Patent Application
20100221544
1. Field of the Invention
The present invention relates to nanoscale silicon particles, hydrogen terminated nanoscale silicon particles, alkyl terminated nanoscale silicon particles and partially alkyl terminated nanoscale particles, their production and their use.
2. Discussion of the Background
Nanoscale silicon powders are of great interest because of their special optical and electronic properties.
The continuous trend, in electronics and optoelectronics, to reduce device sizes down to nanometer scales has led to wide ranging scientific interest in nanoparticles.
The discovery of visible photoluminescence from silicon nanoparticles and nanowires is noteworthy because it raises the possibility of integrating light-emitting devices based on silicon with well-established microelectronics technology.
Because of the large surface/bulk ratio of nanoparticles, the surface properties of nanoparticles are of particular importance for their use in electronic devices.
Methods of producing nanoscale silicon particles have been reported in literature. An aerosol synthesis has been reported by Cannon and coworkers [W. R. Cannon et al., J. Am. Ceram. Soc. 65, 324 (1982), J. Am. Ceram. Soc. 65, 330 (1982)].
Thermal evaporation of silicon wafers by laser ablation [L. N. Dinh et al., Phys. Rev. B 54, 5029 (1996)] or CO2 laser pyrolysis of silane [M. Ehbrecht et al., Phys. Rev. B 56, 6958 (1997)] has also been used to produce nanoscale silicon particles.
Dislodging nanoparticles from porous silicon prepared by electrochemical etching of silicon wafers was reported by Belomoin et al. [G. Belomoin et al., Appl. Phys. Lett. 80, 841 (2002)].
Chemical vapor deposition has been used to produce nanoscale silicon particles on large scale [L. C. P. M. de Smet et al., J. Am. Chem. Soc. 125, 13916 (2003), S. Nijhawan et al., J. Aerosol Science 34, 691 (2003)]. However, the nanoscale silicon particles produced by chemical vapor deposition display pronounced inhomogenity in particle size and morphology [Dutta, W. et al., J. Appl. Phys. 77, 3729 (1995)].
Another approach to producing nanoscale silicon particles uses Zintl salts [R. A. Bley et al. J. Am. Chem. Soc. 118, 12461 (1996)].
Nanoscale silicon particles have been produced by pyrolysis of silane (SiH4). U.S. Pat. No. 4,661,335 describes an aggregated, largely polycrystalline silicon powder with a low density and a BET specific surface area of in a range of 1 to 2 m2/g. The polycrystalline silicon powder is obtained by pyrolysis of silane at temperatures in a range of 500° C. to 700° C. in a tubular reactor. However, the polycrystalline silicon powder produced in this fashion no longer meets present day requirements. Additionally, the pyrolysis process is not economical because the process results in a large content of unreacted silane.
Kuz min et al., Laser Physics, Vol. 10, pp. 939-945 (2000), describe the production of a nanoscale silicon product by means of laser-induced decomposition of silane at reduced pressure. Each individual particle of the powder thereby produced has a polycrystalline core of 3 to 20 nm and an amorphous covering with a diameter of up to 150 nm. No information is given regarding the surface of the silicon powder.
Li et al., J. Mater. Sci. Technol., Vol. 11, pp. 71-74 (1995) describe the synthesis of aggregated, polycrystalline silicon powder by laser-induced decomposition of silane in the presence of argon as diluent gas at atmospheric pressure. No information is given regarding the surface of the silicon powder.
Costa et al., Vacuum, Vol. 45, pp. 1115-1117 (1994) describe an amorphous silicon powder whose surface contains a large proportion of hydrogen. The silicon powder is produced by decomposition of silane by means of a radio-frequency plasma reactor in vacuo.
Makimura et al., Jap. J. Appl. Physics, Vol. 41, pp. 144-146 (2002) describe the production of hydrogen-containing silicon nanoparticles by laser attrition of a silicon target in vacuo in the presence of hydrogen and neon. No information is given as to whether the silicon nanoparticles exist in crystalline or amorphous form.
EP-A-680384 describes a process for the deposition of a non-polycrystalline silicon on a substrate by decomposition of a silane in a microwave plasma at reduced pressure. No information is given regarding the surface properties of the silicon.
Aggregated, nanoscale silicon powders have been produced in a hot-wall reactor [Roth et al., Chem. Eng. Technol. 24 (2001), 3]. A disadvantage of this process is that the desired crystalline silicon is produced together with amorphous silicon. The amorphous silicon is formed by reaction of the silane on the hot reactor walls. Additionally, the crystalline silicon has a low BET specific surface area of less than 20 m2/g and is thus generally too coarse for electronic applications.
Furthermore, the process described by Roth et al. does not produce doped silicon powders. Such doped silicon powders are, on account of their semiconductor properties, of great importance in the electronics industry.
A further disadvantage of the Roth et al. process is that the silicon powder is deposited on the reactor walls and acts as an insulator. As a result of the deposition of silicon on the reactor walls, the temperature profile in the reactor changes. This change in reactor temperature alters the properties of the produced silicon powder.
WO2005049491 ('491) discloses an aggregated, crystalline silicon powder with a BET specific surface area of more than 50 m2/g.
WO2005049492 ('492) discloses an aggregated, crystalline silicon powder with a BET specific surface area of more than 20 to 150 m2/g.
Although the silicon powders disclosed in the '491 and '492 applications show an improved resistance against oxidation and an improved defect density over the state of the art, there is still a need to improve these characteristics of nanoscale silicon particles.
It is one object of the present invention to provide nanoscale silicon particles which
It is another object of the invention to provide as-grown nanoscale silicon particles which have a paramagnetic defect density in the range of 1014 to 1016 l/mg.
It is a further object of the invention to provide as-grown silicon nanoparticles with a BET surface area in the range of 150 to 350 m2/g.
A fourth object of the invention is to provide the nanoscale silicon particles, according to the invention, in the form of aggregates.
A fifth object of the present invention is to provide a process to prepare the nanoscale silicon particles wherein
The process according to the invention comprises two embodiments to prepare the as grown-nanoscale silicon particles. They differ in that in the first one the oxygen is brought into the reactor before formation of the particles, while in the second process the oxygen is brought into the reactor after the formation of the particles.
A sixth object of the invention is to provide essentially hydrogen terminated nanoscale silicon particles having a paramagnetic defect density in the range of 1012 to 1016 l/mg. The hydrogen terminated nanoscale silicon particles are obtained by treating the nanoscale silicon particles with hydrofluoric acid.
A seventh object of the invention is to provide essentially hydrogen terminated nanoscale silicon particles with a paramagnetic defect density in the range of 1013 to 1015 l/mg.
Another object of the invention to provide is a process to prepare essentially hydrogen terminated nanoscale silicon particles having a paramagnetic defect density in the range of 1012 to 1016 l/mg. The essentially hydrogen terminated nanoscale silicon particles are prepared by treating the nanoscale silicon particles with hydrofluoric acid.
A further object of the invention is to provide essentially alkyl terminated nanoscale silicon particles having a paramagnetic defect density in the range of 3×1012 to 3×1016 l/mg. The essentially alkyl terminated nanoscale silicon particles are obtained by treating
Another object of the invention is to provide essentially alkyl terminated nanoscale silicon particles with a paramagnetic defect density in the range of 3×1013 to 3×1015 l/mg.
A further object of the invention is to provide a process to prepare essentially alkyl terminated nanoscale silicon particles having a paramagnetic defect density in the range of 3×1012 to 3×1016 l/mg wherein
Another embodiment of the invention is to provide a process to prepare essentially alkyl terminated nanoscale silicon particles having a paramagnetic defect density in the range of 3×1012 to 3×1016 l/mg.
An additional object of the invention is to provide partially alkyl terminated nanoscale silicon particles having a paramagnetic defect density in the range of 3×1012 to 3×10″ l/mg. The partially alkyl terminated nanoscale silicon particles can be obtained by treating the as-grown nanoscale silicon particles with at least one compound selected from at least one 1-alkene and/or at least one 1-alkyne.
Yet another object of the invention is to provide partially alkyl terminated nanoscale silicon particles having a paramagnetic defect density in the range of 3×1013 to 3×1015 l/mg.
A further object of the invention is to provide a process for preparing partially alkyl terminated nanoscale silicon particles having paramagnetic defect density in the range of 3×1012 to 3×1016 l/mg.
A more complete appreciation of the invention and the attendant advantages thereof will be readily obtained as the same become better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
(I) denotes as-grown nanoscale silicon particles,
(II) denotes essentially hydrogen terminated nanoscale silicon particles,
(III) denotes essentially alkyl terminated nanoscale silicon particles and
(IV) denotes partially alkyl terminated nanoscale silicon particles.
b) The ESR spectrum of the hydrogen-terminated particles of a) is magnified by a factor of four and the spectrum of essentially alkyl-terminated particles is included. An increase of the signal amplitude is observed. The spectrum of the essentially alkyl-terminated particles is significantly less noisy than the other ESR spectra shown. The reduction in noise is due to a longer measurement time and a larger amount of sample volume used for this measurement. Both factors were corrected for.
The term “nanoscale” is understood within the context of the invention to denote silicon primary particles having a mean diameter of less than 100 nm.
The term “as-grown” is understood to denote silicon particles prepared using a silane and hydrogen according to the present invention. There is no further treatment with hydrofluoric acid and/or alkenes or alkynes.
The term “essentially hydrogen terminated” is understood to denote silicon particles which have been additionally treated with hydrofluoric acid.
The term “essentially alkyl terminated” is understood to denote silicon particles which have been additionally treated with hydrofluoric acid and at least one alkene and/or at least one alkyne.
The term “partially alkyl terminated” is understood to denote silicon particles which have been additionally treated with at least one alkene and/or at least one alkyne.
The term “aggregate” is understood to mean that spherical or largely spherical primary particles, such as particles that are first formed in the reaction, coalesce to form aggregates during the further course of the reaction.
The term “doping component” is understood within the context of the invention to denote an element present in the powder according to the invention.
The term “doping substance” is understood to denote the compound that is used in the process in order to obtain the doping component.
The term “microwave range” is understood in the context of the invention to denote a range of 900 MHz to 2.5 GHz, a frequency of 915 MHz being particularly preferred.
One embodiment of the invention is nanoscale silicon particles which
In a preferred embodiment, the paramagnetic defect density of the as-grown nanoscale silicon particles is in the range of 1014 to 1016 l/mg.
In an another embodiment the BET surface area of the as-grown silicon nanoparticles is in the range of 150 to 350 m2/g.
In a preferred embodiment the nanoscale silicon particles according to the invention may be in the form of aggregates. The degree of coalescence of the aggregates can be influenced by the process parameters. These aggregates may form agglomerates during the further course of the reaction. In contrast to the aggregates, which as a rule cannot be decomposed, or only partially so, into the primary particles, the agglomerates form an only loose concretion of aggregates.
Furthermore the relative contribution of the dangling bond resonance of the nanoscale silicon particles according to the invention is in the range of 10 to 90%.
In addition the nanoscale silicon particles according to the invention may be doped. The following elements may preferably be employed as doping components: phosphorus, arsenic, antimony, bismuth, boron, aluminium, gallium, indium, thallium, europium, erbium, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, chromium, iron, manganese, silver, gold, holmium, thulium, ytterbium or lutetium. Most preferred are phosphorus, arsenic, antimony, boron, aluminium, gallium, chromium, iron, manganese, silver or gold. The proportion of these elements in the nanoscale silicon particles according to the invention may be up to 5 wt. %. As a rule a silicon powder may be desirable in which the doping component is contained in the ppm or even ppb range. A range of 1013 to 1015 atoms of doping component/cm3 is preferred.
In addition it is possible for the nanoscale silicon particles according to the invention to contain lithium or germanium as doping component.
Finally, the elements ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper and zinc may also be used as doping component of the silicon powder.
The doping component may in this connection be distributed homogeneously in the particles, or may be concentrated or intercalated in the covering or in the core of the primary particles. The doping components may preferably be incorporated at lattice sites of the silicon. This depends substantially on the nature of the doping substance and the reaction conditions.
Another embodiment of the present invention is a process to prepare the nanoscale silicon particles wherein
The process according to the invention comprises two embodiments to prepare the as grown-nanoscale silicon particles. They differ in that in the first one the oxygen is brought into the reactor before formation of the particles, while in the second process the oxygen is brought into the reactor after the formation of the particles.
The inert gas may be nitrogen, helium, neon or argon, argon being particularly preferred.
The oxygen may be in the form of O2 gas itself. Also O3 and/or NO might serve as an oxygen source.
Preferably the process according to the invention may be carried out in such a way that the starting materials are introduced into reactor in two streams, stream 1 consisting of hydrogen, optionally oxygen, and inert gas and stream 2 consisting of silane, optionally a doping substance and inert gas.
Within the context of the invention a silane may be a silicon-containing compound that yields silicon, hydrogen, nitrogen and/or halogens under the reaction conditions. SiH4, Si2H6, Cl2SiH3, Cl2SiH2, Cl3SiH and/or SiCl4 may preferably be used, SiH4 being particularly preferred.
The process according to the invention is carried out so that the proportion of silane, optionally with the inclusion of the doping substance, in the gas stream is in a range of 0.1 to 90 wt.-%. A high silane content leads to a high throughput and is therefore economically sensible. With very high silane contents however it became more difficult to achieve a high BET specific surface area. A silane content of in a range of 1 to 10 wt. % is preferred. The conversion of silane can be at least 98%.
A doping substance within the meaning of the invention may be a compound that contains the doping component covalently or ionically bonded and that yields the doping component, hydrogen, nitrogen, carbon monoxide, carbon dioxide and/or halogens under the reaction conditions. Particularly preferred are diborane and phosphane or substituted phosphanes such as tBuPH2, tBu3P, tBuPh2P or tBuPh2P and trismethylaminophosphane ((CH3)2N)3P.
The energy input is not limited. Preferably the energy input should be chosen so that the back-scattered, unabsorbed microwave radiation is minimal and a stable plasma is formed. As a rule, in the process according to the invention, the power input is in a range of 100 W to 100 kW, and particularly preferably in a range of 500 W to 6 kW. In this connection the particle size distribution may be varied by the radiated microwave energy.
The pressure range in the process according to the invention is in a range of 10 mbar to 300 mbar. In general a higher pressure leads to nanoscale silicon particles having a lower BET specific surface area, while a lower pressure leads to a silicon powder with a larger BET specific surface area.
The cooling of the reaction mixture may, for example, take place by an external wall cooling of the reactor or by introducing inert gas.
The processes of the invention result in the formation of the unique nanoscale silicon particles showing a high stability in air as well a high amount of reactive Si—H bonds.
Another embodiment of the invention is essentially hydrogen terminated nanoscale silicon particles having a paramagnetic defect density in the range of 1012 to 1016 l/mg obtained by treating the nanoscale silicon particles with hydrofluoric acid.
In a preferred embodiment the paramagnetic defect density of the essentially hydrogen terminated nanoscale silicon particles is in the range of 1013 to 1015 l/mg.
Another embodiment of the invention is a process to prepare essentially hydrogen terminated nanoscale silicon particles having a paramagnetic defect density in the range of 1012 to 1016 l/mg. To prepare the essentially hydrogen terminated nanoscale silicon particles, nanoscale silicon particles are treated with hydrofluoric acid.
The hydrofluoric acid preferably is an aqueous solution having an concentration in a range of 10 to 50 wt. %.
A further embodiment of the invention is essentially alkyl terminated nanoscale silicon particles having a paramagnetic defect density in the range of 3×1012 to 3×1016 l/mg obtained by treating
In a preferred embodiment, the paramagnetic defect density of the essentially alkyl terminated nanoscale silicon particles is in the range of 3×1013 to 3×1015 l/mg.
A further embodiment of the invention is a process to prepare essentially alkyl terminated nanoscale silicon particles having a paramagnetic defect density in the range of 3×1012 to 3×1016 l/mg, prepared by a process wherein
In a preferred embodiment of the invention, the process to prepare essentially alkyl terminated nanoscale silicon particles having a paramagnetic defect density in the range of 3×1012 to 3×1016 l/mg is carried out using the as-grown nanoscale silicon particles. The as-grown nanoscale silicon particles are treated in a one-pot reaction with hydrofluoric acid and at least one compound selected from at least one 1-alkene and/or at least one 1-alkyne. By using this process, side reactions, which may result in the formation of oxygen-containing defects like Si—OH, Si—O—Si and Si—O—C, are minimized.
Typically, hydrofluoric acid is added to suspension as-grown nanoscale silicon particles in at least 1-alkene and/or at least 1-alkyne. The suspension was then left to react for 1 to 10 hours at 80 to 150° C. In the next step the hydrofluoric acid and the remaining at least 1-alkene and/or at least 1-alkyne are removed by distillation at ambient pressure or reduced pressure, and the remaining residue is washed using an alkane. Examples of the alkane include pentane and hexane. The essentially alkyl terminated nanoscale silicon particles can be isolated by centrifuging, decanting and subsequent drying, in an inert atmosphere or in a vacuum.
Another embodiment of the invention is partially alkyl terminated nanoscale silicon particles having a paramagnetic defect density in the range of 3×1012 to 3×1016 l/mg obtained by treating the as-grown nanoscale silicon particles with at least one compound selected from at least one 1-alkene and/or at least one 1-alkyne.
In a preferred embodiment the paramagnetic defect density of the partially alkyl terminated nanoscale silicon particles is in the range of 3×1013 to 3×1015 l/mg.
Another embodiment the invention is a process to prepare partially alkyl terminated nanoscale silicon particles having a paramagnetic defect density in the range of 3×1012 to 3×1016 l/mg. In the process, the as-grown nanoscale silicon particles are treated with at least one compound selected from at least one 1-alkene and/or at least one 1-alkyne.
In an other embodiment the partially alkyl terminated nanoscale silicon particles having paramagnetic defect density in the range of 3×1012 to 3×1016 l/mg are prepared by a process wherein,
In a preferred embodiment the at least one 1-alkene and/or the at least one 1-alkyne used for treating the as-grown or essentially hydrogen terminated nanoscale silicon particles are selected from linear or branched 1-alkenes consisting of 3 to 25 carbon atoms and those consisting of 10 to 20 carbon atoms. Examples include: H2C═CH—(CH2)7—CH3, H2C═CH—(CH2)8—CH3, H2C═CH—(CH2)9—CH3, H2C═CH—(CH2)10—CH3, H2C═CH—(CH2)11—CH3, H2C═CH—(CH2)12—CH3, H2C═CH—(CH2)13—CH3, H2C═CH—(CH2)14—CH3/H2C═CH—(CH2)15—CH3, H2C═CH—(CH2)16—CH3, H2C═CH—(CH2)17—CH3.
The treatment of the as-grown or essentially hydrogen terminated nanoscale silicon particles according to the invention comprises radical induced hydrosilylation, thermally induced hydrosilylation, photochemical hydrosilylation or hydrosilylation mediated by metal complexes.
The treatment comprises using at least one 1-alkene and/or at least one 1-alkyne neat or dissolved in a solvent that is inert toward the reaction conditions. Usually the at least 1-alkene and/or the at least 1-alkyne is used in excess, referred to the nanoscale silicon particles.
Radical-induced hydrosilylation is preferably performed using peroxide type compounds that form radicals under reaction conditions, i.e. diacyl peroxide.
Thermally induced hydrosilylation is preferably performed using temperatures in the range of 100 to 300° C., more preferably the temperatures are in the range of 150 to 250° C.
The types of hydrosilylation are described in Buriak, Chem. Rev. 102, 1272 (2002), which is incorporated as reference.
A further embodiment of the present invention is the use of the as-grown, essentially hydrogen terminated, essentially alkyl terminated and partially nanoscale silicon particles for the production of electrical and electronic components, electronic circuits and electrically active fillers.
While hydrogen-terminated nanoscale silicon particles are found to be stable in ambient atmosphere for at least some hours, the resistance against degradation/oxidation with respect to the initial defect density can be further improved by alkyl termination. The improvement in resistance against degradation/oxidation by alkyl termination is significant, and is more than a factor of two times the resistance against degradation/oxidation of particles which have not been alkyl terminated.
HF etching was performed to produce essentially hydrogen terminated nanoscale silicon particles. In comparison to the as-grown nanoscale silicon particles, these show a decrease of the FTIR absorption intensity of the oxygen peaks at 1080 cm1 (caused by Si—O—Si moieties) and at 2250 cm1 (caused by H—Si—(O,O,O)), indicating the removal of an oxide sheath (
Alkyl termination was performed to produce essentially and partially alkyl terminated silicon nanoparticles by hydrosilylation. When as-grown silicon nanoparticles are hydrosilylated, the FTIR-absorption at 2100 cm−1 is decreased and a large increase of the C—H absorption bands around 2900 cm−1 is observed (partially alkyl terminated particles). The same behavior of the FTIR absorption bands is observed when hydrogen terminated silicon nanoparticles are hydrosilylated. The broad absorption line around 2100 cm−1 consists of several smaller peaks and shoulders. Based on the comparison to the well-known FTIR modes of H on crystalline silicon surfaces, the different vibration modes observed can be assigned to SiH3 (2134 cm−1), SiH2 (2102 cm−1) and SiH (2082 cm−1) vibrations.
The behavior of the hydrogen and alkyl terminated surfaces in ambient atmosphere were studied using ESR measurements on samples stored in air for different amounts of time. The ESR paramagnetic defect density of the essentially hydrogen and essentially alkyl terminated nanoscale silicon particles was normalized to the paramagnetic defect density of the as-grown nanoscale silicon particles of typically 4×10″ l/mg and is plotted in
The paramagnetic defect density of the essentially hydrogen terminated nanoparticles is typically reduced by one order of magnitude compared to the as-grown nanoscale silicon particles. Following hydrosilylation, the paramagnetic defect density of the essentially alkyl terminated nanoparticles is typically 1.2×10″ l/mg.
The ESR spectrum of the hydrogen-terminated nanoscale silicon particles is shown in
The ESR lineshape both of the essentially hydrogen terminated and of the essentially alkyl terminated particles stays mainly unaltered during exposure to air for air for one week apart from a growth of the overall ESR amplitude. However, the powder pattern reappears for the hydrogen-terminated particles after one week storage which indicates that the surface becomes oxidized again.
Relative to their initial paramagnetic defect density, the alkyl-terminated nanoscale silicon particles are more resistant against oxidation in ambient atmosphere than the hydrogen-terminated particles.
The present invention is described by way of example in the Examples hereinafter. Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
The BET surface (Brunauer, Emmett, and Teller surface) is determined according to DIN 66131.
For the electron spin resonance (ESR) measurements, approximately 3 mg of the differently terminated nanoscale silicon particles each were filled into teflon tubes, which were sealed with teflon tape. These teflon tubes were then put inside standard ESR quartz tubes with an outer diameter of 4 mm. Room temperature ESR measurements were performed in a conventional cw X-band ESR spectrometer (Bruker ESP-300, with a TE102 cavity) operating at 9.27 GHz. Phase-sensitive detection and a magnetic field modulation amplitude of 2 Gauss were used.
ESR is used to determine the paramagnetic defect density. The number of paramagnetic defects is calculated from the ESR resonance by double integration and comparison to a known reference standard, phosphorous-doped silicon.
Fourier-transform infrared (FTIR) spectroscopy was performed to study the chemical composition of the particles. Nanoparticles were dispersed in dried spectroscopic grade KBr by the pressed-disk technique.
Apparatus: A microwave generator (Muegge company) is used to produce a plasma. The microwave radiation is focused in the reaction space by means of a tuner (3-rod tuner). A stable plasma is generated in the pressure range from 10 mbar up to 300 mbar and at a microwave output of 100 to 6000 W by the design of the wave guide, the fine adjustment by means of the tuner and the accurate positioning of the nozzle acting as electrode. The microwave reactor consists of a quartz glass tube of 30 mm diameter (external) and a length of 120 mm, which is employed in the plasma applicator.
An SiH4/argon mixture (mixture 1) of 100 sccm (standard centimetre cube per minute; 1 sccm=1 cm3 gas per minute referred to 0° C. and atmospheric pressure) of SiH4 and 900 sccm of argon as well as a mixture of 10000 sccm of each of argon and hydrogen and 5 sccm of oxygen, are fed to the microwave reactor. An output of 500 W from a microwave generator is fed to the gaseous mixture and a plasma is thereby produced. The plasma flare leaving the reactor through a nozzle expands into a space whose volume of ca. 20 l is large compared to the reactor. The pressure in this space and in the reactor is adjusted to 200 mbar. The particles are separated from gaseous substances in a downstream-connected filter unit.
BET: 170 m2/g
TEM: Transmission electron microscopy (TEM) shows that the nanoparticles have a mean diameter of 20 nm and consist of a round, mostly unfacetted crystalline silicon core surrounded by an amorphous shell of SiO2 (
FTIR: A very broad peak around 1080 cm−1 and a peak at 1180 cm−1 are found in the IR absorbance spectrum (
In addition to the evidence from FTIR concerning the location of the Si—H bonds, the high structural quality evident from the TEM picture in
ESR: The results of the ESR measurements of the as-grown nanoscale silicon particles are shown in
(i) The dominant paramagnetic defects of the nanoscale silicon particles according to the invention at the crystalline Si/SiO2 interface are silicon dangling bonds similar to the so called Pb-, Pb0- and Pb1-centers, at the Si/SiO2 interface of crystalline silicon. As the nanoscale silicon particles are oriented arbitrarily with respect to the external magnetic field, these centers contribute to the ESR resonance line in the form of a powder pattern. A powder pattern with g∥=2.0018 and g⊥=2.0091 is included in
(ii) Also at crystalline Si/SiO2 interfaces, isotropic resonances caused by dangling bonds at structural imperfections are often observed with a g-factor of gdb=2.0053 and a linewidth of ΔBpp=6-8 G. In contrast to the Pb-centers, this defect is called dangling bond at Si/SiO2 interfaces. Similarly, the dangling bond signal in amorphous silicon appears at a g-factor of g=2.0055 with a linewidth of ΔBpp=5-7 G. For microcrystalline silicon a g-factor of g=2.0052 was reported. To be able to simulate the ESR spectra observed for the nanoscale silicon particles, a similar Gaussian line with gdb=2.0052 and ΔBpp=6 G has to be included in the deconvolution [J. L. Cantin, H. J. von Bardeleben, J. Non-Cryst. Solids 303, 175 (2002)].
(iii) The weak narrow Gaussian line at gE′=2.0007 with a linewidth of ΔBpp=1.5 G is due to E′-centers inside the quartz glass sample holder. The total fit, which is the sum of the three contributions discussed, matches the experimentally observed resonance lineshape very well as it can be seen in
For the as-grown nanoscale silicon particles a total paramagnetic defect density of typically 4.0×1014 l/mg is observed. However, depending on the exact growth conditions, this concentration can also be as small as 1013 l/mg or as large as 1017 l/mg. Assuming the paramagnetic defect density of the nanoscale silicon particles is assumed to be the density of bulk crystalline silicon, 2.33 g/cm3, this results in a paramagnetic defect density in the range of 2×1016 to 2×1020 cm−3. The relative contribution of the dangling bond resonance is typically 30% in as-grown samples, but can be as small as 10% and as large as 90%.
For the hydrogen termination, 100 mg of nanoscale silicon particles prepared in example 1 were immersed into 1 ml liquid HF (50% in H2O). Washing out the HF was done by adding 10 ml H2O, centrifuging at 13 000 rpm for five minutes and decanting the water/HF mixture. This cleaning process was repeated three times. Finally, the essentially hydrogen terminated nanoscale silicon particles according to the invention were dried in a stream of N2.
FTIR: In comparison to the as-grown particles, both the peaks at 1080 cm−1 and at 2250 cm−1 have clearly decreased in intensity but have not disappeared completely indicating some remaining oxide or native oxide freshly grown after the HF treatment on the surface (
ESR: The ESR spectrum of the essentially hydrogen-terminated nanoscale silicon particles is shown in
Alkyl termination was achieved by thermally-induced hydrosilylation by immersing 100 mg of nanoscale silicon particles prepared in example 1 in 0.5 ml HF (50% in H2O), adding 2 ml of 1-octadecene and heating the particles under permanent stirring and bubbling with N2 for 90 minutes at 150° C. Subsequently, the samples were Washed five times in hexane and tetrahydrofuran (10 ml), again by centrifuging and decanting, before they were dried with N2.
Alkyl-terminated surfaces can also be produced without adding HF during the hydrosilylation. In this case, the 100 mg of nanoscale silicon particles prepared in example 1 were immersed directly in 2 ml of 1-octadecene and further treated as in example 3.
FTIR: The FTIR spectra of the octadecanyl-terminated nanoscale silicon particles of example 3 and 4 are shown in
a),b) show that only H—Si—(Si,Si,Si) takes part in the hydrosilylation, while the concentration of H—Si—(O,O,O) remains effectively unchanged. This is most likely caused by the respective localization of the different Si—H bonds in the nanoparticles. While most of the H—Si—(Si,Si,Si) bonds are expected to be at the surface, the H—Si—(O,O,O) are likely to be in the oxide sheath and therefore not accessible for hydrosilylation.
ESR: The ESR spectrum of the 1-octadecanyl-terminated nanoscale silicon particles of example 3 is displayed in
The paramagnetic defect density of the hydrosilylated particles is increased by a factor of about three relative to the hydrogen-terminated samples. Depending on the exact process conditions, the paramagnetic defect densities can be as small as 3×1012 and as large as 3×1016 mg−1, corresponding to 6×1015 to 6×1019 cm−3. In these samples, both the powder pattern (i) and the dangling bond signal (ii) contribute approximately equally to the paramagnetic defect density.
After preparation, the samples were stored for various times in ambient atmosphere and then characterized by FTIR measurements. In
During storage in air, the paramagnetic defect density of essentially hydrogen terminated samples increases by a factor of 2.5 within one week, while it increases by only a factor of 1.25 in the alkyl terminated samples during the same time.
The above written description of the invention provides a manner and process of making and using it such that any person skilled in this art is enabled to make and use the same, this enablement being provided in particular for the subject matter of the appended claims, which make up a part of the original description.
As used above, the phrases “selected from the group consisting of,” “chosen from,” and the like include mixtures of the specified materials.
All references, patents, applications, tests, standards, documents, publications, brochures, texts, articles, etc. mentioned herein are incorporated herein by reference. Where a numerical limit or range is stated, the endpoints are included. Also, all values and subranges within a numerical limit or range are specifically included as if explicitly written out. Terms such as “contain(s)” and the like as used herein are open terms meaning ‘including at least’ unless otherwise specifically noted.
The above description is presented to enable a person skilled in the art to make and use the invention, and is provided in the context of a particular application and its requirements. Various modifications to the preferred embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the invention. Thus, this invention is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein.
| Number | Date | Country | Kind |
|---|---|---|---|
| 05 019 174.1 | Sep 2005 | EP | regional |
This application claims priority to provisional U.S. Application No. 60/714,842, filed Sep. 8, 2005, and European Application No. 05019174, filed Sep. 3, 2005, both of which are incorporated by reference in their entirety.
| Number | Date | Country | |
|---|---|---|---|
| 60714842 | Sep 2005 | US |
