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WO2001054180A1 - Procede et detergent pour le nettoyage de substrat d'un dispositif semi-conducteur comportant en surface un metal de transition ou un compose de metal de transition - Google Patents

Procede et detergent pour le nettoyage de substrat d'un dispositif semi-conducteur comportant en surface un metal de transition ou un compose de metal de transition Download PDF

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Publication number
WO2001054180A1
WO2001054180A1 PCT/JP2001/000426 JP0100426W WO0154180A1 WO 2001054180 A1 WO2001054180 A1 WO 2001054180A1 JP 0100426 W JP0100426 W JP 0100426W WO 0154180 A1 WO0154180 A1 WO 0154180A1
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WIPO (PCT)
Prior art keywords
transition metal
cleaning
solution
semiconductor device
substrate
Prior art date
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PCT/JP2001/000426
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English (en)
Japanese (ja)
Inventor
Hitoshi Morinaga
Yasuhiro Oomura
Yasuhiro Kawase
Atsushi Itou
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to AU2001228803A priority Critical patent/AU2001228803A1/en
Publication of WO2001054180A1 publication Critical patent/WO2001054180A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • H10P70/273—
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • H10P50/667—
    • H10P70/15—
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

Definitions

  • the present invention relates to a cleaning solution and a cleaning method for a semiconductor device substrate having a transition metal or a transition metal compound, particularly tungsten or copper, on the surface.
  • the surface of the substrate used in the device is required to be further cleaned.
  • contamination on the substrate surface in particular, metal contamination and particle contamination are required to remove metal and particles as much as possible in order to reduce the electrical characteristics and yield of the device.
  • the substrate surface is cleaned with a cleaning liquid to remove metals and particles from the substrate surface.
  • RCA cleaning a cleaning process using a cleaning solution in which an acidic or alkaline solution and hydrogen peroxide are mixed (hereinafter referred to as “RCA cleaning”. (For example, RCA Review (1970.6), p. .207-233)).
  • cleaning is performed by selecting a cleaning solution that matches the contaminants on the substrate surface. For example, if the substrate surface is contaminated by particles or organic matter, “SC-1” or “ Cleaning is performed using a cleaning solution called ammonia, hydrogen peroxide and water, which is called “APM”. The contamination by metal on the substrate surface is cleaned with a cleaning solution called “SC-2” or “HPM” consisting of hydrochloric acid, hydrogen peroxide and water. For contamination of photoresist and resist residue on the substrate surface, cleaning with a cleaning solution called “SPM” consisting of sulfuric acid and hydrogen peroxide is performed.
  • SC-1 cleaning solution called ammonia, hydrogen peroxide and water
  • APM ammonia, hydrogen peroxide and water
  • SPM cleaning solution consisting of hydrochloric acid, hydrogen peroxide and water.
  • SPM sulfuric acid and hydrogen peroxide
  • the cleaning solution containing hydrogen peroxide was used for cleaning after forming the gate electrode on the substrate. Cleaning (RCA cleaning) is applicable.
  • the gate electrode material was a metal such as stainless steel, it was found that the RCA cleaning would corrode the electrode material. As a result of the analysis, it was found that this was due to the fact that hydrogen peroxide in the cleaning solution used for the RCA cleaning dissolves the ionized tungsten.
  • metal electrodes such as tungsten are newly introduced as gate electrode materials for semiconductor devices, and copper and tungsten are newly introduced as wiring materials for semiconductor devices. It has begun.
  • the present invention has been made in order to solve the above-mentioned problem, and is intended for cleaning a substrate having a transition metal or a transition metal compound such as tungsten or copper partially or entirely on its surface.
  • the purpose is to provide a cleaning solution and a cleaning method that simultaneously satisfy the three requirements.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be satisfied by using a specific solution containing a specific surfactant as a cleaning solution. Reached.
  • the gist of the present invention is a cleaning liquid for a substrate for a semiconductor device having a transition metal or a transition metal compound on a surface, the cleaning liquid being selected from the group consisting of the following (A 1), (A 2) and (A 3) Cleaning liquid for a semiconductor device substrate having a transition metal or a transition metal compound on the surface characterized by comprising a solution to be washed, and a semiconductor device having a transition metal or a transition metal compound on the surface characterized by using the cleaning liquid
  • the present invention resides in a method of cleaning a chair substrate.
  • (A 1) - S 0 3 - surfactant having a group (excluding sulfosuccinate diester Le compounds) comprises, p H is 3 or less solution,
  • the cleaning solution of the present invention comprises at least one solution selected from the group consisting of the following (Al), (A2) and (A3).
  • (A 1) - S 0 3 - surfactant having a group comprises, pH is 3 or less solution,
  • (A3) -OS 0 3 - comprises a surfactant comprising a surfactant and / or sulfosuccinic acid di ester compound having a group, solution p H is 4 or more.
  • (A 1) - S 0 3 - surfactant having a group (excluding sulfosuccinic acid diester compound), with the solution pH is 3 or less to more describes details.
  • alkylsulfonic acid compound examples include a compound represented by the following formula (1).
  • R represents an alkyl group, preferably an alkyl group having 8 to 20 carbon atoms
  • X represents hydrogen, a cation atom or a cation atom group.
  • alkyl sulfonic acids e.g., C 8 H 17 S0 3 H and its salts, C 9 H ⁇ 9 S ⁇ 3 H and its salts, C i oH 2 ⁇ S 0 3 H and its salts, C HzgSOgH and its salts , C i 2 H 25 S 0 3 H and salts thereof, C 13 H 27 S0 3 H and salts thereof, C 14 H 29 S0 3 H and salts thereof, C 15 H 31 S0 3 H and its salts, C 16 H 33 S 0 3 H and its salts, C ⁇ 7 H 35 S 0 3 H and its salts, salts of C 1 8 H 37 S 0 3 H and its like.
  • Alkylbenzenesulfonic acid-based compounds include compounds represented by the following formula (2). Things.
  • R represents an alkyl group, preferably an alkyl group having 8 to 20 carbon atoms
  • X represents hydrogen, a cation atom or a cation atom group
  • ph represents a phenylene group.
  • alkylbenzenesulfonic acids examples include dodecylbenzenesulfonic acid and salts thereof.
  • Examples of the alkyl group constituting the alkylnaphthylene sulfonic acid include a compound represented by the following formula (3).
  • II 1 and R 2 each represent an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms
  • X represents hydrogen, a cation atom or a cation atom group
  • m and n each represent 0 to 4 Where l ⁇ m + n ⁇ 7, preferably l ⁇ m + n ⁇ 4.
  • alkylnaphthylene sulfonic acids examples include dimethylnaphthalenesulfonic acid and salts thereof.
  • Examples of the methyltauric acid-based compound include a compound represented by the following formula (4) .o
  • R represents a hydrocarbon group, preferably, C n H 2 n + have C n H 2 n - have C n H 2 n _ 3 or C n H 2n - 5 saturated or unsaturated hydrocarbon group of
  • X represents hydrogen, a cation atom or a cation atom group
  • n represents an integer of usually 8 to 20, preferably 13 to 17. If n, which is the number of carbon atoms of the hydrocarbon group, is too small, attached particles are removed. Ability tends to decrease.
  • the methyl evening Urin acid compounds for example, C i ⁇ H 23 C ON (CH 3) CH 2 CH 2 S_ ⁇ 3 H and salts thereof, C! A H 2 7 C ON (CH 3) CH 2 CH 2 S0 3 H and salts thereof, C 15 H 31 CON (CH 3) CH 2 CH 2 S ⁇ 3 H and salts thereof, C! 7 H 35 C ON (CH 3) CH 2 CH 2 S 0 3 H and its salts , C ⁇ 7 H 33 C ON (CH 3 ) CH 2 CH 2 S0 3 H and salts thereof, C 17 H 31 CON (CH 3) CH 2 CH 2 S0 3 H and salts thereof, C 17 H 29 CON (CH 3 ) CH 2 CH 2 SO 3 H and its salts.
  • alkyl diphenyl ether disulfonic acid compound examples include a compound represented by the following formula (5).
  • R represents an alkyl group, preferably an alkyl group having 8 to 20 carbon atoms
  • X represents hydrogen, a cation atom or a cation atom group
  • ph represents a phenylene group.
  • alkyl diphenyl ether disulfonic acids examples include nonyl diphenyl diterdisulfonic acid and salts thereof, dodecyl diphenyl diterdisulfonic acid and salts thereof, and the like.
  • hypoolefin sulfonic acid-based compound examples include a mixture of a compound represented by the following formula (6) and a compound represented by the following formula (7).
  • R represents an alkyl group, preferably an alkyl group having 4 to 20 carbon atoms
  • X represents hydrogen, a cation atom or a cation atom group
  • m represents an integer of 1 to 10
  • n represents an integer.
  • naphthylene sulfonic acid condensate examples include? -Naphthylene sulfonic acid formalin condensate and salts thereof.
  • a methyltauric acid-based compound, an alkylbenzene sulfonic acid-based compound, and an alkyl diphenyl ether disulfonic acid-based compound are preferably used because of their excellent property of removing particle contamination.
  • alkylbenzenesulfonic acid-based compounds and alkyldiphenyletherdisulfonic acid-based compounds Is particularly preferably used.
  • a methyltauric acid-based compound is preferably used in that it has the same high particle removal properties as when the pH is neutral and has little foaming.
  • diesters of sulfosuccinic acid compounds are represented by the following formula (8), - S 0 3 - is a surfactant having a group, the acidic solution, removed for cleaning ability decreases with time ing. This is presumed to be because sulfosuccinic acid diesters have one —S 0 3 group but have an ester structure, which causes decomposition in acidic solutions.
  • R is an alkyl group optionally substituted with a fluorine atom, preferably an alkyl group having 4 to 20 carbon atoms optionally substituted with a fluorine atom
  • X is hydrogen, a cation atom or a cation. Indicates an atomic group.
  • p H is 3 or less, preferably p H 2 or less, further preferred properly the p H l. 5 or less, particularly preferably pH is 1.0 or less. If the pH is too high, the ability to remove metal contamination will decrease. In the case of alkyl benzene sulfonic acids and alkyl diphenyl ether disulfonic acids, particle removal performance is also high. It is not preferable because it lowers.
  • an acid such as hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, citric acid, or oxalic acid may be added to the solution. These acids may be used alone or as a mixture of two or more.
  • concentration of the acid in the washing solution is usually from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight.
  • a free acid type surfactant is used as the surfactant, the pH of the solution tends to decrease even without adding an acid.
  • Surfactants having a group (excluding sulfosuccinic acid diesters) in a solution containing a concentration of surfactant, relative to the solution, usually 0 0 0 1-1 wt%, preferably Is from 0.002 to 0.5% by weight. If the addition amount of the surfactant is too small, the removal performance of the particle contamination is not sufficient, and even if the surfactant is added beyond this range, there is no change in the removal performance of the particle contamination, the foaming becomes remarkable, and the waste liquid is generated. It is not preferable because the impossibility of decomposition processing increases.
  • (A 2) a solution containing a surfactant comprising a methyltauric acid-based compound will be described in detail.
  • methyltauric acid-based compound examples include a compound represented by the following formula (9). RCON (CH 3 ) CH 2 CH 2 S 0 3 X
  • R optionally substituted hydrocarbon group with a fluorine atom preferably may be substituted with full Tsu atom, C N H 2 n + i , C N H 2 N - have C n H 2 n _ 3 or C n H 2 n -. 5 saturated or unsaturated hydrocarbon group of, X is a hydrogen, a cation atom or a cation atomic group n is typically 8-2 0, preferably 1 3 If the carbon number n of the hydrocarbon group is too small, the ability to remove adhered particles tends to decrease.)
  • the methyl taurine acid compounds for example, CHHZ JJ C ON (CH 3 ) CH 2 CH 2 S 03 H and salts thereof, C 1 3 H 2 7 C ON (CH 3) CH 2 CH 2 S 0 3 H and a salt thereof, C 1 5 H 3 1 CON (CH 3) CH 2 CH 2 S 0 3 H and salts thereof, C 1 Y H 3 5 CON (CH 3) CH 2 CH 2 S 0 3 H and its salts, C 1 7 H 3 3 CON (CH 3 ) CH 2 CH 2 S ⁇ 3 H and its salt, C 17 H 3 1 C ON (CH 3 ) CH 2 CH 2 S 0 3 H and its salt, C 17 H such as 2 9 CON (CH 3) CH 2 CH 2 S 0 3 H ⁇ beauty salts thereof.
  • a solution containing a surfactant consisting of a methyltauric acid-based compound is characterized in that there is no corrosion of electrodes and wiring, particle contamination removal performance, and little bubbling. If there is a lot of bubbles, there will be problems such as bubbles adhering to the substrate, causing an uneven surface reaction, and backflow in the piping when draining the cleaning solution.)
  • the concentration of the surfactant is usually 0.001 to 1% by weight, preferably 0.002 to 0.5% by weight, based on the solution. . If the amount of the methyltauric acid is too small, the particulate contamination removal performance is not sufficient, and if the amount is more than this range, foaming becomes remarkable, which is not preferable.
  • the pH of the solution containing methyltauric acids is usually 0.1 to 13, preferably 0.5 to 11.5.
  • An acid or alkali may be added to the solution to adjust the pH.
  • Acids include hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, citric acid, oxalic acid, and alkalis such as ammonia and quaternary ammonium hydroxide (tetramethylammonium). Monoxide, etc.) and amines (ethylenediamine, triethanolamine, etc.).
  • "(A3) - OS0 3 - comprises a surfactant comprising a surfactant and / or Suruhoko Haq acid diester compound having a group, p H is dissolved solution at 4 or more" to Shoki about.
  • alkyl sulfate compound examples include a compound represented by the following formula (10).
  • R represents an alkyl group, preferably an alkyl group having 8 to 20 carbon atoms
  • X represents hydrogen, a cation atom or a cation atom group.
  • alkyl sulfate-based compound examples include dodecyl sulfate and salts thereof.
  • alkyl ether sulfate compound examples include a compound represented by the following formula (11).
  • R is an alkyl group, preferably an alkyl group having 8 to 20 carbon atoms
  • X is hydrogen, a cation atom or a cation atom group
  • n is the number of moles of ethylene oxide added, usually 1 to 10, preferably 2 Shows an integer of ⁇ 4.
  • alkyl ether sulfates examples include tetraoxyethylene propyl ether sulfate and salts thereof.
  • alkyl phenyl ether sulfate compound examples include a compound represented by the following formula (12), a sulfated oil, a sulfated fatty acid ester compound, and a sulfated oil. Compounds.
  • R is an alkyl group, preferably an alkyl group having 8 to 20 carbon atoms
  • X is hydrogen, a cation atom or a cation atom group
  • n is the number of moles of ethylene oxide added, usually 1 to 10, preferably 2 Represents an integer of up to 4.
  • ph represents a phenylene group.
  • Examples of the sulfosuccinic acid diester compound include a compound represented by the following formula (8).
  • R is an alkyl group optionally substituted with a fluorine atom, preferably an alkyl group having 4 to 20 carbon atoms optionally substituted with a fluorine atom
  • X is hydrogen, a cation atom or a cation. Indicates an atomic group.
  • sulfosuccinic acid diester compound examples include di-2-ethylhexylsulfosuccinic acid and salts thereof.
  • Acids or alkalis may be added to the solution to adjust the pH of the solution.
  • Acids include hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, citric acid, oxalic acid, and alkalis include ammonia, quaternary ammonium hydroxide (such as tetramethylammonium hydroxide), and amines (such as ethylenediamine and triethylamine). And the like are used.
  • -OS 0 3 no corrosion of the solution electrodes, wiring including a surfactant consisting of surfactants and or sulfosuccinate diester Le compounds having a group, high party Kuru decontamination performance, relatively foaming is small that Is the feature.
  • the concentration of the surfactant is to pair the solution, usually from 0.001 to 1 wt% And preferably 0.002 to 0.5% by weight. If the addition amount of the surfactant is too small, the particle contamination removal performance is not sufficient, and even if the surfactant is added in an amount larger than this range, there is no change in the particle contamination removal performance, foaming becomes remarkable, and the waste liquid is biodegraded. It is not preferable because the impossibility of doing so increases.
  • the surfactants used in (A1) to (A3) may be used in the form of a salt or in the form of an acid.
  • the salt include alkali metal salts such as sodium and potassium, ammonium salts, primary, secondary, and tertiary amine salts.
  • the surfactant used does not contain metal salts, acid form, ammonium salt, Preference is given to ethanolamine salts, triethanolamine salts and the like.
  • the cleaning liquid (A1) is preferably used from the viewpoint of simultaneously preventing corrosion of tungsten and copper, removing particles and removing metal contamination, and the cleaning liquid (A2) is preferably used from the viewpoint of removing particles and foaming.
  • the cleaning liquid of the present invention is used for cleaning a substrate for a semiconductor device, it is preferable that the cleaning liquid does not contain metal impurities or particles which, when adhered to the substrate, lower the electrical characteristics or the yield of the device.
  • the content of metal impurities in the cleaning solution is Fe, Al, Zn, and Cu, respectively. It is desirable that the concentration be 0.02 ppm or less.
  • the cleaning liquid used for cleaning mainly for the purpose of removing particles is preferably a surfactant having a —so 3 — group, more preferably an alkylsulfonic acid, an alkylbenzenesulfonic acid, an alkylnaphthylenesulfonic acid, Methyl diphosphoric acid, phosphoric acid sulfonic acid, naphthylene sulfonic acid condensate, fluorine-based surfactant in which hydrogen of the alkyl group of the above surfactant is substituted with fluorine, particularly preferably alkylbenzene sulfonic acid, alkyldiphene Surfactants such as toluene terdisulfonic acid and methyl phosphoric acid are used.
  • a surfactant having a —so 3 — group more preferably an alkylsulfonic acid, an alkylbenzenesulfonic acid, an alkylnaphthylenesulfonic
  • the solvent for the washing liquids (A1) to (A3) of the present invention water or a mixed solvent of an organic solvent and water, preferably water, is usually used.
  • hydrofluoric acid ammonium fluoride
  • an oxidizing agent e.g., sodium fluoride
  • a reducing agent e.g., sodium bicarbonate
  • a complexing agent e.g., sodium bicarbonate
  • Hydrofluoric acid and ammonium fluoride have an effect of etching a silicon oxide film or the like on the substrate surface, and are particularly effective in removing contamination such as photoresist residue firmly adhered to the substrate.
  • the concentration of hydrofluoric acid in the cleaning solution is usually 0.01 to 0.5% by weight, preferably 0.01 to 0.1% by weight, based on the cleaning solution.
  • the concentration of ammonium fluoride in the cleaning solution is usually 0.01 to 30% by weight based on the cleaning solution. If the amount is less than this range, a sufficient etching effect may not be obtained. If the amount is too large, etching of a substrate such as a silicon oxide film may be excessively performed, which may hinder device performance.
  • Examples of the oxidizing agent include hydrogen peroxide, ozone, and hypochlorous acid.
  • Examples of the reducing agent include hydrazine, and examples of the dissolved gas include hydrogen, argon, and nitrogen.
  • the complexing agent amines, amino acids, polyaminopolycarboxylic acids, phenol derivatives, polyaminophosphonic acids, 1,3-diketones and the like are used. That Specific examples include ethylenediamine, diethylenetriamine, 8-quinolinol, o-phenanthroline, glycine, iminodiacetic acid, ethylenediaminetetraacetic acid [EDTA;], trans-1,2-diaminocyclohexane4.
  • the cleaning liquid of the present invention is used for cleaning a semiconductor device substrate having a transition metal or a transition metal compound on the surface.
  • the transition metals in the present invention include W (silver), Cu (copper), Ti (titanium), Cr (chromium), Co (cobalt), Zr (siliconium), Hf (hafnium), Transition metals such as Mo (molybdenum), Ru (ruthenium), Au (gold), Pt (platinum), and Ag (silver).
  • Transition metal compounds are transition metal nitrides, oxides, and silicides. And the like.
  • the transition metals and transition metal compounds present on the surface of the substrate for semiconductor devices include W (tungsten), Cu (copper), Ti (titanium), Cr (chromium), Co (connorth), and Z Transition metals such as r (zirconium), Hf (hafnium), Mo (molybdenum), Ru (ruthenium), Au (gold), Pt (platinum), Ag (silver), and their nitrides and oxides And a transition metal compound such as a silicide.
  • the step of cleaning a substrate having copper on the surface is used for cleaning copper wiring and the substrate surface when copper is used as a wiring material.
  • a cleaning process after forming a copper film on a semiconductor device particularly a cleaning process after performing CMP (Chemical Mechanical Polishing) on a copper film, and a dry etching process on an interlayer insulating film on copper wiring. It is also applied for cleaning after opening a hole.
  • CMP Chemical Mechanical Polishing
  • the step of cleaning the substrate having tungsten on the surface is used for cleaning the gate electrode and the substrate surface when tungsten is used as the gate electrode material.
  • a cleaning step after forming a tungsten film on a semiconductor device in particular, a cleaning step after dry etching of a tungsten film, and a cleaning after ion implantation into an exposed silicon portion.
  • the cleaning liquid of the present invention By using the cleaning liquid of the present invention, particles and metals can be removed without performing ultrasonic irradiation or brush scrub. Therefore, there is a high possibility that the gate electrode will be broken by ultrasonic cleaning or brush scrubbing. If the gate electrode is made of ultra-fine tungsten (for example, the gate electrode has a width of about 0.15 m), the gate electrode And for cleaning the substrate surface.
  • a method for cleaning the substrate a method is used in which the cleaning liquid is brought into direct contact with the substrate. Specifically, dip-type cleaning in which the cleaning tank is filled with the cleaning liquid to immerse the substrate, spray-type cleaning in which the cleaning liquid is sprayed onto the substrate, and cleaning, and high-speed rotation of the substrate while flowing the cleaning liquid from the nozzle onto the substrate Spin-cleaning, etc., that rotates.
  • the washing method is appropriately selected depending on the purpose. Dip-type cleaning is capable of cleaning many substrates at once, but is characterized in that one cleaning takes a long time.
  • Spin-type cleaning is characterized in that the number of substrates that can be cleaned at one time is small, but the time for one cleaning is short.
  • the cleaning time is usually 30 seconds to 30 minutes for dip cleaning, preferably 1 to 15 minutes, and usually 1 second to 15 minutes for spray cleaning and spin cleaning. Preferably it is 5 seconds to 5 minutes. If the cleaning time is too short, the cleaning effect If the result is not enough, if it is too long, the throughput will only worsen, and the cleaning effect will not increase and there is no point.
  • the washing may be carried out at room temperature, or may be carried out usually at a temperature of about 40 to 80 ° C. in order to improve the washing effect.
  • a 4-inch silicon wafer with an oxide film was immersed in an aqueous solution in which alumina was dispersed.
  • the immersed wafer was washed with ultrapure water for 10 minutes and dried by blowing nitrogen.
  • Alumina was selected as a typical example of particles that are extremely difficult to remove when they adhere to the substrate.
  • the number of fine particles adhering to the silicon wafer surface was measured using a laser surface inspection device (LS-500, manufactured by Hitachi Electronics Engineering Co., Ltd.). It was confirmed that these were adhered, and a silicon wafer to which alumina was adhered was obtained.
  • LS-500 manufactured by Hitachi Electronics Engineering Co., Ltd.
  • the obtained silicon wafer to which alumina had adhered was washed by immersing it in a cleaning solution at room temperature for 10 minutes without ultrasonic waves to remove alumina.
  • the cleaning solution is an aqueous solution containing the surfactant and hydrofluoric acid shown in Table 1 at a predetermined concentration, and an acid other than hydrofluoric acid is added so that the pH shown in Table 1 is obtained.
  • a washing solution composed of the aqueous solution was used.
  • the silicon wafer is rinsed with ultrapure water for 10 minutes and dried by blowing nitrogen. After drying, a washed silicon wafer was obtained. Particles remaining on the surface of the obtained cleaned silicon wafer were measured by a laser surface inspection device. Show results—
  • washing liquid As the washing liquid, the same washing liquid as used in (Measurement of attached particles) was used. (Measurement of foamability)
  • the foaming property of the cleaning liquid was measured based on the Ross Miles method described in JIS. Specifically, 50 ml of the washing liquid is previously placed in the lower part of a 50 mm diameter glass tube, and a certain amount (200 ml) of the washing liquid is dropped from the upper part of the glass tube over 30 seconds. The height (mm) of the generated foam was read immediately after the drop and the foaming power was measured. The foaming property indicates the amount of foaming by height (mm), so the higher the height, the easier the foaming.
  • a cleaning solution that is a type of SPM cleaning solution which is a mixture of 97% by weight sulfuric acid and 31% by weight hydrogen peroxide in a 4: 1 volume ratio is used.
  • Example 1 was repeated except that the temperature was set to 100 ° C., which is a normal temperature when cleaning was performed using an SPM cleaning solution. The results are shown in Table 1.
  • Example 1 The same as in Example 1 except that the cleaning liquid used for cleaning the silicon wafer to which alumina was adhered was an aqueous solution containing hydrofluoric acid and / or an acid other than hydrofluoric acid as shown in Table-1. I went to. The results are shown in Table 1.
  • the cleaning was performed in the same manner as in Example 1 except that the same cleaning liquid as used in the measurement of the adhered particles was used. The results are shown in Table 1.
  • hydrofluoric acid is abbreviated as “hydrofluoric acid”.
  • Table 1 (Part 1)
  • R is a mixture of one C 15 H 31 (about 28%), one C 17 H 35 (about 21%), and —C 17 H 33 (about 44%), and R—CON (CH 3 ) C 2 H 4 S0 3 c 1 indicating the Na: is a mixture of R gar CH ⁇ and one C 13 H 27, R-CON (CH 3) shows the C 2 H 4 SQ 3 Na.
  • Example 30 C 12 H 25 OS0 3 M 6.3 A3 1199 None None 83
  • Example 31 C 2 H 25 0 (C 2 H 40 ) 4 S0 3 M 6.3 A3 2750 None None
  • a 4-inch bare silicon wafer is composed of an aqueous solution containing a mixture of 29% ammonia water, 31% hydrogen peroxide water, and water at a volume ratio of 1: 1: 5, a type of SC-1 cleaning solution containing metal ions. It was immersed in the cleaning solution. The immersed silicon wafer was washed with ultrapure water for 10 minutes and dried by blowing nitrogen to produce a silicon wafer contaminated with metal.
  • the silicon wafer contaminated with this metal was cleaned by immersing it in a cleaning solution for 10 minutes at room temperature to remove the metal.
  • the cleaning solution was an aqueous solution containing a surfactant and hydrofluoric acid at a predetermined concentration as shown in Table 2 and an acid other than hydrofluoric acid was added so as to obtain the pH shown in Table 12.
  • a washing solution composed of an aqueous solution was used.
  • the washed silicon wafer was washed with ultrapure water for 10 minutes and dried by blowing nitrogen to obtain a washed silicon wafer.
  • the Fe, Al, and Cu remaining on the surface of the obtained cleaned silicon wafer were quantified, and the substrate surface concentration was calculated.
  • the substrate surface concentration (atoms / cm 2 ) was shown by the average value of the two silicon wafers that had been cleaned and the substrate surface concentration (atoms / cm 2 ) of each substrate was measured for each metal. .
  • the results are shown in Table-2.
  • quantification of Fe, Al, and Cu attached to the silicon wafer surface was performed as follows.
  • Fe, A1, and Cu attached to the surface of the silicon wafer were recovered using a mixed solution of 0.1% by weight of hydrofluoric acid and 1% by weight of hydrogen peroxide.
  • the amounts of Fe, A1, and Cu contained in this solution were measured by a flameless atomic absorption method, and were converted to the substrate surface concentration (atoms / cm 2 ).
  • the cleaning method of the present invention it is possible to achieve a highly clean substrate surface free of contamination without corroding a metal member made of a transition metal or a transition metal compound or the like and without irradiating ultrasonic waves. It is very useful industrially.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

La présente invention concerne un détergent pour un substrat de dispositif semi-conducteur comportant en surface un métal de transition ou un composé de métal de transition, caractérisé par le fait qu'il contient une solution choisie parmi le groupe constitué de (A1), (A2) et (A3). L'invention concerne également un procédé de nettoyage d'un substrat de dispositif semi-conducteur comportant en surface un métal de transition ou un composé de métal de transition, caractérisé par l'utilisation dudit détergent. (A1) consiste en un solution contenant un agent tensioactif comportant un groupe -SO3- (étant entendu que l'agent tensioactif n'est pas un composé diester sulfosuccinique) et présente un pH de 3 au plus. (A2) consiste en une solution contenant un agent tensioactif comportant un composé de méthyltaurine. (A3) consiste en une solution contenant un agent tensioactif comportant un groupe -OSO3- et/ou un agent tensioactif comportant un composé diester sulfosuccinique et présente un pH d'au moins 4.
PCT/JP2001/000426 2000-01-24 2001-01-24 Procede et detergent pour le nettoyage de substrat d'un dispositif semi-conducteur comportant en surface un metal de transition ou un compose de metal de transition Ceased WO2001054180A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001228803A AU2001228803A1 (en) 2000-01-24 2001-01-24 Method and detergent for cleansing semiconductor device substrate having transition metal or transition metal compound on surface

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000-14366 2000-01-24
JP2000014366 2000-01-24

Publications (1)

Publication Number Publication Date
WO2001054180A1 true WO2001054180A1 (fr) 2001-07-26

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Family Applications (1)

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PCT/JP2001/000426 Ceased WO2001054180A1 (fr) 2000-01-24 2001-01-24 Procede et detergent pour le nettoyage de substrat d'un dispositif semi-conducteur comportant en surface un metal de transition ou un compose de metal de transition

Country Status (2)

Country Link
AU (1) AU2001228803A1 (fr)
WO (1) WO2001054180A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103113972A (zh) * 2012-12-29 2013-05-22 上海新阳半导体材料股份有限公司 一种芯片铜互连封装用高效划片液

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07216569A (ja) * 1989-10-26 1995-08-15 Toshiba Corp 洗浄方法
EP0827188A2 (fr) * 1996-08-09 1998-03-04 Mitsubishi Gas Chemical Company, Inc. Liquide de nettoyage pour composants semi-conducteurs et procédé de fabrication de composants semi-conducteurs utilisant ledit liquide de nettoyage

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07216569A (ja) * 1989-10-26 1995-08-15 Toshiba Corp 洗浄方法
EP0827188A2 (fr) * 1996-08-09 1998-03-04 Mitsubishi Gas Chemical Company, Inc. Liquide de nettoyage pour composants semi-conducteurs et procédé de fabrication de composants semi-conducteurs utilisant ledit liquide de nettoyage

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103113972A (zh) * 2012-12-29 2013-05-22 上海新阳半导体材料股份有限公司 一种芯片铜互连封装用高效划片液

Also Published As

Publication number Publication date
AU2001228803A1 (en) 2001-07-31

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