Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/11—Anti-reflection coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B81—MICROSTRUCTURAL TECHNOLOGY
  • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
  • B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
  • B81C1/00388—Etch mask forming
  • B81C1/00396—Mask characterised by its composition, e.g. multilayer masks
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
  • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
  • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
  • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
  • C03C17/10—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals by deposition from the liquid phase
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
  • C03C17/23—Oxides
  • C03C17/25—Oxides by deposition from the liquid phase
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
  • C03C17/23—Oxides
  • C03C17/25—Oxides by deposition from the liquid phase
  • C03C17/256—Coating containing TiO2
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
  • C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
  • C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
  • C03C23/006—Other surface treatment of glass not in the form of fibres or filaments by irradiation by plasma or corona discharge
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/11—Anti-reflection coatings
  • G02B1/111—Anti-reflection coatings using layers comprising organic materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B81—MICROSTRUCTURAL TECHNOLOGY
  • B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
  • B81B2203/00—Basic microelectromechanical structures
  • B81B2203/03—Static structures
  • B81B2203/0361—Tips, pillars
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/21—Oxides
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/21—Oxides
  • C03C2217/212—TiO2
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/21—Oxides
  • C03C2217/217—FeOx, CoOx, NiOx
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/25—Metals
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/25—Metals
  • C03C2217/251—Al, Cu, Mg or noble metals
  • C03C2217/254—Noble metals
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/25—Metals
  • C03C2217/251—Al, Cu, Mg or noble metals
  • C03C2217/254—Noble metals
  • C03C2217/255—Au
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/25—Metals
  • C03C2217/251—Al, Cu, Mg or noble metals
  • C03C2217/254—Noble metals
  • C03C2217/256—Ag
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/25—Metals
  • C03C2217/27—Mixtures of metals, alloys
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/29—Mixtures
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/70—Properties of coatings
  • C03C2217/73—Anti-reflective coatings with specific characteristics
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/10—Deposition methods
  • C03C2218/11—Deposition methods from solutions or suspensions
  • C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/30—Aspects of methods for coating glass not covered above
  • C03C2218/32—After-treatment
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/30—Aspects of methods for coating glass not covered above
  • C03C2218/34—Masking

Definitions

• the invention relates to a method for producing an antireflection surface on an optical element as well as to optical elements with an antireflection surface.
• optical elements examples include gratings, lenses, in particular refractive lenses, defractive structures, CGHs (computer-generated hologram) and refractive micro-optical elements in the form of spherical or aspherical microlenses.
• optical elements For structuring or modulation of wavefronts electromagnetic radiation known optical elements are provided with a surface microstructure, which use optical interference effects.
• optical elements may have a gradient in their optical density, thereby gradually changing their optical properties. Overall, such a modulation of the wavefront after their passage through the optical element is possible.
• structured surfaces are used whose structuring is of the order of magnitude of the wavelength of the light incident on this structuring or below.
• Such surface structures are also referred to as sub-lambda structures.
• a surface structure with substantially evenly arranged elevations or in the order of several nm, in particular from about 10 nm to about 650 nm the usable of an optical element having such a surface structure portion of light having a wavelength between about 155 nm and about 10 microns, which impinges on the optical element at a certain angle, significantly increased because the reflection for light in turn is significantly reduced.
• This antireflection effect occurs when the uniformly arranged elevations or depressions are of an order of magnitude smaller than the wavelength, in particular smaller than half the wavelength, of the radiation impinging on the surface structure.
• the surface structure should have a periodicity of less than about 600 nm when near-IR radiation is to be used.
• An additional problem can arise when the generated anti-reflection surface is formed by a layer which is not sufficiently stably connected to the optical element and, for example, flakes off the optical element due to the stress occurring at a deforming curved surface.
• Such adhesion problems occur in particular with different thermal expansion coefficients of the materials used. Therefore, only a limited circle of materials is suitable for forming an optical element of a first material with an antireflection surface of a second material.
• the optical parameters which the optical element provided with an antireflection surface can correspond to, restricted.
• the object of the invention is therefore to provide a method for producing an antireflection surface on an optical element, by means of which the stated difficulties are reduced.
• Unloaded spherical micelle-like polymer units are generally understood to mean micelles, vesicles or complex aggregates which form in aqueous or organic solution from macromolecular amphiphiles in a spherical structure.
• two separate spherical micelle-like polymer units have the same properties Art a substantially same spatial extent.
• Unloaded spherical micelle-like polymer units used in the method according to the invention arrange themselves on a surface in a self-organization process in a substantially regular arrangement in a layer, as is known, for example, from DE 2004 043 305 A1.
• a layer of spherical micellar polymer units is particularly effective as an antireflection surface for light of a wavelength between about 155 nm and about 10 ⁇ m when the spherical micelle-like polymer units have a diameter of between about 10 nm and about 650 nm.
• micelle-like polymer units can be applied to a surface of a substrate.
• Possible ways in which micelle-like polymer units can be applied to a surface of a substrate are known, for example, from EP 1 027 157 B1.
• the spherical micelle-like polymer units distributed in a substantially regular arrangement on the surface of the optical element form an antireflection surface on the coated optical element.
• the wavefronts impinging on this antireflection surface are altered as desired by the interaction with the micelle-like polymer units.
• the unloaded spherical micelle-like polymer units can be easily generated in step b) if one or more polymers are dissolved in a solution medium, especially in toluene.
• block copolymers have proven to be advantageous.
• one or a mixture of several of the following block copolymers is used as the block copolymer: polystyrene-b-polyethylene oxide, polystyrene-b-poly (2-vinylpyridine), polystyrene-b-poly (4-vinylpyridine).
• polystyrene-b-poly (2-vinylpyridine) is used.
• An alternative antireflective surface may be formed if the method further comprises the step of loading at least a portion of the polymer units with a metal compound or with a metal cluster or with a metal oxide cluster.
• the procedure for loading the polymer units with the compounds mentioned is known from the already mentioned EP 1 027 157 B1. There, these metallic particles are used only as an etching mask for a subsequent plasma treatment of
• micellar polymer units provides an efficient anti-reflection surface on an optical element.
• metal compound one or a mixture of several. ren of the following metal compounds is used:
• step bl at least part of the polymer units is loaded with a metal compound or with a metal cluster or with a metal oxide cluster as step bl) after carrying out step b) and before carrying out step c).
• the loading of at least a portion of the polymer units can also be performed only as step cl) after the implementation of step c).
• the loading takes place in step bl) or in step c1) in solution, in particular in toluene. It can e.g. simply adding a selected metal compound to the solution in which the micelle-like polymer units were generated.
• step bl) or step c1) may be loaded by an electrochemical process with a metal cluster.
• a metal cluster carried by the micelle-like polymer units may also be obtained if the process comprises, as step d), converting at least a portion of the metal compound of a loaded polymer unit into a metal cluster and / or a metal oxide cluster.
• an efficient antireflection surface can also be formed by metal clusters and / or metal oxide clusters which lie freely on the surface of the optical element without a polymer or other shell.
• Such an antireflection surface may be advantageously produced if the method further comprises, as step e), removing the polymer units from the surface of the optical element, wherein substantially regularly arranged metal clusters and / or metal oxide clusters are formed on the surface of the optical element remain.
• metal clusters or metal oxide clusters remain whose respective position on the optical element corresponds to the position previously adopted by the associated remote polymer unit without much change.
• step e) The removal of the polymer units in step e) can advantageously be carried out by etching, reducing or oxidizing.
• the polymer units are removed in step e) by plasma etching, including in particular a
• Argon an oxygen or a hydrogen plasma is used.
• This antireflection surface thus constructed of metal clusters and / or metal oxide clusters, can also be subsequently modified, the method advantageously also comprising, as step f), the metal clusters and / or the metal oxide clusters being deposited by depositing a metal and / or or a metal compound on the metal clusters or metal oxide clusters.
• the antireflection surface changes such that, although the distances between the centers of the metal cluster or metal oxide clusters remain unchanged, the distances between the outer contour of the respective clusters are reduced.
• the deposition of the metal and / or the metal oxide in step f) takes place without current.
• the method known from EP 1 027 157 B1 can be used to produce a microstructure on a surface if the method according to the invention also comprises, as step g), the etching of a microstructure acting as an antireflection surface into the surface of the optical element, wherein the metal clusters and / or metal oxide clusters distributed on the surface of the optical element serve as an etching mask. It is particularly advantageous if the etching of the microstructure into the surface of the optical element takes place in step g) by plasma etching, to which in particular a CF. / Argon plasma is used.
• an optical element having an antireflection surface in that the antireflection surface has spherical micellar-like polymer units having an inner core portion and an outer sheath portion distributed in a film-like layer in a substantially regular arrangement on the surface of the optical element , includes.
• such micelle-like polymer units organize themselves and thus form a microstructure which acts as an antireflection surface.
• the metal cluster comprises one or more clusters of gold, platinum or palladium.
• the antireflection surface comprises one or more clusters of titanium dioxide, iron oxide or cobalt oxide.
• an efficient antireflective surface may be formed when at least a portion of the polymeric units are loaded with a cluster of metallic mixing systems. It is advantageous if the cluster of metallic mixing systems comprises one or more of the following metallic mixing systems: Au / FeO, Au / CoO, Au / CoO, Au / ZnO, Au / TiO 2 , Au / ZrO 2 , AuMl 2 O 3 , AuZIn 3 O 3 , PdMl 2 O 3 ,
• the object of providing an optical element having an antireflection surface is moreover achieved in an optical element having an antireflection surface in that the antireflection surface comprises metal clusters and / or metal oxide clusters which are distributed in a substantially regular arrangement on the surface of the optical element.
• Senses are the metal clusters and / or metal oxide clusters free and without a polymer or other shell on the surface of the optical element.
• FIG. 1 shows schematically a block copolymer
• Figure 2 schematically shows a block copolymer of
• FIG. 1 shows an unloaded micelle having an inner core region and an outer skin region
• FIG. 3 schematically shows the loading of the core region of the block copolymer micelle of FIG. 2 with a metal compound on the one hand or a metal or metal oxide cluster on the other hand and schematically the transfer of the metal compound in the core of the block polymer micelle into a metal or metal oxide cluster;
• Figure 4 schematically shows the coating of an optical
• FIG. 5 schematically shows the transfer of the metal compound in the core region of the block copolymer micelle of FIG. 3 into a metal or metal oxide cluster, after the optical element has already been produced according to FIG.
• FIG. 6 schematically shows the removal of the block copolymer micelles from the surface of the optical element. ments, with manoclusters remaining on the surface of the optical element;
• FIG. 7 shows schematically the etching of a microstructure acting as an antireflection surface into the surface of the optical element
• FIG. 8 schematically shows the enlargement of the nanoclusters remaining after the removal of the block copolymer micelles
• FIG. 9 schematically shows the etching of a modified microstructure acting as an antireflection surface using the enlarged nanoclusters as an etching mask
• FIG. 11 Scanning electron micrographs of surfaces clad with metal clusters, in which the metal clusters have different spatial dimensions and lateral distances.
• FIG. 1 schematically shows a polymer from which spherical micellar-like polymer units can be formed, using the example of a block copolymer as a whole designated 10. This has a nonpolar block 12 and a polar block 14.
• Suitable polymers for the process described below are, for example, graft copolymers, star polymers, dendritic polymers, star block polymers or block star polymers.
• block copolymer 10 preference is given to polystyrene-b-poly (2-vinylpyridine), which is shown in FIG. In this polystyrene forms the non-polar block 12 and poly (2-vinylpyridine) the polar block 14.
• Other well-suited block copolymers are polystyrene-b-polyethylene oxide and polystyrene-b-poly (4 -vinylpyridine). A mixture of said block copolymers can also be used.
• a polymer other than polystyrene may form the non-polar block 12, such as polyisoprene, polybutadiene, polymethylmethacrylate or other polymethacrylates.
• the polar block 14 may be formed besides the above-mentioned polymers polyethylene oxide, poly (2-vinylpyridine) and poly (4-vinylpyridine) by another polymer.
• the diblock copolymer PS-b-P2VP 10 in an amount of about 10 3 to about 100 mg / ml, preferably from about 5 mg / ml, in a non-polar solvent, such as Toluene, dissolved.
• a non-polar solvent such as Toluene
• the diblock copolymers PS-b-P2VP form 10 uncharged micelle-like polymer units in the form of micelles 16a, one of which is shown in FIG. at of these unloaded micelles 16a, the polar P2VP blocks 14 are oriented inwardly and form an inner core region 18, whereas the non-polar PS blocks 12 are oriented outwards and form an outer sheath region 20.
• Such an unloaded micelle 16a is also shown in FIG.
• an optical element 22 is at least partially coated with these micelles 16a, which is illustrated by way of example in FIG.
• the optical element 22, which is shown very schematically there, may be an optical element with an at least partially curved surface, such as e.g. a lens or a corresponding grid, but also an optical element with a plane
• Surface e.g. a flat glass, which is to be provided with an antireflection surface.
• a dipping process is preferably used for coating at least one area of the surface of the optical element 22 in step c) with the micelles 16a.
• the optical element 22 to be coated is immersed in a solution 24 with the micelles 16a, which is shown at 4a in FIG.
• the solution 24 may be, for example, the solution of uncharged micelles 16a in toluene generated above in step b).
• the optical element 22 is pulled out of the solution 24 with as constant a pulling rate as possible of between 0.001 mm / min and 2 m / min.
• a film-like layer 26a of the micelles 16a is formed on the surface region of the optical element 22 immersed in the solution, which can be seen at 4c in FIG.
• a pulling rate of 1 mm / min to 40 mm / min preferably from 1 mm / min to 10 mm / min, particularly preferably 5 mm / min, leads to the desired result.
• step c instead of the dipping method just described, in step c), for example, also a spin coating method can be carried out, as it is known per se.
• the micelles 16a forms an antireflection surface 28a of the optical element 22.
• the micelles 16a depending on the underlying block copolymer 10, each have a diameter of about 10 nm to about 650 nm and thus form a nanostructure with maximum dimensions smaller than the wavelengths of the inserted Radiation is.
• the nanostructure of the antireflection surface 28 can be adjusted by an appropriate selection of the polymers underlying the micelles 16a, which were mentioned above in connection with FIG.
• An appropriate choice of the chain lengths of the nonpolar block 12 and / or the polar block 14 also has an influence on the size of the micelles 16a formed therefrom and thus on the resulting topography of the anti-reflection surface 28.
• the antireflection surface 1 - 28a formed from the micelles 16a causes a smaller proportion of light to be absorbed. is inflected, which is no longer usable. As a result, the angle of incidence, under which light beams can strike the optical element 22, and under which it still passes through these optical beams through the optical element, is significantly increased
• no antireflective surface 28a formed of uncharged micelles 16a is formed on the surface of the optical element 22, but a modified antireflection surface 28b.
• This is formed from a film-like layer 26b of micelles 16b, which are loaded with a metal compound 30.
• a loaded micelle 16b is shown schematically in FIG. 3, wherein particles of the metal compound 30 are indicated as white spheres which are arranged in the core region 18 of the micelle 16b.
• Suitable metal compounds 30 are e.g. Compounds of Au, Pt, Pd, Ag, In, Fe, Zr, Al, Co, Ni, Ga, Sn, Zn,
• Si (OR) with R unbranched or branched C -C -alkyl radical, ferrocene, Zeise salt, SnBu_H or a mixture of several thereof.
• R unbranched or branched C -C -alkyl radical, ferrocene, Zeise salt, SnBu_H or a mixture of several thereof.
• the loading of the unloaded micelles 16a with the metal compound 30 is carried out in a first variant of the method as step bl) after the execution of step b) and before the implementation of step c).
• Micelles 16b loaded with a metal compound 30 are formed, for example, by adding the metal compound 30 to the uncharged micelles 16a in the solution 24 and vigorously stirring them over a longer period of time, for example, for about 24 hours.
• optical element 22 coated with a film-like layer 26b of micelles 16b by inserting the optical element 22 into the solution 24 with the loaded micelles 16b and pulling it out of it in a slow, defined movement as described above in step c ) and shown in Figure 4 at 4a and 4b.
• FIG. 5 A portion of the thus-formed optical element 22 having an antireflection surface 28b formed of charged micelles 16b is shown in FIG. 5, with only the antireflection surface 28b on one side of the optical element 22.
• the loading of the micelles 16a with a metal compound 30 takes place as step cl) after the implementation of step c). That is, first, the optical element 22 is coated with a film-like layer 26a of unloaded micelles 16a in the manner described in connection with FIG. Then, the optical element 22 carrying the unloaded micelles 16a is placed in a solution with the metal compound 30, which is not shown separately here.
• This second variant of the method also results in an optical element having an anti-reflection surface 28b loaded with a metal compound 30 Micelles 16b formed and shown in Figure 5.
• the unloaded micelles 16a can also be electrochemically loaded with a cluster in the form of a metal cluster 32 either in step bl) or in step c1).
• a micelle 16c is shown in FIG. 3, wherein the metal cluster 32 is indicated in the form of a larger hatched sphere.
• Another possibility is to irradiate the micelles 16b with high-energy radiation, in particular with UV light or X-radiation, resulting in clusters in the form of metal oxide clusters 33 in the core region 18 of the micelles 16c, which in FIG hatched larger sphere are indicated.
• step d) of the method takes place as step d) of the method and can optionally be done on the one hand before the coating of the optical element 23 with corresponding micelles 16 or on the other hand after such a coating.
• the micelles 16b which are initially loaded with a metal-containing compound 30, are transferred into the solution 24, which are converted into micelles 16c with metal clusters 32 or metal oxide clusters 33 as described above.
• the micelles 16c are then as described above applied to the surface of the optical element 22 (see Figure 4), resulting in the optical element 22 shown in Figure 5, which comprises an antireflection surface 28c composed of micelles 16c.
• Figure 5 illustrates the above-mentioned second case, i. when an optical element 22 having an antireflection surface 28b is first formed, and the micelles 16b thereof containing one or more metal compounds 30 are converted to micelles 16c with metal clusters 32 or metal oxide clusters 33 by one of the above-described measures ,
• the metal clusters 32 thus formed in the core region 18 of the micelles 16c are, depending on the metal compound or compounds 30 used in step bl) or cl), in particular oxygen-resistant noble metals such as Au, Pt and / or Pd or other metals, such as Fe, Co or Ni.
• metal oxide clusters 32 are formed in the core region 18 of the micelles 16c, these are preferably TiO "or Fe 2 O 3 .
• step d) If the unladen micelles 16a are loaded with a mixture of corresponding metal compounds in step bl) or in step c1), these can also be converted into clusters of metallic mixing systems in step d), for example Au / Fe 2 O_, Au / CoO, Au / Co O, Au / ZnO, Au / TiO 2 , Au / ZrO 2 , AuMl 2 O 3 , AuZIn 3 O 3 , PdMl 3 O 3 , Pd / ZrO 2 , Pt / graphite and / or PtMl 3 O 3 .
• Au / Fe 2 O_ Au / CoO, Au / Co O, Au / ZnO, Au / TiO 2 , Au / ZrO 2 , AuMl 2 O 3 , AuZIn 3 O 3 , PdMl 3 O 3 , Pd / ZrO 2 , Pt / graphite and / or PtMl 3 O 3 .
• the antireflection surface 28a is formed of unloaded micelles 16a
• the antireflection surface 28b is composed of micelles 16b loaded with a metal compound 30 or a mixture of a plurality of metal compounds 30.
• the third possible anti-reflection surface 28c includes micelles 16c, which in turn carry metal clusters 32 or metal oxide clusters 33.
• cluster is to be understood as a collective term for a collection of compounds or pure metals, which are held together by covalent bonds on the one hand or by other forces on the other hand.
• a further modified antireflection surface 34 can now be produced by removing the block copolymers 10 of the micelles 16b or 16c of the antireflection surface 28b or 28c, wherein on the surface of the optical element 22 substantially regularly arranged metal clusters 32 and / or metal oxide Cluster 33 is left behind.
• metal clusters 32 or metal oxide clusters 33 which are arranged on the surface of the optical element 22 and have no polymer or other cladding, are shown in FIGS. 6 to 9 as nanocolusters 32, 33 filled in black.
• the block copolymers 10 of the micelles 16b and 16c are removed in the aforementioned step e), for example by means of an etching, reduction or oxidation process.
• a gas plasma 36 is used, preferably an argon, an oxygen or a hydrogen plasma.
• the treated antireflection Area around the anti-reflection surface 28b, in which the micelles carry 16b particles of the metal compound 30 as a metallic precursor carried out by the plasma treatment, a transfer of the metal compound 30 in a crystalline metallic or oxidic modification in the form of the metal cluster 32 or metal oxide clusters 33rd
• nanoclusters 32 and 33 respectively exist on the surface of the optical element 22 in substantially the same regular arrangement as previously occupied by the micelles 16b and 16c, respectively.
• the respective distance between two nanoclusters 32 and 33 consequently depends on the diameter of the inserted micelles 16b and 16c, which, as already mentioned, can be between about 10 nm and about 650 nm.
• a further modified antireflection surface 38 can be formed, which is illustrated in FIG.
• a microstructure acting as an antireflection surface 38 in the optical element 22 is replaced by a CF.
• the nanoclusters 32 and 33 of the anti-reflection surface 34 serve as an etching mask (see FIG. 7 at 7a).
• the nanoclusters 32 and 33 are removed in a manner known per se from the surface of the optical element 22 (see Figure 7 at 7b), so that the structured anti-reflection surface 38 remains (see Figure 7 at 7c).
• the antireflection surface 34 constructed from the nanoclusters 32 or 33 can still be modified (cf., FIG. 8) by the nanoclusters 32, 33 in the aforementioned step f) by depositing a corresponding metal compound / a corresponding metal on the nanoclusters 32 and 33 to nanoclusters 32a and 33a, respectively. These then form an antireflection surface 34a.
• the enlargement of the nanoclusters 32 and 33 may be e.g. by electroless deposition by introducing the optical element 22 with the antireflection surface 34 into a solution 42, which is mixed with a corresponding metal compound, which is indicated in FIG. 8 at 8a.
• Another variant, which is not shown here in detail, is to enlarge the nanoclusters 32 and 33 forming the antireflection surface 34 by means of electrochemical methods to the nanoclusters 32a and 33a, respectively. The latter are shown in Figure 8 at 8b.
• nanoclusters 32a and 33b which are larger than the nanoclusters 32 and 33, can now also serve as an etching mask for a plasma 40, which is shown in FIG.
• a modified microstructure and thus a modified antireflection surface 38a on the optical element 22 result from the etching mask formed by the larger nanoclusters 32a or 33a Size of the nanoclusters 32 and 33 in step f) is thus a specific etching mask selectively produced.
• the structurally arranged on the surface of the optical element 22 larger nanoclusters 32a and
• the shape of the antireflection surface forming Individual structures and the extent to which these individual structures rise above the surface of the optical element 22 are decisive variables for the optical effect of the antireflection surface 38 or 38a (see Figures 7 and 9).
• the shape of these individual structures which may correspond, for example, to a cylinder, a cone or a pyramid or which may be such that a plurality of individual structures can form a so-called “tapping stone profile", can be set via a suitable choice of polymers, loading materials and the etching process.
• FIG. 10 a shows a scanning electron micrograph of a glass surface on which nanoclusters have been applied, which are shown as white, by the method explained above
• the Gold Cluster Through. diameter is about 36 nm, the lateral distance between two gold clusters is about 150 nm.
• FIG. 10b shows the corresponding glass surface after etching with a CF./Argon plasma.
• a pyramidal etch profile can be seen in the surface of the glass plate.
• the receptacle 10a) takes place in plan view at an angle to the surface of approximately 90 °, the receptacle 10b) takes place at an angle to the surface of approximately 45 °.
• FIG. 11 shows scanning electron micrographs of various cluster structures, from which the possibilities of variation for producing different anti-reflection surfaces can be seen.
• the lateral cluster distances in the images IIa), IIb) and IIc) are in the range of 115 ⁇ 22 nm in the range of 163 ⁇ 34 nm and in the images Hg), Hh) and Hi) in the range of 232 ⁇ 54 nm. These different lateral distances were achieved by using different polymers or polymers different chain lengths are used for applying the Mano cluster.
• these nanostructures can either themselves act as an antireflection surface of the corresponding optical element or serve as an etching mask for a further plasma treatment, whereby a corresponding surface microstructure is etched into the relevant optical element.

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