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  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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  • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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  • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

Definitions

• the present invention relates to a method for the manufacture of a silicon polytype material and to a silicon polytype material, e.g. a silicon polytype material made by the method.
• silicon is a natural candidate for making technological use of the interaction between photons and electrons.
• the indirect bandgap transition characteristics of silicon often makes it an inefficient emitter of light and thus inappropriate for demanding optoelectronic applications.
• Substantial efforts have been made in the past to enhance its luminescence. These efforts include fabricating low-dimensional architectures, for example as described in the papers by Wilson, W. L., Szajowski, P. F. & Brus, L. E. "Quantum confinement in size-selected surface oxidized silicon nanocrystals" in Science 262, 1242-1244 (1993), by Lu, Z. H., Lockwood, D. J. 85 Baribeau, J.
• Twinning superlattice structures are described in detail with respect to silicon and other materials in the paper by Ikonic, Z., Srivastava, G. P. 8& Inkson, J. C. "Electronic properties of twin boundaries and twinning superlattices in diamond-type and zinc-blende-type semiconductors" in Phys Rev. B 48, 17181-17193 (1993) and with respect to germanium in the paper by Ikonic, Z., Srivastava, G. P. 8 ⁇ Inkson, J. C. "Direct optical transitions in indirect semiconductors: The case of Ge twinning superlattices" in Phys Rev. B 52, 1474-1476 (1995).
• the object of the present invention is to provide a method of manufacturing a silicon polytype material which has an almost direct bandgap as well as a silicon polytype material of this kind with the method being relatively simple, economical and capable of use on a large scale with a good yield and with the silicon polytype material having an almost direct bandgap and likewise being capable of being produced simply and in relatively large quantities at low cost.
• a method of manufacturing a macroporous silicon polytype material comprising the steps of:
• step c) subsequently treating the resultant product in an acid to remove any excess metal and metal compound resulting from step b) and leave a macroporous silicon polytype material.
• the silicon compound is preferably at least one of SiO2 and SiN.
• the nanopowder of the silicon compound typically has a diamond structure and is for example a silicon dioxide nanopowder supplied by Sigma- Aldrich 89552 St Germany under the product designation 637246 with 5 to 15nm BET and 99.5 % metals basis, although other silicon compound nanopowders can also be used, i.e. nanopowders with particle sizes in the range from 1 nm to 1 ⁇ m.
• the metal nanopowder is preferably magnesium and in the experiments carried out so far magnesium powder obtained from the company Alfa Ae- sar GmbH 8B CO Kg 76057 Düsseldorf Germany with the product designation 010233L 14803 of -325 mesh size and 99.8% purity was used, although other magnesium or aluminium nanopowders, for example in the size range from 1 nm to 1 ⁇ m, could also be used.
• the acid used for the step c) is preferably HCl, typically 10% HCl but could be another acid such as HNO3, typically 10% HNO3.
• the method may also comprise the further step d) of treating the silicon polytype material of step c) with a further acid to remove a surface oxide layer.
• This step can, if required, be carried out at a later stage, for example when the silicon polytype material of step c) has acquired a native oxide layer or includes residual oxide material, for example immediately prior to use of the silicon polytype material in an electronic or photoluminescent application.
• HF is normally used to remove the oxide or nitride layer from the silicon polytype material.
• the temperature range for step b) is selected to lie in the range 700 0 C to 1000 0 C and most preferably in the range 800°C to 950°C.
• the pressure of the gas atmosphere in the method step b) is conveniently a relatively low pressure, for example in the range from 0.5 bar to 10 bar, especially in the range from 0.8 bar to 1.2 bar.
• the inert gas atmosphere used for step b) preferably includes a further gas or gaseous compound adapted to reduce the silicon compound such as H2 or NH3.
• the result of method step c) is a silicon polytype material which can be described as a 3-dimensional (3D) macro- porous 9 R Si polytype with native surface oxidation, which exhibits a different electronic structure than bulk diamond- structured Si.
• the conduction band minimum in the material made by the method of the invention significantly shifts towards the T point, indicating less momentum transfer required to fulfil the bandgap transition. It is particularly beneficial that to obtain the desired morphology a relatively straightforward synthesis process by magnesiothermic reduction of silica nanoparticles at temperatures in the range indicated facilitates the formation of a 3D macroporous structure as well as the 9R Si polytype growth leading to the distinct electronic property.
• the desired almost direct bandgap is achieved by producing the porous silicon material of 9R polytype and indeed with pores preferably in the range from 100 to 300nm, although pore sizes which are slightly larger or smaller are acceptable particularly since the pore size distribution typically approximates to a Gaussian distribution determined by the particle size of the magnesium or aluminium powder that is used.
• the heating step b) is strongly exothermic and can lead to local heating of the mixture. It is believed that the 9R polytype material actually only arises at temperatures above 650 0 C; however, due to local hot spots heating to 500 0 C can lead to the formation of some re- gions of 9R polytype material. It is preferable if the temperature can be maintained in the range from 800 0 C to 950 0 C since then a high yield of 9R polytype material results with little and preferably no material of bulk diamond structure. Heating to temperatures above 950 0 C is problematic because it is close to the melting point of silicon and can result in destruction of the desired 9R polytype material, particularly at any local hot spots that may occur due to the exothermic nature of the reaction.
• the MgO /Si composites generated by this reaction retained the three dimensional cylindrical morphology and nanoscale features of the Aulaco- seira frustules. After immersion in a IM HCl solution for four hours the selective and complete dissolution of the magnesia took place and the resulting silicon based product retained the 3D morphology and nanoscale features of the Aulacoseira frustules.
• Bao Z. et al. Although the method proposed by Bao Z. et al. initially seems to resemble the method of the present invention there are actually many significant differences.
• gaseous Mg instead of Mg nanopowder and biological silica structures rather than silica nanopowder with a structure of the bulk diamond type.
• Bao et al. conduct their process at a low temperature of 650 0 C, i.e. above the melting point of Mg which is significantly less than the preferred temperature range of 800 to 950 0 C for the present invention.
• the silicon polytype material resulting from the method of the present invention is macroporous, meaning that it has pores predominantly in the size range above 50nm, typically an average pore size of 200nm with a generally Gaussian distribution extending from about 100 to 300nm.
• pore sizes less than lOOnm are possible if the magnesium powder is made correspondingly smaller and could be beneficial. Also larger pore sizes up to l ⁇ m are considered to be practical and useful.
• Figs. Ia and Ib schematic diagrams of the structures offering possibilities for band structure modification of Si crystal.
• the Si atoms are shown as grey circles with Fig. Ia showing a surface oxidized porous structure with high surface to volume ratio (SVR); the black dots indicates oxygen atoms and with Fig. Ib showing a twinning superlattice structure with twinning planes marked by dotted lines. The crystal orientation is reversed at these planes,
• Figs. 2a to 2c the morphology of the 3D macroporous Si polytype of the present invention with Fig. 2a showing a bright field (BF) micrograph showing the interconnected macroporous structure, Fig.2b showing a HRTEM micrograph with the corresponding SAD (selected-area electron diffraction) pattern shown in the inset revealing the polytype superstructure and with Fig. 2c showing a Wiener-filtered HRTEM micrograph magnified from the region marked in Fig. 2b together with the corresponding diffractogram demonstrating the 9R polytype structure.
• a schematic of the 9R stacking sequence is shown in the insert at the top right of Fig. 2c,
• FIGs. 3a to 3c structural and chemical investigation of the macroporous polytype Si before exposure to the HCl solution
• Fig. 3a showing a schematic illustration for the formation of the Si 3D structure with MgO is displayed as grey spheres and polyhedra
• Fig. 3b showing a BF micrograph
• Fig. 3c showing an elemental mapping of the same region as presented in Fig. 3b using the characteristic volume-plasmon energy-losses of MgO and Si to verify the macroporous polytype structure evolution
• the cavities shown as dark patches originate from the void space occupied by the MgO products prior to the reaction with the HCl solution and the light grey areas show the Si material
• Figs. 4a to 4c diagrams confirming a bandgap transition of the natively surface-oxidized 3D macroporous 9R Si polytype with significantly less momentum transfer requirement in comparison to diamond- structured Si, with Fig. 4a showing a 9R-Si diffraction pattern in [110] orientation showing the two positions (dotted circles) at which DF VEELS spectra in Fig.
• Figs 5a to 5c schematic band structures of unfolded (Fig. 5a), one time folded (Fig. 5b) and two times folded superlattice systems (Fig. 5c) with the dashed lines being drawn to facilitate comparison and with E g and k stand for the bandgap energy and the required momentum transfer respectively,
• Fig. 8 a table showing the composition extracted from EDX analyses of the 9R Si polytype after HCl solution treatment, the uncertainty is the statistical error of the peak counts of the two species
• Fig. 9 the microstructure of Si materials synthesized at 650 0 C, which is close to the melting point of metallic Mg, the other growth parameters were unchanged, the material contains mainly diamond- structured Si as revealed by the lattice fringes extending outside the 9R Si polytype
• Fig.10 a simulated map of the energy loss versus electron momentum of a diamond- structured Si specimen with a thickness of 30 nm and an incident electron energy of 200 keV, the Cerenkov losses associated with the surface modes occur mainly at a momentum transfer range below 40 pm 1 .
• a natively surface-oxidized porous structure which is shown as a schematic in Fig. Ia, provides a high surface area to volume ratio (SVR) as well as a stable surface environment.
• SVR surface area to volume ratio
• the white area in the middle of Fig. Ia shows a pore of the porous structure.
• semiconductor polytypes which can be viewed as a special class of twinning superlat- tices, offer the possibility to modulate band structures depending on the stacking sequences of the materials (Figs.
• the twin boundary between the two crystal orientations provides a perfectly lattice-matched interface, which addresses the critical enquiries on the long-term stability due to the presence of excessive strain.
• the 3-dimensional (3D) macropor- ous structure enables further enhancement of the luminescence resulting from both quantum confinement and surface termination effects, thus the optical efficiency for room-temperature operation can be further improved.
• the silicon material of the present invention is an initially natively surface-oxidized 3D macroporous silicon polytype, namely the 9R structure, which possesses a bandgap transition with significantly less momentum transfer requirement in comparison to diamond- structured Si.
• the folding-mediated transition mechanism, quantum confinement and surface termination effects contribute conjunctively to its distinct electronic property.
• Evidence is available from the valence electron energy-loss spectroscopy measurements (VEELS) and associated imaging techniques in a transmission electron microscope (TEM), i.e. the SESAM microscope as described in the paper by Koch, C. T. et al. "SESAM: Exploring the frontiers of electron microscopy" in Microsc. Microanal.
• the present invention has allowed the fabrication of 3D macroporous Si 9R polytypes by magnesio thermic reduction of silica nanoparticles at temperatures above 500 0 C and particularly with a good yield at temperatures above 650 0 C and especially in the range from 800 to 950°C.
• FIGs. 2a to 2c shows the microstructure of the natively surface-oxidized 3D macroporous 9R Si polytype.
• a bright-field (BF) transmission electron micrograph (Fig. 2a) demonstrates the interconnected macroporous structure with pore diameters ranging from 100 to 300 nm. This is confirmed by the scanning electron micrograph shown in Fig. 6.
• the chemical composition was measured by energy-dispersive X- ray spectroscopy (EDX) over a large region and more than 93 at.% of Si and less than 7 at.% of O after absorption corrections were detected (Fig. 7 and the table of Fig. 8) .
• EDX energy-dispersive X- ray spectroscopy
• the high-resolution transmission electron microscopy (HRTEM) micrograph (Fig. 2b) and selected-area electron diffraction (SAD) patterns (insert of Fig. 2b) reveal the 9R polytype superstructure. Compared to the diffraction pattern of diamond- structured Si, two extra diffraction spots are detected between the 000 and 009 reflections, the latter one overlapping with the diamond- structured Si ⁇ 111 ⁇ reflections.
• Fig. 3a shows a schematic of the formation of the 3D macroporous polytype structure.
• the angle between the planes was measured to be about 107.5°, close to the theoretical angle of 109.5° between the (111) and (l ⁇ ⁇ ) planes.
• the elemental mapping shown in Fig. 3c shows the MgO spheres and polyhedra embedded in the Si matrix of sizes comparable to the cavities as shown in Fig. 2a. This provides strong evidence that the macroporous structure is essentially deduced from the void space after removal of MgO by the HCl solution.
• Valence electron energy-loss spectroscopy establishes a direct link between the local electronic structure and spectroscopic features with both high spatial and angular resolution.
• understanding the indirect band transition characteristics of Si by VEELS analyses requires profound pre-knowledge.
• DF VEELS was performed using different momentum transfer ranges at positions 1 and 2 indicated by the dotted circles in the [HO]- oriented diffraction pattern (Fig. 4a) using a collection aperture diameter of about 0.8 nm 1 . Both positions, with the center of the collection aperture located at 0.5 and 1.3 nnr 1 respectively, are sufficiently far from the T point (> 100pm- 1 ) in order to avoid spectral artefacts (see Fig. 10).
• DF VEELS acquired from diamond-structured Si at similar positions in reciprocal space, along F-X direction at 0.5 and 1.3 nm 1 respectively, exhibits a very different spectral behavior.
• the indirect band- gap onset at 1.1 eV is only detected with fairly large momentum transfer at position 2, in accordance with its band structure for the indirect transi- tion close to the X point.
• interband transitions other than the bandgap transition at the X point dominate and the onset of interband transitions is shifted to higher energies.
• the as-grown powder is etched with HCL to remove any Mg and Mg- compounds remaining in the as-grown powder, to further purify the as- grown powder.
• the as-grown powder can be placed into a centrifuge with ethanol or, any other kind of solvent to separate the as- grown powder from the HCL. This process can be repeated for 3 to 5 times to make sure, that an HCL free powder is obtained.
• the as-grown powder After the as-grown powder has been etched with HCL and possibly been placed into a centrifuge to remove any remaining HCL in the as-grown powder, the as-grown powder can either be packaged for sale, or it can be further purified by being placed into an HF solution as described above. If the powder is intended for sale, it may not be etched using HF to prevent to an unnecessary loss of the overall yield of the twinning superlattice structure due to surface oxidation.
• the as-grown powder can again be placed into a centrifuge this time with de-ionized water or, any other kind of solvent to separate the as-grown powder from the HF. This process can also be repeated for 3 to 5 times to make sure, that an HF free powder is obtained.
• This powder can then be transferred to its intended use which can be, for example, the embedding of the obtained nanocrystals into a matrix which can then provide a platform for potential optoelectronic applications, as is disclosed in the publication by Pavesi, L., Dal Negro, L., Mazzoleni, C, Franz ⁇ , G. & Priolo, F. Optical gain in silicon nanocrystals. Nature 408, 440-444 (2000).
• the as-grown powder can be placed into a vacuum oven (Ley- bold Hereaus) and dried, for example, at 80 0 C and at approximately 10 to 20 mbar to obtain a dried as-grown powder.
• the initial Mg and SiO2 powder size used was approximately 100 nm.
• This mixture (dark gray) with excessive Mg was then transferred into a tube furnace for heat treatment under an Ar (95 vol.%) / H2 (5 vol.%) atmosphere at 650 0 C for 12 h.
• the heating rate was kept at 5 K/min.
• the as-grown powders (black) were first immersed in a IM HCl solution for 12 hours at room temperature to remove MgO. Following the etching with HCL, the as-grown powders were placed into a centrifuge to separate them from any residual MgO and/ or Mg followed by the etching off SiO2 using the HF (20%) solution for pure silicon.
• the HF etching process was conducted in an argon-filled glove box, where both oxygen and H2O levels were below 1 ppm.
• the resulting powder was then washed with de-ionized water or, any suitable liquid such as ethanol to separate the as-grown powders from the HF. This process can also be repeated for 3 to 5 times to make sure, that an HF free powder is obtained.
• the surface morphology was investigated using a JEOL 6300F field-emission scanning electron microscope (JEOL, Tokyo, Japan) operated at 15 keV.
• TEM specimens were prepared by dispersing the materials in ethanol followed by sample collection using carbon lacey films.
• HRTEM High-resolution transmis- sion electron microscopy
• JEOL 4000EX transmission electron microscope JEOL, Tokyo, Japan operated at 400 keV.
• the interpretable resolution defined by the contrast transfer function of the objective lens is 0.16 nm.
• Energy-dispersive X-ray spectroscopy (EDX) analysis was carried out using an EDAX system (EDAX, Mahwah, NJ, USA) attached to the Zeiss SESAM microscope (Carl Zeiss, Oberko- chen, Germany) operated at 200 keV.
• EDAX Energy-dispersive X-ray spectroscopy
• Mahwah, NJ, USA EDAX system
• Zeiss SESAM microscope Carl Zeiss, Oberko- chen, Germany
• EFTEM elemental mapping an energy- selecting slit of 0.9 eV was used to obtain the material chemical information.
• DF VEELS spectra were acquired in diffraction mode with a spectrometer entrance aperture of about 0.8 nm" 1 in diameter for the selection of the momentum transfer range.
• Figs 5a to 5c Schematic band structures of unfolded, one time folded and two times folded superlattice systems are shown in Figs 5a to 5c.
• formation of twinning superlattices provides another method to achieve folding-mediated quasi-direct bandgap transtions in indirect semiconductors.
• Polytype superlattices which can be viewed as a special class of twinning superlattices, possess potential band-folding capabilities.
• the band structures of polytype Si materials have been discussed previously, where the bottom of the conduction band clearly shifts from the M point towards the r point as the structure transforms from diamond structure to 6H polytype.
• the field-emission (scanning) transmission electron microscope SESAM Carl Zeiss, Oberkochen, Germany
• SESAM Carl Zeiss, Oberkochen, Germany
• EFTEM valence energy-filtered transmission electron microscopy
• the energy resolution of the microscope defined by the full-width-at-half-maximum (FWHM) of the zero-loss peak is below 90 meV for routine applications.
• the in-column MANDOLINE energy filter provides high dispersion, high transmissivity and high isochro- maticity.

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