WO2019142788A1 - 次亜塩素酸イオンを含む半導体ウェハの処理液 - Google Patents

次亜塩素酸イオンを含む半導体ウェハの処理液 Download PDF

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WO2019142788A1
WO2019142788A1 PCT/JP2019/000938 JP2019000938W WO2019142788A1 WO 2019142788 A1 WO2019142788 A1 WO 2019142788A1 JP 2019000938 W JP2019000938 W JP 2019000938W WO 2019142788 A1 WO2019142788 A1 WO 2019142788A1
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Prior art keywords
ion
hypochlorite
treatment liquid
semiconductor wafer
solution
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PCT/JP2019/000938
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English (en)
French (fr)
Japanese (ja)
Inventor
享史 下田
貴幸 根岸
由樹 吉川
誠司 東野
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Tokuyama Corp
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Tokuyama Corp
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Priority to JP2019566470A priority Critical patent/JP6798045B2/ja
Priority to EP19741609.2A priority patent/EP3726565A4/en
Priority to KR1020207020591A priority patent/KR102766830B1/ko
Priority to SG11202006733TA priority patent/SG11202006733TA/en
Priority to CN201980008715.2A priority patent/CN111684570B/zh
Priority to KR1020257003365A priority patent/KR20250022896A/ko
Priority to US16/962,260 priority patent/US11390829B2/en
Publication of WO2019142788A1 publication Critical patent/WO2019142788A1/ja
Anticipated expiration legal-status Critical
Priority to US17/847,299 priority patent/US12612580B2/en
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P70/00—Cleaning of wafers, substrates or parts of devices
    • H10P70/20—Cleaning during device manufacture
    • H10P70/27—Cleaning during device manufacture during, before or after processing of conductive materials, e.g. polysilicon or amorphous silicon layers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/08—Liquid soap, e.g. for dispensers; capsuled
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/168—Organometallic compounds or orgometallic complexes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/24—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/28—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/60—Wet etching
    • H10P50/66—Wet etching of conductive or resistive materials
    • H10P50/663—Wet etching of conductive or resistive materials by chemical means only
    • H10P50/667—Wet etching of conductive or resistive materials by chemical means only by liquid etching only
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P70/00—Cleaning of wafers, substrates or parts of devices
    • H10P70/50—Cleaning of wafers, substrates or parts of devices characterised by the part to be cleaned
    • H10P70/54—Cleaning of wafer edges
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P70/00—Cleaning of wafers, substrates or parts of devices
    • H10P70/50—Cleaning of wafers, substrates or parts of devices characterised by the part to be cleaned
    • H10P70/56—Cleaning of wafer backside
    • 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 novel processing solution for cleaning an end surface portion and a back surface portion of a semiconductor wafer, which is used in a manufacturing process of a semiconductor element.
  • Excess metal material or the like attached to the end face portion or the back face portion of the semiconductor wafer becomes particles of metal or metal oxide in an ashing step with oxygen or a dry etching step with plasma which is a step after metal wiring and barrier metal formation. Contaminate the inside of the manufacturing equipment. Thereafter, particles may adhere to and contaminate other wafers carried into the manufacturing apparatus. This contamination is called cross contamination. In order to suppress the cross contamination, it is necessary to remove the metal material and the like attached to the end face portion and the back face portion of the wafer before bringing it into the next step.
  • noble metals such as platinum and ruthenium and tungsten are often used in the element formation process. It is known that these metals are difficult to oxidize and dissolve in subsequent etching and cleaning steps, are difficult to remove, difficult to remove, and continue to exist as impurities. Therefore, these noble metals and tungsten are preferably removed from the semiconductor wafer in preference to other metal materials.
  • ruthenium is frequently used as a wiring material of 10 nm or less in the design rule of a semiconductor element because resistance can be reduced compared to the case where copper is used as a wiring material, and therefore, ruthenium should be removed quickly from unnecessary points. Is desired.
  • Tungsten or a tungsten alloy is widely used as a material for a gate electrode, a wiring, a via hole and the like, but since it is deposited by CVD or sputtering, it adheres to places other than the desired part. For this reason, as with ruthenium, it is desirable to quickly remove tungsten from unnecessary points.
  • Patent Document 1 proposes a cleaning method of oxidizing and removing ruthenium by adding a strong acid such as nitric acid to cerium (IV) ammonium nitrate.
  • Patent Document 2 discloses a method of cleaning with a liquid having an oxidation potential of 300 mV or more larger than the standard hydrogen electrode potential.
  • the liquid is an aqueous solution of sodium hypochlorite having a pH of 12 or more, or ammonium hypochlorite.
  • Patent Document 3 an aqueous solution of sodium hypochlorite or an aqueous solution of orthoperiodic acid is used as a method of etching a ruthenium film. And, in this method, ruthenium is etched while supplying benzotriazole to prevent corrosion of copper wiring.
  • Example 5 of Patent Document 4 a pH 7 cleaning solution containing hypochlorous acid is proposed as a cleaning solution capable of effectively removing contamination such as particles on a substrate without deteriorating the characteristics of the above.
  • Patent Document 5 proposes a cleaning composition using tetramethylammonium hypochlorite as an oxidizing agent of a cleaning composition for cleaning a photoresist or residue from a microelectronic substrate.
  • Patent Document 6 proposes a cleaning solution comprising hydrogen peroxide, an organic acid salt and water.
  • Patent document 1 JP-A-2001-234373
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2002-161381 JP, 2009-081247 Japanese Patent Application Publication No. 2003-119494
  • Patent document 1 JP-A-2005-227749 Patent No. 5523325
  • a cleaning solution of pH 7 containing hypochlorous acid is proposed in Example 5 of Patent Document 4, this cleaning solution is used for cleaning a substrate provided with a metal film or a metal oxide film.
  • the purpose is to prevent the occurrence of watermarks, and not to remove the precious metals in particular. Therefore, it is difficult to dissolve ruthenium even if the end face portion or the back face portion of the semiconductor wafer is cleaned with a pH 7 cleaning solution in which 500 ppm of hypochlorous acid is added and the redox potential is adjusted to 612 mV. It was difficult to remove and needed further improvement.
  • ammonia is used as a pH adjuster to adjust the pH of the cleaning solution.
  • ammonia is highly volatile and there is room for improvement in terms of the stability of the cleaning solution.
  • hypochlorite ion and ammonia react to partially generate highly explosive trichloramine, it is difficult to handle the cleaning solution after pH adjustment.
  • the cleaning solution described in Patent Document 5 a cleaning solution containing tetramethylammonium hypochlorite as an oxidizing agent is proposed.
  • the pH of the cleaning solution is more than 12.
  • 17.6% by mass of TMAOCl described as formulation A of Patent Document 5 6.6% by mass of TMACl, 0.43% by mass of TMAH, 85.3% by mass of water, and 0 of Zonyl FSH
  • the formulation A containing 0.5% by mass has a pH of 12.7.
  • this cleaning solution is a cleaning solution used for cleaning the photoresist and the residue, and the metal coating of copper or aluminum containing ruthenium is not cleaned but protected. Therefore, since the cleaning liquid described in Patent Document 5 is not a cleaning liquid intended to remove precious metals, there is room for improvement in that even if the cleaning liquid described in Patent Document 5 is used, the precious metals can not be removed. was there.
  • the cleaning solution described in Patent Document 6 contains hydrogen peroxide and an organic acid salt, and is currently the main flow of an etching solution for tungsten.
  • This cleaning solution has a great advantage in that the damage to the silicon substrate is small.
  • the etching rate for tungsten is not sufficient, and from the viewpoint of throughput improvement, a cleaning solution faster than the etching rate for tungsten and without damaging the substrate is required.
  • the object of the present invention is to easily remove (clean) excess metal material and the like attached to the end face portion and the back face portion of the semiconductor wafer, and in particular, to exert an effect on the removal of noble metals such as ruthenium or tungsten. It is in providing a processing solution.
  • another object of the present invention is to provide a more improved processing solution capable of achieving the above object and reducing alkali metal ions and alkaline earth metal ions to improve the yield of semiconductor devices. It is to provide. In addition to the above, it is another object of the present invention to provide a processing solution which is further excellent in storage stability.
  • hypochlorite ion which is an oxidant for noble metals and tungsten
  • hypochlorite ion which is an oxidant for noble metals and tungsten
  • the hypochlorite ion is stabilized, the storage stability is improved, and the adverse effects due to the alkali metal ion and the alkaline earth metal ion are reduced. I found out what I could do. Further, even when an alkali metal ion or an alkaline earth metal ion is used as a counter cation of hypochlorite ion, the alkali metal ion can be used without impairing the storage stability by setting these in a predetermined concentration range. It has been found that the adverse effects caused by the metal and alkaline earth metal ions can be reduced.
  • the treatment liquid according to the first embodiment is It is a processing liquid which contains (A) hypochlorite ion and (C) solvent, and whose pH at 25 ° C. is more than 7 and less than 12.0.
  • ruthenium or tungsten is oxidized by hypochlorite ion or chlorine.
  • ruthenium is considered to be dissolved as ruthenium oxide ions (RuO 4 ⁇ ) and removed from the system.
  • a process liquid further contains (B1) alkyl ammonium ion as an alkali component. That is, (2) the treatment liquid according to the second embodiment is (A) Hypochlorite ion, It is a processing liquid which contains (B1) alkyl ammonium ion and (C) solvent, and whose pH in 25 degreeC is more than 7 and less than 12.0.
  • the following may be considered as a mechanism by which the processing solution according to the second embodiment etches noble metals, for example, ruthenium. That is, in the presence of the alkyl ammonium ion, it is considered that the activated hypochlorite ion contacts ruthenium, and the ruthenium is oxidized, ionized and removed (see Formula 1).
  • a process liquid further contains at least 1 sort (s) of metal ion chosen from (B2) alkali metal ion and alkaline-earth metal ion of specific amount as an alkali component. That is, (3) the treatment liquid according to the third embodiment is (A) Hypochlorite ion, (B2) at least one metal ion selected from alkali metal ions and alkaline earth metal ions, and (C) a solvent, wherein the concentration of the (B2) metal ion is 1 ppm or more and 20000 ppm or less on a mass basis, It is a processing liquid whose pH at 25 ° C. is more than 7 and less than 12.0.
  • the treatment liquid according to the third embodiment is (A) Hypochlorite ion, (B2) at least one metal ion selected from alkali metal ions and alkaline earth metal ions, and (C) a solvent, wherein the concentration of the (B2) metal ion is 1 ppm or more and 20000 ppm
  • ruthenium is considered to be oxidized, ionized and removed as in the second embodiment.
  • the reaction as described above is remarkable when the alkali metal ion and / or the alkaline earth metal ion is in a specific amount, that is, the concentration is 1 ppm or more and 20000 ppm or less on a mass basis according to the study of the present inventors. I found it going.
  • the present invention can also take the following aspects.
  • the treatment liquid obtained by this method is a treatment liquid in which alkali metal ions and alkaline earth metal ions derived from a salt forming hypochlorite are reduced.
  • alkali metal ions and alkaline earth metal ions derived from a salt forming hypochlorite are reduced.
  • sodium hypochlorite when sodium hypochlorite is used, it is a treatment liquid in which sodium ions (alkali metal ions) contained in the treatment liquid are reduced.
  • problems caused by alkali metal ions and alkaline earth metal ions for example, adhesion of alkali metal to a semiconductor wafer is eliminated, and yield in manufacturing semiconductor devices is increased. It can be improved.
  • a semiconductor wafer having a metal component containing at least one metal (hereinafter sometimes abbreviated as “Ru / W”) selected from the group consisting of ruthenium and tungsten is present on the surface thereof
  • the semiconductor wafer can be cleaned by setting the ruthenium etching rate to 5 nm / min or more, preferably 10 nm / min or more. Further, the semiconductor wafer can be cleaned by setting the etching rate of tungsten to 50 nm / min or more, preferably 100 nm / min or more.
  • the concentration of cations (alkali metal ions and alkaline earth metal ions) remaining on the surface of the semiconductor wafer after cleaning can be adjusted to 1.5 ⁇ if conditions are adjusted. It can also be less than 10 15 atoms / cm 2 , preferably less than 6.2 ⁇ 10 14 atoms / cm 2 .
  • the processing liquid according to the second embodiment exhibits the effect of being excellent in long-term storage stability by setting the concentration of the alkyl ammonium ion in a specific range in addition to the pH.
  • Alkali metal and alkaline earth metal remaining in the manufacturing apparatus and in the semiconductor wafer cause short circuit of the electronic device and the like, leading to a decrease in yield of the semiconductor element, so reducing alkali metal and alkaline earth metal remaining after cleaning Is desired.
  • the concentration of the alkali metal ion and / or the alkaline earth metal ion to 1 ppm or more and 20000 ppm or less on a mass basis.
  • sodium ions and the like remaining after washing can be reduced. Furthermore, the effect of being excellent in long-term storage stability is also exhibited.
  • sodium ions and the like remaining in the manufacturing apparatus and in the semiconductor wafer can be reduced. As a result, sodium ions and the like which are considered to cause short-circuiting of the electronic device can be reduced, so that the yield of the semiconductor element can be improved.
  • Si which is the main material of semiconductor wafers and Si-containing coatings (for example, SiO 2 , Si 3 N 4 , SiOC, SiC, etc.) generated during circuit formation are not excessively etched.
  • Si-containing coatings for example, SiO 2 , Si 3 N 4 , SiOC, SiC, etc.
  • the processing liquid of the present invention can remove noble metals and tungsten adhering to the end face portion and the back face portion without damaging the semiconductor wafer. Therefore, the treatment liquid of the present invention can be suitably used for cleaning a semiconductor wafer in which noble metals and tungsten remain on the surface.
  • the object to be cleaned is not limited to this, and as a matter of course, it can also be used for cleaning a semiconductor wafer having no noble metal or tungsten on the surface.
  • the metals to which the processing solution of the present invention is applied adhere not only to the front surface but also to the end surface and the back surface of the semiconductor wafer by CVD and sputtering mainly used in the semiconductor device process. 1).
  • at least one metal 2 selected from the group consisting of ruthenium and tungsten adheres to the end face 3 and the back face 4.
  • the semiconductor wafer having Ru / W on its surface includes Ru / W present not only outside the semiconductor element formation region on the surface of the semiconductor wafer but also on the end face and back surface.
  • Ru / W is used as a material for metal wiring and barrier metal, it is in a state of being deposited on silicon constituting a semiconductor wafer or silicon oxide laminated on silicon.
  • the processing liquid of the present invention is not particularly limited, it can be suitably employed for cleaning the semiconductor wafer as described above.
  • the treatment liquid contains (A) hypochlorite ion and (C) solvent, preferably at least selected from (B1) alkyl ammonium ion or (B2) alkali metal ion, and alkaline earth metal ion. It contains one kind of metal ion. The following will be described in order.
  • hypochlorite Ion used in the present invention can be generated by dissolving hypochlorite in an appropriate solvent such as water.
  • the salt in hypochlorite is preferably an alkali metal and / or an alkaline earth metal. Among them, sodium is most preferable in consideration of the cleaning effect.
  • the concentration range of hypochlorite ion is preferably 0.05 to 20% by mass. Within the above range, Ru / W can be sufficiently dissolved and washed. When the concentration of hypochlorite ion exceeds 20% by mass, the decomposition reaction of hypochlorite ion tends to occur easily. On the other hand, if the content is less than 0.05% by mass, the etching rate tends to be low, and the cleaning property tends to be reduced. Therefore, the range of hypochlorite ion is preferably 0.1 to 15% by mass, more preferably 0.3 to 10% by mass, and still more preferably 0.5 to 6% by mass, in particular Preferably, it is 0.5 to 4% by mass.
  • the pH of the treatment solution is more than 7 and less than 12 in order to suppress the decomposition reaction of hypochlorite ions in the treatment solution and to suppress the decrease in the concentration of the hypochlorite ions.
  • the pH of the treatment liquid is 7 or less, the decomposition reaction of hypochlorite ions tends to occur, and the concentration of hypochlorite ions tends to decrease.
  • the effect of suppressing the decomposition reaction of hypochlorous acid ion in the treatment liquid to suppress the reduction of the hypochlorite ion concentration may be considered to be "preservation stability".
  • the concentration range of hypochlorite ion is preferably 0.05 to 6% by mass. Within this range, high storage stability can be ensured. When the concentration of the hypochlorite ion exceeds 6% by mass, the decomposition reaction of the hypochlorite ion tends to easily occur. Therefore, in consideration of the etching rate of Ru / W, the cleaning property, and the storage stability of the treatment solution itself, the concentration range of hypochlorite ion is more preferably 0.1 to 6% by mass, 0.3 to 6 % By mass is more preferable, and 0.5 to 4% by mass is particularly preferable.
  • the concentration range of hypochlorite ion is 0.05 to 6% by mass, and the pH is more than 7 and 12 Treatment solutions which are less than are particularly preferred. If it is within the above range, the hypochlorite ion concentration does not easily decrease during storage, for example, a treatment in which Ru / W washability is sufficiently exhibited even after storage for 15 days in the dark at 20 ° C. It can be a liquid.
  • the concentration of hypochlorite ion can be determined by calculation at the time of production of the treatment solution, or can be confirmed by directly analyzing the treatment solution.
  • the concentration of hypochlorite ion described in the following examples was determined by measuring the effective chlorine concentration of the treatment solution. More specifically, potassium iodide and acetic acid are added to a solution containing hypochlorite ion with reference to Ministry of Health, Labor and Welfare Notification No. 3181 (final revision March 11, 2005), and the iodine released is thiothiolated.
  • the effective chlorine concentration was calculated by redox titration with an aqueous solution of sodium sulfate.
  • (C) Solvent In the treatment liquid of the present invention, the remainder other than (A), (B1), (B2) and other additives described in detail below is a solvent, and (A), (B1), After adjustment of (B2) and other additives, the residue is adjusted with a solvent to a total of 100% by mass.
  • Water is most preferably used as the solvent.
  • the water contained in the treatment liquid of the present invention is preferably water from which metal ions, organic impurities, particle particles, etc. have been removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments, etc., particularly pure water or ultrapure water. Is preferred. In that case, the concentration of water is the remainder excluding various drugs.
  • an organic solvent may be used as long as hypochlorite ion is stably present.
  • the organic solvent for example, acetonitrile, sulfolane or the like is used.
  • the treatment liquid of the present invention contains an alkali component.
  • the alkali component at least one metal ion selected from (B1) alkyl ammonium ion (second embodiment) or a predetermined amount of (B2) alkali metal ion and alkaline earth metal ion (third embodiment) Is used.
  • Alkyl ammonium ion used in the second embodiment is included in the treatment liquid in order to improve the storage stability of the treatment liquid and to adjust the pH.
  • the alkyl ammonium ion is not particularly limited, and may be any of a primary alkyl ammonium ion, a secondary alkyl ammonium ion, a tertiary alkyl ammonium ion, and a quaternary alkyl ammonium ion, and these It may be a mixture of Among them, quaternary alkyl ammonium ions are preferable in order to enhance the easiness of production of the treatment liquid itself and the washing effect of the treatment liquid.
  • the carbon number of the alkyl ammonium ion is not particularly limited. Among them, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is further preferable, in order to further facilitate the production of the treatment liquid itself and to enhance the cleaning effect of the treatment liquid.
  • alkyl ammonium ion a quaternary alkyl ammonium ion having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms is suitable.
  • Specific examples of the ion include tetramethyl ammonium ion, tetraethyl ammonium ion and tetrabutyl ammonium ion. If it is said alkyl ammonium ion, the washability of a process liquid will not be affected and the storage stability of a process liquid can be improved.
  • the concentration range of the alkyl ammonium ion is preferably 0.1 to 30% by mass.
  • concentration of the alkyl ammonium ion satisfies this range, the fluctuation of the pH of the treatment liquid can be reduced even if Ru / W is oxidized, dissolved, or removed. As a result, stable etching can be performed, and long-term storage stability is also excellent.
  • the concentration of the alkyl ammonium ion is more preferably 0.15 to 20% by mass, still more preferably 0.3 to 15% by mass, and particularly preferably 0.5 to It is 8% by mass.
  • these alkali metal ions and alkaline earth metal ions may adversely affect the semiconductor wafer (adverse effects such as a decrease in yield of the semiconductor wafer), and the compounding ratio is preferably small, and it is practically limited It is better not to be included. Specifically, it is preferably 1% by mass or less, more preferably 0.7% by mass or less, still more preferably 0.3% by mass or less, and particularly preferably 10 ppm or less, Most preferably, it is 500 ppb or less.
  • the alkyl ammonium ion is present as a counter cation of hypochlorite ion and stabilizes the hypochlorite ion. Further, unlike alkali metal ions and alkaline earth metal ions, the semiconductor wafer does not have an adverse effect (adverse effects such as a reduction in yield of the semiconductor wafer) and contributes to high quality of the semiconductor wafer after cleaning.
  • Alkali metal ions used in the third embodiment and / or alkaline earth metal ions may be a counter ion of hypochlorite ion which is carried into the treatment liquid as a salt for generating hypochlorite ion, in consideration of the productivity of the treatment liquid itself. Is preferred. Therefore, the type is determined by the raw materials used. For example, if sodium hypochlorite is used to adjust the hypochlorite ion, sodium ions will be present in the treatment solution. However, it is also possible to prepare a solution containing hypochlorite ion which does not contain the metal ion and add the metal ion thereto.
  • At least one metal ion selected from alkali metal ions and alkaline earth metal ions may be only alkali metal ions, only alkaline earth metal ions, or both. It may be When both are included, the concentrations detailed below are based on the total amount of both.
  • the concentration of metal ions should be 1 ppm or more and 20000 ppm or less on a mass basis. If it is in the said range, even if it oxidizes, melt
  • the concentration of metal ions is less than 1 ppm on a mass basis, the ratio of paired ions of hypochlorite ions decreases, and the decomposition of hypochlorite ions is promoted.
  • concentration of metal ions exceeds 20000 ppm by mass, since many metal ions serving as counter ions are present, hypochlorite ions can be stably present, but the surface of the semiconductor wafer after cleaning Is contaminated with metal ions. As a result, the yield of the semiconductor device is lowered.
  • the sodium (metal ion) less than 1 ⁇ 10 15 atoms / cm 2 remains on the cleaned surface of the semiconductor wafer by adjusting the compounding amount. Can. As a result, it can be suitably used as a cleaning liquid for the back surface and the end surface of the semiconductor wafer.
  • the concentration of metal ions is 1 ppm to 20000 ppm on a mass basis, 10 ppm to 15000 ppm, more preferably 200 ppm to 13000 ppm, and still more preferably 1000 ppm or more and 10000 ppm or less. If it is in the said range, even if Ru / W is removed (washing), pH of a process liquid does not fluctuate and it can process stably.
  • the following method is adopted to satisfy the requirements of the present invention It may be prepared as follows. Specifically, sodium hypochlorite may be dissolved in water and then brought into contact with a cation exchange resin to replace sodium ions with hydrogen ions. When the reduction of metal ions is insufficient, the reduction can be achieved by repeating the above-mentioned operation of contacting with the cation exchange resin.
  • amines preferably organic amines
  • the organic amine is not particularly limited as long as it is an amine to be an ammonium ion, an alkyl ammonium ion or the like. Among them, preferred is an organic amine to be a quaternary alkyl ammonium ion.
  • the carbon number of the quaternary alkyl ammonium ion is also not particularly limited, but is preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably an alkyl group having 1 to 5 carbon atoms, and specifically , Tetramethyl ammonium ion, tetraethyl ammonium ion, tetrabutyl ammonium ion.
  • blend the quantity whose pH of a process liquid satisfies the range of 7 or more and 10.0 or less. However, this amine is not an essential component.
  • the treatment liquid according to the third embodiment contains a specific amount of metal ions, it exhibits excellent effects even when amines are not contained.
  • the metal ion can be produced directly from the hypochlorite aqueous solution by adjusting the production conditions. Therefore, it is preferable that only a specific amount of metal ion is contained, in consideration of the easiness of production of the treatment liquid.
  • the processing solution of the present invention may, if desired, contain additives conventionally used in semiconductor processing solutions as long as the object of the present invention is not impaired.
  • an acid e.g., a metal corrosion inhibitor, a fluorine compound, an oxidizing agent, a reducing agent, a chelating agent, a surfactant, an antifoaming agent, etc. can be added.
  • the treatment liquid of the present invention contains the above (A) hypochlorite ion and the above (C) solvent, preferably contains the above (B1) alkyl ammonium ion, or contains a predetermined amount of (B2) metal ion, As well as other additives as needed.
  • the pH of the treatment liquid of the present invention is more than 7 and less than 12 depending on the amount of each component, the pH of the treatment liquid does not fluctuate and is stably removed even if Ru / W is oxidized, dissolved or removed. it can. Furthermore, if it is in the said range, it can be set as the process liquid excellent in long-term storage stability. When the pH of the processing solution is 12 or more, the etching rate of Ru / W decreases remarkably.
  • the pH of the treatment liquid is more preferably 8 or more and less than 12 and still more preferably 8 or more and less than 11.
  • the method for producing the treatment liquid of the present invention is not particularly limited.
  • the treatment liquid according to the first embodiment can be manufactured according to the process for producing the treatment liquid according to the second or third embodiment.
  • the method of producing the treatment liquid according to the second and third embodiments will be described by taking the case of using water as a solvent as an example.
  • the treatment liquid according to the second embodiment can be produced by preparing an ion exchange resin to which alkyl ammonium is added, and bringing the ion exchange resin into contact with an aqueous solution containing hypochlorite ion.
  • Step of preparing an ion exchange resin to which alkyl ammonium is added An aqueous solution containing alkyl ammonium ion or halogenated alkyl ammonium ion, specifically, an aqueous alkyl ammonium hydroxide solution is brought into contact with an ion exchange resin, Prepare the ion exchange resin to which was added.
  • the alkyl ammonium to be added to the ion exchange resin is not particularly limited, and may be any of primary alkyl ammonium, secondary alkyl ammonium, tertiary alkyl ammonium and quaternary alkyl ammonium. It may be a mixture of these.
  • the alkyl ammonium ion contained in the treatment liquid is preferably a quaternary alkyl ammonium ion. Therefore, the alkyl ammonium is preferably a quaternary alkyl ammonium.
  • the carbon number of the quaternary alkyl ammonium is also preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms, as in the case of the quaternary alkyl ammonium ion.
  • a specific compound is, for example, tetramethyl ammonium hydroxide. Therefore, in the present embodiment, it is preferable to prepare an ion exchange resin to which alkyl ammonium is added by bringing a tetramethyl ammonium hydroxide aqueous solution into contact with the ion exchange resin.
  • the ion exchange resin to be used is a well-known cation exchange resin, it can be used without a restriction
  • hydrogen type ion exchange resin and sodium type ion exchange resin can also be used.
  • a hydrogen-type ion exchange resin is preferable because sodium is contained in the resulting treatment liquid.
  • the hydrogen type ion exchange resin weakly acidic or strongly acidic ion exchange resin can be used.
  • hypochlorite ion An aqueous solution containing hypochlorite ion can be prepared by dissolving hypochlorite in water.
  • hypochlorite calcium hypochlorite, sodium hypochlorite and the like can be mentioned, but sodium hypochlorite is preferable in terms of storage stability and good handling.
  • a treatment liquid containing hypochlorite ion and alkyl ammonium ion can be produced.
  • the step of ion exchange in (b) may be repeated.
  • cations such as sodium and calcium which become counter ions of hypochlorous acid contained in an aqueous solution containing hypochlorite ion.
  • alkali metal ions such as sodium and calcium and alkaline earth metal ions contained in the processing solution cause a decrease in the yield of semiconductor devices.
  • the total of the alkali metal ion and the alkaline earth metal ion contained in the treatment liquid is 1% by mass or less, preferably 0.7% by mass or less, more preferably 0.3% by mass or less More preferably, it is 10 ppm or less, and particularly preferably 1 ppm or less.
  • the treatment liquid of the present invention is applied to a manufacturing process in which the design rule of a semiconductor device is 10 nm or less, alkali metal ions and alkaline earth metal ions at 10 ppm level affect the yield of the semiconductor device. It is preferable that it is 500 ppb or less.
  • the aqueous solution containing hypochlorite ion was made to contact ion exchange resin, and alkali metal ion and alkaline earth metal ion were reduced.
  • the treatment liquid of the present invention may be produced by mixing an aqueous solution containing hypochlorite ion and an aqueous solution containing alkyl ammonium ion, and the cation is reduced to the ion exchange resin to which alkyl ammonium is added.
  • An aqueous solution containing hypochlorite ion may be brought into contact to produce the treatment solution of the present invention.
  • the process (c) which adjusts pH can be included after the said (b) process.
  • the pH of the treatment solution is adjusted by passing the treatment solution obtained in step (b) through a cation exchange resin of hydrogen type, or by adding an acid such as hydrochloric acid. Yes (adjusted to the acid side).
  • the treatment liquid obtained in step (b) is passed through a hydroxide type anion exchange resin, or the treatment liquid is added with an alkyl ammonium hydroxide solution such as a tetramethyl ammonium hydroxide solution. PH can be raised (adjusted to the alkaline side).
  • the treatment liquid according to the third embodiment can be produced by using hypochlorite as an aqueous solution and reducing metal ions, which are counterions of hypochlorite ions, from the solution.
  • a method of reducing metal ions a method may be employed in which an ion exchange resin and hypochlorite are brought into contact with each other to replace metal ions with hydrogen ions.
  • the treatment solution according to the third embodiment is manufactured by adsorbing the metal ion contained in the aqueous solution containing hypochlorite ion to the ion exchange resin to adjust the metal ion concentration (1 ppm or more and 20000 ppm or less). can do.
  • the ion exchange resin can be used without particular limitation as long as it is a cation exchange resin such as a strongly acidic ion exchange resin, a weakly acidic ion exchange resin, or the like.
  • a cation exchange resin such as a strongly acidic ion exchange resin, a weakly acidic ion exchange resin, or the like.
  • the method for bringing the cation exchange resin into contact with the aqueous solution of sodium hypochlorite is not particularly limited, and any known method may be employed. Specifically, it is a method of contacting a column containing a cation exchange resin by passing an aqueous solution of sodium hypochlorite.
  • the ion exchange resin may be regenerated.
  • the regeneration method of the ion exchange resin is not particularly limited, and a known method may be adopted. Specifically, it is a method of passing hydrochloric acid or sulfuric acid through a column in which a cation exchange resin is sealed after passing an aqueous solution of sodium hypochlorite. Moreover, you may include the process (c) which adjusts the pH of a process liquid similarly to 2nd Embodiment after the said process.
  • the storage method of the treatment liquid of the present invention is not particularly limited, it is preferable to store at a temperature of 20 ° C. or less because the decomposition of hypochlorite ion increases with an increase in temperature.
  • hypochlorite ions are also decomposed by ultraviolet light, storage in the dark is preferable. If such storage conditions are applied, storage stability of the treatment liquid can be further enhanced.
  • the washing conditions under which the treatment liquid of the present invention is used are in the range of 10 to 80 ° C., preferably 20 to 70 ° C., and may be appropriately selected in accordance with the washing conditions of the washing apparatus to be used.
  • the etching rate of Ru / W changes with the cleaning temperature. Therefore, in order to improve the washability of Ru / W, the temperature for washing may be selected as 50 to 70 ° C. in the above temperature range. If the temperature is in the range of 50 to 70 ° C., the etching rate can be increased, and the process can be performed with a simple apparatus with high operability. For example, it is known that the washability is different between the case of single-wafer washing and the case of batch washing even when the same washing conditions are selected. Therefore, when the cleaning property of Ru / W is insufficient depending on the system of the cleaning apparatus, the cleaning conditions may be appropriately selected such as setting the cleaning temperature high.
  • the time for using the treatment liquid of the present invention is in the range of 0.1 to 120 minutes, preferably 0.5 to 60 minutes, and may be appropriately selected depending on the conditions of etching and the semiconductor element to be used. Although an organic solvent such as alcohol can be used as a rinse solution after using the treatment solution of the present invention, it is sufficient to rinse with deionized water.
  • the treatment liquid of the present invention can etch Ru / W efficiently.
  • the etching rate can be 5 nm or more / minute or more, preferably 10 nm / minute or more.
  • the etching rate can be 50 nm or more / minute or more, preferably 100 nm / minute or more.
  • the remaining amount of metal for example, sodium is less than 1.0 ⁇ 10 15 atoms / cm 2 , preferably less than 6.2 ⁇ 10 14 atoms / cm 2. Can be reduced.
  • the treatment liquid of the present invention can be suitably used in a method of manufacturing a semiconductor element including the step of removing Ru / W attached to the end face portion and the back face portion of the semiconductor wafer.
  • PH measurement method The pH of the treatment solution (30 mL) prepared in Examples and Comparative Examples was measured using a bench-top pH meter (LAQUA F-73, manufactured by Horiba, Ltd.). The pH was measured after the treatment solution was adjusted and stabilized at 25 ° C.
  • the prepared brown solution is subjected to oxidation-reduction titration using a 0.02 M sodium thiosulfate solution (manufactured by Wako Pure Chemical Industries, Ltd., for volumetric analysis) until the color of the solution turns from brown to very pale yellow, and then a starch solution is added. A light purple solution is obtained. To this solution was further added successively a 0.02 M sodium thiosulfate solution, and the effective chlorine concentration was calculated with the point of becoming colorless and transparent as an end point. The hypochlorite ion concentration was calculated from the obtained available chlorine concentration. For example, if the effective chlorine concentration is 1%, the hypochlorite ion concentration will be 0.73%.
  • the alkyl ammonium ion concentration in the treatment solutions of the examples and comparative examples was determined by calculation from pH, hypochlorite ion concentration, and sodium ion concentration.
  • the surface of the silicon wafer was observed with a 20000 ⁇ microscope. At this time, a case where some foreign matter was observed was regarded as defective (B), and a case where no foreign matter was confirmed was regarded as excellent (A). Although the origin and composition of the foreign matter are not necessarily clear, it is considered that any component dissolved in the processing solution has re-adhered on the wafer surface. In the case where the Ru etching rate is extremely low, it takes time to remove the Ru film, and therefore, the foreign matter is not evaluated.
  • Each sample piece cut into 10 ⁇ 20 mm is immersed in 30 mL of the treatment liquid of the example and the comparative example for 1 minute. After that, four rinse solutions were prepared in which 30 mL of ultrapure water was placed in a container made of fluorine resin in advance, and each sample piece after immersion in the treatment solution was immersed and cleaned for 1 minute while being shaken. Thereafter, the concentration of Na contained in the fourth rinse solution was analyzed using high frequency inductively coupled plasma emission spectrometry (iCAP 6500 DuO, manufactured by Thermo SCIENTIFIC).
  • iCAP 6500 DuO high frequency inductively coupled plasma emission spectrometry
  • the residual Na concentration exceeds 1.0 ⁇ 10 15 atoms / cm 2, it may remain on the surface of the semiconductor device, and the yield of the semiconductor device may be significantly reduced.
  • the lower limit of quantification (detection limit) of this measurement method was less than 6.2 ⁇ 10 14 atoms / cm 2 .
  • the evaluation result by this measurement is an index indicating the tendency of sodium contained in the processing liquid to remain on the wafer when the processing liquid is used to clean the semiconductor wafer. Even when the residual Na concentration exceeds 1.0 ⁇ 10 15 atoms / cm 2 , the residual Na concentration can be reduced by repeatedly performing the washing. The following criteria were evaluated.
  • Example 1 Manufacturing of treatment solution
  • Pretreatment of ion exchange resin Hydrogen type ion exchange resin 200 mL of a strongly acidic ion exchange resin (manufactured by Organo Inc., Amberlite IR-120 BNa) was charged into a glass column having an inner diameter of about 45 mm (Bio Column CF-50TK manufactured by AsOne). Thereafter, 1 L of 1 N hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd., for volumetric analysis) is passed through the ion exchange resin column to exchange it into a hydrogen type, and 1 L of ultrapure water is passed to wash the ion exchange resin. Liquid.
  • ⁇ (A) Process> Furthermore, 1 L of a 10% tetramethylammonium hydroxide solution is passed through 209 mL of a 2 meq / mL-R ion exchange resin that has been exchanged to a hydrogen form, and the ion exchange resin is ionized to a tetramethyl ammonium (TMA) form from a hydrogen form. I replaced it. After ion exchange, 1 L of ultrapure water was passed to wash the ion exchange resin.
  • TMA tetramethyl ammonium
  • Example 2 The same operation is performed as in Example 1, except that the amount of ion exchange resin in the step (a) is 282 mL and the concentration of the sodium hypochlorite aqueous solution in the step (b) is 4.20% by mass. A treatment solution of the described composition was obtained. The evaluation results are shown in Table 3.
  • Example 3 The same procedure is performed as in Example 1 except that the amount of ion exchange resin in step (a) is 141 mL and the concentration of the sodium hypochlorite aqueous solution in step (b) is 2.10% by mass. A treatment solution of the described composition was obtained. The evaluation results are shown in Table 3.
  • Example 4 The same procedure as in Example 1 is carried out to obtain a treatment liquid, and further, as a pH adjustment step (c), the treatment is carried out on a glass column packed with 50 mL of 2 meq / mL-R cation exchange resin exchanged to hydrogen form. By passing the solution, a treatment solution having the composition described in Table 2 was obtained. The evaluation results are shown in Table 3.
  • Example 5 After performing the same operation as in Example 1 to obtain a treatment liquid, as a pH adjustment step (c), further add 25% tetramethylammonium hydroxide (TMAH) solution to the treatment liquid until the pH reaches 11.5. Were added to obtain a treatment solution of the composition described in Table 2. The evaluation results are shown in Table 3.
  • TMAH tetramethylammonium hydroxide
  • Example 6 The same operation is performed as in Example 1, except that the amount of ion exchange resin in the step (a) is 31 mL and the concentration of the sodium hypochlorite aqueous solution in the step (b) is 0.46 mass%. A treatment solution of the described composition was obtained. The evaluation results are shown in Table 3.
  • Example 7 In Example 1, the amount of ion exchange resin in the step (a) is 564 mL, the flow rate of 10% tetramethylammonium hydroxide solution is 2 L, and the concentration of the sodium hypochlorite aqueous solution in the step (b) is 8. The same operation as in 39% by mass was performed to obtain a treatment liquid having the composition described in Table 2. The evaluation results are shown in Table 3.
  • Example 8 In Example 1, the amount of ion exchange resin in step (a) is 705 mL, the flow rate of 10% tetramethylammonium hydroxide solution is 2 L, and the concentration of the aqueous sodium hypochlorite solution in step (b) is 10.2. The same operation as in 49% by mass was performed to obtain a treatment liquid having the composition described in Table 2. The evaluation results are shown in Table 3.
  • Example 9 Sodium hypochlorite pentahydrate (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) is dissolved in water so that the amount of hypochlorite ion is 2.15% by mass, the composition described in Table 2 The processing solution of The evaluation results are shown in Table 3.
  • Comparative Example 1 The same procedure as in Example 1 is carried out to obtain a treatment liquid, and further, as a pH adjustment step (c), the treatment is carried out on a glass column packed with 203 mL of 2 meq / mL-R cation exchange resin exchanged to hydrogen form. By passing the solution, a treatment solution having the composition described in Table 2 was obtained. The evaluation results are shown in Table 3.
  • Comparative example 2 The same procedure as in Example 1 is carried out to obtain a treatment liquid, and further, as a pH adjustment step (c), the treatment is carried out on a glass column packed with 208 mL of 2 meq / mL-R cation exchange resin exchanged to hydrogen form. By passing the solution, a treatment solution having the composition described in Table 2 was obtained. The evaluation results are shown in Table 3.
  • Comparative example 3 The same procedure as in Example 1 is carried out to obtain a treatment liquid, and further, as a pH adjustment step (c), the treatment is carried out on a glass column packed with 209 mL of 2 meq / mL-R cation exchange resin exchanged to hydrogen form. By passing the solution, a treatment solution having the composition described in Table 2 was obtained. The evaluation results are shown in Table 3.
  • Comparative example 4 The same procedure as in Example 1 is carried out to obtain a treatment solution, and then a 25% tetramethylammonium hydroxide solution is added to the treatment solution until the pH reaches 13.0 as a pH adjustment step (c). A treatment solution of the composition described in Table 2 was obtained. The evaluation results are shown in Table 3.
  • Table 1 shows the composition of each processing liquid
  • Table 3 shows an evaluation result.
  • the processing solution of the present embodiment had a high etching rate of ruthenium and tungsten, was effective for removing these metals, and did not leave any foreign matter.
  • the processing solutions of Examples 5 and 6 have low etching rates at 23 ° C., but by raising the etching temperature, the etching rates are improved, and it has been confirmed that they can be used practically without any problem. Since the treatment liquid of Example 9 contains a large amount of Na ions, the residual amount of Na after washing is large, but such residual Na can be sufficiently reduced by repeatedly washing. Moreover, if it is a processing liquid of this embodiment, it is excellent also in storage stability.
  • the treatment solution of the present embodiment was evaluated etching with respect to Si-containing film produced during a primary material Si and circuit formation of a semiconductor wafer (SiO 2, Si 3 N 4 ), both 0.1 nm / It was confirmed that it was less than a minute, and that ruthenium and tungsten to be removed could be efficiently etched.
  • Comparative Examples 1, 2 and 3 have a low pH and a slow etching rate. In addition, after etching, foreign matter remains, and storage stability is low.
  • Example 10 Acetonitrile was added to the treatment liquid obtained in Example 2 to obtain a treatment liquid having the composition described in Table 4. The pH of this processing solution and the etching rate at 23 ° C. for the Ru film were evaluated. The results are shown in Table 4.
  • Example 11 To the treatment solution obtained in Example 2, sulfolane was added to obtain a treatment solution having the composition described in Table 4. The pH of this processing solution and the etching rate at 23 ° C. for the Ru film were evaluated. The results are shown in Table 4.
  • the treatment liquid of Examples 10 and 11 has the same composition as that of Example 2 except that water and an organic solvent are used in combination as the solvent.
  • the Ru etching rate changed depending on the type of organic solvent. It was found that Ru etching rate decreased for both acetonitrile and sulfolane.
  • Example 12 Manufacturing of treatment solution
  • Pretreatment of ion exchange resin Hydrogen type ion exchange resin Acrylic hypoion (WK40L, manufactured by Mitsubishi Chemical Corporation) is sealed in a column as a weakly acidic ion exchange resin, and a sodium hypochlorite aqueous solution prepared to have a predetermined hypochlorite ion concentration is passed through the column.
  • the treatment solution shown in Table 5 was obtained.
  • an ion exchange resin having an ion exchange capacity equivalent to 1.3 mmol / L Na ion is enclosed in a column, and a 3% aqueous solution of sodium hypochlorite Was obtained by passing through a column.
  • Example 13 The same procedure is performed as in Example 12 except that an ion exchange resin having an ion exchange capacity equivalent to 1.2 mmol / L Na ion is enclosed in a column, and a treatment liquid having a composition described in Table 5 is obtained. The results are shown in Table 5.
  • Example 14 In Example 12, an ion exchange resin having an ion exchange capacity equivalent to 6.5 mmol / L Na ion is enclosed in a column, and the same operation is carried out except that a 2% aqueous sodium hypochlorite solution is passed through the column. To obtain a treatment solution of the composition described in Table 5. The results are shown in Table 5.
  • Example 15 In Example 12, an ion exchange resin having an ion exchange capacity equivalent to 1.6 mmol / L Na ion is enclosed in a column, and the same operation is performed except that a 4% aqueous sodium hypochlorite solution is passed through the column. To obtain a treatment solution of the composition described in Table 5. The results are shown in Table 5.
  • Comparative example 5 The same operation as in Example 12 was performed except that an ion exchange resin having an ion exchange capacity equivalent to 290 mmol / L Na ion was enclosed in a column, to obtain a treatment liquid having the composition described in Table 5. The results are shown in Table 5.
  • Comparative example 6 The same operation as in Example 12 was carried out except that an ion exchange resin having an ion exchange capacity equivalent to 287 mmol / L Na ion was enclosed in a column, to obtain a treatment liquid having the composition described in Table 5. The results are shown in Table 5.
  • Comparative example 7 Comparative Example 1 The same operation as in Example 12 is carried out except that the ion exchange resin is contacted until the sodium ion concentration contained in the treatment solution becomes 10 ppb or less, to obtain a treatment solution having the composition described in Table 5. The results are shown in Table 5.
  • Example 16 In Example 12, an ion exchange resin having an ion exchange capacity equivalent to 3.4 mmol / L Na ion is enclosed in a column, and the same operation is carried out except that an 8% aqueous sodium hypochlorite solution is passed through the column. To obtain a treatment solution of the composition described in Table 5. The results are shown in Table 5.
  • the treatment solutions of Examples 12 to 15 have a high ruthenium etching rate, can perform treatment with little residual sodium after washing, and are excellent in storage stability.
  • Example 16 the etching rate of ruthenium was good, and it could be confirmed that it could be used without any problem in practical use. Since the treatment liquid of Example 16 contains a large amount of Na ions, the residual amount of Na after washing is large, but such residual Na can be sufficiently reduced by repeatedly washing.

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EP19741609.2A EP3726565A4 (en) 2018-01-16 2019-01-15 HYPOCHLORITON TREATMENT LIQUID FOR SEMICONDUCTOR WAFER
KR1020207020591A KR102766830B1 (ko) 2018-01-16 2019-01-15 차아염소산 이온을 포함하는 반도체 웨이퍼의 처리액
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US16/962,260 US11390829B2 (en) 2018-01-16 2019-01-15 Treatment liquid for semiconductor wafers, which contains hypochlorite ions
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Cited By (15)

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WO2020100924A1 (ja) * 2018-11-14 2020-05-22 関東化学株式会社 ルテニウム除去用組成物
WO2021059666A1 (ja) 2019-09-27 2021-04-01 株式会社トクヤマ ルテニウムの半導体用処理液及びその製造方法
JP2021090051A (ja) * 2019-11-22 2021-06-10 株式会社トクヤマ 次亜塩素酸第四級アルキルアンモニウム溶液、その製造方法および半導体ウエハの処理方法
JPWO2022050273A1 (https=) * 2020-09-03 2022-03-10
WO2022114036A1 (ja) 2020-11-26 2022-06-02 株式会社トクヤマ 半導体ウェハの処理液及びその製造方法
JPWO2022131186A1 (https=) * 2020-12-18 2022-06-23
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KR20220136262A (ko) 2021-03-31 2022-10-07 가부시끼가이샤 도꾸야마 반도체용 처리액
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