CA2308302A1 - Nanometric structures - Google Patents

Nanometric structures Download PDF

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Publication number
CA2308302A1
CA2308302A1 CA002308302A CA2308302A CA2308302A1 CA 2308302 A1 CA2308302 A1 CA 2308302A1 CA 002308302 A CA002308302 A CA 002308302A CA 2308302 A CA2308302 A CA 2308302A CA 2308302 A1 CA2308302 A1 CA 2308302A1
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Prior art keywords
substrate
metal
polymer
clusters
core
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French (fr)
Inventor
Joachim Spatz
Martin Moller
Thomas Herzog
Stefan Mossmer
Paul Ziemann
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Universitaet Ulm
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Priority claimed from DE19747815A external-priority patent/DE19747815A1/en
Priority claimed from DE19747816A external-priority patent/DE19747816A1/en
Priority claimed from DE19843411A external-priority patent/DE19843411A1/en
Application filed by Individual filed Critical Individual
Publication of CA2308302A1 publication Critical patent/CA2308302A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31144—Etching the insulating layers by chemical or physical means using masks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32139—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer using masks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Abstract

The invention relates to nanometric structuring and decorating of substrates.
The invention especially relates to surface decorated substrates on which ordered nanometric surface structures are deposited, said structures being comprised of metal and/or metal oxide clusters and/or semiconductor clusters.
The invention also relates to a method for producing and applying said surface decorated structures in order to epoxidize C3-C8-alkenes or to oxidize CO to CO2, and relates to surface structured substrates, especially Pt, Au, GaAs, InyGaAs, AlxGaAs, Si, SiO2, Ge, SixNy, SixGaAs, InP, InPSi, GaInAsP, glass, graphite, diamond, mica, SrTiO3 or the doped modifications thereof, which are nanometrically structured over macroscopic areas. In addition, the invention relates to a method for the production of said surface structured substrates.
The invention is based on the film formation of core shell polymer systems whose core areas are selectively modified or charged with corresponding metal compounds in a solution and construct the structures which are orderly arranged in the thin films. These films which are deposited on the substrate surfaces are selectively etched in such a way that the organic polymer components are completely removed and, as a result, the substrate is decorated in an orderly arrangement by the inorganic residues. The structured films can further serve as masks which make it possible to selectively etch the substrate and to transfer such a structure, said structure given by the film, to the substrate.

Description

Description The present invention relates to structuring and decorating substrates on the n~axiret~ic scale. In particular, the present invention relates to surface-decorated substrates comprising nanometrically ordered surface structures of metal andlor metal-oxide clusters and/or semiconductor clusters, and further to a method for the ~att~rs~ mar~aca~e arr~ y icatirn of said method to epoxidate C, - C, alkenes or to oxidize from CO into CO,. The present invention also relates to surface-structured substrates, in which case the structuring runs nanometrically across macroscopic zones, In particular Pt, Au, GaAs, (n,,GaAs, RIYGaAs, Si, SiO,, Ge, Si"GaAs, InP, InPSi, GalnAsP, glass, graphite, diamond, mica, SrTi(~
or their doped modifications, and a method for their preparation. The invention is based on the film formation of corc~shell polymer systems of which the core zones are modifred, i.e.
charged selectively in solution with corresponding metal compounds. These films, which are precipitated on the structure's surface, may be selectively etched in such a manner that the organic polymer component will be wholly removed, and in the process the substrate will be decorated by means of the inorganic residues, resulting in a regular configuration. Furthermore the structured films may be used as masks, allowing selective substrate etching, and hence to transfer a structure, which is predetermined by the film, into the substrate.
Fine ly dispersed precious-metal catalysts are the basis of important chemical processes such as hydration, selective oxidation of alkenes, alkynes and aromatics to form alcohols, epoxies, ketones, aldehydes and carboxylic acids, oxidation of CO, decomposition of nitrous oxides (N~ into nitrogen and a corresponding oxidation product (H,O, COz), and reaction of methane and carbon dioxide to form a synthesis gas (COIN,).
An irnportant crlter(on for the activity and selectivity of catalysts is that metal particles are deposited on an appropriate, and usually oxidic, support. For instance, while pure gold is, in contrast to members of the platinum group, catalytically inert, in conjunction with an oxidlc support, it provides a highly active catalytic system. The selection of anoxidic support assumes a determinant role in activating and restructuring acatalytically active particulate surface during a catalytic cycle. The support's structure, and its chemical interaction with the precious metal, degrade the activity and selectivity of the catalyst. The ptecipitation of platinum layers onto su~dic or oxidic supports of well-defined surface stnrctures leads to custom-made, highly active catalytic systems. Zeblites of variable but well-defined pore structures cause an increase in active surface and, in conjunction with the "right" precious metal, also to an increase both in selectivity artd in activity. In the case of modem three~vay catalysts, CeQ is used as a prorlnoter along w'tth the precious metal (Pt, Pd, Rh) and the support (S'~, AhO~, ), said CeC~ storing and releasing the oxygen needed for the reaction. The catalytic process is deasively improved (hereby relative to those using catalysts lacking promoters.
t3esides the topography and kind of the support, the sizes, and the mutualspacings, of the precious-metal particles also are critical in regard to the stability and effectiveness of the catalysts.
Hoanrever, high catalytic activity is attained in particular with particles smaller than 5nrn.
An important objective in the further development of heterogeneous catalyst systems relates to the regut~r corr~guration of precious-metal particles that are 1 to 3 nm in size.
Periodic and aperiodic microstructures from several microns to several 100 nm are prepared for electronic and optical components, sensors, and in micro-engin~ering, by mearts of lithography.
Heretofore optical lithography has been very successful in making structures larger than 180 nm. l~s this procedure is a parallel one, which moreover allows high production flow, it has been the unambiguously predominant process for producing microelectronic cirouits. The attainable t7n)nlmum structural size.is dictated by a technical tradeoff between the physically possible resolution and the depth of field required by the equipment. Standard production dimensions of integrated circuits already are less than 350nm. Utilization of X-ray radiation under technically rigorous cond'ttions results in dimensions of about 90 nm.
For some time it has been feasible, using electron or ion beam lithography, to attain nanometric structures, and corresponding equipment is commercially available.
Atom beam frthography controls the interaction of the atom beams with the optical masks, and allows production of large-scale line patterns and various 2D periodic structures with a resolution less than 100 nm. In this procedure atoms are directly d~posited on a substrate, or ate used to modrty organic resists.
This further reduction of geometric dimensions permits not only further mlnialurization, but also permits utilization of dimension-dependent physical properties, such as quantum effects, supertemomagneticproperties, or electron plasma-ion resonance. However, the conversion Into mactoscopic effects or test values requires high uniformity of an ensemble of microscopic structures.
For structures smaller than 1 d0 nm that are of interest in this connection, conventional lithographic procedures are exceedingly difficult and nakedly economical. New procedures must be developed, complementary to the conventional ones, which will depend either on size-controlled growth of inorganic structures or on molecular concepts of organic and macromotecular chemistry. Only a few Implementations are known:
(1) Making use of crystal growth ors GaAs (311 )8 oriented substrates, not only small units, but also well-ordered quantum-dot structures can be prepared. Following the growth of a thin film of InGaAs above a buffet layer ofAIGaAs, the stressed InGaASs ~Im breaks up into small pieces which are spontaneously buried underAIGaAs. In this manner ordered rows of AIGaAs microcrystals with a core of planar InGaAs dots are formed naturally. The sizes and distances between the dots can be independently controlled solely by means of growth parameters. The photoluminescence spectra of the dots are characterized by high efficiency and narrow line widths.
(2) A two- or muki-block copolymer consists of chemically different macromolecular chains, which are covalently connected at the ends or another molecular position (for Instance in the Base of star or graft block copolymers). In most cases different blocks do not mix with one another, and separate themselves into so-called micro-domains.
The size and morphological order of said microdomains is determined in part by the proportions by volume of the individual blocks and by the molecular weight distribution.
Changing the volume proportion of the polymer blocks allows adjustment of different microdomain structures such as spheres, cylinders and lamellas. Typically the periods so attained run between 10 and 200 nm.
Because it is possible to chemically and physically distinguish the ~connecfed macromol~acular blocks, the chemically differentmicrodomains can be selectively charged of marked. This result is far instance attained by absorbing solvents or by a selective reaction with a transition metal. The transition metal frequently is used to achieve polymer contrast in electron microscopy.
Microphase separation also can be observed in ultra-thin films. The critical factortherein is tine extent to which the microdomain structure, and its organization, are affected by the surface and boundary-surface energies and by geometric constriction.
Park et al., in Science 189y, 276, 7401 and also inAppl. Phys. Lett. 1896, 68, 2586), describe transferring the microdomain structure of a two-block copolymer to a silicon nitride substrate beneath. Two distinct techniques based on reactive ion etching allow making holes 20 nm in diameterwith a periodicity of 40nm, and also the corresponding inverse structure. In the same way related ducts 30 nm in diameter and spaced by 15 nm could be transferred to a substrate. In this process, the microdomain, Consisting of the polybutadiene of a polystyrene-b-polybutadiene two-block copolymer, were reacted with ozone gas and dissolved out of the polystyrene matrix or marked with osmium atoms. Hoth procedures resulted in local inhomogeneitieswith respect to etching resistance, thereby in the end allowing use of two-block copolymer patterns as masks for nanometric surface structures. Such patterns, when in the range of a few nanometers, can be used in principle in engineering for making nanometric structures and as lithographic masks.

However the procedures described in the state of the art incur the drawback that they are economically prohibiYrve and/or are restricted to very special systems.
Accordingly it is the objective of the present invention to develop a versatile concept, based on organic or macromolecular chemistry, which allows nanometric structuring and decoration of substrates. In particular, the Invention makes available a method that allows nanometric surface decoration of substrates by means of ordered deposition of defined metal or metahoxide Clusters on a substrate, and furthermore substrates of which the surfaces are decorated with said defined metal or metal-oxide clusters that are suitable as catalysts In the epoxidation of C, - CB or in the oxidation of CO to COs. Such a method in particular allows for the controlled preparation of compound clusters from acatalytically active metal component and a metal oxide, the relative proportions being systematicallyvariable.
Furthermore an economic, i.e. an efficient method of the invention based on the molecular concepts of organic or macromolecul8rchemistry, is provided, which allowsrtanorrietric surface structuring substrates, that is preferably in the range under 20 nm, preferably lass than 5 nm, across macroscopic zones. The invention also offers structur~d substrates in the lowemanometric range that are characterized by a large depth to-width ratio, that is, the heights and depths of these structures are many times larger than the lateral dimensions_ This problem is solved by the invention by the embodiments set forth in the claims.
tn particular, in a first aspect of !he invention, a method is created to manufacture surface-decorated substrates, comprising the following stages:
(a) introducing a polymer into an appropriate solvent, while forming a dissolved core-shell polymer system, (b) charging at least part of the polymer cores with one or more identical or different metal compounds, (c) depositing the charged tote-shell polymer system prepar~i in stage (b) in the form of a film on at least one side of a substrate in such manner that said core-shell polymer system is corr~gured in a regular structure in the film, and 52960.014 (d) removing th8 polymer, producing the core-shell polymer system, while generating metal clusters and/or clusters of metal compounds on the substrate surface, w'tthout significant changes in the structure produced by the core-shell polymer system.
In a preferred embodiment of this method for surface-decorating substances in the nanometer range, and before stage c), metal compounds) contained in the pohymer core is (are) chemically treated and/or irradiated by high-energy u.v., x-rays or electron beams, whether in solution or in the film, and are converted into metal or a metal oxide. !n the course of stage (d) of this method of the invention, the polymer is removed preferably by etching, reduction or oxidation. Etching by means of a reactive plasma, preferably an oxygen plasma, is especially preferred.
This method of the first embodiment of the invention surprisingly allows orderly precipitation, in art orderly and very simple manner, of discrete metal clusters or metal-oxide dusters onto different substrates, while forming regular, i,e.
ordered,nanometric structures.
Even semiconducting clusters, such as Si and Ge, can be prepared in very simple manner by the method of the invention. Moreoverthe method of the invention, usingmicellarsystems from amphiphilic block copolymers, allows oldered deposition of minute, catalytically highly active metal particles on nearly arbitrary substrates.
A second embodiment of the present invention relates to a method for preparing surface-structured substrates, which comprises the following stages:
(a) irrtroduclng a polymer lrrtcs an appropriate solvent, while forming a dissolved care-shell polymer system, (b) charging at least some of the polymer cores with one or several, identical or different metal compounds, (c) depositing the core-shell polymer system prepared in stage (b) in the form of a film on at feast one side of a substrate in such a manner that the core~shell polymer system is configured as a regular structure irt the film, and (d) subJecfing the substrate prepared in stage (c) to a reactive ion etching procedure, to art ion sputtering procedure, or to a wet chemical procedure, or a combination thereof, the film deposited on the substrate being removed and the regular structure produced by the core-shell polymer system being converted as a function of the-kind of Charge of the polymer cores as well as of the duration of the reactiv~ ion etching and/or ion sputtering andlor the wet-chemical procedure into substrate relief structure.
In a preferred embodiment of this method of the invention tonanometrically surf8ce-structure substrates, at least part of the metal compounds contained in the polymer cores is inverted, before film deposition or following film formation, by chemicaltreatment and/or high-energy irradiation such as u.v., x-rays or electron beams, into one or more metal particles and/or metal-oxide particles in each polymer core.
This method of the irtVention allows manufacturing of such surface structures as holes, strips, troughs and dot-IiKe elevations of a width or diameter preferably between 1~ and lOQnm, and a depth, or height that may be a multiple of the lateral dimensions, in a corresponding substrate. These surface structures also are called relief structures of the substrate.
The expression "core-Shell polymer system" herein denotes for instance macromolecular amphphile$ which associate in aqueous or organic solution and may form well-defined spherical or rod-shaped micelles, lamellas, vesicles or complex aggregates.
Consequently, the invention also includes systems generally called host/guest systems wherein a moleurtar cavity, i.e. a molecule inner space, namely tf~e polymer core, generated by the polymer (host compound), can be charged, i.e. complexed with a guest compound, that is a particular metal compound.
The polymer used )n the method of the invention, which is produced in solution of such a core-shell-polymer system, preferably is selected from block copolymers, graft copolymers, mil~oa~n st~l~xs, , star polymers with different branches,dendritic polymers, micro gel-particles, star block copolymers and core-shell latex polymers.
More preferred are the following polymers, namely polystyrene-b-polyethyleneoxide, polysfyrenez-b-poly(2-vinylpyridine), polystyrene-b-poly(4 vinylpyridine) polymer or a mixture 52960-p14 thereof. The polystyrene block therein however mgy be replaced also by other non-polar polymers, for instance polyisopropene, polybutadiene, polymethylmethacrylate or other polymethacrylates. The second, or polar block in such a two-block copolymer may be one ~nrhieh interacts as strongly as possible with the particular metal compound being used. Illustrati~rely such are polyacrylic acid, polymethacrylic acid, amino-substituted polystyrenes, polyacrylates or polymethacrylates, amino-substituted polydienes, polyethylene-imines, saponified polyoxazolines or hydrogenatedpolyacrylonitrile. The first block also may he a polar polymer, provided howevet than then the metal compound is selected in such manner that foremost , i.e, selectively, it interacts with the second polar block.
Typically the above polymer systems are dissolved in a selective solvent, fot instance toluene, ai a rate from about 10'~ to about 100 mg/ml, preferably about 5 mg/ml. Following several, for instance 12 hours approximately, the solution is reacted w'tth one or more metal compound$ in stage (b) of the method of the invention and then is strongly agitated, for instance for about 24 h, in order to charge at least some of the polymer cores, formed by the core-shell polymer system, with the metal compound(s).
For example, such metal compounds are compounds of Au, Pt, Pd,Ag, In, Fe, Zr, AI, Co, Ni, Ga, Sn, zn, Ti, 8i and Ge in the corresponding oxidation stages or mixtures thereof. Specific examples are HAuCI,, MeAuCI,, where Me denotes an alkali metal, HzPtCh , Pd(Ac)a,Ag(Ac), AgNO,, InCI, , FeCI, , Ti(OR),, TiCI,, Ti CI, , CoCI, , I~iCtZ, SiCI,, GeCI,, GaH, , ZnEt,, AI(OR), , zr(OR)~, where R is a straight-chain or a branched-C~ - C8 alkyt residue,ferrocene, Zeise salt or SnBu,H or mixtures thereof. Preferably the metal compound is HAuCI,, Typical inputs are 0,01 to 2.0 molecular precursor units per monomer unit of the polar polymer block.
In stage (c) of the method of the invention, the deposition of the film is carried out in single or multiple layers onto at least one side of a substrate, preferably by dipping, pouring, SPA coating or by adsorption from a diluted solution. Mare preferably however the deposition of single or mukiple layers is carried out by dipping inta dilute solutions. For example the films are produced by drawing a substrate out of the solution at speeds, for instance from 0.007 mmlmin to 2 m/min. Such macroscopically covering films have a layer thickness of, for instance, one or more charged two-block copolymer_micelles, that is from 5 to 800nm. An exemplary mono-micellar film is therefore as thick as a micelle. The polymer cores, that is for instance the micelles or corresponding molecule cavities, charged with the metal compound and/or the metal particles, are in the process precipitated substantially intact, while a regular structure Is being formed in the film. The polymer cores, which are charged either with a metal compound as a precursor for the reduction to the corresponding metal, or already are charged with the corresponding metal particles or rhetal-oxide particles, arrange themselves in this process on their own into a regular structure on the substrate surface.
Rpplicable substrates are precious metals, oxidic glasses, monocrystalline or mutticrystalline substrates, semiconductors, metals with or without a inactivated surface, insulators or in general substrates that are highly resistant to the etching procedures below. In particularthese are Pt, Au, GaAs, InyGaAs, A~GaAs, Sl, SiO~, Ge, Si~NY, SixGaA,s, lnp, GaInAsP, glass, graphite, diamond, mica, SrTICI~, and their doped modifiCCaations_ The applicable sub$trates may be flat, laminar (far instance mica flakes of a length < 15p. ) and also those with laminar, curved (convex or concave) surfaces (for instance microglass balls or mlcroquarta balls of diameters fot instance 1 to 80 ~).
The coating thickness is adjusted in a metallic precursor stage in solution by means of the molecular weight of the amphiphilic block Copolymers, by the size of the particles and also by the degree of polymerization of the (for instance micelle-forming) block, forming a regular structure, also by the magnitude of the charge, the particle size for instance being 1 !0 20nm and the inter particle distance being 20 to 400 nm, preferably 20 to 200 nm.
The cluster uniformity attained by the method of the first embodiment of the present Invention, and ifs regular configuration, is achieved by means of the homogeneous distributicins of the salts in solution on the micelles and by the uniform size distribution of the two-block copolymer micelles (Fig. 1 ).
This structure, i.e. the ordering, produced by the core-shell polymer system, with at least some 52980.014 of the polymer cores being selectiv~ly marked or charged by one or more metal compound(s), is not degraded in the particular ensuing stage (d).
A9 already discussed above, the polymer produdng the care-shell polymer system in the manner of step (d) of the method of the first aspect of this invention, with concomitant generation of metal clusters and/or clusters or metal compounds on the substrate surface, is completely removed without significantly changing the structure or configuration pf the dusters on the substrate surface as erected by the core-shell polymer system, In the process, the polymer Is removed, for instance by etching, reductioh or oxidation. These procedures also may be carried out at higher temperatures; especially etching is carried out using a reactive plasma, preferably an oxygen plasma. Furthermore, reactive gas plasma procedures (CFA, H~ SF~ or oxidation in an oxidizing atmosphere at raised temperatute, etching by high-energy irradiation, in particular by electromagnetic beams or partide beams such as electron beams, orpyrolysis, also may be used to remove the polymer enclosure.
The above techniques used in step (d) of the first embodiment of the method of the invention remove, In a residue-free manner, the organic polymer enclosure at the desired site or in the desired zone, and convert the metallic precursor stage into its crystalline Me orMeO"
modifications In the form of agglomerates of small Me arMeO, particles, the so-called clusters.
Depending on the metal compounds used in stage (b), the precipitated dusters are, in particular, oxygen-resistant precious metals such as Au, Pt, Pd or oxides, for instance semicondueting oxides such as TiOZ, or magnetic particles such as certain modigcativns of Fe,O" Fe, !vo or Ni.
The precipitation of metallic mixed systems such as Ru/Fe20, , AuICoO, AulCo, O,, AuIZnO, AuITiO,, AuIZrO~, Au/A~O, , Aulln=O, , PdIAl,O, , PdlZrO=, Pt/Al=CJ~
and Pt/graphite will succeed by mixing a solution of a polymer system used in the manner of the invention with a mixture of the particular metal compounds.
For example, to separate "naked" metal/metal-oxide clusters, the micelles containing metal Baits produced by one of the above polymer systems are deposited in the form of an ultrathin film on the selected substrate and thereupon the polymer sheath is selectively removed by oxygen-plasma treatment, bum-off in an oxygen rich atmosphere, pyrolysls or by other reducing conditions such as in a hydrogen plasma.
In this treatment, the transition-metal compound is converted into the elemental metal or, under oxidizing conditions, into metal-oxide particles. The thermal reduction or the conversion of precious-metal compounds in an oxygen atmosphere produces a narrow particle distribution similar to that resulting from burning the polymer by means of the above described plasma process (F)g. 2).
The above described method allows preparing clusters of various sites in particular of gold, platinum, pa~t(adium, nickel, titanium dioxide, iron oxide and cobalt oxide.
SurPaoetaste corroborate the preCipltationfor instance of Au, Pt, In, Co, Pd, TiQ Fe,g as well as of the particular mixed systems, in particularAu/F~O, , AulCoO, AuCo, 04, ~r~n0, AuTiO" I~u2rQ,, Au/Al=O, , Au/In,O, , Pd/AIxO, , PdZrO,, Pt/Al=O, and Pt/graphite. The cluster diameters can be adjusted for instance to be between 4.5 and 9 00 nm by varying the input weights of the carrespondingmetal compound as precursorto the correspondingsoluliori of the core-sell polymer system. The periodicity, that Is the surface configuration of the MeJMeO~
clusters regularly arrayed on the substrate surface can be adjusted to be between approximately nm, preferably 20 nm and 400 nm, by the degree of polymerization of the initially used polymer sy.$tem.
Surprisingly the method of the invention, which Is based on the self-organization of a core-shell polymer system acting as a template for the regular precipitation of Me clusters and/or MeOx, clusters, allows manufacturing in vent' simple and economical manner nanometric surface-decorated substrates.
Nanometric, surface-deeoratedsubstrates, containing metal clusters and/or metal-oxide clusters and produced by the method of the invention comprise at least on one side clusters of metal atoms and/or metal compounds of a diameter preferably 0.5 to 1 OOnm and mutually apart preferably up to 400 nm which are regularly arrayed on the substrate surface.
In particular these nanometric clusters may be clusters of gold, platinum, palladium, titanium dioxide, iron oxide and cobalt oxide. Furthermore the surface-decorated substrates of the invention may contain clusters of, for instance, Au/FeZO, , AuICoO, Au/Co, 0,,, AuIZnO, AuITi4,, Au/ZrOZ, Au/A1,0, , Au/1n,0, , Pd/AlsO, , PdIZrO~ Pt/graphite, or Pt/A1,0, . Preferred substrates are Pt, Au~aAs, In"GaAs, AIxGaAs, S1, SiOb Ge, Si"N~,. S~,GaAs, InP, InPSi, GaInAsP, glass, graphite, diamond, mica, SrTiO, or their doped modifications.
The substrates prepared by the method of the invention and decorated withnanometric mefial clusters and/or metal-oxide cluster, that is, nanometric particles, are characterized by their high uniformity and also by their high heal resistance. When annealing gold particles 7.5 nm high, only a slight decrease in height was observed even after prolonged thermal loading.
This condition is shown in Fig. 3. The slight decrease .above 400°C can be explained by the conversion of primarily formed gold oxide into gold.
After i 2 hour annealing at T = 800'C, the ordering remains preserved, as can be seen in ~t (atxmic force microscope) pictures (Fig. 4).
Besides high thermal strength, the nanometric particles also show high resistance to chemicals. Once particle formation has been completed, the nanometric clusters ate stable relative to solutions containing sulfuric acid and chlorides, allowing advantageous chemical reactions at these nanometric precious-metal clusters.
In one implementation of the rt~ethod of the Invention, the block-copolymer micelles are also charged with different metal salts in solution. As shown by spectroscopic electron-energy losses, these mixed systems are incorporated into the micelles in a nighty dispersed manner.
Each micelle also is homogeneously charged with both inorganic components. The precipitation of the invention of the hybrid systems and the ensuing gas-plasmatreatment res111t in "naked" highly disperse mixed clusters such as Au/Ti0" AuIFes4, or AuICo,O, on different substrates_ Fig. 5 reproduces high-power pictures of manoftticellar films following gas-plasma treatment, and shows regularly arrayed nanometric clusters of identical sizes.

Another object of the present invention relates to using the above defined aurfac~
decorated substrates In the epoxidation of C, - Cdalkenes or in the oxidation of CO to COs.
As already mentioned, catalytic oxidation of CO into COZ is an important field of application for precious metals deposited on metal oxides (Au/T i0~, Au/Fe,O, , or AuICo,O,)_ This process is significant, tot instance, in the field of fuel cells.
Catalysis cakes place at the boundary surface df precious-metaflsupport. In particular as regards methanol-driven fuel cells, hydrogen is obtained by means of the so-.called steam-reforming process. The generated products are 75 % hydrogen, 25 % carbon dioxide and traces of carbon monoxide.
However the carbon-.monoxide residue poisons the anode catalysts. Therefore the CO
content must be decreased by selective oxidation into COs In general, high catalytic activity at love consumption of precious metal is desired. This goal is attained in the invention by using the smallest possible particles and hence increased active surface and maximal boundary surface in heterogeneous catalysis between precious metal and metal oXide.
As shown in Table 1 below, the specific catalyst strongly affects the activation energy of oxidation.
Table 1: activation energy for the CO -,~ CO, for heterogeneous systems Precious metal Support Activation Temperature C

Pd Al,O3 or ZrO, .._ 150 -200 graphite or Als O, 150 - 200 Au AlZ O, 150 - 200 Au TiO, about 80 Au/Fez O, or AulfiO, at 80°C are about as catalytically active and selecfive as PtlAI,O, at 154-200°C. As regards methanol fuel cells in particular, an activation temperature less than 100°C is fundamental.
Besides hydrogenation, precious-metal particles also are significant as oxidation catalysts. Ethylene oxidation by molecular oxygen at silver colloids is used industrially to 14 5~~14 manufacture ethylene oxide. Salts of alkali -(preferably) cesium compounds or alkaline earth metals are used as promoters. However, this procedure is restricted to the ethylene-ethylaneoxide system and so far has not been applicable to longer-chain alkenes, In this respect the European patent application 0 709 360 A1 describes metaUmetal-oxide- catalysts prepared by the conventional co-precipitation method and used in the epoxidation of higher alkenes.
Within the Scope of the above defined method of the invention in its first embodiment, heterogeneous catalysts are manufactured by depositing the micelle-stabif~d precious-metal particles on an oxidic su~ort (for instance SiO~, said catalysis being characterized, r~lative to homogeneous systems, by high stabif~ty, activity and selectivity and by requiring little consumption of precious metals while offering high catalytic activity. By using the block copolymer micelles of the above-defined method of the invention, the particle size and the inter-particle distance and the ensuing active surface may be accurately adjusted.
On account of the residue-fnae removal of the polymer and the simultaneous conversion of the Metal salts by the gas plasma procedure, there result well-defined metaUmetal-oxide compound systems on different substrates such as mica, glass or quartz.
(n order to attain good film formation, the Iniceltes are for instance deposited on a planar substrate (Fig. 6). I=of example the supports used may bemicroglass balls or microquartz balls or mica flakes having a smooth surfiace, because the speck surface of the support and the quantity of precious metal can be accurately computed for such micro-balls.
The ptoportion by weight of precious metal in this procedure is less than in conventional powder catalysts.
Table 2; charging Pd clusters (5 nm size) on glass balls-Glass balls (~,) m(Pd)/m(ball) [mglg) % Pdlcatalysx 1000 0.0027 0.00027 100 0.027 0.0027 0.27 0.027 5 ~ 0.5 0.05 ,-o.~r 2.7 0.27 The quantities of precious metals available for catalysis depend on the size of the glass balls. Typical catalysts based on palladium/supports have values of 1-10 %
precious metal.
When using block copolymer micelles, Such a high content in precious metals cannot be attained, however it is not absolutely required because the size and inter particle distances can be exactly adjusted using this concept. As a result, even a lov~ler quantity of precious metals Will resuk in the same or similar catalytic activity.
As regards the second embodiment of the method of the invention, the input, which is uniformly distributed on the polymer cores, can be converted in solution by reduction or oxidation and/or by high-energy radiation, into each single polymer core, into single or several metal particles or metal-oxide particles, or may be precipitated by adding an appropriate component in the polymer core, the particular core-shell structure of the polymer system directly affecting the size of the particles formed in the core-shell polymer systems.
In this procedure at least part of the metal compounds contained in the polymer cores are converted in solution by reduction or oxidation into one or several metal particles) andlor metal-oxide particles) in each single polymer core to such an extent that part of the charged polymer cores contain one or several metal atoms arldlot one or several metal compounds. If, for instance, HAuCI, is used as the metal compound, then the Au~' ions charging the polymer cores of the particular core-shell polymer system can be reduced in solution by reduction or oxidation to such an extent that some of the charged polymer cores contain one or more gold atoms and one or more Au~ ions. If such a reduction of the metal compounds charging the polymer cores is carried out in solution, then the reducing agent is preferably hydrazine.
In stage (d) of the second embodiment of the method of the invention, the film together uv'tth the substrate at least partly covered by the film is subjected to reactive ion etching, to ion sputtering, or to a wet-chemical procedure or a combination thereof. The sttuctures precipitated onto the substrate surface act as masks, which are transferred into the corresponding substrate by etching, the film deposited on the substrate being removed in residue-free manner at the desired site or zone, and the regular structure produced by the core-shell polymer systerrl being converted into a substrate topographical structure because of, and as a function of, the kind of charge on the polymer core and the duration of r~active ion etching and/or ion sputtering andlor the wet-chemical procedure. Preferably ion etching is used with argon, ozone, oxygen and their mixtures, and even more preferred is ion sputtering_ Depending on the duration of etching, and as a function of the polymer core charges, the film deposited on the substrate is etched away In such manner that as a result the substrate being used also is removed, as a result of which surface-structured substrates produced by the second aspect of the method of the invention, which have a relief structure of lateral dimensions between preferably 1 and 100 nm across macroscopic zones, and in particular holes, troughs, strips, dot heights as well as their inverse structures with lateral dimensions illustratively between 1 and 100 nm, also may be produced in the substrates across macroscopic zones.
The structures' heights and depths so attained may be a multiple, for instance 20-fold to 100-fold, of the lateral dimensions.
If for instance, on the one hand micelles charged with gold-atoms, and on the other hand micelles or molecular cavities charged with gold-compounds, are present in precipitated form on the substrate next to uACharged micelles, then, depending on charge, and in selective manner, first the gold-atom charged micelles will be etched away, far instance byAr sputtering, while for instance forming holes. Then the uncharged micelles, and lastly the gold-compound charged micelles will be etched away. The result is formation of, for instance, islands, as a result of which the predetermined, regular stnrcture present in the precipitated film, and acting as a mask, are transferred by etching into the corresponding substrate in the form of a relief topography.
BELIEF DESCRIPTION OF THE DRAWINGS
The Figures are as follows:

$296-pia Fig. 1 shows scanning force microscope pictures of substrates of the invention decorated in the nanometric range: (a) Pt diameter = 7nm on vitreous silica;
(b) pd diameter =
nm on mica; (c) gold diameter = 8 nm on glass.
Flg. 2 shows a scanning force microscope picture of 8nm high nanodusters on glass following treat treatment in an oxygen atmosphere (T = 2000, p(~) = 0.5 bar, t =120 min). The length of an image edge is 1 p.
Fig. 3 shows the dependence of 7.5 nrn high gold clusters on glass on the duration of annealing at three different temperature.
Pig, 4 shows a scanning force microscope picture ofnanometrically decorated surface struduree of the irnrer,tion, where, following oxygen plasma treatment, the gold clusters on glass were annealed for 12 h at T = 800°C at standard atmosphere.
Flg. 5 shows scanning force microscope pictures of gold/metal-oxide hybrid systems on glass: (a) 5 nm high gold/titanium-oxide clusters; (b) 5 nm high gold/cobalt-oxide clusters; (c) 5 nm high gold lronroxide clusters following oxygen plasma treatment; the length of an image side Isle.
Flg. 6 schematically shows the micelle (metal clusters) dimensions vs microglass spheres (upper sphere: before removing the polymer enclosure; lower sphere:
following removal of the polymer enclosure).
Fig. 7 shows scanning force microscope pictures of nanometrically surface-decorated substrates of the invention according to Example 1, where naked gold clusters are precipitated on mica: (a)Audiameter= l2nm, periodicity=80nm; (b) Au diameter=3nm;
periodicity=28 nm; (c) Au diameter = 1 nm, periodicity = 140 nm, Ft9~ 8 shows a scanning force microscope picture of xnanometricallysurface-decorated substrate of the invention according to Example 2, where naked gold clusters were precipitated on a Si wafer, Au diameter = 3 nm, periodicity = 120 nm.

Fig. 9 shows a scanning force microscope of a nanometrically surface decorated substrate of the invention according to Example 3, where naked gold ctuaters were precipitated on GaAs; Au diameter = 3 nm, periodicity ~ 70 nm.
Fig.10 shows scanning force microscope pictures ofnanometricallysurface decorated substrates of the invention according to Example 4, where naked gold Clusters were precipitated on SrTiO; ; Au diameter= 3 nm, periodicity = 120 nm: (a) before annealing; (b) after annealing at 800°C in an Ar/0= atmosphere.
Fig. 11 shows a scanning force microscope picture of a nanometrically surface~-decorated substrate of the invention according to F~cample 5, where naked gold clusters were precipitated on a diamond film: Au diameter = 3 nm, periodicity =120 nm.
Fig.12 shows transmission electron microscope (TEM) pictures of mono,micellar films according to Example 8, consisting of (a) polystyrene - b-poly[ethyleneoxide)(LiAuCl,~osj~
micelles, where the Au~ ions were reduced by electron beams into the film, and (b) poly[styrene]~ - b-. poly((2-vinylpyridine)(HAuCI,)o~, where the Au~" ion in solution was converted into Au and the growth of an approximately 6nrn diameter crystal was induced in each micelle before film formation; the particular TEM pictures are followed by schematics of the particular films.
Fiig.13 shows a scanning force microscope picture of a mono-micellar polymer film of poly(styrene)~~ -b- poly[(2-vinylpyridine)(HAuCh)o,~]4~ micelles on a Si wafer according to Example 9; the length of an image side Js 2.5 p.
Fig.14 shows scanning force microscope pictures of theGaAs wafer structured by the method of the invention according to Example 10. (a) 400 holes and (b) 400 Islands; the length of an image side Is 1.25 u.
Fig, 95 shows the 3-D structure of 400 hales in theGaAs wafer structured by the method of the invention according to Example 10.

Fig. 18 shows scanning force microscope pictures of a GaAs relief structured by the method of the invention according to. Example 11: (a) = topography and (b) =
friction; the length of an image side Is 2 w.
Fig. 17 sh~nrs further scanning force microscope pictures of a GaAs topography structured by the method of the invention according to Example 11: (a) =
topography and (b) _ deviatwns of the amplitude signal; the length of an image side Is 1.25 ~.
I=ig. 18 shows the sectional height function of an etched GaAs wafer according to Example 11.
Fiig.19 shows a high-resolution scanning electron microscope picture of anartometric surface-decorated substrate of the invention according to Example 12, naked cobalt clusters having been precipitated on a Si wafer Co diameter = 12 nm, periodicity = 80 nm; the cobalt duster's magnetic moment as a function of the magnetic field at T = 50 K is also shown.
Fig. 20 shows a scanning force microscope picture of a nanometric surface-decorated substrate of the invention according to Example 13, where naked nickel clusters were precipitated onto a mica substrate: Ni diameter = 8 nm; periodicity = 140 nm.
Fig. 21 shows a scanning force microscope picture of ananometric, surface-decorated substrate of the Invention according to Example 14, where naked gold clusters were precipitated on a Ei-wafer; Au diameter = 8 nm; periodicity =100 nnl.
Fig. ZZ shows a scanning force microscope picture of a nanometric surface-decorated substrate of the invention according to F_xample 15, where naked platinum dusters were precipitated on a gold monocrystal substrate (100): Pt diameter = 4 nm;
periodicity = 40 nm.
IFig. 23 shows a 3-D plot of InGaAs quantum dots on a GaAs wafer structured by the method of the invention and according to Example 16.
The present invention is elucidated by the Examples below.
EXAMPLE 1:
The precipitation in the manner of the invention of regularly ordered gold clusters on a mica substrate across macroscopic zones having a diameter of 12 nm, 3 nm or 1 nm and a 52880.014 periodiaty resp. of 80 nrn, 25 nm or 140 nm is successfully carried out In each case using a 5 mg/ml polyatyreneJ~ brpoly((2-vinylpyridine)(HAuCl4)aoleso toluene solution, a S mglml polyjsturene]~- b- polyj2 vinylpyrjdine)(HAuCl4)oshs toluene solution, or a 5 mg/ml poly(styr'ene]~~oo .b.po,lyj(2-vinylpyridine)(HAuCI,,)o,~]~ toluene solution by drawing a freshly cleaved mica substrate at a draw speed of 13 mmlmin and subsequentlytreating it in a 200 watt oxygen plasma for 20 min. Fig. 7 shows scanning force microscope pictures of the nanometric surface-decorated substrates of the invention.
EXAMPLE 2:
The precipitation of the method of the invention of regularly ordered gold clusters on a Si substrate with thermally grown oxide or thin natural oxide across macroscopic zones having a diameter or 3 nm and a peridodicity of 120 nm is implemented using a 5 mg/ml poly jstyrene],.,~
- b-poly j(2 vinylpyridine)(HAuCI,)o.~O toluene solution by drawing anSi wafer at a draw speed of 12 mm/min (Si wafer with thermal oxide) or at 6 mmlmin (Si wafer with oxide coating) and subsequently treating it in a 240 w oxygen plasma for 20 min. Fig. 8 shows a scanning force microscopic picture of the nanometric surface decorated substrate of the invention.
E3(AMPLE 3:
The precipitation in the manner of the method of the invention of regularly ordered gold clusters on a GaAs substrate ac~oas macroscopic zones having a diameter of 3 nm and a periodicity of TD nm is implemented using a 5 mg/m1 poly(styrene],~oo -b-polyj(2-vinylpyridine)(HAuCh)o,],~ toluene solution by drawing a freshly cleaved mica substrate at a draw speed of 18 mm/min and then treating it in a 200 w oxygen plasma for 2D
min. Fig. 9 shows a s canning force microscope picture of the nanometric surtace-decorated substrat~.

EXAMPLE 4:
52880.014 The precipitation in the manner of the method of the irwention of regularly ordered gold clusters on an SrTiO, substrate across macroscopic zones having a diameter of 3nm and a periodicity of 120 nm is implemented using a 5 mg/ml poly jstyrene]"~ -b-poly[(2-vinylpyridine)(HAuCI,~,~ toluene solution by drawing an SrTi01 monocrystal substrate (104) at a draw rate of 4 mmlmin and subsequently treating it in a 200 w oxygen plasma for 20 min.
Subsequent annealing in an argon/oxygen atmosphere at 80Q'C for 15 irlin proved the structure is stable under these conditions, F.ig. 10 shows scanning force microscope pictures of the nanometrlc surface-decorated substrate of the invention before and after annealing.
EJ(AMPLE 5:
The precipitation in the manner of the method of !he invention of regularly ordered gold clusters on a diamond substrate across macroscopic zones having a diameter of 3nm and a periodicity of 120 nm is implemented using a 5 rriglml poly[styrene]~» -b-polyj(2-vinylpyridlne)(HAuCL,)a,~],,~ toluene solution by drawing a freshly cleaved mica substrate at a draw rate of 4 mm/min and then treating it In a 150 w oxyg~n plasma for 10 min. Fig_ 11 shows a scanning fotce microscope picture of the nanometric surface-decorated substrate of the invention.
FrXANIPLE 6:
The epoxidation of 1-octane was investigated in ~ mini-reactor. Block copolymer micelles filled with gold-chloride/titanium-tetrachloridewere precipitated as catalyst on deaved pieces of mica. The coating of the cleaved pieces of mica 10 to 50p in size was carried out using a solution of 5 mg/ml of polyjstyrenej~ -b-poly[2-vinylpyridine)(HAuCI,b ~ (TiCI, )o,,]~ in toluene. The cleaved pieces of mica were dried.on a cellulose web. Then the polymer was decomposed in a tubular heater in an oxygen atmosphere (T = 200C, p(O~ = 0.5 bar, t = 120 min), the metal components being precipitated in the form of small mixed clusters on the mica.

The cleaved pieces of mica were scurried in octane and following octane addition molecular oxygen was directly blown into the solution. The yield of 1-octane oxide at 1Q0°C was 38°k.
EXAI~I1PLE 7:
The oxidation catalysis of CO into CO= was investigated on block-copolymer micelles containing gpi~chloridetron-trichloride deposited on cleaved pieces of mica.
Tlte coating of the to 50 ~ size cleaved pieces of mica was implemented using a solution of 5 mglml poly[styreneJ~ -b-poly[(2-vinylpyridine)(HAuCI,~o., (FeCi, )a~,~ in toluene.
The cleaved pieces of mica were dried on a cellulose web. Thereupon and in the manner described in Example 8, the polymer was decomposed in a tubular oven in an oxygen atmosphere (T =
200°C, p(Os) =
0.5 bar, t = 120 min). The catalyst was enclosed in athermostatted glass tube and the reaction gas (1 % CO,1 % f~, 75 % f-1z, 23 % N, was made to flow by. In the reaction of CO into Cq the CO was converted by half.
EXAMPLE 8:
Mono-micellar films composed of (a) poly[at~rreneJ,s,a -b- poly[ethyleneoxide)-(~A~rCI,)a~ micelles, where the Atr~' ions are reduced in the film by electron beams and hence the precipitation of many Au crystals in a micelle was attained, and (b)poly[styrene]~ -b-poly((2-vinylpyridine)(HAuCI,)°~j~, where the Au~' in solution is converted into Au and the gtowth of a crystal about B nm in diameter is induced in each micelle for film formation, are prepared by drawing a carbon-coated Cu grid each time using a 5 mg/ml toluene solution and a draw speed of 7 mmlmin. Fig.12 shows TEM (transmission electron microscope) pictures as well as the particular films in schematic form.

EXAMPLE 9:
52960.014 A mono-micellar polymer film ofpoty[stytene],~~ -b- poly[(2-vinylpyridine)(HAuCl4)o,,],,so micelles on a Si wafer was prepared by drawing the substrate from a 5 mglml concentrated solution of toluene at a draw speed of 10 mmlmin. Fig. 13 shows the force microscope picture.
F~KAMPLE 10:
A mono-micellar polymer film consisting of poly[styrene],.,oo -b-poly[(2-vinylpyridine)],,~
micelles on a GaAs wafer was etched withAr ions (1.1 Kev, 12 pa/cm~ for 15 min, and, in the case of the holes, each micelle was charged with one Au particle 1 Onm in diameter and in case of islands, 4 out of 10 of the 2-~inylpyridine units were neutralized with one HAuCI, in solution.
Fig. 74 shows a force microscope picture of a GaAs wafer of such a structure.
EXAMPLE 11:
A micellar film Consisting of polyjstyrene]"oo -b-poly[(2-vlnylpyridine)(I~AuCI')o,d]~so micelles was precipitated by drawing a GaAs substrate at a speed of 2 mm/min from a 5 mglml concentration solution. The non-covering micetlar film acting as an etching mask was etched for 15 min by means ofAr ions (1_1 hfev,12 palcm2.). Fig.16 shows no relative contrast of the coefficient of friction at the surface. OnIyGaAs could be detected after etching. Fig_ 17 shows another segment of the same film and Fig. 17b shows the deflection perpendicularto the surface of the scanning force microscope needle. The two-siepGaAs relief so produced is shown in profile in Fig. 18.
E?4AMPt~ 12:
The precipitation by the method' of the invention of regularly ordered cobalt clusters on a silicon substrate with thermally grown oxide or thin natural oxide across macroscopic zones 12 nm in diameter and a periodicity of 80 nm is imple~rnented using a 5 mg/ml poly jstyrene]~~
-b- poly[(2-vinyipyridine)(CoCt~~,4]~~o toluene solution by drawing a Si wafer at a dravy speed of 5298p.p14 13 mm/min (Si wafer with thermal oxide) or of 6 mm/min (Si wafer with thin oxide coating) and ensuing treatment in a TO w oxygen plasma for 15 min. Fig. 19 shows a scanning force microscope picture of the nanometric surface-decorated substrate of the invention and the associated magnetization curve at T = 50K. The ab~ene~ of hysteresis indicates super 'ferromagnetic properties of the cobalt clusters.
EXAMPLE 13:
The precipitation of the method of the invention of regularly ordered nickel clusters on a mica substrate across macroscopic zones 6 nm in diameter and with a periodicity of 'l40nm is implemented by a 5 mg/rnl poly(styrene,y"~-~~iyj(2-vinylpyridine)(l~liC~
)off toluene solution by drawing a freshly cleaved mica substrate at a draw speed of 12 mm/min for 5 rnin. Fig. 20 shows a scanning force mictoscope picture of thenanometriC, surface-decorated strbsttate of the invention.
E3CAM1PLE 74:
The precipitation of the method of the invention of regularly ordered gold clusters on a silicon substrate with thermally grown oxide or this natural oxide across macroscopic zones havinrg a diameter of 8 nm and a periodicity of 100 nm is implemented using a 5 mg/ml polystyrene]"~ -b-poly((2_yinylpyrtdine)(i-IAuC4)a.~ toluene solution by drawing anSi wafer at a speed of 15 mm/min ~Si wafer with thermal oxide) or 10 mm/rriin (Si wafer with 'thin oxide coating) and ensuing treatment in a 100 w trifluoromethane plasma for 10 min.
Fig. 21 shows a scanning force microscope picture of the nanometric, surface-decorated substrate of the invention.

EXAMPLE 15:
52960-01<
The precipitation of the method of the invention of regularly ordered platinum clusters on a gold substrate across mactoscopic zones 4 nm in diameter and having a periodicity of 40nm is implerne~ed using a 5 mg/ml polyjstyrene],~ -b-poly[(2-vinylpyridine)(K[PtGI, C=H,~)o,,l,~
toluene solution by drawing a gold monoctystai substrate (100) at a speed of 12 mmlmin and by ensuing treatment in a 120 w oxygen plasma for 10 min. Fig. 22 shows a scanning force microscope picture of the nanometric, surface decorated substrate of the invention.
EXAMPLE 18:
A mono-micellar polymer film consisting of poly[styrene]~~ -b-poly j(2-yinylpyridine)(HAuCI,)o,,),,~ micelles was precipitated by drawing a semiconductlng-layer substrate jGaAs, 3 nm); InGaAs (10 nm) and GaAs (substrate)] at a speed of 10 mm/min out of a 5 mg/ml solution. The micellar film as etching mask was etched 15 min byAr' ions (1.1 Kev, 12 y~alcm2). Fig. 23 shows a 3D structure of the quantum dtsts so prepared.
Photoluminescence test corroborate that the islands in Fig. 23 are indeed "quantum dots°.

Claims (31)

1. A method for manufacturing nanometrically surface-decorated substrates, comprising the stages:
(a) introducing a polymer into an appropriate solvent while forming a dissolved core-shell polymer system, (b) charging at least some of the polymer cores with one or more identical or different metal compounds, (c) depositing the core-shell polymer system prepared as a film in stage (b) in such manner on at least one side of a substrate that the core-shell polymer system is configured in a regular structure, and (d) removing the polymer erecting the core-shell polymer system while producing metal clusters and/or metal-compound clusters an the substrate surface without thereby significantly modifying the structure erected by the core-shell polymer system.
2. Method as claimed in claim 1, where the metal compound(s) contained in the core-shell polymer system is (are) converted chemically and/or by high-energy irradiation in solution or in the film into the metal or a metal oxide prior to stage (c).
3. Method as claimed in either of claims 1 and 2, wherein the polymer is removed in stage (d) by etching, reduction or oxidation.
4. Method as claimed in claim 3, wherein the polymer is removed using oxygen plasma.
5. A method for manufacturing nanometric surface-structured substrates, including the stages:

(a) introducing a polymer into an appropriate solvent while forming a dissolved core-shell polymer system, (b) charging at )east some of the polymer cores with one or more identical or different metal compounds, (c) depositing the core-shell polymer system prepared in stage (b) in the form of a film on at least one side of substrate in such manner that the core-shell polymer system is configured in a regular structure in the film, and (d) subjecting the substrate prepared in stage (c) to reactive ion etching, ion sputtering or a wet-chemical procedure or a combination thereof, whereby the film deposited on the substrate shall be removed and the regular structure generated by the core-shell polymer system is .converted Into a substrate relief topography by means of and depending on the kind of charge on the micelle cores and the duration of etching and/or ion sputtering and/or the wet-chemical procedure.
6. Method as claimed in claim 5, wherein at least some of the metal compounds contained in the polymer cares will be converted by chemical treatment and/or by high-energy irradiation before deposition as a film or after film formation into one or more metal particle(s) and/or metal-oxide particle(s) in each individual polymer core.
7. Method as claimed in either of claims 5 and 6, wherein at least some of the metal compounds contained in the polymer cores are converted in such manner in solution by reduction .or oxidation into one or more metal particle(s) and/or metal-oxide particle(s) in each individual polymer core, that some of the charged polymer cores contain one or more metal atoms and/or one or more metal compounds.
8. Method as claimed in claim 7, wherein the reduction in solution is carried out using hydrazine.
9. Method as claimed in one of claims 5 through 8, wherein argon ion sputtering is carried out in stage (d).
10. Method as claimed in one of claims 1 through 9, characterized in that the polymer is selected from block copolymers, graft copolymers, miktoarm starpolymers, star polymers having different branches, dendritic polymers, microgel particles, star block copolymers, block star polymers and core-shell latex polymers.
11. Method as claimed in claim 10, wherein the polymer is polystyrene-b-polyethyleneoxide, polystyrene-b-poly(2-vinylpyridine), polystyrene-b-poly(4-vinylpyridine) or a mixture thereof.
12. Method as claimed in one claims 1 through 11, wherein the metal compound is selected from Compounds of Au, Pt, PdAg, In, Fe, Zr, Al, Co, Ni, Ga, Sn, Zn, Ti, Si .and Ge in the corresponding oxidation stages or mixtures thereof.
13. Method as claimed in claim 12, wherein the metal compound is selected from HAuCl4, MeAuCl4, where Me denotes alkali metal, H2PtCl~, Pd(Ac)2, Ag(Ac), AgNo3 , InCl3, FeCl3 Ti(OR)4, TiCl4, TiCl3 , CoCl3 , NICl2, SiCl4, GeCl4, GaH3 , ZnEt2, Al(OR)4 ,Zr(OR)3 , Si(OR)4, where R denotes a straight-chain or a branched C1- C~ alkyl residue, ferrocene, a Zeise salt and SnBu3 H or mixture thereof.
14, Method as claimed in claim 13, wherein the metal compound is HAuCl4.
15. Method as claimed in one of claims 1 through 14, wherein the substrate is selected from the precious metals, oxidic glasses, monocrystalline ar multi-crystalline substrates, semiconductors, metals with ar without a passivated surface, or insulators.
16. Method as claimed in Claim 15, wherein the substrate is selected fromSi, SiO2, Pt, Au, GaAs, In y GaAs, Al x GasAs, Ge, Si x N y, Si x GaAs, InP, InPSi, GaInAsP, glass, graphite, diamond, mica, SrTiO2, or their doped modifications.
17. Method as claimed in one of the above claims, wherein the film deposition in single or multiple layers is carried out by dipping, pouring, spin coating or by adsorption in diluted solution.
18. Method as claimed in claim 17, wherein the deposition in single or multiple layers is carried out by dipping in dilute solutions.
19. Method as claimed in either of Claims 17 and 18, wherein the film thickness implemented in stage (c) is between 5 and 800 nm.
20. A nanometrically surface-decorated substrate comprising clusters of metal atoms and/or metal compounds at its surface, where the clusters are configured in a regular pattern on the substrate surface.
21. Substrate as claimed in claim 20, where the clusters are of a diameter between 0.5 and 100 nm.
22. Substrate as claimed in either of claims 20 and 21, where the clusters are regularly arrayed on the substrate surface at spacings up to 400 nm.
23. Substrate as claimed in one of claims 20 through 22, where the clusters are composed of identical or different metal atoms and/or metal oxides.
24. Substrate as claimed in claim 23, where the clusters consist of gold atoms.
25. Substrate as claimed in claim 23, where the clusters consist of Au/Fe x O
z , Au/CoO, Au/Co3 O4, Au/ZnO, Au/TO2, AuZrO2 , Au/AI2O3 , Au/In2O3 , Pd/AI2O3 , Pd/ZrO z, Pt/graphite or Pt/AI2O3.
26. Substrate as claimed in one of claims 20 through 25, where the substrate is selected from Pt, Au, GaAs, In y GaAs, Al x GaAs, Si, SiO z, Ge, Si x N y , Si x GaAs, InP, InPSi, GaInAsP, glass, graphite, diamond, mica, SrTiO3, or their doped modifications.
27. Application of the nanometric surface-decorated substrate claimed in one of claims 20 through 28 to the epoxidation of C3 - C~alkenes or in the oxidation of CO to CO2.
28. Surface-structured substrate manufactured in the manner of a method claimed in one of claims 5 through 19.
29. Surface-structured substrate having a relief topography of lateral dimensions between 1 and 100 nm across macroscopic zones.
30. Substrate as claimed in claim 29, selected from precious metals,oxidic glasses, mono-crystalline or multi-crystalline substrates, semiconductors, metals with or without a passivated surface or insulators.
31. Substrate as claimed in claim 38, selected from Pt, Au, GaAs, In y GaAs, AI x GaAs, Si, SiO2, Ge, Si x N y ,Si x GaAs, InP, InPSi, GaInAsP, glass, graphite, diamond, mica, SrTiO3 or their doped modifications.
CA002308302A 1997-10-29 1998-10-29 Nanometric structures Abandoned CA2308302A1 (en)

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DE19747815A DE19747815A1 (en) 1997-10-29 1997-10-29 Production of surface-structured substrates used in the manufacture of electronic components
DE19747816A DE19747816A1 (en) 1997-10-29 1997-10-29 Production of surface-structured substrates used in the manufacture of electronic components
DE19747815.8 1997-10-29
DE19843411.1 1998-09-19
DE19843411A DE19843411A1 (en) 1998-09-19 1998-09-19 Production of surface decorated substrates
PCT/EP1998/006874 WO1999021652A2 (en) 1997-10-29 1998-10-29 Nanostructures

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ATE246542T1 (en) 2003-08-15
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WO1999021652A3 (en) 1999-07-15
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