EP1594607A1 - Procede pour produire des motifs de structures physiques, chimiques ou biologiques sur des supports - Google Patents

Procede pour produire des motifs de structures physiques, chimiques ou biologiques sur des supports

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Publication number
EP1594607A1
EP1594607A1 EP03727442A EP03727442A EP1594607A1 EP 1594607 A1 EP1594607 A1 EP 1594607A1 EP 03727442 A EP03727442 A EP 03727442A EP 03727442 A EP03727442 A EP 03727442A EP 1594607 A1 EP1594607 A1 EP 1594607A1
Authority
EP
European Patent Office
Prior art keywords
nanostructures
excitation
chemical
carrier
plasmons
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03727442A
Other languages
German (de)
English (en)
Inventor
Dieter Institut für Angewandte Physik KERN
Heinrich Hoerber
Christoph Lienau
Erik Nibbering
Manfred Wick
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eberhard Karls Universitaet Tuebingen
Original Assignee
Europaisches Laboratorium fuer Molekularbiologie EMBL
Eberhard Karls Universitaet Tuebingen
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Filing date
Publication date
Application filed by Europaisches Laboratorium fuer Molekularbiologie EMBL, Eberhard Karls Universitaet Tuebingen filed Critical Europaisches Laboratorium fuer Molekularbiologie EMBL
Publication of EP1594607A1 publication Critical patent/EP1594607A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/251—Colorimeters; Construction thereof
    • G01N21/253—Colorimeters; Construction thereof for batch operation, i.e. multisample apparatus
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55—Specular reflectivity
    • G01N21/552—Attenuated total reflection
    • G01N21/553—Attenuated total reflection and using surface plasmons
    • G01N21/554—Attenuated total reflection and using surface plasmons detecting the surface plasmon resonance of nanostructured metals, e.g. localised surface plasmon resonance
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/18—Diffraction gratings
    • G02B5/1847—Manufacturing methods
    • G02B5/1857—Manufacturing methods using exposure or etching means, e.g. holography, photolithography, exposure to electron or ion beams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00351—Means for dispensing and evacuation of reagents
    • B01J2219/00427—Means for dispensing and evacuation of reagents using masks
    • B01J2219/00432—Photolithographic masks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00497—Features relating to the solid phase supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277—Apparatus
    • B01J2219/00497—Features relating to the solid phase supports
    • B01J2219/00504—Pins
    • B01J2219/00509—Microcolumns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J2219/00277—Apparatus
    • B01J2219/00497—Features relating to the solid phase supports
    • B01J2219/00527—Sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00585—Parallel processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/0059—Sequential processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00596—Solid-phase processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00653—Making arrays on substantially continuous surfaces the compounds being bound to electrodes embedded in or on the solid supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00655—Making arrays on substantially continuous surfaces the compounds being bound to magnets embedded in or on the solid supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00659—Two-dimensional arrays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/00603—Making arrays on substantially continuous surfaces
    • B01J2219/00675—In-situ synthesis on the substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00709—Type of synthesis
    • B01J2219/00711—Light-directed synthesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00709—Type of synthesis
    • B01J2219/00713—Electrochemical synthesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/0072—Organic compounds
    • B01J2219/00722—Nucleotides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/0072—Organic compounds
    • B01J2219/00725—Peptides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00718—Type of compounds synthesised
    • B01J2219/0072—Organic compounds
    • B01J2219/00731—Saccharides
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B40/00—Libraries per se, e.g. arrays, mixtures
    • C40B40/04—Libraries containing only organic compounds
    • C40B40/06—Libraries containing nucleotides or polynucleotides, or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B40/00—Libraries per se, e.g. arrays, mixtures
    • C40B40/04—Libraries containing only organic compounds
    • C40B40/10—Libraries containing peptides or polypeptides, or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B40/00—Libraries per se, e.g. arrays, mixtures
    • C40B40/04—Libraries containing only organic compounds
    • C40B40/12—Libraries containing saccharides or polysaccharides, or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B50/00—Methods of creating libraries, e.g. combinatorial synthesis
    • C40B50/14—Solid phase synthesis, i.e. wherein one or more library building blocks are bound to a solid support during library creation; Particular methods of cleavage from the solid support
    • C—CHEMISTRY; METALLURGY
    • C40—COMBINATORIAL TECHNOLOGY
    • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
    • C40B60/00—Apparatus specially adapted for use in combinatorial chemistry or with libraries
    • C40B60/14—Apparatus specially adapted for use in combinatorial chemistry or with libraries for creating libraries
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/06—Illumination; Optics
    • G01N2201/062—LED's

Definitions

  • the present invention relates to a method for producing patterns of physical, chemical and / or biochemical structures on a carrier by means of a spatially resolved transfer of electrons and / or energy from the nanostructures on the carrier.
  • microarray technology developed for this, in which many different sensor molecules are packed tightly in one predefined patterns on a carrier surface have become the standard method, especially in the area of parallel analysis of biological samples. It will e.g. used in the analysis of gene expression, in genetic diagnostics, in biological and pharmaceutical research and for the determination of genetically manipulated organisms in the food industry.
  • microarray technology requires simple, reproducible and inexpensive methods in order to offer a sufficient number of different molecules in the smallest space with high quality and quality.
  • An essential problem in the production of microarrays from complex molecules with high density and large variation is the often reproducible location-specific application of molecules on the carrier surfaces. In principle, these are the following two methods known for the production of DNA arrays.
  • finished macromolecules are applied to the carrier surface either in the form of drops (spotting) using a printing needle (US Pat. No. 6,101,946), micropipettes (US Pat. No. 5,601,980) or inkjet printers (US Pat. No. 5,927,547).
  • the diameter of the molecule fixation points (spots) in these methods are 50 ⁇ m to 200 ⁇ m. A thicker application or smaller spot sizes are not possible with this technique.
  • an in situ synthesis of array molecules from monomers takes place directly on a support by means of photochemically or electrostatically mediated reactions.
  • This method is a photolithographic technique in which specific end protective groups are removed by means of light masks or photomasks specially produced for this purpose, thus enabling direct solid-phase synthesis of the DNA on a carrier surface (WO 92/10092).
  • the location information or position of the oligonucleotide sequence to be addressed is given by the light mask applied in each case.
  • This fixed sequence, or permutation of masks defines a rigid pattern of the synthesized sequences.
  • the aim of the present invention is to increase the effectiveness of the synthesis methods for the production of microarrays and to provide a flexible, effective and inexpensive method for the spatially resolved production of molecular patterns on a carrier, which also serves as the basis for the production of semiconductor Molecular hybrid structures can serve for the area of so-called molecular electronics.
  • the invention primarily proposes a method with the features mentioned in claim 1.
  • An extension of the possible uses of the invention is the subject of the remaining dependent and independent claims 2 to 24, the wording of which, like the wording of the abstract, is made by reference to the content of the description.
  • the above-mentioned aim is achieved according to the invention in that the reactions or changes taking place on the surface of the carrier due to the antenna properties of the nanostructures present on the carrier surface as a result of an excitation of their plasmons and a subsequent transfer of energy and / or Electrons are induced on molecules chemically or physically bound to their surface.
  • the method according to the invention thus comprises the generation of patterns of physical, chemical and / or biochemical structures on a carrier by means of a spatially resolved transfer of electrons and / or energy from the nanostructures or nanoparticles on the carrier, this transfer being carried out by selective excitation of the Plasmons are induced in the nanostructures.
  • the physical, chemical or biochemical structures are understood to mean chemical or biochemical molecules of all kinds, cells or cell components, virus particles, individual atoms, electrons or the like.
  • Interface metal / dielectric or semiconductor / dielectric called. Due to the strong localization of the plasmons at the Interfaces, one speaks here of surface plasmon, their properties are very sensitive to the physical parameters of the boundary layer. Metal / semiconductor nanostructures have a characteristic plasmon spectrum, which is determined by the material (density, effective mass of the conduction electrons), their external shape and size, as well as the coupling with the environment, e.g. an interaction with a surface, with other nanostructures and thus whose density, or with a surrounding gaseous, liquid or solid medium is determined. For simplified geometries (e.g.
  • the frequency of the plasmon resonance can be derived directly from Maxwell's equations (H. Raether, Surface Plasmons, Springer Tracts Mod. Phys., Vol 111, Springer, 1988, U. Kreibig, M. Vollmer, Springer Ser. Mat. Sei. 25, Springer, 1995).
  • the resonance frequency ⁇ P results when ( ⁇ ( ⁇ ) + 2 ⁇ m ) 2 + ⁇ 2 ( ⁇ ) 2 assumes a minimum.
  • ⁇ ( ⁇ ) + i ⁇ 2 ( ⁇ ) denotes the complex frequency-dependent dielectric function of the nanoparticle.
  • R denotes the radius of the sphere, e the elementary charge, ⁇ 0 the vacuum dielectric constant, m e the effective mass and N the total number of conduction electrons in the sphere.
  • the plasmon resonances are between 350 and 650 nm depending on the size of the sphere (U. Kreibig, M.
  • the resonance frequency can be varied over a wide range by varying the doping, ie the electron density N / R 3 , and specifically covering the near, middle and far infrared range (R.
  • the attenuation of the plasmon resonance is in turn determined by the dielectric function, the size and shape of the nanoparticle.
  • metallic nanoparticles it is typically a few 10 to 100 meV (Feldmann) and a few meV in the infrared spectral range.
  • a strong local resonance increase of the electrical field occurs due to its antenna effect resulting from the Maxwell equations (L. Novotny et al. Phys. Rev. Lett. 79, 645 (1997)).
  • This means that a spectral resonant excitation of the nanoparticle can generate a local electrical plasmon field, the geometric dimensions of which are no longer determined by the wavelength of the light as in conventional optics, but by the size and shape of the nanostructure.
  • this electric field increase is used for the selective, local induction of elementary photochemical processes.
  • the basic principle of the invention is that in metallic or semiconducting nanostructures (FIG. 1) plasmons are generated locally on a carrier by electrical or electromagnetic excitation, which as a result of an energy and / or electron transfer into the physical, chemical or biological structures in these structures trigger changes.
  • the type and strength of the interactions between the nanostructures and the physical, chemical or biological structures on them depends on the combination of the materials, the density and environment of the structures, their absorption and emission spectra, their physical and / or chemical coupling, their relative distance, their distance from the carrier surface and the timing of the excitation.
  • the plasmons are optically excited by nanostructures applied to a carrier.
  • the excitation occurs when both the energy and the momentum of the incident light field match that of the plasmons (resonance).
  • a selective excitation of the plasmon resonance of a certain group of nanostructures can thus be achieved with the help of the variation of the wavelength (energy), the angle of incidence (pulse), the polarization and the intensity of the incident light.
  • fs pulses femtosecond pulses
  • An fs pulse is shorter in time than the typical oscillation periods of molecular excitations, and at the same time it causes a practically instantaneous initialization of vibronic core movement in the molecule. Because of its relatively large spectral width, an fs pulse leads to a superposition of many synchronous oscillations in phase in the excited state. This is used according to the invention to initiate a synchronous and effective electron and / or energy transfer to the structures located thereon.
  • Ultrashort light pulses with time durations of 10 to 100 fs have spectral widths of 10 - 100 meV and can therefore be spectrally adjusted to the plasmon resonances.
  • This enables an impulsive excitation of vibronic core movements in the molecule, whereby the dynamics of the core movement can be controlled within certain limits by choosing the amplitude, color and phase composition of the light pulse.
  • This results in possibilities for the coherent control of elementary photochemical reactions, both in electronically excited states in the visible and ultraviolet Spectral range (A. Assion et al., Science 282, 919 (1998)) as well as for reactions in the electronic ground state when excited with ultrashort infrared pulses in the spectral range between 500 and 4000 cm “1 (T. Witte et al., J. Chem. Phys. 118, 2021 (2003)).
  • the energy and / or electron transfer from the excited nanostructures to the physical, chemical and / or biochemical structures located on them can take place according to different mechanisms.
  • the plasmon can decay by emitting a photon that is in resonance with an absorption line in the spectrum of the structure on it and is therefore absorbed (radiation coupling). If the distance is appropriate, energy can also be transmitted using a near-field coupling (Förster transfer). Another possibility is the excitation of the nanostructures by electron transfer to the structures on them.
  • the basic mechanism for optically induced electron transfer is e.g. at D.S. Ginger in Physical Rev. B Vol. 59, No. 16, 10622-29: "Photoinduced electron transfer from conjugated polymers to CdSe nanocrystals" in the reverse direction.
  • the spatial pattern i.e. the positions of the nanostructures at which the optical excitation takes place and from which the energy and / or electron transfer is to take place can in principle be defined according to the invention by two different methods.
  • the plasmons of selected nanostructures can be excited in a spatially resolved manner. This can be achieved, for example, by using photomasks which cover individual carrier regions and only leave the nanostructures open to the incident light, on which the energy and / or electron transfer takes place during the irradiation and the subsequent reaction is to take place.
  • a serial radiation and Excitation of carrier areas with a laser writer, analogous to a laser printer or scanner, is also possible and is covered by the inventions.
  • the entire carrier surface is irradiated uniformly and simultaneously.
  • properties of the nanostructures which can be predetermined intrinsically during the design of the carrier are now used.
  • the excitation wavelength, excitation duration, excitation polarization and / or intensity can be specified by the choice of materials, size, shape, arrangement and environment of individual nanostructures or groups.
  • variable patterns of nanostructures can be selectively and spatially resolved.
  • spectra for the corresponding nanostructures are determined on the carrier before the irradiation.
  • the coated nanostructures can be custom-made to match the corresponding spectra previously defined.
  • the advantage of this embodiment variant is that the entire carrier surface can be irradiated in each reaction step. Plasmon excitation and energy and / or electron transfer only take place on the nanostructures which have the corresponding spectra, the other nanostructures remain unchanged In this way, complex photomasks can be dispensed with in whole or in part.
  • the plasmons in the nanostructures can also be excited electrically.
  • the carrier or structures applied to it must be made of an electrically conductive material.
  • the nanostructures should advantageously be electrically insulated in such a way that there is no electron transport or only electron transport through electron tunnels in the insulation layer. This can be achieved by applying a conductive layer to an insulating carrier, followed by an insulator layer a few nanometers thick.
  • the metallic or semiconducting nanostructures can be produced on this sandwich.
  • An electrical potential difference between the conductive lower layer and the nanostructures - for example as the potential difference between the base electrode and an electrolyte covering the structures - enables the excitation of plasmons in the nanostructures by means of electrons tunneling through the insulator layer.
  • the localized electrical excitation can take place in that the conductive substrate is applied in a structured manner to a suitably modified semiconductor chip, for example an SRAM chip (Static Random Access Memory), so that well-defined local areas of a few micrometers in size are specifically defined suitable voltage can be assigned.
  • a suitably modified semiconductor chip for example an SRAM chip (Static Random Access Memory)
  • SRAM chip Static Random Access Memory
  • Nanostructures made of gold, silver, gallium arsenide (GaAs) or other materials known from the physics of quantum dots are particularly preferably produced.
  • GaAs gallium arsenide
  • a combination of different materials for nanostructures is also possible, but this may be limited by the manufacturing processes used.
  • the nanostructures applied to the carrier have dimensions in the sub-micrometer range, preferably less than 200 nm. It must be taken into account here that with spherical nanostructures the intensity of the local electric field is proportional to the square of the volume of the nanostructure. Therefore, nanostructures with dimensions in the range from 2 to 100 nm are particularly preferred because, on the one hand, they allow the field to be localized to dimensions far below the wavelength of the light and, on the other hand, they ensure a sufficiently high field intensity.
  • the distances between individual nanostructures can be varied and are a possible parameter in the design of the support structures for adapting the coupling parameters for the interactions between the nanostructures and the physical, chemical and / or biological structures located thereon.
  • the nanostructures have different shapes on a carrier. You can e.g. be circular or elliptical or have some other geometric shape. The shape and size of the nanostructures and the material, in combination with other factors, determine the spectral properties of the plasmons and their
  • Another way to increase the spectral variability of the plasmons of the nanostructures is to use special spacing and / or coupling elements and their spacing for the nanostructure from the carrier, or between the nanostructures and the structures on them (Fig. 2 and Fig. 3). All spacers and / or coupling elements known to the person skilled in the art can be used for this.
  • All spacers and / or coupling elements known to the person skilled in the art can be used for this.
  • the spacing and / or coupling structures used between the carrier, the nanostructures and the physical, chemical and / or biological structures thereon not only function as a connecting element, but also modulate the interactions between the excited nanostructure and the applied or synthesized physical, chemical and / or biological structures and the excitation properties of the structures.
  • the energy and / or electron transfer can, according to the invention, not only take place on the above-described nanostructures raised over the carrier surface.
  • corresponding structures can also be sunk in a carrier material for this purpose or be present in the form of depressions or holes on the carrier surface. In this case, too, these structures have dimensions in the nanometer range, preferably below the exciting wavelength.
  • surface plasmons on depressed structures reference is made to the following article: L. Martin-Moreno et al., Phys. Rev. Lett. 2001, Vol. 86, 6, p. 11 14-1117 "Theory of extraordinary optical transmission through subwavelength hole arrays".
  • different materials can be used as supports (FIG. 4).
  • dielectric materials such as glass, plastics, silicon oxide and ceramic are preferably used.
  • the carrier In the case of electrical excitation, the carrier must at least partially consist of conductive structures. Layers and structures made of metal oxides can be used as insulators. Examples from semiconductor technology are well known for this.
  • a material that is transparent to the light is used for the carrier.
  • An example of such a slide can be an ordinary glass slide.
  • FIG. 5 shows an example of a slide which can be used as a carrier and is subdivided into eight regions (1 to 8), it being possible for individual of these regions to be subdivided further into four different levels (FIG. 6).
  • the nanostructures can also be excited from the lower side facing away from the nanostructures.
  • the particular advantage here lies in the use of an excitation under total reflection conditions at the upper boundary surface of the support, which only allow excitations very close to this surface, such as those from Stout AL and Axelrod D .: in “Evanescent field excitation of fluorescence by epi -illumination microscopy, Applied Optics Vol.28, pp. 5237-5242 (1989) have been described, as a result of which there is no radiation of the wider environment, for example the reagents in solution. The conditions of reflection are described by Snell's law: with the refractive index n-i and ß: the angle to the surface normal in the medium n 2 .
  • any reactions can be produced via the nanostructures used for localization and as an antenna, which can be induced by an energy and / or electron transfer.
  • Chemical and / or biochemical reactions such as synthesis, cleavage, coupling of functional groups, isomerization, conformational change, enzymatic or binding reactions, etc., are particularly preferably carried out.
  • the physical, chemical or biological structures mentioned above on the nanostructures can be, for example, reactants or molecular constituents which are to take part in the desired reaction.
  • molecules acting as catalysts, such as enzymes can be coupled to the nanostructures, which interact with the reactants from the environment and catalyze the chemical reaction.
  • polymer compounds are synthesized on the nanostructures, in particular it is a spatially resolved synthesis from monomers such as e.g. Nucleotides, amino acids, sugar units and other molecular components for the production of microarrays of chemical compounds.
  • monomers such as e.g. Nucleotides, amino acids, sugar units and other molecular components for the production of microarrays of chemical compounds.
  • polymeric compounds such as DNA, RNA, aptamers and their derivatives such as PNA or thioRNA, peptides, proteins, complex carbohydrates and other chemical compounds can be produced in a spatially resolved manner.
  • the synthesis of oligonucleotide sequences will be dealt with here (FIG. 7).
  • the coupling of the individual nucleotides can take place according to the classic method, in which the protective groups have to be removed before each synthesis step.
  • the site-specific cleavage of the protective groups is induced by the energy and / or electron transfer from the nanostructures to the start sequences or to the sequences already synthesized. After a The sequence repeats the attachment of a nucleotide or a nucleotide sequence to the deprotected sequences.
  • the molecular arrays produced by the method according to the invention can advantageously be used for analytical purposes.
  • the fields of application for arrays produced in this way include a large number of investigations in medical and / or veterinary diagnostics, drug development,
  • the method according to the invention can also be used in the field of sensors.
  • the starting materials present in a sample to be examined influence the spectral properties of the nanostructures, the emission spectrum, that is to say the color and / or spectral bandwidth or their luminous intensity.
  • An induced coupling of sample elements or a reaction induced by the sample particles - such as splitting off groups, changing the surface charge - can be a trigger for this.
  • specifically stimulated plasmons from nanostructures can be used to selectively activate coupled chromophores.
  • the chromophore By selecting the chromophore, the emission wavelength range and thus the color variation can be determined.
  • This can be used in the field of organic light-emitting diodes (LED), which are used in modern display technology, as optical data storage or as an indicator of a reaction, a condition - e.g. pH value of a solution or a hazardous substance.
  • the described method can be used to derive electrons from the nanostructures by means of electrodes into a downstream electronics.
  • nanostructures can thus be used as a type of switch or a pattern of nanostructures as a switch array in molecular electronics.
  • the biochemical, physical or chemical structures applied to the nanostructures can be used as passive delay elements or as damping elements or else as active elements, that is to say as an electron source or line.
  • Fig. 1 Schematic representation of metal / semiconductor
  • Nanostructures The specific properties of the nanostructures are given by the material, their external shape and size as well as by the coupling with the environment. Any differences in material are indicated here by the different hatching.
  • Fig. 2 Schematic representation of metal / semiconductor nanostructures with applied molecular
  • Fig. 4 Schematic representation of various combinations of metal / semiconductor nanostructures with applied molecular spacers (rectangles) and physical, chemical or biochemical structures (circles) located thereon, applied to different carrier materials, which are indicated by the different hatching.
  • Fig. 5 Exemplary schematic representation of a
  • Fig. 6 Exemplary representation of a carrier with different resolution levels with a schematic structure of nanostructures.
  • Photochromic materials change their optical and / or electrical properties when exposed to light and therefore offer options for use as optical data storage.
  • the state of the data storage device can, for example, be due to the light-induced conversion between different isomers of a molecule can be achieved.
  • Particularly optically bistable fulgides eg the phenyl-thiophene fulgide Ph-TF, S. Rath et al., J. Lum. 94, 156 (2001) are interesting candidates because they convert the colored C Isomer and the colorless E isomer is made possible.
  • the E-isomer shows no absorption resonance in the visible spectral range and has a factor of 10 less at 600 nm optical density.
  • the E isomer shows an absorption resonance at 350 nm.
  • the E isomer converts to the C isomer, while the irradiation from visible light around 600 nm leads to photoisomerization from C to E.
  • the reaction times for isomerization reactions are in the picosecond range and have been investigated in detail (M. Handschuh et al., J. Phys. Chem. A 101, 502 (1997).
  • suitable pulse sequences of visible and UV pulses optically reversible between C and E isomer are switched.
  • the plasmonic nanostructures were chosen so that their plasmon resonances match the absorption band of the C isomer. This could be ensured in the present example by choosing spherical gold nanoparticles with a size of approximately 50 nm (T. Klar et al., Phys. Rev. Lett. 80, 4249 (1998)).
  • the linker material By selecting the linker material, the molecules can be selectively coupled to the nanoparticle.
  • undesired secondary reactions for example fluorescence suppression by charge transfer, can be reduced. All molecules in the C state are prepared by exposure to UV light.
  • Irradiation of visible light pulses with a central wavelength of 600 nm allow selective excitation of the plasmon resonance of the nanoparticle.
  • this is transferred to the molecule by near-field radiation coupling (Förster transfer).
  • Förster transfer This results in a selective, local switching of the molecules that are located in the near field of the resonantly excited nanoparticles. Based on this principle, single-molecule switches in high density can be optically addressed.

Abstract

La présente invention concerne un procédé pour produire des motifs de structures physiques, chimiques ou biologiques sur un support, au moyen d'un transfert à résolution locale d'électrons et/ou d'énergie à partir des nanostructures qui se trouvent sur le support. Selon le procédé, ce transfert est induit par une excitation sélective de plasmons dans les nanostructures. L'excitation des plasmons s'effectue notamment par voie électrique au moyen d'un rayonnement électromagnétique et/ou au moyen d'un rayonnement par faisceau d'électrons.
EP03727442A 2002-05-06 2003-05-06 Procede pour produire des motifs de structures physiques, chimiques ou biologiques sur des supports Withdrawn EP1594607A1 (fr)

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US5424186A (en) * 1989-06-07 1995-06-13 Affymax Technologies N.V. Very large scale immobilized polymer synthesis
US6051380A (en) * 1993-11-01 2000-04-18 Nanogen, Inc. Methods and procedures for molecular biological analysis and diagnostics
US6180415B1 (en) * 1997-02-20 2001-01-30 The Regents Of The University Of California Plasmon resonant particles, methods and apparatus
WO2001039285A2 (fr) * 1999-11-08 2001-05-31 Nova Crystals, Inc. Emetteurs de lumiere excites par des electrons au moyen d'un couplage de photons plasmons ameliore par des nanostructures et procede de fabrication correspondant
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