EP2501842B1 - Procédés de grossissement de nanoparticules avec une haute résolution spatiale sur une surface de substrat - Google Patents

Procédés de grossissement de nanoparticules avec une haute résolution spatiale sur une surface de substrat Download PDF

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EP2501842B1
EP2501842B1 EP10778575.0A EP10778575A EP2501842B1 EP 2501842 B1 EP2501842 B1 EP 2501842B1 EP 10778575 A EP10778575 A EP 10778575A EP 2501842 B1 EP2501842 B1 EP 2501842B1
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precious metal
substrate
metal nanoparticles
substrate surface
nanoparticles
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EP2501842A2 (fr
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Christoph Morhard
Claudia Pacholski
Joachim P. Spatz
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Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
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Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
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    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1605—Process or apparatus coating on selected surface areas by masking
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/1612—Process or apparatus coating on selected surface areas by direct patterning through irradiation means
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1664—Process features with additional means during the plating process
    • C23C18/1667—Radiant energy, e.g. laser
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • C23C18/1841—Multistep pretreatment with use of metal first
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1889—Multistep pretreatment with use of metal first
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
    • Y10T428/24612—Composite web or sheet
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • Y10T428/24909—Free metal or mineral containing

Definitions

  • the present invention relates to methods for spatially resolved magnification and size fine tuning of noble metal nanoparticles on a substrate surface, and to the nanoparticle assemblies and nanostructured substrate surfaces so prepared and their use.
  • nanostructures especially ordered structures of noble metal nanoparticles on substrate surfaces, have found great interest in a variety of applications in various fields.
  • gold nanoparticles can be used in biochemical sensors ( Dyckman and Bogatyrev (2007), Russian Chemical Reviews 76 (2), 181-194 ) and as etching masks for the production of biomimetic interfaces and interfaces ( Lohmüller et al. (2008), NANO LETTERS 8 (5): 1429-1433 ).
  • noble metal nanoparticles of given diameters could also be advantageously used in new transistors (Sato et al. (1997), American Institute of Physics 82 (2), 696-702) or for fluorescence quenching (US Pat. Fan et al. (2003), PNAS, 100 (1), 6297-6301 ) be used.
  • the size of noble metal nanoparticles, in particular gold nanoparticles can in principle be applied before application to the substrate surface, eg when using metal colloids (US Pat. Kimling et al. (2006) J. Phys. Chem. B., 110, 15700-15707 ), or after application, eg by electroless deposition using a reducing agent ( Hrapovic et al.
  • particle size gradients are generated either by electroless deposition from a solution containing elemental gold as above, but varying the rate at which a nanoparticle-coated substrate surface is withdrawn from this solution or by irradiation with a laterally intensity-modulated light field.
  • a related task was to provide the appropriate nanoparticle assemblies and nanostructured substrate surfaces.
  • a further object was the provision of the nanoparticle arrangements and nanostructured substrate surfaces prepared according to the invention for various uses which hitherto were not suitable for such noble metal nanoparticle arrangements owing to the inadequate or inadequate size possible fine adjustment of noble metal nanoparticles on a substrate surface.
  • the above-mentioned main object can be achieved by providing the method according to claim 1, in which a substrate coated with (preferably fixed) noble metal nanoparticles is contacted with a noble metal salt solution and localized by UV irradiation of certain predetermined areas and controlled enlargement of the nanoparticles in these areas is initiated.
  • a substrate coated with (preferably fixed) noble metal nanoparticles is contacted with a noble metal salt solution and localized by UV irradiation of certain predetermined areas and controlled enlargement of the nanoparticles in these areas is initiated.
  • EP 1 626 106 A2 For example, a dried metal colloid film is subjected to laser irradiation.
  • the laser irradiation is not used for reduction, but for removal of molecules of the dispersion medium, which initially keep the fine metal particles separated. After removal, aggregation and formation of larger metal particles occurs.
  • EP 1760 527 A1 discloses the irradiation of a polymer film on a substrate to fix or chemically modify the polymer components of that film.
  • a substrate coated with noble metal nanoparticles in the above step a) can in principle be carried out by all methods known in the prior art.
  • a noble metal colloid layer can be applied to the substrate surface (see Hrapovic et al., Supra).
  • Another preferred method according to the invention is the production of a noble metal nanoparticle arrangement on a substrate by micellar nanolithography, more particularly micellar block copolymer nanolithography (BCML) (see, for example, US Pat EP 1 027 157 ).
  • micellar block copolymer nanolithography a micellar solution of a block copolymer is deposited on a substrate, for example by dip coating, and forms, under suitable conditions on the surface, an ordered film structure of chemically distinct polymer domains including, but not limited to, type, molecular weight, and concentration Block copolymer depends.
  • the micelles in the solution can be loaded with inorganic salts, which can be reduced to inorganic nanoparticles after deposition with the polymer film.
  • a plasma treatment for example with hydrogen plasma, is generally carried out.
  • the substrate material used in the invention is basically not particularly limited and may include any material as long as it is stable under the conditions of the process of the present invention and does not interfere with or interfere with the reactions taking place.
  • the substrate can be made, for example, of glass, SiO 2 , silicon, metals (with or without passivated surfaces), semiconductor materials, eg GaAs, GaP, GaInP, AlGaAs, (optionally doped) metal oxides, eg ZnO, TiO 2 , carbon (graphite , Diamond), polymers, etc., and composite materials thereof.
  • transparent substrates such as glass or ITO on glass are preferred.
  • the noble metal of the nanoparticles is not particularly limited and may include any noble metal known in the art for such nanoparticles, or composites of plural noble metals (hybrid particles) or mixtures of a noble metal with another metal.
  • the noble metal is selected from the group consisting of Au, Pt, Pd, Ag or mixtures / composites of these metals and most preferably is gold.
  • the original nanoparticles typically have diameters in the range of 1 nm to 100 nm, preferably 4 nm to 30 nm.
  • the interparticle distances can be varied over a wide range as desired, for example in one Range of 20 to 1000 nm, typically in the range of 30 to 250 nm.
  • the substrate may, if necessary, after the application of the nanoparticles, but before their enlargement, be treated with an agent which supports the adhesion of the nanoparticles.
  • an agent which supports the adhesion of the nanoparticles it is preferable to treat the substrate with an agent which the adhesion of the Supported gold nanoparticles.
  • silane in particular selected from the group consisting of 3-aminopropyltriethoxysilane (APS), 3-mercaptopropyltriethoxysilane (MPS), N- [3- (tri-methoxysilyl) propyl) ethylenediamine, 3- [2- (2-aminoethylamino) ethylamino] propyltrimethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyl) tris (trimethylsiloxy) silane and 3-mercaptopropyltrimethoxysilane.
  • APS 3-aminopropyltriethoxysilane
  • MPS 3-mercaptopropyltriethoxysilane
  • 3- [2- (2-aminoethylamino) ethylamino] propyltrimethoxysilane 3-
  • the noble metal salt solution contacted with the substrate surface in step c) is an aqueous metal salt solution to which has been added an organic compound which upon or after UV irradiation forms organic radicals which act as a reductant for the noble metal ions serve.
  • This organic compound is preferably selected from the group consisting of aldehydes, ketones or alcohols, in particular C 1 -C 10 -alcohols. More preferably, the C 1 -C 10 alcohol is selected from methanol, ethanol, propanol, butanol and ethylene glycol.
  • the proportion of organic compound can vary the speed and the extent of reduction by the skilled person can be easily adjusted by routine experimentation.
  • the volume ratio of aqueous metal salt solution to organic compound will range from 100: 1 to 1: 2, more preferably 10: 1 to 1: 1, eg 3: 1 or 1: 1.
  • the noble metal salt solution is a gold salt solution, preferably a HAuCl 4 solution.
  • the duration of UV irradiation may vary depending on the extent of nanoparticle enlargement desired and the particular substrate parameters, and a suitable irradiation time may readily be set by a person skilled in the art with routine experimentation.
  • the UV irradiation is carried out for a duration in the range of 1 to 60 minutes, preferably 1 to 15 minutes, and at a wavelength in the range of 200 to 600 nm, preferably 200 to 400 nm.
  • the method according to the invention is preferably carried out such that the conditions of the UV irradiation are varied for at least two different regions of the substrate so that at least two different regions with different average diameters of the noble metal nanoparticles are produced on the substrate.
  • This variation of the conditions of UV irradiation is or includes, for example, a variation of the irradiation time.
  • the method of the invention is performed using a mask (step e)) to cause localized growth of the noble metal nanoparticles in predetermined regions of the substrate.
  • the mask has structures which allow diffraction of the irradiated UV light under suitable irradiation conditions, and the method is carried out under such conditions, in particular a suitable wavelength, that a diffraction pattern or pattern of brightness is formed on the substrate surface during the irradiation and the growth of noble metal nanoparticles is selectively induced in the more irradiated areas of the diffraction pattern or pattern of brightness.
  • These structures may include, for example, one or more pinhole apertures having a small hole diameter, preferably ⁇ 100 ⁇ m, more preferably ⁇ 10 ⁇ m, other diffraction gratings, diffraction edges, periodic patterns or gradients such as gradual gray filters.
  • the pinhole diaphragms may, for example, have a circular, elliptical, rectangular or triangular shape.
  • the pinhole (n) has a circular diameter such that a diffraction pattern of concentric rings is formed on the substrate surface during irradiation, and the generated different regions having different mean diameters of the noble metal nanoparticles also become a pattern form concentric rings.
  • These arrangements include two or more distinct regions of noble metal nanoparticles with one average diameter in the range of 5-200 nm, preferably 5-20 nm, and an average spacing in the range of less than 1 .mu.m, preferably from 30 to 250 nm, wherein in each of the different areas noble metal nanoparticles having a predetermined different average diameter and the various areas of differing mean diameters of the noble metal nanoparticles form one or more geometric patterns which are formed by diffracting radiation at circular, elliptical, rectangular, triangular pinholes, edges or other periodically arranged patterns as well as gradients like gradual gray filters resulting diffraction patterns or brightness patterns / correspond.
  • the various regions form a pattern of concentric rings.
  • nanostructured substrate surfaces and arrangements of noble metal nanoparticles obtainable with the above inventive methods on a substrate form advantageous application possibilities in a wide variety of fields due to the possibility of finely adjusting the particle size with high spatial resolution and precise representation of geometric patterns with several sharply separated regions of different particle size.
  • another aspect of the present invention also relates to the use of these nanostructured substrate surfaces and devices in the fields of biochip technology, imaging technology, electronics, information processing, spectroscopy, sensor technology, optics, lithography.
  • the devices are selected from the group consisting of a mask, in particular a lithographic or photomask, a biochip, a sensor, an optical device, in particular a Fresnel lens, an optical grating, a microlens array or a transistor.
  • a further subject of the invention also relates to the devices themselves, which comprise such nanostructured substrate surfaces or arrangements.
  • these devices are a mask, in particular a lithographic or photomask, a biochip, a sensor, an optical device, in particular a Fresnel lens, an optical grating, a microlens array or a transistor.
  • the sample to be exposed consisting of SiO 2 whose surface had gold nanoparticles with a mean diameter of about 9 nm ( Fig. 2 ) was treated with silane (gas phase deposition of 3-aminopropyltriethoxysilane (APS): Sample + 30 ⁇ L APS (in separate dish) in a desiccator for 30 minutes at 0.3 mbar, then 1 h at 80 ° C in the oven Exposure in a small container. To the vessel was added a 1: 1 mixture of 0.25% gold salt solution (HAuCl 4 ) and ethanol. The amount of solution was measured so that the sample was covered by a liquid film about 1 mm high.
  • silane gas phase deposition of 3-aminopropyltriethoxysilane (APS): Sample + 30 ⁇ L APS (in separate dish) in a desiccator for 30 minutes at 0.3 mbar, then 1 h at 80 ° C in the oven Exposure in a small container.
  • To the vessel was added
  • UV was irradiated without a mask (commercial UV lamp, wavelength: 410 nm). Exposure times of 2 '30 "gave particle diameter of about 13 nm ( Fig. 4 ); Exposure times of 3 'diameter of about 15 nm ( Fig. 5 ).
  • the diffraction integral can not be solved analytically after application of the Fresnel approximation, but only numerically.
  • the resulting diffraction pattern reacts extremely sensitive to the smallest changes in the distance or the aperture diameter. Since a realization of constant conditions (completely planar sample, completely planar mask, no "wave formation" of the solution,) can be realized only with great effort, a simpler (qualitative) approach was chosen for the subsequent experimental arrangements and images.
  • the sample to be exposed was placed in a small vessel. To the vessel was added a solution of 1.5 ml of 0.25% gold salt solution (HAuCl 4 ) and 0.5 ml of ethanol. The amount of the solution was so dimensioned that the sample is covered by a ca. 1 mm high liquid film. As a mask, aluminum foil perforated with holes between 0.6 mm and 2 mm was used. This mask was placed about 1.1 mm above the sample. It was then exposed to UV light for 10 or 30 minutes.
  • AuCl 4 gold salt solution
  • Fig. 6 shows the localized growth of gold nanoparticles at 10 minutes UV irradiation using a mask with a circular pinhole (approximate diameter: 1 mm).
  • a circular pinhole approximately 1 mm.
  • no (at least not clear) further diffraction rings can be seen. This could eg at an unfavorable exposure time for the mask size.
  • Fig. 9 shows the results using a slightly elliptical shadow mask and an exposure time of 10 minutes. Diffraction structures are visible and these were recorded with increasing magnification. Again, the relatively sharp demarcation of the individual rings becomes clear.
  • Fig. 8 shows the results using a circular shadow mask and an exposure time of 30 minutes.
  • the longer exposure time leads to a very strong growth in the exposed areas. This can be seen in particular at the overview shot (very bright ring structure).
  • the area between the dark interior and the edge has been enlarged to a greatly enlarged area.
  • the gold particles in the highest magnification ( Fig. 8d ) form a clearly recognizable edge.
  • a purely qualitative determination of the size in the SEM leads to a radius of about 10 nm of the smaller (upper half of the picture) and about 17 nm of the larger particles (lower half of the picture).
  • Fig. 7 shows the results using a further circular shadow mask and an exposure time of 30 minutes. Here again diffraction patterns can be seen. Again, the clearly demarcated ring structure is clearly visible.

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Claims (17)

  1. Procédé servant à agrandir avec une résolution spatiale des nanoparticules de métaux précieux, qui sont présentes sur un substrat, comprenant les étapes suivantes :
    a) la fourniture d'un substrat revêtu de nanoparticules de métaux précieux,
    b) éventuellement la fonctionnalisation du substrat avec un agent, qui soutient l'adhérence des nanoparticules de métaux précieux au niveau du substrat,
    c) l'établissement d'un contact du substrat avec une solution saline de métaux précieux, dans lequel la solution saline de métaux précieux est une solution saline de métaux précieux aqueuse, à laquelle a été ajouté un composé organique, qui forme, dans le cas d'une exposition à un rayonnement UV, des radicaux organiques, qui servent de moyens de réduction pour les ions de métaux précieux,
    d) l'exposition à un rayonnement UV du substrat au contact de la solution saline de métaux précieux, ce qui permet d'entraîner une réduction du sel de métaux précieux et une séparation sans courant du métal précieux élémentaire sur les nanoparticules de métaux précieux et un accroissement correspondant des nanoparticules de métaux précieux dans les zones exposées au rayonnement du substrat,
    e) éventuellement l'utilisation d'un masque pour entraîner un accroissement localisé des nanoparticules de métaux précieux dans des zones prédéfinies du substrat.
  2. Procédé selon la revendication 1, caractérisé en ce que le métal précieux est choisi parmi le groupe composé d'or, d'argent, de palladium et de platine.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le substrat revêtu de nanoparticules de métaux précieux est fourni par une lithographie micellaire à copolymères séquencés (BCML) ou par application d'une couche de colloïdes de métaux précieux sur la surface de substrat.
  4. Procédé selon l'une quelconque des revendications 1 - 3, caractérisé en ce que l'agent, qui soutient l'adhérence de nanoparticules de métaux précieux au niveau du substrat, est un silane, en particulier choisi parmi le groupe, qui est constitué de 3-aminopropyltriéthoxysilane (APS), de 3-mercaptopropyltriéthoxysilane (MPS), de N-[3-(triméthoxysilyle)propyle)éthylène-diamine, de 3-[2-(2-aminoéthylamino)éthylamino]propyltriméthoxy-silane, de 3-aminopropyldiméthylméthoxysilane, de 3-aminopropyle)-tris-triméthylsiloxy)silane et de 3-mercaptopropyltriméthoxy-silane.
  5. Procédé selon l'une quelconque des revendications 1 - 4, caractérisé en ce que le composé organique, qui a été ajouté à la solution saline de métaux précieux, est un aldéhyde, une cétone ou un alcool, de préférence un alcool en C1-C10.
  6. Procédé selon l'une quelconque des revendications 1-5, caractérisé en ce que les conditions de l'exposition à un rayonnement UV varient pour au moins deux zones différentes du substrat de sorte qu'au moins deux zones différentes avec des diamètres moyens différents des nanoparticules de métaux précieux soient produites sur le substrat.
  7. Procédé selon l'une quelconque des revendications 1 - 6, caractérisé en ce que l'étape e) est réalisée en utilisant un masque, qui contient un ou plusieurs diaphragmes perforés avec un diamètre de trou < 10 µm, d'autres réseaux de diffraction, des arêtes de diffraction ou des gradients tels des filtres de gris graduels, et dans des conditions telles que dans le cas de l'exposition à un rayonnement, un motif de diffraction ou un motif de clarté est formé sur la surface de substrat et l'accroissement des nanoparticules de métaux précieux est entraîné de manière sélective dans les zones plus fortement exposées à un rayonnement du motif de diffraction ou du motif de luminosité.
  8. Procédé selon la revendication 7, caractérisé en ce que l'étape e) est réalisée en utilisant un masque, qui contient un ou plusieurs diaphragmes perforés avec un diamètre de trou < 10 µm de forme circulaire, elliptique, rectangulaire ou triangulaire.
  9. Procédé selon la revendication 8, caractérisé en ce que le/les diaphragme(s) perforé(s) a/ont un diamètre de forme circulaire de sorte que lors de l'exposition à un rayonnement, un motif de diffraction soit formé par des anneaux concentriques sur la surface de substrat et les différentes zones produites avec différents diamètres moyens des nanoparticules de métaux précieux forment également un motif d'anneaux concentriques.
  10. Procédé servant à fabriquer une surface de substrat nanostructurée, comprenant les étapes a) - e) selon l'une quelconque des revendications 1 - 9 ainsi qu'en outre l'étape suivante :
    f) la soumission du substrat avec l'ensemble de nanoparticules de métaux précieux obtenu lors des étapes a) - e) selon l'une quelconque des revendications 1 - 9 à au moins une étape de décapage, lors de laquelle les nanoparticules de métaux précieux agissent en tant que masque décapant, ce qui permet de produire une forme en relief souhaitée de la surface de substrat par décapage sélectif dans des zones prédéfinies du substrat en conservant le motif de l'ensemble de nanoparticules de métaux précieux.
  11. Procédé servant à fabriquer une surface de substrat nanostructurée selon la revendication 10, comprenant les étapes a) - e) selon l'une quelconque des revendications 7 - 8, ainsi qu'en outre l'étape suivante :
    f) la soumission du substrat avec l'ensemble de nanoparticules de métaux précieux obtenu lors des étapes a) - e) selon l'une quelconque des revendications 7 - 8 à au moins une étape de décapage, lors de laquelle les nanoparticules de métaux précieux agissent en tant que masque décapant, ce qui permet de produire une forme en relief souhaitée de la surface de substrat par décapage sélectif dans des zones prédéfinies du substrat en conservant le motif de l'ensemble de nanoparticules de métaux précieux.
  12. Procédé servant à fabriquer une surface de substrat nanostructurée selon la revendication 10, comprenant les étapes a) - e) selon la revendication 9 ainsi qu'en outre l'étape suivante :
    f) la soumission du substrat avec l'ensemble de nanoparticules de métaux précieux obtenu lors des étapes a) - e) selon la revendication 9, pour lequel différentes zones avec des diamètres moyens différents des nanoparticules de métaux précieux forment un motif d'anneaux concentriques, à au moins une étape de décapage, lors de laquelle les nanoparticules de métaux précieux agissent en tant que masque décapant, ce qui permet de produire une forme en relief de la surface de substrat, qui correspond à une lentille de Fresnel, par décapage sélectif dans des zones prédéfinies du substrat en conservant le motif de l'ensemble de cercles concentriques.
  13. Surface de substrat nanostructurée pouvant être obtenue avec le procédé selon la revendication 11 ou 12.
  14. Ensemble de nanoparticules de métaux précieux, en particulier de nanoparticules d'or, d'argent, de palladium et de platine ou de particules hybrides de celles-ci, sur un substrat, pouvant être obtenu selon l'une quelconque des revendications 7 à 9, dans lequel l'ensemble comprend deux zones différentes ou plus de nanoparticules de métaux précieux avec un diamètre moyen dans la plage de 5 - 200 nm et avec un espacement moyen dans la plage inférieure à 1 µm, dans lequel sont présentes dans les différentes zones respectivement des nanoparticules de métaux précieux avec un diamètre moyen différent spécifié, et que les différentes zones avec différents diamètres moyens des nanoparticules de métaux précieux forment un ou plusieurs motifs géométriques, qui correspondent à des motifs de diffraction ou des motifs de luminosité se formant par diffraction du rayon au niveau de diaphragmes, arêtes de forme circulaire, elliptiques, rectangulaires, triangulaires ou au niveau d'autres motifs disposés de manière périodique ainsi qu'au niveau de gradients tels que des filtres de gris graduels.
  15. Utilisation de la surface de substrat nanostructurée selon la revendication 13 ou l'ensemble selon la revendication 14 dans les domaines de la technologie de la biopuce, de la technique d'imagerie, de l'électronique, du traitement des informations, de la spectroscopie, de la technologie de détection, de l'optique, de la lithographie, en particulier pour fabriquer un masque de lithographie ou un photomasque, une biopuce, un capteur, un dispositif optique, en particulier une lentille de Fresnel, un réseau optique, un réseau de microlentilles ou un transistor.
  16. Dispositif comprenant la surface de substrat nanostructurée selon la revendication 13 ou l'ensemble selon la revendication 14.
  17. Dispositif selon la revendication 16, dans lequel un masque, en particulier un masque de lithographie ou un photomasque, est une biopuce, un capteur, un dispositif optique, en particulier une lentille de Fresnel, un réseau optique, un réseau de microlentilles ou un transistor.
EP10778575.0A 2009-11-16 2010-11-15 Procédés de grossissement de nanoparticules avec une haute résolution spatiale sur une surface de substrat Active EP2501842B1 (fr)

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DE102009053406A DE102009053406A1 (de) 2009-11-16 2009-11-16 Verfahren zur räumlich aufgelösten Vergrößerung von Nanopartikeln auf einer Substratoberfläche
PCT/EP2010/006938 WO2011057816A2 (fr) 2009-11-16 2010-11-15 Procédés de grossissement de nanoparticules avec une haute résolution spatiale sur une surface de substrat

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DE102010023490A1 (de) 2010-06-11 2011-12-15 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Dreidimensionale metallbedeckte Nanostrukturen auf Substratoberflächen,Verfahren zu deren Erzeugung sowie deren Verwendung
WO2015053828A2 (fr) 2013-06-15 2015-04-16 Brookhaven Science Associates, Llc Formation de surfaces antiréfléchissantes
US10290507B2 (en) 2013-06-15 2019-05-14 Brookhaven Science Associates, Llc Formation of antireflective surfaces
DE102013111785A1 (de) * 2013-10-25 2015-04-30 Osram Oled Gmbh Optoelektronisches Bauelement und Verfahren zum Herstellen eines optoelektronischen Bauelementes
US11135649B2 (en) * 2018-02-27 2021-10-05 Arizona Board Of Regents On Behalf Of Arizona State University Direct metal printing with stereolithography

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US8361553B2 (en) * 2004-07-30 2013-01-29 Kimberly-Clark Worldwide, Inc. Methods and compositions for metal nanoparticle treated surfaces
EP1760527B1 (fr) * 2005-09-05 2012-06-06 DWI an der RWTH Aachen e.V. Méthode photochimique pour fabriquer des substrats surface-décorés à l'échelle nanométrique
DE102007014538A1 (de) 2007-03-27 2008-10-02 Carl Zeiss Ag Verfahren zur Erzeugung einer Antireflexionsoberfläche auf einem optischen Element sowie optische Elemente mit einer Antireflexionsoberfläche
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WO2011057816A3 (fr) 2011-08-11
WO2011057816A2 (fr) 2011-05-19
US9169566B2 (en) 2015-10-27
DE102009053406A1 (de) 2011-05-19
US20120244322A1 (en) 2012-09-27

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