WO2013075712A1 - Surfaces de solides à base de systèmes à deux ou à plusieurs composants présentant des nanostructures composites, constitués de métaux, de semi-conducteurs ou d'isolants - Google Patents

Surfaces de solides à base de systèmes à deux ou à plusieurs composants présentant des nanostructures composites, constitués de métaux, de semi-conducteurs ou d'isolants Download PDF

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Publication number
WO2013075712A1
WO2013075712A1 PCT/DE2012/200077 DE2012200077W WO2013075712A1 WO 2013075712 A1 WO2013075712 A1 WO 2013075712A1 DE 2012200077 W DE2012200077 W DE 2012200077W WO 2013075712 A1 WO2013075712 A1 WO 2013075712A1
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solid
amorphous
crystalline
layer
thermal treatment
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PCT/DE2012/200077
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German (de)
English (en)
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Danilo BÜRGER
Heidemarie Schmidt
Ilona Skorupa
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Helmholtz-Zentrum Dresden - Rossendorf E.V.
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Publication of WO2013075712A1 publication Critical patent/WO2013075712A1/fr

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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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/26—Bombardment with radiation
    • H01L21/263—Bombardment with radiation with high-energy radiation
    • H01L21/268—Bombardment with radiation with high-energy radiation using electromagnetic radiation, e.g. laser radiation
    • 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
    • H01L21/322—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to modify their internal properties, e.g. to produce internal imperfections
    • H01L21/3221—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to modify their internal properties, e.g. to produce internal imperfections of silicon bodies, e.g. for gettering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
    • H01L31/035209—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
    • H01L31/035218—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum dots
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/011—Manufacture or treatment of multistable switching devices
    • H10N70/021—Formation of switching materials, e.g. deposition of layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/20—Multistable switching devices, e.g. memristors
    • H10N70/231—Multistable switching devices, e.g. memristors based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/881—Switching materials
    • H10N70/884—Switching materials based on at least one element of group IIIA, IVA or VA, e.g. elemental or compound semiconductors

Definitions

  • the invention relates to functionalized solid surfaces of metals
  • Semiconductors and insulators which have a defined chemical composition on the nanometer and micrometer length scale.
  • the thermal treatment of solid surfaces includes Rapid Thermal Annealing (RTA) on the second-time scale, Flash Lamp Annealing (FLA) on the millisecond to microsecond timescale, and pulsed laser Annealing (PLA - pulsed
  • the advantage of the PLA results from the fact that after absorption of the laser light of a defined wavelength and energy density in the solid surface emitted by the laser light electrons on a time scale of 1 ps to 1 ns deliver the absorbed energy to the atomic lattice of the solid. This takes the
  • the time dependence of the lateral and vertical temperature profile is determined by the locally applied PLA parameters and by the dependent on the properties of the solid heat transport in the heated solid surface during and after the thermal treatment with PLA.
  • phase change is accompanied by a change in thermodynamic quantities, latent heat and specific heat. Any change in the composition of a two- and multi-component system is accompanied by a change in the crystal structure.
  • Non-variant reactions are those in which in binary systems three phases are in equilibrium.
  • Solid body of different two- and multi-component systems at a high critical temperature and at a high critical pressure called.
  • an irregular, lamellar eutectic microstructure of Si plates in an Al matrix forms when an AlSi binary system is thermally treated and has a low solidification rate of less than 0.1 m / s (RTA, FLA).
  • the plate spacing depends on the solidification rate.
  • Dotants in semiconductor materials can be locally thermally activated by thermal treatment by means of PLA.
  • Makarovsky [Makarovsky, O. u. a .: Direct writing of nanoscale light-emitting diodes. Advanced Materials. 22 (2010), 3176-3180.] Showed this for manganese acceptors in the p-type GaMnAs layer of nanoscale light-emitting diodes.
  • EP 1 738 402 B1 describes the production of solar cells, especially the dilution of dopants, also called uniform redistribution of dopants.
  • DE 10 2010 044 480 A1 describes the production of thin-film solar cells, the recrystallization of an amorphous first layer of a semiconductor material and the epitaxial growth of a layer-wise applied and recrystallized second layer of a second semiconductor material. The dopants should not redistributed and an unstructured seed layer is used for uniform recrystallization.
  • semiconductors in the PLA treatment become about 1000 nm
  • the heating of the semiconductor can also take place at a depth of 10 ⁇ to 50 ⁇ , wherein the temperature in the deeper areas of the semiconductor is much lower, so possibly lying there
  • temperature sensitive materials e.g. Polymers
  • the melting point for the semiconducting solids is typically up to 1000 nm. In poorly thermally conductive solids, such as silicon and GaAs, is typically up to 1000 nm. In poorly thermally conductive solids, such as silicon and GaAs, is typically up to 1000 nm. In poorly thermally conductive solids, such as silicon and GaAs, is typically up to 1000 nm. In poorly thermally conductive solids, such as silicon and GaAs, is typically up to 1000 nm. In poorly thermally conductive
  • the melting depth of solids can be greater and is for semiconducting
  • Solid state layer structures with silicon or GaAs at about 3 to 5 ⁇ are solid state layer structures with silicon or GaAs at about 3 to 5 ⁇ .
  • High-temperature oxide layers have a typical thickness of 0 to 2000 nm and can thus be completely or partially thermally treated by means of PLA.
  • Phononenbelus which is required for melting, have an extremely high surface power density. In this case, usually only thin, near-surface layers of the solid with a thickness of typically 10 nm
  • Pulsed lasers with microsecond laser pulses require to reach the
  • Phonon occupation for the melting of the solid surface only a low surface power density.
  • the time during which the solid is heated and dissipated during heat energy from the solid surface to adjacent colder regions of the solid is up to three orders of magnitude compared to PLA treatment with nanosecond laser pulses elevated. This requires a higher energy density.
  • the solid surface or - back side is preheated by thermal treatment and thus the thermal stress during spike annealing (peak healing) of the
  • the preheating of the solid is also advantageous because in the thermal treatment (spike annealing) lower energy densities are needed, a better process control is possible and thermal stresses can be reduced.
  • contaminated silicon is used to enrich metal atoms in phosphorus doped regions of silicon in which the metal atoms have an increased solubility and to bind by forming precipitates.
  • substitutionsmischkristalle the foreign atoms are completely dissolved in the solid state.
  • Typical metallic substitution mixed crystals are the alloys iron-chromium, iron-nickel, gold-copper, gold-silver and copper-nickel.
  • the solubility of non-isovalent impurities in semiconductors (Si: P, Si: Mn, Ge: Mn) in the solid state is typically 10 16 to 10 21 impurities per cm 3 .
  • solid state of aggregation is typically 10 21 to 10 22 foreign atoms per cm 3 .
  • Mixed crystals can be formed.
  • solubility of foreign atoms and foreign molecule groups in insulators is incomplete for certain phases, for example, form Si0 2 and Na 2 0 in the crystalline state numerous defined phases.
  • the solubility of foreign atoms and foreign molecule groups in metals, semiconductors and insulators in the liquid state is increased compared to the solubility of impurities in solids in the solid state.
  • the concentration of foreign atoms in a solid in the solid state is greater than the solubility of the foreign atoms in the solid, then the distribution of the foreign atoms is in a metastable state. The redistribution of foreign atoms in a solid in the solid
  • Physical state which is in a metastable state, is dependent on the diffusion parameters of the foreign atoms in the solid on very long time scales. For example, place at room temperature by extrapolation of the diffusion coefficient manganese in GaAs: Mn manganese only a space-changing operation in the average of all 10 20 seconds instead.
  • Mn manganese only a space-changing operation in the average of all 10 20 seconds instead.
  • Mn is theoretically achieved only after even longer times at room temperature. At 600 to 700 ° C, the phase separation can be shortened to a few seconds due to manganese exchange processes.
  • Power semiconductors with a field stop layer by performing at least a short-term first temperature treatment with ⁇ and a relatively longer temperature treatment with T 2 , wherein Ti is greater than T 2 and wherein the
  • Dopant concentration between 1 ⁇ 10 12 / cm 3 and 1 ⁇ 10 15 / cm 3 may be.
  • Atomic, molecular and ionic species of a process gas can during the thermal treatment in areas of a solid in the liquid
  • Solid surface to be incorporated dopants contains.
  • uniform distribution of the dopants in the recrystallized solids can be achieved with a maximum surface concentration of about 8 x 10 14 cm "2.
  • a medium can be applied to the solid body that contains the dopant. The gas atmosphere reduces the evaporation of dopant.
  • Amorphous Solids can recrystallize under the action of laser light, and crystalline solids can amorphize under the action of laser light, for example, silicon amorphizes above a recrystallization rate of 10 to 15 m / s (depending on crystal orientation) and germanium above one
  • the recrystallization rate during the PLA treatment depends on
  • Convective flows may occur within a molten solid due to density differences along temperature gradients and surface tensions.
  • Solid surface d 0 ' is smaller than the capillary length l c , then dominate
  • the capillary length l c indicates how much a liquid, depending on the capillary diameter and the density of the liquid and the surrounding medium, increases at a given contact angle, thereby compensating for the effect of the surface tension effects.
  • Quantum trenches and quantum barriers can be selectively mixed locally by thermal treatment by means of PLA.
  • Stanowski Stanowski, R. et al .: Laser rapid thermal annealing of quantum semiconductor wafers: a one step bandgap engineering technique.
  • Applied Physics A Materials Science & Processing. 94 (2009), No. 3, 667-674.
  • the object of the invention is to functionalized solid surfaces
  • novel materials Indicate metals, semiconductors and insulators for novel materials in metal semiconductor and ceramic technology.
  • the novel materials should have a defined chemical composition on the nanometer and micrometer length scale.
  • phase separation correct redistribution parameters locally redistributed (local phase separation) and have in areas which have a different temperature than adjacent areas, a different concentration of impurities than the adjacent areas.
  • the phase separation can be caused by local laser irradiation of the solid or by self-organized local redistribution.
  • Process gas are completely recrystallized as a single crystal.
  • the interfacial structure of the amorphous / crystalline interface may be designed, for example, by using prestructured crystalline substrate for low temperature growth of amorphous thin films on or through it
  • the interface may be designed during implantation with an ion type.
  • Solid surface be distributed.
  • the implantation can be done through masks or cover layers of different thicknesses. Getter regions for impurities in the solid surface are defined during low temperature growth and / or during implantation.
  • Getter areas have a higher melting temperature than the surrounding solid state material and have a much lower solubility for impurities in the solid state than the surrounding solid state material in the liquid state.
  • Nanosecond microsecond time scale under a process gas accounts for the snow plowing effect during thermal processing.
  • the redistribution of the foreign atoms in the liquid phase of the solid can be achieved by external
  • Nanosecond microsecond time scale under a process gas takes into account the crystal orientation-dependent recrystallization rate during the thermal treatment.
  • Solid material is easily volatile, are completely covered by a Getter für and / or thermally treated under a process gas under pressure.
  • thermal treatment in the roll-to-roll process of solid materials for the transparent electronics should be close to the triple point of the
  • Solid state material for example, using Bernoulli's law with moving process gas to be worked.
  • composition of solid surfaces during thermal treatment by ablation and evaporation effects is also to reduce the thermal stress during the local redistribution of impurities in metals, semiconductors and insulators.
  • Solid surface by using structured interfaces between a crystalline or amorphous surface substrate and the impurity or surface layer with two- and multi-phase systems, by using defined lateral and depth getter regions in the impurity or surface layer, as well as local
  • Stoichiometry of the solid leads in the heated near-surface region can be reduced by thermal treatment of the solid in a process gas, the relative velocity of the process gas and the solid and the flow rate of the process gas should be as large as possible. Atom specific evaporation and ablation is also reduced by the use of a capping layer with properties of a getter material.
  • the advantage of this production method is the high flexibility in the preparation of various chemical compositions for new PhaseChange materials (PCM), the integrability of the PhaseChange materials in germanium, silicon and germanium silicon technology when using multi-phase systems with Ge or silicon without damage to underlying areas, the low conductivity of the surface layer outside the segregated regions and (Fig. 5 c) the ability to specifically adjust the shape and volume of the PhaseChangeMaterials by an appropriate distribution of the multi-phase system in the surface layer, by the structuring of the cover layer and by the Laserausheilparameter. It eliminates the top-down processing step to define the phase change material. Furthermore, the write signal is used to reach the High Resistance State (HRS) and the Low Resistance State (LRS) in the
  • PhaseChangeMaterial better separated.
  • the shape of the PhaseChangeMaterial determines the number of non-volatile writable states.
  • the number of nonvolatile resistive states increase with increasing deviation of the shape of the PhaseChange material from the spherical shape.
  • the advantage of this production method in the production of support materials with a network of biocidal and biocompatible or biophilic areas is the transferability to arbitrarily shaped support materials, the integrability for support materials in the silicon and germanium technology, the structuring of selected areas in two- or three-dimensional support materials.
  • the cell size d s of the network can be determined before the thermal treatment by selecting the chemical composition of the multiphase system (A, B) in the
  • Laser Ausheilparameter be determined. After the thermal treatment, the overgrowth of the cell walls can be controlled by local application of heat to the electrically conductive cell walls of the network of biocidal material ( ⁇ '), as well as by local energy supply by light absorption in the network cells, the growth of biomaterial can be controlled in the network cells.
  • ⁇ ' electrically conductive cell walls of the network of biocidal material
  • One advantage is that the network can be produced over a large area and quickly, without damaging the underlying substrate (1).
  • Multiphase systems in quantum layers, quantum wires, quantum dots and quantum pyramids changed laterally and vertically.
  • Fig. 1 describes the production of functionalized solid surfaces of
  • Fig. 2 a, b shows the preparation of a functionalized solid with defined nanostructures at a distance d t from the sample surface.
  • Fig. 2 c, d, e shows the preparation and use of defined SiGeC nanostructures for the integration of photonics in silicon technology.
  • Fig. 3 a, b, c illustrates the production of a network of magnetizable nanoparticles in an electrically conductive or in an insulating layer of a semiconductor and its use for the spin-polarized scattering of
  • FIG. 3 d, e, f illustrates the preparation of a network of biocidal nanoparticles and microparticles in an electrically conductive or in an insulating layer of a biophilic material to increase the adhesion of biomaterials to support materials.
  • FIG. 4 a, b shows the production and use of a network of electrically polarizable nanoparticles in the diffusion region of solar cells for the sorting of photogenerated charge carriers.
  • Fig. 4 c, d, e shows the preparation of a functionalized solid with defined nanostructures for
  • PhaseChange materials in an insulating matrix on the sample surface PhaseChange materials in an insulating matrix on the sample surface.
  • Fig. 5 a, b illustrates the production of magnetic, ferroelectric
  • Fig. 5 c, d shows the modification of defined SiGeC nanostructures for the integration of photonics in silicon and germanium technology.
  • Fig. 6 shows the redistribution of components of one or more metallic multiphase systems in the surface layer (2) by local thermal
  • FIG. 7 illustrates the possibility of successively performing the deposition and thermal treatment of surface layers (2m ') on a substrate to prepare regions having different mixing phases (A, ⁇ ', B, B ', C, C).
  • Fig. 8 shows the redistribution of impurities in the layer by local
  • the lateral mixing of different two-phase and multi-phase systems is less than 100 nm, preferably less than 50 nm and particularly preferably less than 10 nm.
  • the two- and multi-phase system areas or the surface layer (2) are amorphous, amorphous-crystalline or crystalline and consist of at least one semiconductor material and / or at least one metallic material and / or at least one insulator material.
  • the settable composition or distribution of the impurities or compositions of the bicomponent and polyphase system regions in the functionalized surface layer becomes after the thermal treatment by the combination the mixtures of metallic, semiconducting and insulating material limited prior to the thermal treatment
  • a cover layer may be applied to the surface layer, wherein the melting temperature of the cover layer 4 is preferably higher than the melting temperature of the amorphous, amorphous-crystalline or crystalline surface layer 2.
  • the components of the two- and multi-phase system or the amorphous, amorphous crystalline, or crystalline surface layer with impurities may form a network structure upon certain application of the surface layers.
  • network structure consists of biocidal network walls and biophilic network cells.
  • the solid is produced by the following steps:
  • an interface (3) can form between the substrate and the amorphous, amorphous-crystalline or crystalline surface layer (2) with foreign atoms.
  • a cover layer can be applied before the thermal treatment, which can be removed after the thermal treatment together with the continuous segregated area on the surface of the surface layer 2 '.
  • the surface layer or the amorphous, amorphous-crystalline or crystalline surface layer is prepared by growth with foreign atoms, it can be distributed laterally and vertically homogeneously and / or in clusters.
  • the amorphous-amorphous-crystalline surface layer 2 can be made of at least one mixture of semiconductor material and / or of metallic material and / or of insulator material or a combination of these mixtures, wherein one or more getter regions 5 can be introduced before the thermal treatment and whose melting temperature is higher than the melting temperature of the amorphous, amorphous-crystalline or crystalline surface layer 2 at the location of the getter regions 5.
  • the registered energy density of the laser light used in thermal treatment of the properties of amorphous, amorphous crystalline and / or crystalline layer with impurities (2) or the surface layer (2) is determined and this energy density is less than 5 Jcm "2 per emitted laser pulse and the photon energy of the laser light used is above the band gap of the semiconductor
  • the backside of the substrate may be thermally treated to reduce thermal stresses.
  • one or more lasers of different wavelengths may be used locally in the thermal anneal.
  • the solid may be used as a new phase-change material prepared in the top-down process, wherein the shape of the phase-change material may vary between spherical and pyrimdal-tropic, and wherein the phase-change material having a shape deviating from the spherical shape has multiple resistance states.
  • the solid can be used as a network with biocidal components ( ⁇ ') in the cell walls and biophilic or biocompatible components ( ⁇ ') in the network cells to increase the adhesion of biomaterials to the support material, the mesh size being comparable to that of the biomaterial is.
  • the solid thus produced may be used as an optoelectronic device comprising nanopyramids, quantum dots, quantum wells, and quantum wells of SiGeC, SiGeSn, and SiSnC, wherein the electronic band gap of the composite nanostructures is smaller than the electronic band gap of the surrounding host material and wherein the emitted light can be emitted from the side edges light or perpendicular to the surface by using a getter as a waveguide, the solid state.
  • the solid according to the invention can be used as a carrier material for the production of thin, locally n- or p-doped carbon materials (for example graphene, graphite) by surface doping.
  • n- or p-doped carbon materials for example graphene, graphite
  • the solid according to the invention is as a network for spin-polarized scattering of charge carriers in electrically conductive or insulating layers of a semiconductor material, or for sorting photogenerated charge carriers in the diffusion region of solar cells, the networks of magnetizable and / or electrically polarizable nanoparticles (6 ') and / or magnetizable and / or electrically polarizable line paths (6 ") exist.
  • the solid according to the invention can be used as an optoelectronic component with ternary nanopyramids or quantum dots in semiconductor heterostructures, preferably InGaAs in GaAs / AIAs or SiGe in Si / Ge, wherein the component of the heterostructure having the higher melting temperature serves as the getter layer.
  • Another use is as a transparent optoelectronic device of intrinsically n-type oxides in which the solubility of acceptor-like impurities in the liquid phase during the thermal treatment in the process gas is extremely increased, so that the acceptor-like impurities after cooling on lattice sites of the Arrange solids.
  • Another possible use is as a sensor for electric or magnetic fields, wherein the solid in the surface layer (2) a Composite with anisotropic clusters and wherein the anisotropic clusters are electrically polarizable and / or magnetizable.
  • the solid body can be used as uniform / regular nanostructures, for example for nanoimprint lithography, wherein the nanostructures can be used directly as masks, or can be chemically specifically etched out of the solid and subsequently these etched out nanostructures are filled with other materials.
  • Fig. 1 a, b shows the preparation of the functionalized solid surfaces of metals, semiconductors and insulators with nanostructures before the thermal
  • the semiconductor may be, for example, an element semiconductor (Ge, Si), an Ill-V semiconductor (GaAs, GaP, GaN) or an Il-Vl semiconductor (ZnTe, ZnO).
  • the solid body comprises a substrate having a crystalline surface (1), on which an amorphous, amorphous crystalline or crystalline layer with impurities is applied or prepared, wherein an interface layer (3) is formed between these two layers, and this can be structured.
  • the thickness d 0 of the amorphous, amorphous crystalline or crystalline layer with impurities (2f) is less than 2000 nm, and the lateral and vertical of the clustered and non-patterned impurities in the amorphous, amorphous crystalline or crystalline layer is determined in the preparation.
  • the amorphous, amorphous crystalline or crystalline layer (2f) one or more getter regions (5) are introduced whose melting temperature is higher than the melting temperature of the amorphous, amorphous crystalline or crystalline layer.
  • a cover layer (4) is applied, whose
  • Melting temperature is higher than the melting temperature of the amorphous, amorphous crystalline or crystalline layer.
  • the lateral and vertical of the impurity in the amorphous, amorphous crystalline or crystalline layer (2 ') is changed. The thermal treatment leads to
  • molten layers (2 ') and (2") are preferably also to a melting of the boundary layer (3), particularly preferably also to a melting of the bordering on the interface crystalline surface of the substrate (2 ") .
  • the total thickness of the molten layers (2 ') and (2") is d 0 '. Due to the thermal treatment, preferably under a process gas of velocity v G , defined nanostructures (6 ') are produced by lateral and vertical redistribution of the foreign atoms. On the molten layer with impurities (2 ') can be caused by the thermal
  • Both the cover layer with properties of a getter material (4) and the layer with clustered impurities can be after the thermal treatment by physical or chemical etching of the
  • Fig. 1 c, d describes the production of functionalized solid surfaces with bi- and Mehrstoffsystemen of metals, semiconductors and insulators, which have a defined chemical composition on the nanometer and micrometer length scale before the thermal treatment (Fig. 1 c) and after the thermal treatment (Fig. 1 d).
  • the multi-substance system may be, for example, SiGeC, GeSbTe, AIP, Ag-Cu-Mg.
  • the solid body comprises a substrate having a crystalline surface (1 k) or having an amorphous surface (1 a), on which an amorphous, amorphous crystalline or crystalline surface layer having two- or multiphase systems (2) is applied or prepared, between them two layers forms an interface (3), and this can be structured.
  • the thickness d 0 of the amorphous, amorphous crystalline or crystalline surface layer with two or more phase systems (2) is less than 2000 nm and the lateral and vertical distribution of different two- and multi-phase systems in the amorphous, amorphous-crystalline or crystalline surface layer (2) becomes of the preparation.
  • the amorphous, amorphous crystalline or crystalline surface layer (2) are one or more
  • a cover layer (4) whose melting temperature is higher than the melting temperature of the amorphous, amorphous-crystalline or crystalline surface layer (2).
  • the thermal treatment leads to the melting of the amorphous, amorphous-crystalline or crystalline surface layer (2), preferably also to a melting over the boundary surface (3), more preferably also to a melting of the boundary surface adjacent crystalline or amorphous surface of the substrate ( 1 ).
  • the total thickness of the molten layers (2 ') and (2 ") is denoted d 0 ' by the thermal treatment, preferably under a process gas which is at a velocity v G relative to the surface layer 2 moved, defined nano- and microstructures of two and
  • Multiphase systems B produced by lateral and vertical redistribution of the two- and multi-phase systems. In the depth of the melted
  • a layer with a very high concentration of a component of a two- and multi-phase system ( ⁇ ') are formed. Both the cover layer with properties of a getter material (4) and the continuous segregated region on the surface of the layer 2 'with a very high concentration of individual
  • Fig. 2 a, b shows the preparation of the solid with defined nanostructures at a distance d t from the sample surface.
  • the layer with foreign atoms (2) has a continuous getter area (5) is introduced.
  • the interface (3) between the amorphous, amorphous crystalline and / or crystalline layer (2f) and the crystalline surface substrate (1) is structured.
  • the thermal treatment of the solid melts to a depth of d 0 'and recrystallized.
  • the structures of the interface (3) influence the recrystallization rate in the impurity layer (2f) and the lateral and vertical redistribution of impurities in the impurity layer (2) after the thermal treatment (2f ). Due to the
  • Impurities may be different in the impurity layer (2f) and there may be areas with an increased concentration of foreign atoms in the impurity layer (2f) which is on the continuous Getter Scheme (5) in the depth d of t areas with clustered impurity (6 ') in the layer (2f) form.
  • the shape of the regions of clustered impurity atoms (6 ') is mainly due to the distribution of impurities in the layer (2f) before the thermal treatment, the structure of the interface (3) and the distance d t and
  • Foreign atoms are used for a melting direction along the (1 1 1) - Crystal orientation expected.
  • Island-shaped nanostructures are expected for a melting direction along the (100) crystal orientation.
  • the regular arrangement of the nanostructures is determined by the pattern of the boundary layer (3).
  • the component of heterostructures for example AlAs in GaAs / AIAs heterostructures and Si in Si / Ge heterostructures, can be used which has a higher melting point. There may be regular fluctuations in the distribution of the foreign atoms in the
  • Solid state surface (InGaAs in GaAs, GeSi) can be prepared by complete thermal treatment without complete separation of the foreign atoms and the solid state material. Regularly formed clusters with novel optical, magnetic and transport properties can be produced. The thermal treatment changes the distribution of foreign atoms of high concentration and low solubility in quantum layers, quantum wires, quantum dots, and quantum pyramids laterally and vertically.
  • Fig. 2 c, d, e shows the preparation and use of defined SiGeC nanostructures for the integration of photonics in silicon and germanium technology.
  • Nanostructures may take the form of quantum dots and quantum pyramids and are formed at a distance d t from the sample surface.
  • the getter region may consist of a single continuous layer or of several, preferably two, continuous layers of a total thickness d g of the superposed layers
  • the getter layer (5) As a continuous getter layer (5), components of heterostructures, for example, SiC in SiC / GeC heterostructures or Si in Si / Ge heterostructures, may be used, provided that they have a higher melting point than the surface layer (2m).
  • the getter layer (5) may also be used as a waveguide for the light emitted by the GeC nanostructures ( ⁇ ') formed at a depth d t . In this case, the emitted light (21) is transported to the ends of the waveguide.
  • the material can be metallized.
  • the getter layer (5) causes a band bending of the adjacent regions of the surface layer (2m '), so that upon application of an electrical voltage to the front-side electrode (S) and the back-side electrode (O) charge carriers are injected into the GeC nanostructures and radiantly recombine there ,
  • Polyphase system ( ⁇ ', ⁇ ') can be produced without complete separation of the multiphase systems by thermal treatment.
  • Fig. 3 a, b, c) shows the production of a network consisting of magnetizable nanoparticles in the nodes of the network or of magnetizable nanoparticles in the nodes of the network and magnetizable
  • a layer with magnetic impurity atoms (2f) of a high concentration and a low solubility is produced.
  • the thermal treatment and by the structuring of the boundary layer (3) the magnetic impurities are redistributed and gassed on the cover layer with properties of a getter material (4).
  • a continuous layer with clustered foreign atoms (6 ') can form on layer (2f ").
  • the network of magnetizable nanoparticles is chemically or physically etched the cover layer with properties of a getter material (4). and the layer of clustered impurities exposed on layer (2f)
  • Magnetic field B magnetized. Local external magnetic fields B in the region above the coercive field strength of the network can be generated by above and / or below flowing ring currents at a distance of a few nm from the network. An external magnetic field of 0.3 T is needed to complete the
  • the ring currents or possibly currents through the network can be used to write information.
  • the current used between the structured contacts is used as read current. If the read current now flows through the network between the structured contacts (15) then spin-up polarized charge carriers (8) in the layer (2f) are propagated in one direction of the network perpendicular to the direction of the current flow and spin-down polarized charge carriers (9 ) in the layer (2f) in the opposite direction of the network perpendicular to Direction of the current flow is deflected by spin-dependent scattering in the network. After switching off the magnetic field occurs due to the Hall effect caused separation of negative and positive charge carriers perpendicular to
  • the magnitude of the voltage U s is given by the difference in the chemical potential of the spin-up and spin-down polarized charge carriers.
  • Fig. 3 d, e, f shows the preparation of a network of biocidal nano-
  • the adhesion correlates with the match between feature size of the biophilic or biocompatible surface areas of the support material, ie the size of the network cells.
  • It is a surface layer (2m) with locally on the nanometer and micrometer scale varying laterally and vertically distributed components of a multi-phase system (A, B) in the surface layer (2m) applied to a preferably structured substrate (1).
  • a thickness d 0 of the surface layer of about 100 nm is sufficient for use as a carrier material for biomaterials.
  • the surface layer (2) preferably consists of a mixed phase containing Ag, Cu and / or Mg for use as a carrier material for biomaterials.
  • the surface layer (2) should be thicker than 5 nm, more preferably thicker than 10 nm.
  • biophilic material also one or more of the following components C, H, O, N, P, S, Cl, I, Br, Ca, K, Na, V, Fe, Mn can be used.
  • a network with biocidal walls By using a network with biocidal walls, the adhesion of the biomaterials to the area of the network cells is limited. This allows the separation of biomaterials in individual network cells.
  • a network with different sized network cells By using a network with different sized biomaterials can be deposited in the individual network cells.
  • the segregation of the biocidal material ( ⁇ ') is particularly high and can reach a maximum depth of d 0 ( Figure 3 e).
  • the sample is moved under the laser (sample scan). If the network is two-dimensional, an xy table can be used for the sample scan. If the sample is three-dimensional, an xyz table can be used for the sample scan.
  • the sample scan and the scan site dependent laser annealing parameters are correlated to set a particular cell size.
  • Fig. 4 a, b shows the preparation of a network of electrically polarizable
  • the electrically polarizable nanoparticles are said to be accessible via the
  • Form depth range d 0 evenly distributed. This is achieved by getter regions (6) introduced in the same way in the layer (2f), by the distribution of the foreign atoms in the layer (2f) before the thermal treatment and / or by the use of laser light of different wavelengths and thus different penetration depths and
  • the layer (2f) is to be exposed after the thermal treatment by chemical or physical etching of the cover layer with properties of a getter material (4) and the layer of clustered impurities (7).
  • the metallization of the solar cell for applying the front contact (11) on the surface layer (12) with the thickness dpv and for applying the bottom contact (backside contact) (11 ') takes place after removing the cover layer with the properties of
  • the electrically polarizable nanoparticles have a large anisotropy and are polarized by a single application of an electric field so that the photogenerated charge carriers drift in the region of the local electric fields of the electrically polarizable nanoparticles in the direction of the corresponding contact of the solar cell.
  • electrons in the local electric fields in the diffusion region drift in the direction of the front contact (11) and holes in the local electric fields in the direction of the back contact (11 ').
  • Fig. 4 c, d, e) shows the preparation of a functionalized solid with defined nanostructures in an insulating matrix ( ⁇ ') on the sample surface of a surface layer (2m) with locally on the nanometer and micrometer scale varying laterally and vertically distributed components of a multiphase system (A, B) in the functionalized surface layer before (Fig. 4 c)), during and after (Fig. 4 d, e) of a partial separation of the components of the multiphase system by thermal treatment.
  • a backside electrode (O) for example in the form of a strip grid, for example as a 1 ⁇ m wide aluminum strip or platinum strip, is applied to the substrate (FIG. 4c).
  • the melting point of the multiphase system (B) is lowest in the area above the backside electrode (O).
  • the surface layer is structured such that the regions ( ⁇ ') above the backside electrode are highest and are about 10 to 20 nm higher than the adjacent regions ( ⁇ '), compare FIG. 4 d).
  • the specific material removal during physical etching can be used.
  • a transparent cover layer (4) having a melting point higher than the melting point of the surface layer (2) is applied to the surface layer (2) and a laser is scanned over the entire surface or only selectively above the regions ( ⁇ ') of the back surface electrode (O) (Fig. 4d)).
  • the parameters of the laser radiation are adjusted so that the components of the multiphase system segregate in the region ( ⁇ ') above the backside electrode.
  • a 10 to 20 nm thick layer is removed from the surface layer and the continuous segregated region.
  • Front side electrode (S) for example in the form of a strip grid
  • Fig. 5 a, b shows the production of magnetic, ferroelectric
  • the starting point for this preparation is a layer of foreign atoms (2f) with spherical and / or structurally anisotropic clustered impurities (6) in the impurity layer (2f) prior to thermal treatment.
  • the formation of spherical clusters (6) in the formation of the layer with foreign atoms (2f) is energetically most favorable.
  • the solid body in the region of the spherical clusters is locally melted, for example by means of a mask, and then recrystallized again.
  • the lateral and vertical heat conduction is used to provide lateral and vertical redistribution
  • the recrystallization heat delivered to the directly surrounding solid material leads to a delayed recrystallization in the region of the clusters.
  • the clusters and the solid state material must have a
  • Transducers are already being used in heat assisted thermal writing for 25x25 nm 2 large memory cells.
  • Fig. 5 c, d) shows the modification of defined SiGeC nanostructures for the integration of photonics in the silicon and germanium technology.
  • the starting point is formed by existing GeC nanostructures, which were formed in segregated areas of the SiGeC layer of the surface layer (2 '), for example in the form of quantum dots and quantum pyramids.
  • Further thermal treatment modifies the GeC nanostructures to have anisotropic properties after modification.
  • anisotropic GeC nanostructures generate charge carriers by absorbing light. These photogenerated charge carriers can recombine and the light emitted thereby has its starting point in the GeC nanostructures and is preferably emitted in the direction perpendicular to the surface layer.
  • the wavelength of the emitted light (21) depends on the anisotropy of the GeC nanostructures, on radiative recombination centers, and on the position of quantized states on the energy scale in the GeC nanostructures.
  • anisotropic, optically active nanostructures is not limited to SiGeC structures.
  • Other mixed phase systems may consist of SiGeSn, SiSnC and GeSnC.
  • the forming nanostructures and the solid state material must have a different density, so that in the liquid phase
  • Nanostructures can move relative to the surrounding solid state material.
  • FIG. 6 shows the redistribution of components of one or more metallic multiphase systems in the surface layer (2m) by local thermal treatment under a process gas.
  • the areas to be thermally treated locally may be roughened or shadow or resist masks may be used. These areas are labeled 2ma.
  • the resulting metallic surface has regions of defined lateral composition variation and can be used as a substrate for the preparation of thin, locally n- or p-doped carbon materials
  • graphene, graphite can be used by surface doping.
  • Surface doping results in electron exchange between carbon layers and a dopant (contained in A, B, B 'or A') deposited on the surface layer (2m ') onto which the carbon materials, e.g. are prepared by CVD, see FIG. 6.
  • Fig. 7 illustrates the possibility of successively performing the deposition and thermal treatment of surface layers (2m ') on a substrate to prepare regions having different mixed phases (A, ⁇ ', B, B ', C, C).
  • regions having different mixed phases A, ⁇ ', B, B ', C, C.
  • Carbon materials are prepared. After the preparation of the
  • Carbon materials, these are detached from the surface layer and applied to a silicon substrate with a thermally or naturally grown silicon dioxide cover layer.
  • the surface layer (2m ') on crystalline (1 k) or amorphous substrate (1 a) may be flexible.
  • this method for the first time enables the surface doping of n- and p-doped regions in thin carbon materials.
  • Fig. 8 shows the redistribution of impurities in the layer (2f) by local
  • Litigation process (17) is stored.
  • the speed of the process control v P is preferably directed opposite to the speed of the process gas v G.
  • the process gas (20), the solid and the sample guide (17) are in a process chamber (18) arranged.
  • the local thermal treatment can take place via a transducer (16) and via an inlet window (19) in the process chamber (18) under a non-flowing and / or another flowing process gas.
  • the static pressure of a non-flowing process gas should preferably be above the triple point of the solid.
  • ) between the process gas v G and the sample guide v P and the flow of the process gas which determines the density of the process gas p G are
  • triple point of the solid lies.
  • oxygen, nitrogen, helium, argon or a mixture or compound with these substances and other noble gases can be used.
  • an oxygen-containing process gas should be selected in oxidic solids or a nitrogen-containing process gas in nitridic solids. This reduces evaporation and ablation effects during the thermal treatment and reduces the magnitude of a possible stoichiometric imbalance on the surface of the solid after thermal treatment.
  • the redistribution of the impurity atoms under a process gas is preferably used for the production of transparent conductive oxide layers on a flexible substrate in a roll-to-roll process.
  • the solubility of the foreign atoms in the liquid phase of the solid (ZnO: P) and the removal (annealing) of intrinsic, electrically active defects (V 0 ) by thermal treatment under a process gas only possible.

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Abstract

L'invention concerne des surfaces de solides fonctionnalisées présentant des composites à base de systèmes à deux ou à plusieurs composants, constitués de métaux, de semi-conducteurs et d'isolants ou d'atomes étrangers, qui présentent une composition chimique définie de l'ordre du nanomètre et du micromètre pour de nouvelles nanostructures et microstructures composites.
PCT/DE2012/200077 2011-11-22 2012-11-22 Surfaces de solides à base de systèmes à deux ou à plusieurs composants présentant des nanostructures composites, constitués de métaux, de semi-conducteurs ou d'isolants WO2013075712A1 (fr)

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CN112687359B (zh) * 2020-12-25 2024-02-09 华中科技大学 纳米电流通道层中绝缘绝热材料与纳米晶粒金属材料的筛选与匹配方法

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