Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B08—CLEANING
  • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
  • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
  • B08B3/04—Cleaning involving contact with liquid
  • B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B08—CLEANING
  • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
  • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
  • B08B3/04—Cleaning involving contact with liquid
  • B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
  • B08B3/12—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by sonic or ultrasonic vibrations
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/26—Organic compounds containing oxygen
  • C11D7/265—Carboxylic acids or salts thereof
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/32—Organic compounds containing nitrogen
  • C11D7/3281—Heterocyclic compounds
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
  • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
  • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
  • C23G1/08—Iron or steel
  • C23G1/088—Iron or steel solutions containing organic acids
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
  • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
  • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
  • C23G1/10—Other heavy metals
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
  • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
  • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
  • C23G1/12—Light metals
  • C23G1/125—Light metals aluminium
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
  • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
  • C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
  • C23G1/26—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions using inhibitors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/42—Stripping or agents therefor
  • G03F7/422—Stripping or agents therefor using liquids only
• • 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
• • 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
  • C11D2111/16—Metals
• • 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 subject of the present invention is an optimized method comprising the use of a solution based on particular ionic liquid of the PIL type (liquid protic ionic according to the English terminology or protic ionic liquid), said solution being used for cleaning, stripping, electrolytic degreasing, derestriction of surfaces such as metals, ceramics, glasses, semiconductors and plastics, said surfaces having been oxidized and / or contaminated with oils or greases and / or having have been covered with a protective coating, or else soiled by particles or any other residue.
• PIL type liquid protic ionic according to the English terminology or protic ionic liquid
• the process according to the invention uses a solution containing a protic ionic liquid obtained by acid-base reaction with at least one acid containing at least one carboxylic function and a base which is an imidazole diamine.
• the surfaces to be treated must be previously free of any contamination of organic and / or inorganic impurities that can come from the parts development steps (forming, machining using a lubricant or cutting liquid or protection, storage, ... etc).
• organic solvents are flammable, highly volatile and toxic (including carcinogens and mutagens).
• VOC Volatile Organic Compound
• the patent application WO2006 / 088737 describes the use of ionic liquids containing either an imidazolium cation, a pyridinium cation, pyrrolidinium, ammonium or even phosphonium.
• the ionic liquids are used in the "pure" state, that is to say that in this case, the ionic liquid consists entirely of ions and must contain less than 1% of impurities. If the ionic liquid is derived from the reaction of an acid with a base such as imidazole or derivative, then the degree of proton transfer of the acid must be greater than 99%. In addition, their use is limited to the cleaning of semiconductor surfaces.
• the Applicant has discovered that a multicomponent solution based on a particular type of ionic liquid could be used in surface cleaning processes such as metals, ceramics, glasses, semiconductors and plastics, in particular. having good cleaning efficiency.
• the particular type of ionic liquids in the composition of the solution is easy to obtain and can be economically manufactured.
• it has the particularity of being easily regenerable - and therefore reusable - for example thermally
• Another advantage of the process of the invention is that it can be implemented by minimizing the risks of chemical attack by corrosion.
• PILs protic ionic liquids according to the English terminology or protic ionic liquid
• protic ionic liquids are easily produced by combining a Bronsted acid and a
• the main distinguishing feature of PILs from other ionic liquids is the proton transfer from the acid to the base, leading to the presence of proton donor or acceptor sites, resulting in specific properties for PILs. and different from other ionic liquids.
• Ionic liquids of the PIL type have a proton available for a hydrogen bond and are obtained according to the following mechanism: B + AH o HB + A " where AH is an acid and B a base
• the acid-base equilibrium implies that the acid reaction base is not total and therefore, the so-called "multi-constituent" solution used in the process of the invention comprises the acid, the base and the ionic liquid resulting therefrom.
• Cleaning process means any method of cleaning, stripping, degreasing (electrolytic or not), derisinage, applied to surfaces such as metals, ceramics, glasses, semiconductors and plastics, said surfaces having been oxidized and / or contaminated with oils or greases and / or having been covered with a temporary protective coating or not, or else soiled by any type of soiling, in the form of particles for example.
• temporary protective coating is generally meant any type of coating that has been used for the protection or treatment of the material in previous development steps.
• the invention relates to an optimized surface cleaning method of the metal, ceramic, glass or plastic composite material type such as semiconductors, in which said surface is treated with a solution comprising a mixture of an ionic liquid of the PIL type.
• the acid or acids may be either acetic acid or propionic acid used alone or in combination with a second acid having a function carboxylic acid such as maleic acid, lactic acid, succinic acid, oxalic acid.
• the acid is either acetic acid or propionic acid, used alone.
• acetic acid or propionic acid are used in combination with lactic acid or succinic acid.
• the subject of the invention is an optimized method of degreasing and / or surface etching of metal, ceramic, glass, plastic or semiconductor composite material, in which said surfaces are sprinkled and / or immersed with in a solution comprising a mixture of a PILs ionic liquid, an imidazole diamine and at least one acid containing at least one carboxylic function.
• the process according to the invention uses a solution containing a protic ionic liquid obtained by acid-base reaction with at least one acid containing a carboxylic function and a base which is a diamine, the said acid or acids containing at least one less a carboxylic function and the base being an imidazole diamine.
• the one or more acids may be either acetic acid or propionic acid used alone, or in combination with a second acid having at least one carboxylic function such as maleic acid, lactic acid, succinic acid, oxalic acid.
• the acid is either acetic acid or propionic acid, used alone.
• acetic acid or propionic acid are used in combination with lactic acid or succinic acid.
• the diamine imidazole type has the following formula:
• R1 H or alkyl group containing 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms.
• the solution comprises a mixture of 1-ethylimidazole, acetic acid and 1-ethylimidazolium acetate.
• the solution comprises a mixture of 1-butylimidazole, acetic acid and 1-butylimidazolium acetate.
• the solution comprises a mixture of 1-methylimidazole, acetic acid and 1-methylimidazolium acetate.
• the solution comprises a mixture of 1-ethylimidazole, propionic acid and 1-ethyl imidazolium propionate.
• the solution comprises a mixture of 1-butylimidazole, propionic acid and 1-butylimidazolium propionate.
• the solution comprises a mixture of 1-methylimidazole, propionic acid and 1-methylimidazolium propionate.
• the solution comprises a mixture of 1-ethylimidazole, 1-ethylimidazolium propionate, propionic acid, succinic acid and 1-ethylimidazolium succinate.
• the solution used according to the invention is obtained by bringing the acid or acids into contact with the base in proportions such as the ratio x / y, where x is the number of imidazole functions or the number of nitrogen atoms. and therefore of basic equivalent, and y the number of carboxylic functions, between 0.5 and 2.0, and more preferably between 0.9 and 1.1.
• the contacting is generally carried out with stirring.
• the solution is used without dilution, but it is not excluded that it contains a co-solvent, such as water for example. With water, dilution rates of up to 30% can be used.
• the ionic liquid solution of PIL type implemented according to the process of the invention advantageously has a pH generally between 6.0 and 8.0, preferably between 6 and 7.5.
• Said solution is brought into contact with the surface to be treated preferably by spraying or by immersion of said surface in a treatment bath containing the solution described above.
• the modes of contact “spraying” and “immersion” can also be combined, and possibly supplemented by mechanical brushing.
• the temperature of the solution or of the treatment bath is generally between 15 and 80 ° C., preferably between 30 and 70 ° C.
• the treatment bath containing the solution based on ionic liquid is subjected to ultrasound.
• the ultrasonic generators used according to the method of the invention may be at single or variable ultrasound frequency and in particular be submersible to be installed in existing tanks.
• the ultrasound frequency is generally between 20 and 160 kHz, preferably between 30 and 80 kHz.
• the duration of the treatment is generally between 1 and 60 minutes, preferably less than 30 minutes.
• the treated part (s) is (are) rinsed (s) with water, for example by immersion in a tank of dimensions adapted to those of the room or even with the help of jets of water.
• the conditions of use of the degreasing / pickling bath common to the following examples are as follows.
• the ultrasound heated bath is a TRANSSONIC device type T570 / H of the brand ELMA ®. Its characteristics are as follows: internal dimensions of the tank: 240 x 137 x 100 mm, ultrasonic frequency: 35 kHz, - power: 360 W
• the following operations are successively carried out: soaking of the parts to be treated in a bath containing the PILs-type ionic liquid solution, - heating of the bath and implementation of the ultrasound for the time required for the part to be treated, rinsing with water. water then drying with a blower parts.
• Example 1 Draising of silicon wafers with a solution containing a mixture of 1-ethylimidazole, acetic acid and 1-ethylimidazolium acetate (according to the invention)
• the wafer is a very pure silicon wafer used for the manufacture of integrated circuits. Silicon wafer cleaning tests are carried out with a solution containing a mixture of 1-ethylimidazole, acetic acid and 1-ethylimidazolium acetate. The solution is prepared using an x / y ratio (number of imidazole functions / number of carboxylic functions) equal to 1.
• wafer T3 1, 8 ⁇ m
• wafer T5 13 ⁇ m
• the wafers are immersed in a bath containing the solution at a temperature of between 50 ° C. and 55 ° C., at a pH of 6.1 (at 1M in water), using ultrasound. After treatment, the wafers are rinsed with ultra pure water.
• Table 1 summarizes the tests carried out and the results obtained in terms of removal rate of the resin. This is quantified visually by optical microscope observation (magnification 50). It is found that the removal rate of the resin is 100% when the entire surface of the sample is completely gray and matte knowing that before treatment, the wafers have a brown surface with iridescence. Observation under the microscope clearly reveals a totally resin-free surface.
• Example 2 Draising of silicon wafers with various solutions of "pure” ionic liquids (not in accordance with the invention).
• Silicon wafers having a thickness of 1, 8 and 13 ⁇ m on which a resin of the SU-8 2005 type has been deposited have been treated according to the protocol of Example 1 with various solutions of "pure" ionic liquids whose composition is specified below and corresponds to the ionic liquids described in the patent application WO2006 / 088737.
• the tests below are summarized in Table 2 below:
• Example 3 Derivatization of silicon wafers with a solution containing a mixture of propionic acid, 1-ethylimidazolium propionate, succinic acid and 1-ethylimidazolium succinate (according to the invention)
• Silicon wafer derisinage tests were carried out according to the same protocol as Example 1 but using a mixture of propionic acid, 1-ethylimidazolium propionate, succinic acid and 1-ethylimidazolium succinate.
• the solution was prepared using a ratio x / y (number of imidazole functions / number of carboxylic functions) equal to 1 and the pH of the solution is 6.4.
• the solution has, among others, good characteristics of non-flammability since its flash point (according to NF EN ISO 2719) is 120 0 C and its point of fire (NF
• EN ISO 2592 is also 120 ° C.
• the removal efficiency of the resin is complete even for low immersion times.
• Example 4 Cleaning of aluminum vials coated with bituminous ink with five solutions (according to five embodiments of the invention):
• the flasks are immersed in a bath containing a solution of ionic liquid PILs type 1, the solution being diluted or not with 30% vol. of water, the bath being heated to different temperatures (30 and 60 ° C) over different durations (5 and 20 minutes). Ultrasound is carried out in the bath.
• vials were treated according to the process described above by setting the treatment time to 5 minutes and using 4 different solutions (SOL 2 to SOL 5), the respective compositions of which are as follows:
• SOL 2 mixture of 1-butylimidazole, acetic acid and 1-butylimidazolium acetate (solution prepared according to a ratio x / y equal to 0.95)
• SOL 3 mixture of 1-ethylimidazole, acetic acid and 1-ethylimidazolium acetate
• SOL 5 mixture of 1-ethylimidazole, propionic acid and propionate of
• Table 5 shows that for this application and the fixed treatment operating conditions, SOL 2 and SOL 5 solutions are the most suitable.
• Aluminum flasks are cleaned in an ultrasonic tank according to the protocol described in Example 4 but using pure ionic liquid solutions which are:
• Example 6 Cleaning copper, stainless steel and molybdenum parts by treatment with a solution containing a mixture of 1-ethylimidazole, acetic acid and 1-ethylimidazolium acetate (SOL 3), according to the invention
• Tests for cleaning metal parts of various types and having greasy and dirty surfaces are carried out using a solution containing a mixture of 1-ethylimidazole, acetic acid and 1-ethylimidazolium acetate.
• the solution is prepared at an x / y ratio of 1.0 in a pH of 6.1 bath and a temperature of 55 ° C in which ultrasound is applied.
• the duration of treatment is 5 minutes.
• the parts treated according to the process of the invention are either copper, stainless steel or molybdenum.
• the surface finish after treatment is clear and bright.
• a blue-colored ionic liquid is obtained, attesting to the presence of Cu 2+ cations in solution and to a stripping of the surface by dissolving the surface oxide layer. copper.
• molybdenum parts which have complex shapes (recesses, threads, which are dirt retention zones), they also have after treatment, a glossy appearance and good wettability when rinsing with water.
• Example 7 Cleaning of stainless steel test pieces with different solutions according to the invention
• Sheet metal test pieces (dimensions: 70 ⁇ 10 mm) made of stainless steel having been greased beforehand by immersing them in cutting oil for 48 hours and storage for 1 week before carrying out the cleaning method according to the invention.
• test pieces are immersed for 5 minutes in a treatment bath at 55 ° C. (with use of ultrasound) containing a solution which is chosen from the SOL2 to SOL5 solutions described in Example 2.
• the effectiveness of the degreasing is evaluated by a qualitative wettability test which consists of observing the homogeneity of the water film present on the surface of the test piece treated and rinsed with water. If the film remains homogeneous over a period of 30 seconds, the test is positive as to the good degreasing efficiency.
• Example 8 Cleaning stainless steel test pieces by treatment with a solution containing a mixture of propionic acid, 1-ethylimidazole, 1-ethylimidazolium propionate, lactic acid and 1-ethylimidazolium lactate (according to US Pat. invention)
• a cleaning test was conducted according to the same protocol as that of Example 7 (except immersion time equal to 10 min) with a solution containing a mixture of propionic acid, 1-ethylimidazolium propionate, acid lactic and lactate 1- ethylimidazolium. This was prepared by contacting propionic acid and lactic acid with 1-ethylimidazole in a ratio x / y equal to 1. The pH of the solution is equal to 6.5 (1M in 1). 'water).
• the cleaning test leads to good wettability and satisfactory degreasing efficiency.
• Example 9 Cleaning of stainless steel test pieces by treatment with a solution containing a pure ionic liquid (1-butyl-3-methylimidazolium hydrogensulfate, not in accordance with the invention).
• Example 8 The same type of treatment as that of Example 8 was carried out with a pure ionic liquid: 1-butyl-3-methylimidazolium hydrogensulfate. Its pH is acidic (1.0 to 100 g / i). The wettability of the surface is good but on the other hand, at the end of the treatment, the part has a surface with strongly oxidized zones because of the strong acidity of the surface. solution.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Life Sciences & Earth Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Detergent Compositions (AREA)
• Cleaning Or Drying Semiconductors (AREA)

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• 2008
  • 2008-10-09 FR FR0805579A patent/FR2937048B1/fr active Active
• 2009
  • 2009-10-08 EP EP09752202A patent/EP2331672A1/de not_active Withdrawn
  • 2009-10-08 WO PCT/FR2009/001194 patent/WO2010040917A1/fr active Application Filing

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