WO2007113637A1 - Composition liquide à plusieurs phases et lentille optique commandée par électromouillage - Google Patents
Composition liquide à plusieurs phases et lentille optique commandée par électromouillage Download PDFInfo
- Publication number
- WO2007113637A1 WO2007113637A1 PCT/IB2007/000839 IB2007000839W WO2007113637A1 WO 2007113637 A1 WO2007113637 A1 WO 2007113637A1 IB 2007000839 W IB2007000839 W IB 2007000839W WO 2007113637 A1 WO2007113637 A1 WO 2007113637A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxide
- nanoparticles
- liquid
- fluoride
- conductive liquid
- Prior art date
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B26/00—Optical devices or arrangements for the control of light using movable or deformable optical elements
- G02B26/004—Optical devices or arrangements for the control of light using movable or deformable optical elements based on a displacement or a deformation of a fluid
- G02B26/005—Optical devices or arrangements for the control of light using movable or deformable optical elements based on a displacement or a deformation of a fluid based on electrowetting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
- G02B3/12—Fluid-filled or evacuated lenses
- G02B3/14—Fluid-filled or evacuated lenses of variable focal length
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B13/00—Optical objectives specially designed for the purposes specified below
- G02B13/001—Miniaturised objectives for electronic devices, e.g. portable telephones, webcams, PDAs, small digital cameras
- G02B13/0055—Miniaturised objectives for electronic devices, e.g. portable telephones, webcams, PDAs, small digital cameras employing a special optical element
- G02B13/0075—Miniaturised objectives for electronic devices, e.g. portable telephones, webcams, PDAs, small digital cameras employing a special optical element having an element with variable optical properties
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
- G02B2207/101—Nanooptics
Definitions
- the invention relates to a multi-phase liquid composition.
- the invention also relates to an optical lens driven by electrowetting containing a multi-phase liquid composition of the invention.
- a cell is defined by two transparent non-conductive plates and side walls.
- the lower plate which is non-planar, comprises a conical or cylindrical depression or recess, which contains a drop of a non-conductive or non-conductive liquid.
- the remainder of the cell is filled with an electrically conductive liquid, immiscible with the non-conductive liquid, having a different refractive index and substantially the same density.
- An annular electrode which is open facing the recess, is positioned on the rear face of the lower plate. Another electrode is in contact with the conductive liquid.
- the conductive liquid may be an aqueous liquid containing salts or an organic liquid containing ionic compounds.
- the non- conductive liquid is typically an oil, an alkane or a mixture of alkanes, possibly halogenated.
- the conductive liquid and the non-conductive liquid must have some specific common properties in order to provide a very performing lens to be used as a variable focus liquid lens, an optical zoom and any other optical device using electrowetting in an inside or outside environment.
- It is an object of the invention to provide multi-phase liquid compositions comprising a conductive liquid and a non-conductive liquid, the non-conductive liquid being immiscible in the conductive liquid, these liquids having a high difference of refractive index, advantageously greater than or equal to about 0.2, preferably between about 0.2 and 0.4.
- the invention relates to a multi-phase liquid composition
- a multi-phase liquid composition comprising a conductive liquid and a non-conductive liquid, the non-conductive liquid being immiscible in the conductive liquid, the conductive liquid comprising nanoparticles.
- the invention in another aspect, relates to a multi-phase liquid composition
- a multi-phase liquid composition comprising a conductive liquid and a non-conductive liquid, the non-conductive liquid being immiscible in the conductive liquid, the non-conductive liquid comprising nanoparticles.
- the invention in still another aspect, relates to a multi-phase liquid composition
- a multi-phase liquid composition comprising a conductive liquid and a non-conductive liquid, the non-conductive liquid being immiscible in the conductive liquid, the conductive liquid and the non-conductive liquid comprising nanoparticles.
- the difference of refractive index between both liquids is advantageously greater than or equal to about 0.2, preferably between about 0.2 and 0.4.
- the density of both liquids is the same or is similar. This means it is acceptable that the difference of densities may vary within a short range. Typically, it is preferred the difference of densities is not more than about 3.10 "3 g/cm 3 at 20 0 C.
- the dispersion of nanoparticles in one or both liquid phases may have effective impact on density, refractive index and/or viscosity, as explained below.
- the person skilled in the art may select the nanoparticles (especially nature, size) and/or their amount that are useful to adjust the refractive index of one liquid phase and the difference of refractive index between both liquid phases. These particles may also be chosen to adjust other parameters, such as the density of the phase in order to adjust it as close as possible to that of the other phase.
- nanoparticles are used to increase the refractive index and the density of the non-conductive or the conductive liquid.
- nanoparticles are used to increase the refractive index of the non- conductive or the conductive liquid, without increasing or increasing too much the density. More specifically, nanoparticles are used to increase the difference between each refractive index of each liquid, without increasing or increasing too much the density.
- nanoparticles are used to increase the density of the non- conductive or the conductive liquid, without modifying or modifying too much the refractive index.
- Viscosity can be obtained from the Chong's equation:
- ⁇ is the dynamic viscosity (in Pa.s)
- ⁇ m is the critical volume fraction
- ⁇ a corresponds to the liquid viscosity
- Refractive index from the composite liquid is deduced from the Maxwell-Garnet equation (assuming a mean field approximation, valid for small volume fractions): with ⁇ the dielectric constant in the visible range.
- ⁇ n is the refractive index variation between the pure liquid and the liquid containing particles.
- refractive index may be obtained using particles and/or liquids or other components of higher refractive index.
- a solution of silica nanoparticles in ethylene glycol has been used as a high density liquid, because this material has a relatively low refractive index.
- nanoparticles are nanometric solid materials, transparent in the visible range, small in size (the particles should not substantially or not at all diffuse light), for example particle size lower than about 50 nanometers, preferably lower than about 20 nanometers, more preferably lower than about 10 nanometers, and well dispersible in conductive and/or non conductive liquids.
- the nanoparticles present a density of about 2 g/cm 3 to about 20 g/cm 3 , preferably of about 4 g/cm 3 to about 15 g/cm 3 .
- the liquids containing the nanoparticles have good optical qualities; they are still transparent, present a low diffusion and high Abbe numbers (dispersive power).
- the shape of the nanoparticles is preferably chosen to avoid light polarization and scattering.
- the particles are preferably spherical or close to a spherical shape.
- nanoparticles By extension, other materials could be used as nanoparticles to increase density and refractive index. Materials should be chosen depending on the optical requirements. As an example, titanium oxide could be used to screen UV light.
- Nanoparticles can also be used to make conductive a liquid which is non conductive per se, in other words nanoparticles are useful to confer conductivity to a non conductive liquid, such as for example a non conductive liquid which is non miscible with another non conductive liquid.
- nanoparticles are made of but are not limited to silver, platinum or carbon and dispersed in a poorly conducting liquid to increase the conductivity.
- nanoparticles dispersed in one or both liquids are made of one or more materials having a strong absorption in the UV light wavelength range, typically at wavelength below about 360 nm, but a very low absorption in the visible light wavelength range. These materials are made of titanium oxide or cerium oxide for example. Such particles are deemed to absorb the UV light coming through the electrowetting device and thus protect some liquids and/or insulating layer and/or hydrophobic coatings comprised in the electrowetting device from UV degradation.
- nanoparticles dispersed in one or both liquids are made of one or more materials having a strong absorption in the IR wave lengths, particularly in the Near-IR, preventing from implementing an IR filter on the lens.
- a filter is necessary when the electrowetting device is an optical device comprising a numerical imaging sensor, usually sensitive to IR wave lengths, particularly in the Near-IR wave lengths.
- nanoparticles comprise at least one visible light transparent material, such as silica, and containing IR absorbing molecules embedded in the materials. These molecules are preferentially absorbing infrared and transparent to visible light.
- the IR absorbing molecules embedded in the particles are organic metal complex infrared absorbing dyes.
- the organic metal complex is of the aminothiophenolate type, as described in US patent application 2002/0125464 A1.
- the multiphase composition is made of two non miscible liquids and only one of them comprises nanoparticles being conductive.
- the dispersing medium is thus more conducting than the other liquid, allowing electrowetting phenomenon to occur with liquids that are not necessarily conductive in the beginning. This feature allows the use of a much broader range of liquids, including liquids being much more chemically stable.
- liquid not containing water an example of such liquid being a high refractive index liquid made of oily molecules on the one side, and a low refractive index liquid like fluorinated solvent on the other side, particles being dispersed either in the high or low refractive index liquid.
- mixtures of two or more different materials can be used as nanoparticles to be dispersed in one or both of the liquids.
- oxides and/or fluorides may be used, and for example those chosen from among indium fluoride (InF 3 ), indium oxide (In 2 O 3 ), tin fluorides (SnF 2 or SnF 4 ), tin oxide (SnO 2 ), barium fluoride (BaF 2 ), barium oxide (BaO), bismuth fluoride (BiF 3 ) and bismuth oxide (Bi 2 O 3 ).
- Particles can be coated by organic ligands in order to increase the colloidal stability, especially in organic solvent or media.
- Ligands are usually molecules similar to the dispersing media and chemically functionalized to bind the surface of the inorganic particles.
- nanoparticles based on silica, titanium or aluminum oxide can be dispersed in an non-conductive oil.
- PDMS polydimethylsiloxane
- Shape of the nanoparticles is spherical to avoid light polarization and scattering.
- titanium oxide particles mean 2.5 nm in diameter, made and dispersed by nano-H Company in a silicon oil SIP6827 (phenyltrimethoxysilane, company ABCR). Liquids have been characterized with and without particles:
- Viscosity is also higher than expected, presumably because the model only considers the nanoparticles as hard spheres whereas it is coated by molecules having an intrinsic viscosity.
- yttria particles (Y 2 O 3 ) have been dispersed in the same oil SIP6827 (ABCR) at 50 g/L and characterized:
- nanoparticles can be dispersed in the non-conductive phase in order to increase the density as well as the refractive index.
- Nanoparticles based on ytterbium, gadolinium, titanium, indium, tin, bismuth, zirconium, barium have a density high enough in order to increase the density of the non-conductive phase already at low concentration of nanoparticles.
- Dispersion of the nanoparticles can be done in the oil by the mean of an organic surface around the metal oxide or fluoride.
- the size of the nanoparticles may be around 5 nm in order to avoid the diffraction and the diffusion of the light. By this way, the suspension stays clear and transparent.
- Nanoparticles can be dispersed in the conductive phase, either in water or in ethylene glycol which are already components of the conductive phase. In this case, the density can be adjusted to be equilibrated with the oil.
- SiO 2 was purchased from Nyacoi nanotechnogies (reference product DP 5820, 30% in ethylene glycol).
- ZrO 2 was purchased from Nyacoi nanotechnologies (product stabilized 20%in acetic acid).
- the viscosity is rather low and the density has been significantly increased.
- the refractive index stays reasonably low.
- the liquid is reasonably dispersive since the Abbe number is higher than 50.
- SL-5267 is a polyphenyl ether high refractive index compound provided by NUSIL Silicone technology. Electrowetting experiments have been done on these liquids.
- the hydrophobic substrate was Parylene C on stainless steal.
- the applied voltage increased from 0 to 120 V. Under these conditions, the contact angle of the oil in the conductive phase increased from 45 to 105 without saturation phenomena. (See Figure 7). Hysteresis stays rather low.
- the interfacial tension was 30.82 mN/m
- compositions have been made where the proportion of nanoparticles can vary (SiO 2 : about 20 nm; ZrO 2 : about 5 to about 10 nm):
- the electrical conductive liquid comprises at least one conventional freezing-point lowering agent.
- freezing-point lowering agent mention may be made of alcohol, glycol, glycol ether, polyol, polyetherpolyol and the like, or mixtures thereof. Examples thereof include the following agents: ethanol, ethylene glycol (EG), monopropylene glycol (MPG), 1 ,2-propane diol, 1 ,2,3-propane triol (glycerol), and the like, and mixtures thereof.
- the multi-phase liquid composition comprises a non- conductive liquid that is immiscible in the conductive liquid.
- This said non-conductive liquid comprising an organic or an inorganic (mineral) compound or mixture thereof.
- organic or inorganic compounds include a Si-based monomer or oligomer, a Ge-based monomer or oligomer, a Si-Ge-based monomer or oligomer, a hydrocarbon, or a mixture thereof.
- the hydrocarbon may be linear or branched and may contain one or more saturated, unsaturated or partially unsaturated cyclic moiety(ies).
- the hydrocarbon has advantageously from 10 to 35 carbon atoms, preferably from 15 to 35 carbon atoms. Hydrocarbons having less than 10 carbon atoms are less preferred since miscibility into the conductive liquid may occur.
- the hydrocarbon may comprise one or more insaturation(s) in the form of double and/or triple bond(s). More than 2 or 3 double or triple bonds are not preferred considering the risk of decomposition with UV radiations. Preferably the hydrocarbon does not contain any double or triple bonds, in which case the hydrocarbons are referred to as alkanes in the present specification.
- the hydrocarbon may further comprise one or more heteroatoms, as substituants and/or as atoms or group of atoms interrupting the hydrocarbon chain and/or ring.
- heteroatoms include, but are not limited to, oxygen, sulfur, nitrogen, phosphor, halogens (mainly as fluorine, chlorine, bromine and/or iodide). Care should be taken that the presence of one or more heteroatom(s) does not impact the immiscibility of the two liquids.
- the hydrocarbon is or comprises:
- a linear or branched alkane such as decane (C 1 0H 22 ), dodecane (C 12 H 24 ), squalane (C 30 H 62 ), and the like;
- alkane comprising one or more rings, such as tert-butylcyclohexane (C 10 H 20 ), and the like;
- a fused ring system such as ⁇ -chloronaphthalene, ⁇ -bromonaphthalene, cis,trans- decahydronaphthalene (Ci 0 Hi 8 ), and the like;
- a mixture of hydrocarbons such as those available as Isopar ® V, Isopar ® P (from
- nanoparticles can be dispersed in one or several of the following silicon-based compound:
- each of R1 , R2 and R' independently represents alkyl, (hetero)aryl, (hetero)arylalkyl, (hetero)aryialkenyl or (hetero)arylalkynyl and n is comprised between 1 and 20, preferably between 1 and 10, more preferably n is 1 , 2, 3, 4 or 5 and with the precision that n is greater than 2 in formula 1c;
- R1 , R2 and R' are as defined above and m is comprised between 1 and 20, preferably between 1 and 10, more preferably m is 1 , 2 or 3;
- R2 X R4 wherein R1 and R2 are as defined above, and each of R3 and R4 independently represents alkyl, (hetero)aryl, (hetero)arylalkyl, (hetero)arylalkenyl or (hetero)arylalkynyl.
- alkyl means a straight or branched alkyl radical having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms; preferred alkyl includes methyl, ethyl, /7-propyl, /so-propyl; alkyl radical may be halogenated, for instance may comprise a 1 , 1 , 1 -trif luopropyl group;
- - (hetero)aryl means an aromatic or heteroaromatic radical containing from 5 to 12 atoms, forming at least one, preferably one, aromatic and/or heteroaromatic ring, said ring(s) being optionally substituted by one or more halogens, preferably 1, 2 or 3 halogen atoms (mainly fluorine, chlorine and/or bromine), and being optionally fused with one or more saturated, partially saturated or unsaturated ring system;
- preferred (hetero)aryl is phenyl or naphthyl, optionally substituted with 1 , 2 or 3 halogen atoms;
- (hetero)arylalkyl is as defined above for each of the alkyl and (hetero)aryl radical; preferred (hetero)arylalkyls include benzyl, phenethyl, optionally substituted with 1 ,
- - (hetero)arylalkenyl and (hetero)arylalkynyl correspond to radicals wherein the (hetero)aryl moiety is as defined above, and alkenyl and alkynyl represent a straight or branched alkyl radical, as defined above, further comprising one or more, preferably one, double bond or one or more, preferably one, triple bond, respectively.
- the nanoparticles can be dispersed in one or several of the following specific silicon- based species: - hexamethyldisilane, diphenyldimethylsilane, chlorophenyltrimethylsilane, phenyltri- methylsilane, phenethyltris(trimethylsiloxy)silane, phenyltris(trimethyisiloxy)silane, polydimethyl- siloxane, tetraphenyltetramethyltrisiloxane, poly(3,3,3-trifluoropropylmethylsiloxane), 3,5,7-triphenylnonamethylpentasiloxane, 3,5-diphenyloctamethyltetrasiloxane, 1 ,1 ,5,5-tetraphenyl-1 ,3,3,5-tetramethyltrisiloxane, and hexamethylcyclotrisiloxane.
- the nanoparticles can be dispersed in one or several of the following germane based species:
- R', R1 , R2, R3, R4 and n are as defined above.
- the non-conductive liquid may contain one or several of the following specific germane based species: hexamethyldigemnane, diphenyldimethylgermane, phenyltrimethyl- germane.
- the non-conductive liquid comprises at least one Si- and/or Ge-based compound substituted by one or more phenyl groups and/or other groups like fluorinated or non fluorinated alkyl (ethyl, n-propyl, n-butyl), linear or branched alkyls, chlorinated or brominated phenyl groups, benzyl groups, halogenated benzyl groups; or a mixture of Si- and/or Ge-based compounds wherein at least one compound is substituted by one or more phenyl groups and/or other groups like fluorinated or non fluorinated alkyl (ethyl, n-propyl, n-butyl), linear or branched alkyls, chlorinated or brominated phen
- the nanoparticles can be dispersed in the non-conducting liquid in the presence of wetting agents.
- organic or inorganic (mineral) compounds - and/or of wetting agents, specifically on Parylene or Cyclotene, or other non-conductive (isolating) layer or coating having a high surface energy (> 30 mN/m) - are presented in Tables 1 , 2 and 3 below:
Abstract
La présente invention concerne une composition liquide à plusieurs phases comprenant un liquide conducteur et un liquide non conducteur, une nanoparticule étant dispersée dans l'un au moins de ces liquides. La présente invention concerne également une lentille optique commandée par électromouillage comprenant la composition liquide à plusieurs phases, cette lentille optique se présentant sous la forme d'une lentille liquide à focale variable ou étant incluse dans celle-ci, un zoom optique ainsi qu'un appareil comprenant cette lentille optique et un circuit de commande ou une unité électronique permettant de commander ladite lentille. L'appareil est un appareil photo, un téléphone cellulaire, un endoscope ou une caméra vidéo dentaire.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP06356037 | 2006-03-31 | ||
EP06356037.9 | 2006-03-31 |
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WO2007113637A1 true WO2007113637A1 (fr) | 2007-10-11 |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7573646B2 (en) | 2006-07-12 | 2009-08-11 | Varioptic S.A. | Liquid lens interconnection |
WO2011157826A1 (fr) * | 2010-06-18 | 2011-12-22 | Samsung Lcd Netherlands R & D Center B.V. | Elément et fluide d'électromouillage |
US8304067B2 (en) * | 2007-09-07 | 2012-11-06 | Samsung Electronics Co., Ltd. | Method of fabricating liquid film, method of arranging nano particles and substrate having liquid thin film fabricated using the same |
US9494790B1 (en) | 2014-09-29 | 2016-11-15 | Amazon Technologies, Inc. | Electrowetting element and fluid |
US20170045203A1 (en) * | 2015-08-13 | 2017-02-16 | Abl Ip Holding Llc | Configurable lighting device using a light source and optical modulator |
EP3418252A1 (fr) * | 2017-06-20 | 2018-12-26 | Vestel Elektronik Sanayi ve Ticaret A.S. | Lentille liquide à points quantiques, dispositifs les contenant, procédé de fabrication d'une lentille liquide à points quantiques et procédé de fonctionnement d'un dispositif électronique électroluminescent |
WO2019183335A1 (fr) * | 2018-03-22 | 2019-09-26 | Corning Incorporated | Agents de récupération de transmission pour formulations de lentilles liquides |
WO2019225975A1 (fr) * | 2018-05-23 | 2019-11-28 | 엘지이노텍(주) | Lentille liquide, et module de prise de vues et dispositif optique comprenant cette lentille liquide |
WO2021038453A1 (fr) | 2019-08-29 | 2021-03-04 | Haute Ecole Arc | Dispositif d'usinage laser |
RU2813451C1 (ru) * | 2023-01-31 | 2024-02-12 | Общество с ограниченной ответственностью "КСПАНСЕО" (ООО "КСПАНСЕО") | Жидкая линза, снабженная ей контактная линза и интраокулярное устройство |
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WO2003069380A1 (fr) * | 2002-02-14 | 2003-08-21 | Koninklijke Philips Electronics N.V. | Lentille a foyer variable |
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Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7573646B2 (en) | 2006-07-12 | 2009-08-11 | Varioptic S.A. | Liquid lens interconnection |
US8304067B2 (en) * | 2007-09-07 | 2012-11-06 | Samsung Electronics Co., Ltd. | Method of fabricating liquid film, method of arranging nano particles and substrate having liquid thin film fabricated using the same |
CN102947743B (zh) * | 2010-06-18 | 2018-12-14 | 利奎阿维斯塔股份有限公司 | 电润湿元件和流体 |
US10126543B2 (en) * | 2010-06-18 | 2018-11-13 | Amazon Technologies, Inc. | Water content of a fluid of an electrowetting element |
US20130109764A1 (en) * | 2010-06-18 | 2013-05-02 | Samsung Lcd Netherlands R & D Center B.V. | Electrowetting element and fluid |
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WO2011157826A1 (fr) * | 2010-06-18 | 2011-12-22 | Samsung Lcd Netherlands R & D Center B.V. | Elément et fluide d'électromouillage |
US9494790B1 (en) | 2014-09-29 | 2016-11-15 | Amazon Technologies, Inc. | Electrowetting element and fluid |
US10018829B1 (en) | 2014-09-29 | 2018-07-10 | Amazon Technologies, Inc. | Electrowetting element and liquid |
WO2017027698A1 (fr) * | 2015-08-13 | 2017-02-16 | Abl Ip Holding Llc | Dispositif d'éclairage configurable utilisant une source de lumière et un modulateur optique |
US20170045203A1 (en) * | 2015-08-13 | 2017-02-16 | Abl Ip Holding Llc | Configurable lighting device using a light source and optical modulator |
EP3418252A1 (fr) * | 2017-06-20 | 2018-12-26 | Vestel Elektronik Sanayi ve Ticaret A.S. | Lentille liquide à points quantiques, dispositifs les contenant, procédé de fabrication d'une lentille liquide à points quantiques et procédé de fonctionnement d'un dispositif électronique électroluminescent |
WO2019183335A1 (fr) * | 2018-03-22 | 2019-09-26 | Corning Incorporated | Agents de récupération de transmission pour formulations de lentilles liquides |
WO2019225975A1 (fr) * | 2018-05-23 | 2019-11-28 | 엘지이노텍(주) | Lentille liquide, et module de prise de vues et dispositif optique comprenant cette lentille liquide |
WO2021038453A1 (fr) | 2019-08-29 | 2021-03-04 | Haute Ecole Arc | Dispositif d'usinage laser |
RU2813451C1 (ru) * | 2023-01-31 | 2024-02-12 | Общество с ограниченной ответственностью "КСПАНСЕО" (ООО "КСПАНСЕО") | Жидкая линза, снабженная ей контактная линза и интраокулярное устройство |
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