripping composition
US7144848B2 (en) Cleaning compositions containing hydroxylamine derivatives and processes using same for residue removal
KR101031926B1 (en) Microelectronic cleaning compositions containing ammonia-free fluoride salts
US6514352B2 (en) Cleaning method using an oxidizing agent, chelating agent and fluorine compound
CN1193410C (en) Cleaning solution for removing residue
US20060003910A1 (en) Composition and method comprising same for removing residue from a substrate

Legal Events

Date Code Title Description
A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20060516

A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20060516

A711 Notification of change in applicant

Free format text: JAPANESE INTERMEDIATE CODE: A711

Effective date: 20080226

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A821

Effective date: 20080226

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20090526

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20090811

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20100119

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20100415

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20100727

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20100803

R150 Certificate of patent or registration of utility model

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20130813

Year of fee payment: 3

S533 Written request for registration of change of name

Free format text: JAPANESE INTERMEDIATE CODE: R313533

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20130813

Year of fee payment: 3

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

LAPS Cancellation because of no payment of annual fees