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WO2012128627A1 - Procédé de nettoyage d'une surface - Google Patents

Procédé de nettoyage d'une surface Download PDF

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Publication number
WO2012128627A1
WO2012128627A1 PCT/NL2012/050174 NL2012050174W WO2012128627A1 WO 2012128627 A1 WO2012128627 A1 WO 2012128627A1 NL 2012050174 W NL2012050174 W NL 2012050174W WO 2012128627 A1 WO2012128627 A1 WO 2012128627A1
Authority
WO
WIPO (PCT)
Prior art keywords
droplet
nanobubbles
liquid
solvent
cleaning
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/NL2012/050174
Other languages
English (en)
Inventor
Shangjiong Yang
Jacques Cor Johan Van Der Donck
Antonie Ellert Duisterwinkel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
Original Assignee
Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO filed Critical Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
Publication of WO2012128627A1 publication Critical patent/WO2012128627A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling

Definitions

  • the invention relates to a method of cleaning a surface using continuously generated nanobubbles.
  • the invention further relates to a system for enabling cleaning a surface using continuously generated nanobubbles.
  • a method of cleaning a surface using electrochemically generated nanobubbles is known from Z.Wu et al "Cleaning using nanobubbles: defoulin by electrochemical generation of bubbles" .
  • a surface conceived to be cleaned is submerged in an electrolyte in which nanobubbles are generated.
  • the nanobubbles interacting with the surface remove (part of) thin film layer on the surface and by doing so clean the surface.
  • the method of cleaning a surface comprises the steps of:
  • a method of cleaning a surface is known from JP 2009 101299, wherein nanobubbles homogeneously dispersed in a liquid are used. It is a
  • the nanobubbles are generated directly and instantly on the surface to be cleaned within the droplet which is pre-seeded on the surface. This results in a substantial increase of the cleaning efficiency, in particular, for particles up to 20nm in size.
  • the droplet comprises the nanobubbles generated using electrolysis.
  • the surface or at least a portion of it must be conductive to form a part of the electrolysis electric circuit.
  • electrolysis of water is used.
  • the droplet is formed by one or more needle-like electrodes. It will be appreciated, however, that a plurality of droplets may be formed at the same time on the surface using a suitable plurality of electrodes.
  • the one or more needle-like electrodes are adapted to conduct the droplet-forming liquid to the surface.
  • the droplet comprises the nanobubbles generated by mixing of two solvent liquids.
  • the droplet comprising the nanobubbles is a droplet of an electrolyte which is displaced over the surface using an electrowetting matrix, the surface forming a part of the electrowetting matrix.
  • the droplet (or droplets) formed on the surface may be efficiently and controllably displaced when the surface acts as a first electrode in the electrowetting set-up. More details on this embodiment will be given with reference to Figure 3.
  • the droplet When applying the electrowetting principle, the droplet may be displaced over the surface by applying a sequence of potentials to electrodes forming the electrowetting matrix.
  • a further conduit arranged in fluid communication with the droplet may be provided for conducting the liquid away from the surface.
  • the contaminants accumulated in the droplet are conducted away from the surface.
  • the said droplet of liquid comprises dissolved gas, the method further comprising the step of maintaining the temperature of the said droplet in the range of 25 - 45 degrees Celsius.
  • the gas is selected from the group consisting of: hydrogen, helium, methane, nitrogen, oxygen, argon, carbon dioxide, air.
  • the system for enabling cleaning a surface using continuously generated nanobubbles comprises:
  • Figure 1 presents in a schematic way an embodiment wherein water electrolysis is applied for generating nanobubbles and displacing the droplet over the surface.
  • Figure 2 presents in a schematic way an embodiment wherein two solvents are used for generating nanobubbles and displacing the droplet over the surface.
  • Figure 2a presents an embodiment wherein continuous cleaning of a surface is enabled.
  • Figure 3 presents in a schematic way an embodiment wherein an electrowetting matrix is used for generating nanobubbles and displacing the droplet over the surface.
  • Figure 4 presents in a schematic way an embodiment of the system according to the invention wherein the droplet comprises dissolved gas.
  • Figure 1 presents in a schematic way an embodiment 10 wherein water electrolysis is applied for generating nanobubbles and displacing a droplet over the surface.
  • the surface 2 may relate to any suitable surface which has to be made substantially free from surface contaminations.
  • the surface 2 may relate to a surface of a wafer.
  • the method of the invention is suitable for cleaning other surfaces, plain or patterned.
  • extreme ultraviolet lithography reticles, glass plates, and other substrates, especially for semiconductor industry: integrated circuit, light emitting diode, flat panel display, photovoltaics, and nanotechnology-produced items may be successfully cleaned.
  • a liquid droplet 3 comprising nanobubbles 3a is generated on the surface 2 .
  • an electrolysis set-up is used.
  • the electrolysis set-up comprises a voltage source 5 adapted to generate voltage between the surface 2 and a working electrode 4.
  • the working electrode may be needle formed. It will be appreciated that for realization of the electrolysis set-up the surface 2 should be electrically conductive.
  • the working liquid water may be used.
  • the water may be supplied by a suitable conduit (not shown), or, alternatively, the working electrode 4 may be provided with a conduit for supplying water to the surface 2.
  • the droplet of a suitable liquid for example, water
  • the surface 2 will be subject to cleaning.
  • the working electrode 4 may be suitably displaced.
  • the displacement pattern is pre-programmed.
  • a further conduit 4a is provided.
  • the further conduit is
  • the new clean droplets may be generated and the cleaning procedure may be resumed. It will be appreciated that a plurality of individual droplets comprising nanobubbles may be generated and displaced in this way.
  • Figure 2 presents in a schematic way an embodiment 20 wherein two solvents are used for generating nanobubbles, displacing the droplet over the surface. This particular embodiment is based on the insight that when two solvent liquids having different gas solubility are mixed in a droplet 23, generation of nanobubbles 23a will occur.
  • a conduit 24 may be provided which comprises a suitable bifurcation for conducting a first solvent liquid, such as alcohol, and a second solvent liquid, such as water towards the surface 22 conceived to be cleaned.
  • a first solvent liquid such as alcohol
  • a second solvent liquid such as water
  • the first solvent liquid may be conducted using the arm 24a and the second solvent liquid may be conducted using the arm 24b.
  • a further conduit 25 is provided for removing particles from the surface .
  • the supply conduit 24 and the further conduit 25 are movable in accordance with each other over the surface 22. It will be appreciated that a plurality of individual droplets comprising nanobubbles may be generated and displaced in this way.
  • FIG 2a presents in a schematic way an alternative embodiment allowing for continuous cleaning of the surface.
  • the embodiment 200 is in general similar to the embodiment 20 shown in Figure 2, except that in the present embodiment separate conduits 240a, 240b are provided for each liquid.
  • the liquids exiting from a distal portion of each respective conduit 240a, 240b mix directly in the droplet 23. This improves the efficiency of nanobubble formation at the surface as the interaction between the two liquids takes place substantially at the surface.
  • the conduits 240a and 240b are being synchronously moved with respect to the surface 22. It will be appreciated that, in principle, either the conduits may be moved or the surface may be moved.
  • Figure 3 presents in a schematic way an embodiment 30 wherein an electrowetting matrix is used for generating nanobubbles and displacing a droplet over the surface.
  • This particular embodiment is based on the insight that electrowetting principle may be used for displacing the droplet over the surface 32, which is conceived to be cleaned.
  • a suitable electrolyte such as diluted ammonia may be selected.
  • the droplet having surface portions 33a, 33b and comprising nanobubbles 33a', formed between the surface 32 and the matrix 34 may be displaced.
  • the matrix 34 may comprise a suitable number of electrode portions 36a, ... 36n which can be energized separately by the voltage pulses. It will be also appreciated that a plurality of individual droplets may be generated and displaced over the surface 32 in this way.
  • Figure 4 presents in a schematic way an embodiment of the system according to the invention wherein the droplet comprises dissolved gas.
  • a suitable substrate 41 comprising a surface to be cleaned may be adapted to be movable in the direction schematically indicated by arrow 48. It will be appreciated that any type of linear or planar movement of the substrate may be envisaged.
  • a droplet of liquid 46 is provided on the surface.
  • the droplet according to the invention is capable to carry-out local cleaning or, alternatively, may be used for cleaning ultimately the whole surface.
  • the substrate 41 may be displaced with respect to a supply conduit 42 from which the droplet is provided.
  • the supply conduit 42 may be arranged to combine an inflow of a suitable gas 43 and an inflow of a suitable liquid 44.
  • the supply 42 may be arranged to conduct a liquid suitably saturated with gas. It is found that good results may be achieved when the concentration of a gas is about 100 -110%. It is also found that provided the temperature of the droplet is about 25 - 45 degrees Celsius, the nanobubble generation inside the droplet is optimal.
  • either gas or liquid may be heated by a controller 45, or the substrate 41 may be heated with the controller 47. It will be appreciated that the controller may be adapted to operate a suitable heater (not shown). When the droplet is suitably heated, the gas dissolved in the liquid is nucleated leading to production of nanobubbles on the surface.
  • Suitable gasses to be used in the system according to the present aspect of the invention are: hydrogen, helium, methane, nitrogen, oxygen, argon, carbon dioxide, or air.
  • the surface cleaning method according to the aspects of the invention set forth in the foregoing is specifically suitable for removing particles of about 20 nm from a surface. Good results for local and extended cleaning are obtained.
  • the liquid is frequently or continuously freshened, the contaminated liquid being conducted away from the surface to a suitable container.
  • the method of cleaning the surface according to the aspects of the invention is suitable not only for cleaning a surface, but may also be used in a groove, a depletion, or in an area between two substrates. The latter makes the method of the invention particularly versatile for industrial applications, in particular in

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Cleaning By Liquid Or Steam (AREA)

Abstract

L'invention concerne un procédé de nettoyage d'une surface à l'aide de nanobulles générées en continu. Ce procédé comprend les étapes consistant à générer une gouttelette d'un liquide formant les nanobulles sur la surface ; à déplacer la gouttelette sur la surface pour amener les nanobulles à éliminer des contaminations à partir de la surface ; à conduire le liquide à l'opposé de la surface pour éliminer lesdites contaminations. L'invention porte en outre sur un système pour permettre le nettoyage d'une surface à l'aide de nanobulles générées en continu.
PCT/NL2012/050174 2011-03-22 2012-03-21 Procédé de nettoyage d'une surface Ceased WO2012128627A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11159171A EP2503032A1 (fr) 2011-03-22 2011-03-22 Procédé pour le nettoyage d'une surface
EP11159171.5 2011-03-22

Publications (1)

Publication Number Publication Date
WO2012128627A1 true WO2012128627A1 (fr) 2012-09-27

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL2012/050174 Ceased WO2012128627A1 (fr) 2011-03-22 2012-03-21 Procédé de nettoyage d'une surface

Country Status (2)

Country Link
EP (1) EP2503032A1 (fr)
WO (1) WO2012128627A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10219670B2 (en) 2014-09-05 2019-03-05 Tennant Company Systems and methods for supplying treatment liquids having nanobubbles
CN116103741A (zh) * 2021-04-06 2023-05-12 重庆立道新材料科技有限公司 除垢装置

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104475393A (zh) * 2014-11-24 2015-04-01 广东省农业科学院蚕业与农产品加工研究所 一种果蔬清洗消毒方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009101299A (ja) 2007-10-24 2009-05-14 Fuji Xerox Co Ltd マイクロナノバブル発生方法、マイクロ流路の洗浄方法、マイクロナノバブル発生システム、及び、マイクロリアクター
US20090120460A1 (en) * 2007-11-09 2009-05-14 Tennant Company Soft floor pre-spray unit utilizing electrochemically-activated water and method of cleaning soft floors

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009101299A (ja) 2007-10-24 2009-05-14 Fuji Xerox Co Ltd マイクロナノバブル発生方法、マイクロ流路の洗浄方法、マイクロナノバブル発生システム、及び、マイクロリアクター
US20110168210A1 (en) * 2007-10-24 2011-07-14 Fuji Xerox Co., Ltd. Micro-nano bubble generating method, microchannel cleaning method, micro-nano bubble generating system, and microreactor
US20090120460A1 (en) * 2007-11-09 2009-05-14 Tennant Company Soft floor pre-spray unit utilizing electrochemically-activated water and method of cleaning soft floors

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
RAJ K DASH ET AL: "Electrowetting on dielectric-actuation of microdroplets of aqueous bismuth telluride nanoparticle suspensions", NANOTECHNOLOGY, IOP, BRISTOL, GB, vol. 18, no. 47, 28 November 2007 (2007-11-28), pages 475711, XP020129533, ISSN: 0957-4484 *
SARA AGHDAEI ET AL: "Droplet mixer based on electrowetting", JOURNAL OF PHYSICS: CONFERENCE SERIES, INSTITUTE OF PHYSICS PUBLISHING, BRISTOL, GB, vol. 142, no. 1, 1 December 2008 (2008-12-01), pages 12071, XP020148289, ISSN: 1742-6596 *
SHANGJIONG YANG: "Manipulating Surface Nanobubbles", 9 October 2008 (2008-10-09), Twente, NL, pages 1 - 123, XP055035594, Retrieved from the Internet <URL:http://doc.utwente.nl/60029/1/thesis_S_Yang.pdf> [retrieved on 20120816] *
WU Z H ET AL: "Cleaning using nanobubbles: Defouling by electrochemical generation of bubbles", JOURNAL OF COLLOID AND INTERFACE SCIENCE, ACADEMIC PRESS, NEW YORK, NY, US, vol. 328, no. 1, 1 December 2008 (2008-12-01), pages 10 - 14, XP025589341, ISSN: 0021-9797, [retrieved on 20080909], DOI: 10.1016/J.JCIS.2008.08.064 *
Z.WU ET AL., CLEANING USING NANOBUBBLES: DEFOULING BY ELECTROCHEMICAL GENERATION OF BUBBLES

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10219670B2 (en) 2014-09-05 2019-03-05 Tennant Company Systems and methods for supplying treatment liquids having nanobubbles
CN116103741A (zh) * 2021-04-06 2023-05-12 重庆立道新材料科技有限公司 除垢装置

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