WO2003092881A1

WO2003092881A1 - Method for producing patterns of physical, chemical or biochemical structures on carriers

Info

Publication number: WO2003092881A1
Application number: PCT/EP2003/004728
Authority: WO
Inventors: Dieter Kern; Heinrich Hoerber; Christoph Lienau; Erik Nibbering; Manfred Wick
Original assignee: Universität Tübingen; Embl (European Molecular Biology Laboratory)
Priority date: 2002-05-06
Filing date: 2003-05-06
Publication date: 2003-11-13
Also published as: AU2003233242A1; EP1594607A1; AU2003233242A8

Abstract

The invention relates to a method for producing patterns of physical, chemical and/or biochemical structures on a carrier by means of a local transfer of electrons and/or energy from the nanostructures on the carrier. According to said method, said transfer is induced by selective excitation of the plasmons in the nanostructures. The excitation of the plasmons occurs in an especially electrical manner by means of electromagnetic radiation and/or electron radiation.

Description

Process for creating patterns of physical, chemical or biochemical structures on supports

description

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.

In biological and medical research as well as in medical analytics, there is a great need for effective methods for analyzing complex mixtures of molecules such as DNA, proteins, sugars, metabolic metabolites etc. The 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.

In manufacturing, 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. In the first method, 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 μm to 200 μm. A thicker application or smaller spot sizes are not possible with this technique. In the second method, 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). In this method, 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. With this method, significantly smaller spot sizes and higher densities than with the first method can be achieved, the efficiency of the individual synthesis of 80% to 95% per synthesis step achieved so far limits the applicability of these techniques to short oligose sequences or to a few variations of Sequences. In addition, this method is associated with considerable technical, time and cost expenditure.

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.

To achieve this object, 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. In the present invention, 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.

Collective excitations (electron density waves) of an electron gas of a metal or semiconductor on a plasmons

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. planar surface or spheres with a radius that is much smaller than the wavelength), 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). Especially for spherical nanoparticles in a dielectric medium with a dielectric function ε _m , the resonance frequency ω _P results when (ει (ω) + 2ε _m ) ² + ε ₂ (ω) ² assumes a minimum. Here ει (ω) + iε ₂ (ω) denotes the complex frequency-dependent dielectric function of the nanoparticle. The dielectric function of conductive nanoparticles can often be reproduced well by a free electron model (Drude model), with the resonance frequency then being ωp ² = (N e ² ) / (4 π εo m _e R ³ ). R denotes the radius of the sphere, e the elementary charge, ε ₀ the vacuum dielectric constant, m _e the effective mass and N the total number of conduction electrons in the sphere. For spherical metallic nanostructures made of silver, the plasmon resonances are between 350 and 650 nm depending on the size of the sphere (U. Kreibig, M. Vollmer, Springer Ser. Mat. Sei. 25, Springer, 1995, SR Emory et al., J. Am Chem. Soc. 120, 8009, (1998)), with gold particles with dimensions from 1 nm to 100 nm, resonance frequencies between about 500 nm and 700 nm are observed (U. Kreibig, M. Vollmer, Springer Ser. Mat. Sei. 25, Springer, 1995. T. Klar et al., Phys. Rev. Lett. 80, 4249 (1998)). In the case of semiconducting nanostructures, 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. Hillenbrand et al., Nature 418, 159 (2002) ). The attenuation of the plasmon resonance is in turn determined by the dielectric function, the size and shape of the nanoparticle. For metallic nanoparticles, it is typically a few 10 to 100 meV (Feldmann) and a few meV in the infrared spectral range. It is known that in the near field of the nanostructure 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.

In the present invention, 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.

In a preferred embodiment, 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.

Laser systems which can generate femtosecond pulses (fs pulses) are particularly well suited for the excitation of plasmons. 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.

In the first embodiment variant, 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.

In the second embodiment variant, the entire carrier surface is irradiated uniformly and simultaneously. For variable, selective, spatially resolved excitation of selected nanostructures and thus for the generation of the desired pattern, the 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. These highly specific spectral properties of the nanostructures in connection with the design of their arrangement on a support and the physical, chemical or biological structures on them enable site-specific optical excitation, defined by the choice of excitation parameters such as color, spectral bandwidth, intensity, polarization or angle of incidence of the Light, and thus replace one or more masks. With this second method, variable patterns of nanostructures can be selectively and spatially resolved. In this embodiment, spectra for the corresponding nanostructures are determined on the carrier before the irradiation. Alternatively, the coated nanostructures can be custom-made to match the corresponding spectra previously defined.

For the correlation between the physical properties of the nanostructures and their specific excitation spectra, reference is made to the following articles: B. Palpant, Physical Review B, Vol 57, No. 3, pp. 1963-1970, “Optical properties of gold clusters in the size ranks 2- 4 nm "; M. Gaudry, Physical Review B, Vol 64, 085407-1 -7," Optical properties of Au / Ag-clusters embedded in aluminum: Evolution with size and stoichiometry "; Steven R. EmoiN, J. Am. Chem. Soc. 1998, 120, 8009-8010," Direct observation of Size-Dependend Optical Enhancment in Single Metal Nanoparticles ". 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 two possibilities described above for the targeted excitation of selected nanostructures can be combined according to the invention. This considerably increases the possible range of variation of the patterns to be produced on the carrier surface.

The plasmons in the nanostructures can also be excited electrically. In this case, 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. In a preferred embodiment, 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. The combination of the two excitation mechanisms - optical and electronic excitation of the plasmons at the nanostructures - is possible and is part of the invention.

Other excitation and transfer mechanisms known from physics are also possible, e.g. the use of electron beams, tunnel and force microscopes, and are encompassed by the invention.

Metals, alloys or semiconductor structures are advantageously used as materials for the nanostructures. Nanostructures made of gold, silver, gallium arsenide (GaAs) or other materials known from the physics of quantum dots are particularly preferably produced. A combination of different materials for nanostructures is also possible, but this may be limited by the manufacturing processes used.

According to the invention, 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.

In a particularly preferred embodiment, 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

Interaction coupling with the connected structures.

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. For examples of possible spacing and / or coupling elements and their effect on the associated plasmon spectra, reference is made to the following articles: Dustin J. Maxwell, J. Am. Chem. Soc. 2002, 124, pp. 9606-9612, "Self-Assembled Nanoparticle Probes for Recognition and Detection of Biomolecules"; DS Ginger, Physical Rev. B, Vol 59, No. 16, pp. 10622-10629, "Photoinduced electron transfer from conjugated polymers to CdSe nanocrystals"; Yun Wei, Science 2002, Vol 297, pp. 1536-1540, "Nanoparticles with Raman Spectroscopic Fingerprints for DNA and RNA Detection"; Wensha Yang, Nature materials 2002, Vol 1, pp. 253-257, "DNA-modified nanocrystalline diamond thin-films as stable, biologically active substrates"; Zhang Lin, Langmuier 2002, 18, pp. 788- 796, "DNA Attachment and Hybridization at Silicon (100) Surface". 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.

All methods known from the prior art can be used to generate the nanostructures on the carrier surface. Depending on the size of the structures, either conventional techniques derived from semiconductor manufacturing, such as Electron beam lithography and reactive or physical ion etching, or new self-organizing chemical surface structuring methods can be used. It is also possible for so-called stamping techniques to generate specific binding sites for colloidal particles of corresponding size, which take over the function of the described nanostructures.

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. As an alternative, 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. For 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". According to the invention, different materials can be used as supports (FIG. 4). In the case of optical excitation, dielectric materials such as glass, plastics, silicon oxide and ceramic are preferably used. 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.

In a preferred embodiment variant, 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). In the case of a transparent carrier material, 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 .

According to the invention, 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. Alternatively, 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.

In a particularly preferred embodiment of the invention, 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. With this method, 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.

As an example, the synthesis of oligonucleotide sequences will be dealt with here (FIG. 7). For this purpose, 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. According to the invention, however, 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,

Quality control of biological agents, forensics, the investigation of plant metabolites, analysis in the context of environmental protection, research and development and the like. a ..

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.

Applications in areas outside of microarray technology are also the subject of the present invention. For example, specifically stimulated plasmons from nanostructures can be used to selectively activate coupled chromophores. 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. In addition to carrying out chemical or biochemical reactions, the described method can be used to derive electrons from the nanostructures by means of electrodes into a downstream electronics. Individual 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.

The invention is explained below with reference to the figures and exemplary embodiments.

The drawings show:

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

Spacers (rectangles) and physical, chemical or biochemical structures on them

(Circles).

Fig. 3: Schematic representation of various

Combinations of metal / semiconductor nanostructures with attached molecular spacers (rectangles) and physical, chemical or biochemical structures (circles) on it.

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

Slide which is suitable as a support for the production of samples of physical, chemical or biochemical structures.

Fig. 6: Exemplary representation of a carrier with different resolution levels with a schematic structure of nanostructures.

7: Exemplary example of an oligonucleotide synthesis on a nanostructure induced on the basis of the specific excitation of its plasmon spectrum.

Working Example

As a special application example, the induction of a local photochromic switching process will be discussed. 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. While the C-isomer around 600 nm has a strong absorption band with a width of about 100 nm and an optical density of 0.04, 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. Upon exposure to UV light, 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). By suitable pulse sequences of visible and UV pulses, optically reversible between C and E isomer are switched.

If Fulgid coatings are now applied to a carrier with plasmonic nanostructures, this enables spatially local optical switching between the C and E isomers. In the present example, 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)). By selecting the linker material, the molecules can be selectively coupled to the nanoparticle. At the same time, 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. In the present example, this is transferred to the molecule by near-field radiation coupling (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.

The present invention is not limited to the application examples described above. Rather, many modifications are possible that can be achieved by experts and are therefore also encompassed by the invention.

Claims

claims

1. A method for generating 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 located on the carrier, characterized in that this transfer by selective excitation of the plasmons in the nanostructures is induced.

2. The method according to claim 1, characterized in that the excitation of the plasmons takes place electrically or / and by means of electromagnetic radiation or / and by means of electron radiation.

3. The method according to any one of claims 1 to 2, characterized in that the spatially resolved transfer of electrons and / or energy from the nanostructures by spatially targeted excitation of the plasmons at the respective

Nanostructures.

4. The method according to claim 3, characterized in that a spatially targeted excitation of the plasmons of the nanostructures by irradiation of the partially covered by a mask

Carrier comes about.

5. The method according to claim 3 or claim 4, characterized in that a spatially targeted excitation of the plasmons of the nanostructures by the localized electrical

Excitation takes place using suitable circuit electronics.

6. The method according to any one of claims 3 to 5, characterized in that a spatially targeted excitation of the plasmons of the nanostructures is achieved by serial irradiation of the nanostructures.

7. The method according to claim 1 or 2, characterized in that the entire carrier surface is irradiated simultaneously.

8. The method according to claim 7, characterized in that the position of the nanostructure on the carrier at which the transfer of

Electrons and / or energy takes place through which the spectral properties of the respective nanostructures are defined.

9. The method according to claim 8, characterized in that the spectral properties of the nanostructures by a

Combination of materials, size, shape, arrangement, coupling type and environment can be defined.

10. The method according to any one of the preceding claims, characterized in that a selective excitation of the plasmons in the nanostructures is achieved by a suitable combination of the wavelength, the angle of incidence, the polarization, the duration of excitation and the intensity of the incident radiation.

11. The method according to any one of the preceding claims, characterized in that the nanostructures consist at least in part of metals, alloys and / or semiconductor material, in particular gold, silver or / and GaAs.

12. The method according to any one of the preceding claims, characterized in that the nanostructures have dimensions smaller than 1 μm, preferably less than 200 nm, in particular between 2 nm and 100 nm.

13. The method according to any one of the preceding claims, characterized in that the carrier consists of a material transparent to the light.

14. The method according to any one of the preceding claims, characterized in that a pattern on a carrier by changing the physical, chemical or biochemical

Structures on at least one of the nanostructures are created and / or induced.

15. The method according to claim 14, characterized in that the change in the physical, chemical and / or biochemical structures taking place on the nanostructures involves a chemical and / or biochemical reaction, in particular synthesis, cleavage, coupling of functional groups, isomerization, conformational change, enzymatic and / or binding reactions.

16. The method according to claim 15, characterized in that the chemical and / or biochemical reactions, polymerization reactions, in particular for the synthesis of DNA, RNA, aptamers and their derivatives such as PNA or thioRNA,

Peptides, proteins, complex carbohydrates or other chemical compounds.

17. The method according to claim 16, characterized in that the polymerization reactions by coupling individual

Ingredients after a spatially resolved transfer of Electron and / or energy induced removal of protecting groups takes place.

18. The method according to any one of the preceding claims, characterized in that the pattern synthesized on the carrier

Form an array of different chemical and / or biochemical compounds with known composition and localization.

19. The method according to any one of the preceding claims, characterized in that the patterns synthesized on the carrier can be used as activatable sensors by means of spatially and / or time-resolved plasmon excitation of the nanostructures.

20. The method according to any one of the preceding claims, characterized in that different emission spectra of a pattern of physical, chemical and / or biochemical structures are induced by site-specific excitation of the plasmons of the underlying nanostructures.

21. The method according to any one of the preceding claims, characterized in that the excitation of a pattern of different physical, chemical and / or biochemical structures can be used as a color-tunable organic LED and / or for the construction of a screen.

22. The method according to any one of the preceding claims, characterized in that after the selective excitation of the

Plasmons electrons can be derived from the nanostructures by means of electrodes in a downstream electronics.

23. The method according to any one of the preceding claims, characterized in that individual nanostructures can be used as switches or a pattern of nanostructures as switch arrays in molecular electronics.

24. The method according to any one of the preceding claims, characterized in that the biochemical, physical and / or chemical structures applied to the nanostructures are used as an electron source or line for the construction of active elements, as passive delay elements and / or as attenuation terms in molecular electronics can.