EP2152928A1

EP2152928A1 - Modified multichannel structures

Info

Publication number: EP2152928A1
Application number: EP08750022A
Authority: EP
Inventors: Jörn Volkher WOCHNOWSKI; Jürgen HECK
Original assignee: Universitaet Hamburg
Current assignee: Universitaet Hamburg
Priority date: 2007-05-03
Filing date: 2008-05-05
Publication date: 2010-02-17
Also published as: WO2008135542A1; DE102007020800A1; DE102007020800B4

Abstract

The invention relates to a modified multichannel structure, wherein the multichannel structure has at least 10, preferably at least 100, particularly preferably at least 1000, and most preferably at least 10,000 channels, and an inner coating and/or particles are brought into the channels of the multichannel structure. The invention also relates to a method for the production of the modified multichannel structure and to the use thereof.

Description

Modified multi-channel structures

The invention relates to modified multi-channel structures, to processes for their production and to the use of the modified multichannel structures.

Channel systems such as polycapillary structures are used in a variety of technical fields. Thus, in addition to monocapillaries, polycapillary structures are known above all as op- tics for focusing X-ray and neutron radiation (MA Kumakhov, FF Komarov, Multiple Reflection from Surface X-Ray Optics, Physics Reports 191, No. 5 289-350, 1990). Polycapillary structures are also increasingly used as microcontainers, separators or microreactors for medical, chemical and biological applications (Optical Technologies from Berlin and Brandenburg, Newsletter No. 7, July 2003). They are produced from regularly arranged, uncoated glass capillaries or glass rods with the help of various drawing and sintering processes. The known multichannel systems are not internally coated.

Multi-channel structures can be produced with almost any geometrical parameters of both the inner channels and the overall structure. The above-mentioned polycapillary structures are currently produced exclusively from glass, since glass is the sole material because of its unique technical-physical and chemical properties (high radiation resistance, very good moldability, optimum flow properties and ease of processing), which meets the high requirements for production fully complied with polycapillary structures (V. Arkadiev, A. Bjeouhmov, Handbook of Practical X-Ray Fluorescence Analysis, Springer, 107-111, 2006).

DE 198 52 722 C1 describes a process for coating individual monocapillars and the use of coated monocapillars or bundles of coated monocapillars for certain catalytic and optical applications.

However, it has been found that the applicability of coated monocapillars is limited and their use in the art has not been successful. The same applies to a subsequent bundling of individually internally coated monocapillars (see DE 198 52 722 C1, column 2, lines 15-19), inter alia due to the high cost and the unfavorable in relation to the number of channels outer diameter corresponding capillary bundles.

There is therefore a need for further modified cavity structures which have an improved usability, both for technical and economic reasons, for example for catalytic and / or optical purposes. This object is achieved by the modified multi-channel structure according to claims 1 to 8. The invention also relates to a method for producing a modified multi-channel structure according to claims 9 to 31 and to the use of a modified multi-channel structure according to claims 32 and 33.

The modified multichannel structure according to the invention is characterized in that (a) it has at least 10, preferably at least 100, more preferably at least 1000 and most preferably at least 10000 channels (eg at least several tens of thousands such as 20,000, 30,000, 40,000, 50,000 or more) and (B) in the channels of the multi-channel structure an inner coating and / or particles are introduced.

The term "multichannel structure" here refers to a structure which already exists prior to the introduction according to the invention of the inner coating and / or of the particles and which consists of a plurality of channels arranged at regular intervals at regular intervals and open at the ends. Examples of multi-channel structures are polycapillaries, composite lenses made of individual mono- and / or polycapillaries, monolithic lenses made of individual mono- and / or polycapillaries, photonic crystals and monolithic integral microlenses.

The inner diameters of the individual channels of the multi-channel structures are usually in the range of 1 nm to 10 mm. Preferably, the inner diameters are smaller than 1000 μm, in particular smaller than 100 μm.

For example, in general, the inner diameter of the

Compound lens channels made of mono- capsules in the range of 1 to 10 mm, monolithic lenses made from monocapillaries in the range of 0.1 to 1 mm, in assembled lenses made of polycapillaries in the range of 10 to 100 μm, in monolithic lenses made of polycapillaries in the range of 1 to 10 μm and in monolithic integral microlenses in the range of 0, 3 to 1 μm.

Polycapillaries are usually monolithic structures having a plurality of channels, which channels are of substantially equal length and usually have a length to internal diameter ratio of at least about 100: 1, preferably at least about 1000: 1. Polycapillaries may, for example, contain more than 10 ³ to more than 10 ⁶ channels which have internal diameters of, for example, less than 1 mm to less than 1 μm.

Photonic crystals are artificial periodic structures of a dielectric (e.g., glass) having specific optical properties. In addition to glass, other materials can also be used. Photonic crystals are used, for example, in optical metrology, communications and life sciences and are described in VP Bykov, "Spontaneous emission in a periodic structure", Soviet Physics JETP, American Institute of Physics, New York 1972, 35, 269 and K Busch et al. (Ed.), "Photonic Crystals - Advances in Design, Fabrication, and Characterization", Wiley-VCH, 1st Edition, 2004.

Monolithic integral microlenses are very largely miniaturized multi-channel structures which, for example, can have channels with inner diameters of about 0.3 to 1 μm.

Various multichannel structures are commercially available from, for example, IfG-Institute for Scientific Instruments GmbH, Berlin-Adlershof, Germany, Unisantis Europe GmbH, orgsmarienhütte, Germany and X-Ray Optical Systems, Inc. (XOS®), East Greenbush, NY, USA.

Multi-channel structures often have a relatively thin channel wall in direct comparison to their outer wall. This channel wall is significantly thinner than the outer wall of monocapillaries, as it serves only for the separation of the channels and has no structure-supporting function as in monocapillaries. This is possible with multichannel structures because of their monolithic overall structure.

The modified multi-channel structure according to the invention has a large inner surface and a large quotient of inner surface to inner volume. As a result, it is possible, for example, to carry out catalytic reactions with high efficiency and high throughput in the presence of a suitable coating or suitable particles.

Modified multi-channel structures according to the invention can have a wide variety of shapes and geometries. Examples of suitable shapes are cylindrical and non-cylindrical, for example elliptical or parabolic multi-channel structures.

The multichannel structure according to the invention preferably consists of glass.

Furthermore, it is preferred that the multi-channel structure contains heat conducting wires or heat conducting wires, eg by introducing metals, in particular heat conducting wires, into the multi-channel structure during the production of the multi-channel structure (eg in the stretching process). This ensures an isotropic temperature distribution within the multi-channel structure, which has a positive effect on thermal coating processes (see below) and in particular on applications of the invention. Modified multi-channel structure according to the invention at higher temperatures.

The coating and / or the particles of the modified multi-channel structure according to the invention usually contain an element other than carbon from the second to fifth main group or a subgroup of the Periodic Table of the Elements.

In a preferred embodiment, the coating and / or the particles contain an element selected from the group consisting of Zr, V, Cr, Mo, W, Ni, Cu, Pd, Pt, Au, Fe, Al, Re, Rh, Ru and Ir, with the elements Ni, Cr, Mo, Cu, Pd, Pt, Rh, Ru and Ir being particularly preferred. Coatings and particles containing these elements are particularly suitable for catalytic applications.

In another preferred embodiment, the coating and / or the particles contain an element selected from the group consisting of Be, Ni, Pt, Cu, Pd, Ag, W, Re, Ir, Os, Au, Pb, Bi and U, wherein the elements Ni, Ag, Au, W, Pb, Pt, Bi and U are particularly preferred. Coatings and particles containing these elements are particularly suitable for optical applications and applications in the guidance of electromagnetic radiation.

The coating and / or particles can consist, for example, of metal layers and / or metal particles, of metal oxide layers and / or metal oxide particles or of metal carbide layers and / or metal carbide particles. A coating and / or particles for optical applications particularly preferably consist of amorphous metal layers and / or amorphous metal particles. A coating and / or particles for catalytic applications particularly preferably consist of crystalline metal oxide layers and / or crystalline metal oxides. oxide particles. The thickness of the coating can be varied within wide ranges depending on the inner diameters of the individual channels. For example, a coating according to the invention may have a thickness in the range from 1 to 1000 nm (frequently in the range from 10 to 250 nm, for example about 100 nm).

The invention also relates to a method for producing the modified multi-channel structures according to the invention. This method is characterized in that the inner coating and / or the particles by a wet chemical process

(For example, wet chemical impregnation, dip coating), a photolytic process (for example, laser coating), an electrochemical process (for example, an electrochemical coating process), a plasma technology process or a gas phase process are introduced into the multi-channel structure.

Wet-chemical methods for introducing the inner coating and / or the particles into multi-channel structures are particularly applicable to multi-channel structures whose inner channels have diameters of at least 400 μm. In particular, with relatively small diameters of the inner channels, it is advantageous to add wetting agent to the coating solution. Examples of suitable wetting agents are sulfates of unbranched primary C 1 -C 6 -alcohols, such as sodium lauryl sulfate, and benzenesulfonates preferably substituted with branched C 1 -C 8 -alkyl groups, such as sodium dodecylbenzenesulfonate. Suitable commercially available wetting agents are, for example, wetting agents H 135 and DL from Enthone, Inc., West Haven, CT, USA.

Examples of gas-phase processes are chemical vapor deposition (CVD), chemical vapor infiltration

(CVI) or Physical Vapor Deposition (PVD). In particular, methods are suitable in which the interior Layering and / or the particles by chemical vapor deposition of organometallic compounds, for example chemical vapor deposition of organometallic compounds (OMCVD), chemical vapor infiltration of elemental compounds, for example chemical vapor infiltration of organometallic compounds (OMCVI), or gas phase epitaxy of organometallic compounds, for example gas phase epitaxy Organometallic compounds (OMVPE) into which multichannel structures are introduced. The term "elemental organic compound" refers in particular to a compound which contains a non-carbon element from the second to fifth main group or a subgroup of the Periodic Table of the Elements and organic groups and / or carbonyl, which directly and / or chemically EIe- ment the fifth or sixth main group are bound to the respective element. Suitable organometallic compounds for gas-phase processes are in particular also complex or coordination compounds which contain an organic ligand and / or carbonyl. Complex or coordination compounds which contain a ligand selected from the group consisting of carbonyl, hexafluoroacetylacetonato and acetylacetonato are preferred.

Coating processes using high temperatures or energies, such as physical vapor deposition or chemical vapor deposition, can destroy the thin channel wall of multi-channel structures due to the action of energy. By the chemical vapor deposition of organometallic compounds, in particular the chemical vapor deposition of organometallic compounds (OMCVD), here a coating process is provided, can be carried out with the coatings of multi-channel structures at relatively low temperatures, without the thin channel walls of the muI tikanalstrukturen damage or destroy. The invented The method according to the invention is also particularly suitable for producing modified multi-channel structures with special or complex geometries, such as elliptical multi-channel structures.

In a preferred embodiment, a method for producing the modified multi-channel structure according to the invention comprises the steps

(a) evacuating the multi-channel structure, establishing a pressure gradient between the ends of the multi-channel structure,

(b) setting the entire multi-channel structure to a constant temperature in the range of 273 K to 2073 K, preferably 293 K to 873 K, which is 50 K to 150 K, preferably 80 K to 120 K below the decomposition temperature of the precursor material .

(c) evaporating a precursor material and transporting the precursor material through the multichannel structure through the pressure gradient,

(D) deposition of a coating and / or particles of the precursor material by locally limited supply of energy.

To carry out this method, the multi-channel structure is first of all connected in a gastight manner to a vacuum system by means of a temperature-stable adhesive, preferably a two-component adhesive. A suitable vacuum system is described, for example, in DE 198 52 722 C1. Examples of suitable two-component adhesives are epoxy resin adhesives, which are temperature-stable up to about 450 K, and silicone adhesives, which are temperature-stable up to about 570 K. Before the further process steps, the adhesive is cured for a sufficient time. Optionally, prior to step (a), the inner surfaces of the channels of the multi-channel structure may be activated. This activation of the inner surfaces can be carried out, for example, by passing molecular oxygen, preferably at a temperature in the range from 480 K to 773 K. By activating the inner surfaces, their adsorption capacity is significantly improved, thus significantly increasing the affinity of the coating material for the inner surfaces. Therefore, activating the inner surfaces can also positively influence the type of growth behavior of the coating on the inner surfaces.

Further, prior to step (a) and optionally before activating the interior surfaces, the channels of the multi-channel structure may be cleaned. This can be done for example by plasma treatment, for example by an inductively or capacitively generated plasma, chemical processes and / or evacuation with simultaneous annealing. In particular, the cleaning of the inner channels of the multi-channel structure by evacuation at a pressure below 10 ^{~ 3} mbar with simultaneous annealing, preferably at a temperature in the range of 473 K to 773 K occur. By cleaning the channels, it is possible, above all, to remove any organic contaminants of the inner surfaces by combustion to carbon dioxide and thus to achieve improved adhesion of the inner coating or of the particles to the inner surface.

For transporting the precursor material through the channels of the multi-channel structure, a pressure gradient is established between the ends of the multichannel structure. For this purpose, the multi-channel structure is evacuated from one of its ends. Here, a minimum pressure of less than 10 ^-2 mbar at this end, preferably set less than 10 ^"mbar and most preferably less than 10 ^{~ 4} mbar. The transport of the precursor material Furthermore, the multi-channel structure can also be supported by an adjustable carrier gas flow.

Subsequently, the entire multi-channel structure is set to a constant basic temperature in the range from 273 K to 2073 K, preferably 293 K to 873 K, which is 50 K to 150 K, preferably 80 K to 120 K below the decomposition temperature of the precursor material. The constant basic temperature can be adjusted, for example, by heating or heating with a heater (e.g., electric heater or induction furnace) or by coupling in electromagnetic waves (e.g., microwave or infrared radiation).

The precursor material is vaporized and transported through the multichannel structure by the pressure gradient, optionally with the assistance of the carrier gas stream. The precursor stream and optionally the carrier gas stream can be preheated to a defined temperature, this temperature being 50 K to 150 K, preferably 80 K to 120 K below the decomposition temperature of the precursor material.

The deposition of a coating and / or of particles from the precursor material takes place by locally limited supply of energy. This energy supply locally sets a temperature which is equal to or greater than the decomposition temperature of the precursor material. A local temperature in the range from 273 K to 2073 K, particularly preferably 293 K to 873 K, is preferably set by locally limited supply of energy. As a result of the decomposition of the precursor material, the inner coating and / or the particles are deposited on the inner surface of the channels.

Preferably, the supply of energy by a heat or radiant heater, an oven, a laser, microwave radiation and / or a plasma. Especially in multichannel structures with many channels, it is difficult to realize an isotropic energy supply desirable for the controllable deposition of the inner coating and / or the particles. It is therefore a particular advantage that the adjustment of the multi-channel structure according to the invention to a constant basic temperature below the decomposition temperature of the precursor material can reduce the local additional energy supply necessary for the coating.

The temperature, which is set locally limited, can be unchanged over the duration of the coating process. In the course of the coating process, however, this temperature can also be varied. Thus, in particular in the case of an autocatalytic acceleration of the decomposition of the precursor material by its decomposition product, the locally limited temperature can be reduced in the course of the coating process. Such autocatalytic growth of the coating is observed, for example, when bis (1,1,5,5,5-hexafluoro-2,4-pentanedionato) palladium (II) is used as the precursor material, in particular when hydrogen is used as the carrier gas is used.

Optionally, by subsequent passage of a gas, a chemical, physical and / or morphological change of the coating and / or the particles can be effected. Examples of suitable gases are oxygen, hydrogen or nitrogen. For example, by treatment with oxygen, metal coatings or metal particles can be oxidized to catalytically active metal oxides or impurities removed by combustion, for example from organic radicals to carbon dioxide. The method for producing the modified multi-channel structures according to the invention may further comprise performing an in-situ process analysis and process control. This makes it possible to optimize the process. Process analysis can be carried out, for example, by optical measurement methods, by online mass spectrometry or by taking gas samples and by gas chromatography.

To optimize the process, it is also possible to carry out a product analysis of the modified multichannel structures produced according to the invention. For this purpose, suitable preparations can be made for carrying out an analysis, for example cross-sections by means of an ultramicrotome for energy-dispersive X-ray measurements, in particular a two-dimensional X-ray mapping, as well as for trans-electron microscopic or scanning electron microscopy investigations. Likewise, a measurement of the inner surfaces of the channels, e.g. by means of BET or mercury porosimetry, as well as a determination of the channel internal diameter distribution and the change in the corresponding parameters brought about by the modifications made.

Various precursor materials can be used in the process according to the invention. It is advantageous if the precursor material is a sublimable material, with an easily sublimable material being preferred.

Preference is given to a precursor material which contains an element other than carbon from the second to fifth main group or a subgroup of the Periodic Table of the Elements and organic groups and / or carbonyl which are chemically directly and / or via an element of the fifth or sixth main group to the respective element are bound. In particular, the precursor material may be an organometallic compound having at least one metal-carbon bond, or a complex or coordination compound containing an organic ligand and / or carbonyl. Complex or coordination compounds which contain a ligand selected from the group consisting of carbonyl, hexafluoroacetylacetonato and acetylacetonato are preferred.

In a preferred embodiment, the Precursorma- material contains an element which is selected from the group consisting of Zr, V, Cr, Mo, W, Ni, Cu, Pd, Pt, Au, Fe, Al, Re, Rh, Ru and Ir, with the elements Ni, Cr, Mo, Cu, Pd, Pt, Rh, Ru and Ir being particularly preferred. Particularly preferred is a precursor material which is selected from the group consisting of

Bis (l, l, l, 5,5,5-hexafluoro-2,4-pentanedionato) palladium (II),

nickelocene,

Chromium hexacarbonyl,

Tris (2, 2, 6, 6-tetramethyl-3, 5-heptanedionato) chromium (III),

Rhodium (III) acetylacetonate, copper (II) trifluoroacetylacetonate,

Copper (II) acetylacetonate and

Bis (hexafluoroacetylacetonato) copper (II).

In another preferred embodiment, the precursor material includes an element selected from the group consisting of Be, Ni, Pt, Cu, Pd, Ag, W, Re, Ir, Os, Au, Pb,

Bi and U, with the elements Ni, Ag, Au, W, Pb, Pt, Bi and U being particularly preferred. Particularly preferred is a

Precursor material selected from the group consisting of

Bis- (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato) palladium (II), tetracarbonylnickel, nickelocene, 2,2,6,6-tetramethyl-3,5-heptanedionato-silver (I. ) Tris (2, 2, 6, 6-tetramethyl-3, 5-heptanedionato) bismuth (III),

tetraethyl lead,

Bis (2,2,6,6-tetramethyl-3,5-heptanedionato) lead (II),

Uranium hexafluoride, uranocene,

uranium acetate,

tungsten hexacarbonyl,

Dimethyl (hexafluoroacetylacetonato) gold,

Tetrakis (triphenylphosphine) platinum (0), bis (hexafluoroacetylacetonato) platinum (II),

Bis (acetylacetonato) platinum (II),

Dimethyl (1, 5-cyclooctadiene) platinum (II),

Methyl (triphenylphosphine) gold (I) and

Bis (1,1,1,5,5, 5-hexafluoro-2, 4-pentanedionato) lead (II).

In yet another preferred embodiment this is

Precursor material selected from the group consisting of

Tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS),

Tetrabutoxysilane, triethoxyphenylsilane, methyltripropoxysilane, 1, 2-bis (trimethoxysilyl) ethane, 1, 2-bis (triethoxysilyl) ethane,

Phenethyltrimethoxysilane, isobutyltriethoxysilane, tris

(2-methoxyethoxy) vinylsilane, octyltrimethoxysilane, phenyltriethoxysilane, octyltriethoxysilane, Al (O-iso-C ₃ H ₇ ) ₃ , Ti (O-iso-

C ₃ Hv) ₄ , Zr (OtC ₄ H ₉ ) ₄ , Zr (0-.Ti-C ₄ H ₉ ) ₄ and their derivatives and mixtures.

The method according to the invention may also include destroying the multi-channel structure, preferably by chemical dissolution of the multi-channel structure. The choice of the agent for the chemical dissolution of the multichannel structure depends on the material of the multichannel structure. A suitable means for dissolving a multi-channel structure consisting of glass is, for example, hydrofluoric acid. It is also possible to destroy the multi-channel structure by mechanical or physical methods, eg by breaking. By the destruction the multi-channel structure, the inner coating and / or the particles can be released. Thus, the method according to the invention also offers the possibility of producing special solid-state structures.

Solid-state structures with very small dimensions, for example nanostructured solid-state structures, can have significantly different mechanical, optical, electrical and magnetic properties compared to corresponding macroscopic systems. Technologies that enable controlled, locally defined growth of such structures will be of considerable importance in the future.

The process according to the invention therefore also makes available a technology which makes it possible to produce particles-in particular metallic particles-with very narrow size distributions in relatively large quantities. In this case, an agglomeration of the particles is avoided by their fixation on the inner surface of the channels of the multi-channel structures. The maximum diameter of the individual particles is limited by the diameter of the channels. By using multi-channel structures with suitable channel internal diameters, it is also possible to produce nanoparticles with a very homogeneous particle size distribution. Through the given channels a controllable synthesis with an organized arrangement and functionalization is possible.

Likewise, tubes and rods can be produced by a uniform inner coating, the diameter of which is determined by the diameter of the channels. When selecting multi-channel structures with suitable channel internal diameters, the production of so-called nanotubes (eg carbon nanotubes, CNTs), nanorods and nanowires (eg nanopillars, nanorods, nanowires, nanofibers or nanofilaments) is possible in relatively large quantities. The type of growth (layer growth or particle growth) can be controlled by selecting the material of the multi-channel structures, the precursor material and the coating parameters (eg temperature or temperature gradient, pressure, residence time or contact time). For example, coatings with high surface area, in particular rough layers and / or particles, are particularly suitable for catalytic applications. By contrast, smooth coatings are advantageous for applications in guiding electromagnetic waves.

The invention also relates to the use of the modified multi-channel structures according to the invention. In particular, the invention relates to the use of the modified multi-channel structures according to the invention for carrying out catalytic reactions (microreactors), for separation processes, e.g. as a membrane, separator, (molecular) sieve or as a (molecular) filter, as a memory (microcontainer) or for shaping, guiding, focusing and amplifying electromagnetic waves or particle radiation.

Modified multi-channel structures according to the invention can be used both for homogeneous catalytic and heterogeneous catalytic applications, e.g. catalytic gas phase reactions are used. Modified multi-channel structures for catalytic applications preferably contain particles, particularly preferably nanoparticles with a narrow size distribution. Examples of catalytic gas phase reactions are C, C bond-forming reactions, oligomerization reactions and oxidation reactions.

Modified multi-channel structures according to the invention can also be used, in particular, for the shaping, guiding, focusing and amplification of electromagnetic waves or particle radiation, in particular of microwaves, the wavelength range from 100 cm to 1 mm, of visible light, the wavelength range of 380 to 750 nm being particularly preferred, of UV radiation, the wavelength ranges being from 50 to about 190 nm (VUV range) and 1 to 50 nm (EUV range) are particularly preferred, of laser radiation, X-rays and particle radiation (γ-radiation and neutron radiation) can be used. Particularly preferred is the hard X-radiation, in particular the discrete wavelengths of the CuKα radiation (8 keV) and the MoKa radiation (17 keV), as well as the high-energy range of the hard X-radiation with an energy greater than 15 KeV. Also preferred is the use for X-ray lithographic applications such as Soft X-ray Lithography (SXRL) at 1-2 keV or deep X-ray lithography such as Deep X-ray Lithography (DXRL) at 4 to 10 keV. Also preferred is the use for X-ray microscopic applications in the spectral range of about 2 to about 4 nm (water window).

A particular advantage of the modified multi-channel structures according to the invention is their improved long-term stability when used for shaping, guiding, focusing and amplifying electromagnetic waves or particle radiation. In the case of uncoated multi-channel structures, for example made of lead glass, energy recordings, for example by X-ray exposure, lead in the long term to material damage to the multi-channel structures and thus to loss of intensity and the unusability of the structures. In the modified multi-channel structures according to the invention, such material damage can be at least partially avoided.

The use of multichannel structures modified according to the invention for focusing EUV radiation or X-radiation for (X-ray) lithographic applications, for example in mask exposure for semiconductor production, is also particularly preferred. Likewise, the invention also relates to the use of the modified multi-channel structures according to the invention as a matrix for the production of nanoparticles and other nanoparticles by deposition of appropriate coatings and / or particles and subsequent destruction of the glass structure. Examples of preferred nanoparticles are nanotubes (eg carbon nanotubes (CNTs), nanorods and nanowires (eg nanopillars, nanorods, nanowires, nanofibers or nanofilaments) for nanotechnological and medical applications, for example as contrast agents (nanoparticles) or as nanoparticles Stents (microrods, ie micro hollow rods), cosmetic applications, eg titanium oxide particles as UV filters, nanomechanical or optical applications, eg as anisotropic components of system elements or as non-linear optical components.

The invention will now be explained in more detail with reference to selected examples.

Example 1

A glass polycapillary structure having a length of 50 mm and a maximum outside diameter of 7.20 mm was used which contained about 40,000 channels with a channel internal diameter of 29.5 μm. This polycapillary structure was connected in a gastight manner by means of a two-component adhesive to a vacuum system according to the apparatus described in DE 198 52 722 C1 and cleaned from the inside by simultaneous heating to 650 K and passing 1000 mbar of molecular oxygen. Subsequently, a constant basic temperature of the polycapillary structure of 296 K was set. Bis (1, 1, 1, 5, 5, 5-hexafluoro-2, 4-pentanedionato) palladium (II) was used as pre cursor. The pressure gradient used was 10 ^" mbar vs. 10 ^{~ 5} mbar, a localized temperature of 600 K was set in sections in a first phase over a period of 240 minutes in a second phase and in a second phase the local temperature set via the furnace system gradually over a time cavities of 300 minutes to about 380 K reduced. 5000 mbar oxygen to 10 ^-5 mbar by the inner channels of the Polykapillarstruktur Subsequently, at about 678 K conducted in semi-continuous operation. by this step, an oxidation of the metallic palladium carried on of the catalytically active species in the oxidation state + II.

The modified polycapillary structure thus prepared was used in a heterogeneous catalytic process. Ethene was passed through the modified polycapillary structure in a continuous procedure. Gaseous products were separated by a specially designed cooling trap system and the unreacted ethene was recycled. The resulting products were analyzed by GC / MS coupling and separated by distillation or chromatography. It could be shown that by catalytic ethenoligomeri- (analogous to the SHOP process) α-terminal olefins were formed.

Example 2

A polycapillary structure was connected to a vacuum system as in Example 1 and cleaned from the inside. Subsequently, a constant basic temperature of the polycapillary structure of 296 K was set. Bis (1,1,1,5,5-hexafluoro-2,4-pentanedionato) palladium (II) was used as precursor. The pressure gradient used was 10 ^{~ 3} mbar against 10 ^{~ 5} mbar. By means of a mobile furnace system, a locally limited temperature of 600 K was set in sections in a first phase over a period of 120 minutes. In a second phase, the local temperature set via the kiln system was continuously reduced to about 380 K over a period of 500 minutes. 500 mbar oxygen to 10 ^-5 mbar by the inner channels of the Polykapillarstruktur Subsequently, at about 380 K in batch operation conducted and thereby the remaining carbon in the particles removed by combustion to CO2. Finally, the polycapillary structure was removed and placed completely in hydrofluoric acid in a bowl for 72 hours. To improve internal wettability, surfactants were added to the hydrofluoric acid. Additionally, the hydrofluoric acid was warmed cautiously to about 320 K to accelerate the kinetics. Upon complete decomposition of the polycapillary structure, the hydrofluoric acid was removed and the nanoparticles remained supported on the shell wall. The nanoparticles were investigated by scanning electron micro- scope (LEO 1525, 5 kV acceleration voltage) and trans- electron microscopy. At game 3

A polycapillary structure was connected to a vacuum system as in Example 1 and cleaned from the inside. Subsequently, a constant basic temperature of the polycapillary structure of 296 K was set. Bis (1,1,1,5,5-hexafluoro-2,4-pentanedionato) palladium (II) was used as precursor. The used pressure gradient was 10 ^{~ 4} mbar against 10 ^{~ 5} mbar. In a first phase, a locally limited temperature of 435 K was set in sections in a first phase over a period of 360 minutes by means of a mobile furnace system. In a second phase, the local temperature set via the furnace system was continuously reduced to about 380 K over a period of 1200 minutes. Finally, the polycapillary structure was removed and placed completely in hydrofluoric acid in a bowl for 48 hours. To improve internal wetting, surfactants were added to the hydrofluoric acid. Additionally, the hydrofluoric acid was warmed cautiously to about 320 K to accelerate the kinetics. Upon complete decomposition of the polycapillary structure, the hydrofluoric acid was removed and the microtubes were supported on a scanning electron microscopic slide. The microtubes were examined by scanning electron microscopy (LEO 1525, 5 kV acceleration voltage) and by transelectron microscopy.

Claims

claims

1. Modified multi-channel structure in which

a) the multi-channel structure is at least 10, preferably min ^¬ least 100, more preferably at least 1000, and most preferably at least 10,000 channels, and b) in the channels of the multichannel structure a coating interior use and / or particles are introduced.

2. Multi-channel structure according to claim 1, wherein the multi-channel structure is selected from the group consisting of polycapillaries, composite lenses made of individual mono- and / or polycapillaries, monolithic lenses made of individual mono- and / or Polykapil ^¬ laren, photonic crystals and monolithic integral microlenses.

3. Multi-channel structure according to claim 1 or 2, wherein the multi-channel structure consists of glass.

4. Multi-channel structure according to one of claims 1 to 3, wherein the multi-channel structure contains heat conducting or Wärmeleitdrähte.

5. Multi-channel structure according to one of claims 1 to 4, wherein the coating and / or the particles contain a non-carbon element from the second to fifth main group or a subgroup of the Periodic Table of the Elements.

6. multi-channel structure according to claim 5, wherein the coating and / or the particles of an element selected from among Group consisting of Be, Zr, V, Cr, Mo, W, Ni, Cu, Pd, Pt, Au, Fe, Al, Re, Rh, Ru, Ir, Ag, Os, Pb, Bi and U, wherein the Elements Ni, Cr, Mo, Cu, Pd, Pt, Rh, Ru, Ir, Ag, Au, W, Pb, Bi and U are particularly preferred.

7. Multi-channel structure according to one of claims 1 to 6, wherein the coating and / or the particles of metal layers and / or metal particles, preferably made of amorphous metal layers and / or amorphous metal particles.

8. multi-channel structure according to one of claims 1 to 6, wherein the coating and / or the particles of metal oxide layers and / or metal oxide particles, preferably consist of crystalline metal oxide layers and / or crystalline metal oxide particles.

9. The method for producing the modified multi-channel structure according to any one of claims 1 to 8, wherein the inner coating and / or the particles by a wet chemical method, a photolytic method, an electrochemical method, a plasma technology method or a gas phase method in the Multi-channel structure are introduced.

10. The method of claim 9, wherein the inner coating and / or the particles by chemical vapor deposition

(CVD), chemical vapor infiltration (CVI) or physical vapor deposition (PVD) are introduced into the multi-channel structure.

11. The method of claim 10, wherein the inner coating and / or the particles by chemical vapor deposition of organometallic compounds (OMCVD), chemical vapor infiltration of organometallic compounds (OMCVI) or Gas phase epitaxy of organometallic compounds (OMVPE) are introduced into the multi-channel structure.

12. The method of claim 10 or 11, comprising the steps

(b) setting the entire multi-channel structure to a constant base temperature in the range from 273 K to 2073 K, preferably 293 K to 873 K, which is 50 K to 150 K, preferably 80 K to 120 K, below the decomposition temperature of the precursor material,

(c) vaporizing a precursor material and transporting the precursor material through the multichannel structure through the pressure gradient, and

(D) deposition of a coating and / or particles of the precursor material by locally limited supply of energy

includes.

13. The method of claim 12, wherein before step (a) the inner surfaces of the channels of the multi-channel structure are activated.

14. The method of claim 13, wherein activating the inner surface by passing molecular oxygen, preferably at a temperature in the range of 480 K to 773 K occurs.

15. The method according to any one of claims 12 to 14, wherein prior to step (a) and optionally before activating the inner surfaces, the channels of the multi-channel structure are cleaned.

16. The method of claim 15, wherein the cleaning of the channels of the multi-channel structure by plasma treatment, chemical processes and / or evacuation takes place with simultaneous annealing.

17. The method of claim 16, wherein the cleaning of the channels of the multi-channel structure by evacuation at a pressure below 10 ^" mbar with simultaneous annealing, preferably at a temperature in the range of 473 K to 773 K occurs.

18. The method according to any one of claims 12 to 17, wherein in step (a), a minimum pressure of less than 10 ^{~ 2} mbar, preferably less than 10 ^{~ 3} mbar, and more preferably less than 10 ^{~ 4} mbar is adjusted.

19. The method according to any one of claims 12 to 18, wherein the transport of the precursor material is supported by the multi-channel structure in step (c) by a carrier gas stream.

20. The method according to any one of claims 12 to 19, wherein in step (d) a local temperature in the range of 273 K to 2073 K, preferably 293 K to 873 K, is set.

21. The method according to any one of claims 12 to 20, wherein the supply of energy in step (d) by a heat or radiant heater, an oven, a laser, microwave radiation and / or a plasma takes place.

22. The method according to any one of claims 12 to 21, further comprising the passage of a gas for chemical, physical and / or morphological change of the coating and / or the particles.

23. The method of claim 12, further comprising performing in situ process analytics and process control.

24. The method according to any one of claims 12 to 23, wherein the precursor material is a sublimable material.

25. The method according to any one of claims 12 to 24, wherein the precursor material contains a non-carbon element from the second to fifth main group or a subgroup of the Periodic Table of the Elements and organic groups and / or carbonyl which chemically directly and / or via a Element of the fifth or sixth main group are bound to the respective element.

26. The method according to any one of claims 12 to 25, wherein the precursor material is an organometallic compound having at least one metal-carbon bond, or a complex or coordination compound containing an organic ligand and / or carbonyl.

27. The method of claim 26, wherein the complex or coordination compound contains a ligand selected from the group consisting of carbonyl, hexafluoroacetylacetonato and acetylacetonato.

28. The method according to any one of claims 12 to 27, wherein the precursor material is an element selected from the group consisting of Be, Zr, V, Cr, Mo, W, Ni, Cu, Pd, Pt, Au, Fe, Al, Re , Rh, Ru, Ir, Ag, Os, Pb, Bi and U, wherein the elements Ni, Cr, Mo, Cu, Pd, Pt, Rh, Ru, Ir, Ag, Au, W, Pb, Bi and U are particularly preferred.

29. The method according to any one of claims 12 to 28, wherein the precursor material is selected from the group consisting of

Chromium hexacarbonyl,

Tris (2, 2, 6, 6-tetramethyl-3, 5-heptanedionato) chromium (III),

Rhodium (III) acetylacetonate,

Copper (II) trifluoroacetylacetonate,

Copper (II) acetylacetonate,

Bis (hexafluoroacetylacetonato) copper (II),

Bis- (1,1,1,5,5, 5-hexafluoro-2, 4-pentanedionato) -palladium (II),

tetracarbonylnickel,

nickelocene,

2,2,6,6-tetramethyl-3, 5-heptanedionato-silver (I),

Tris (2, 2, 6, 6-tetramethyl-3, 5-heptanedionato) bismuth (III),

tetraethyl lead,

Bis (2,2,6,6-tetramethyl-3,5-heptanedionato) lead (II),

Uranium hexafluoride,

uranocene,

uranium acetate,

tungsten hexacarbonyl,

Dimethyl (hexafluoroacetylacetonato) gold,

Tetrakis (triphenylphosphine) platinum (0),

Bis (hexafluoroacetylacetonato) platinum (II),

Bis (acetylacetonato) platinum (II),

Dimethyl (1, 5-cyclooctadiene) platinum (II),

Methyl (triphenylphosphine) gold (I) and

Bis (1,1,1,5,5, 5-hexafluoro-2, 4-pentanedionato) lead (II).

30. The method according to any one of claims 12 to 25, wherein the precursor material is selected from the group consisting of tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate

(TMOS), tetrabutoxysilane, triethoxyphenylsilane, methyltripropoxysilane, 1,2-bis (trimethoxysilyl) ethane, 1,2- Bis (triethoxysilyl) ethane, phenethyltrimethoxysilane, isobutyltriethoxysilane, tris (2-methoxyethoxy) vinylsilane, octyltrimethoxysilane, phenyltriethoxysilane, octyltriethoxysilane, Al (O-ISO-C ₃ H ₁ ) ₃ , Ti (O-ISO-C ₃ H ₁ ) ₄ , Zr (O-UC ₄ H ₉ ) ₄ , Zr (O-Ti-C ₄ Hg) ₄ and their derivatives and mixtures.

31. The method according to any one of claims 9 to 30, comprising in a further step destroying the multi-channel structure, preferably by chemical dissolution of the multi-channel structure.

32. Use of a modified multi-channel structure according to any one of claims 1 to 8 or a modified multi-channel structure prepared according to any one of claims 9 to 31 for performing catalytic reactions, for separation processes, for shaping, guiding, focusing and amplifying electromagnetic waves or particle radiation or as Matrix for the production of nanoparticles and nanoparticles.

33. Use according to claim 32 as a matrix for the production of nanoparticles and nanoparticles, in particular for medical, cosmetic, nanotechnological or optical applications.