Porous silicon nanocrystals in a silica aerogel matrix
© Amonkosolpan et al.; licensee Springer. 2012
Received: 27 April 2012
Accepted: 5 July 2012
Published: 17 July 2012
Silicon nanoparticles of three types (oxide-terminated silicon nanospheres, micron-sized hydrogen-terminated porous silicon grains and micron-size oxide-terminated porous silicon grains) were incorporated into silica aerogels at the gel preparation stage. Samples with a wide range of concentrations were prepared, resulting in aerogels that were translucent (but weakly coloured) through to completely opaque for visible light over sample thicknesses of several millimetres. The photoluminescence of these composite materials and of silica aerogel without silicon inclusions was studied in vacuum and in the presence of molecular oxygen in order to determine whether there is any evidence for non-radiative energy transfer from the silicon triplet exciton state to molecular oxygen adsorbed at the silicon surface. No sensitivity to oxygen was observed from the nanoparticles which had partially H-terminated surfaces before incorporation, and so we conclude that the silicon surface has become substantially oxidised. Finally, the FTIR and Raman scattering spectra of the composites were studied in order to establish the presence of crystalline silicon; by taking the ratio of intensities of the silicon and aerogel Raman bands, we were able to obtain a quantitative measure of the silicon nanoparticle concentration independent of the degree of optical attenuation.
Keywordsporous silicon nanoparticle luminescence Raman silica aerogel oxygen energy transfer 78.66.Jg 78.67.-n 78.67.Bf
Silica aerogels are rigid, highly meso-porous structures with pores on the scale of about 10 to 50 nm with a range of extreme properties: these include low refractive index (1.02 to 1.05 compared to 1.46 for bulk silica in the green spectral region), low density (greater than 90% air by volume), high optical transparency and low thermal conductivity. They have recently been demonstrated to provide a gas-permeable support for many types of nanoscale materials (metal nanoparticles, dye molecules, or semiconductor nanoparticles; see, for example, [1–4]) and, thus, are of potential interest for applications such as catalysis , sensing, photochemistry and coherent anti-Stokes Raman . Aerogels are readily prepared from the liquid phase in arbitrary shapes and large volumes and so provide the possibility of long path lengths (of, quite easily, several centimetres) for light interacting with any embedded, optically active nanoparticles.
Porous silicon (PSi) grains may be formed by very diverse means: these include the electrochemical etching of bulk single-crystal substrates  followed by pulverisation of the etched layer or, as for all the porous particles here, the stain etching of macroscopic silicon powder grains . Depending on the details of the etching process, the etched pores can be selected to be in the micro-, meso- or macro-porous range (approximately 2, 2 to 50, and > 50 nm respectively). By these routes, very large surface area to volume ratios may be obtained. The porous silicon surface can be prepared with hydride (Si-H) or oxide (Si-O-Si) termination, or thermally hydrosilylated to facilitate anchoring of a wide range organic molecules . The presence of quantum-scale crystalline silicon particles leads to optical emission bands which can be tuned through the visible and near-IR spectral range and which can easily dominate the optical response of the composite material [9, 10]. Furthermore, energy transfer via excitons within the porous silicon nanoparticles (PSi NPs) to chemical species adsorbed on (or bonded to) the NP surface has been demonstrated for a number of chemical species [11–13]; this process gives the potential for a connection between optical excitation of the composite and gas-phase chemistry within the silica pores.
However, only a few studies have been carried out on aerogel-silicon nanoparticle composites, and the main focus has been on Si nanoparticles (rather than porosified Si grains) aimed at optoelectronic applications  though some composites have been produced by pressing pellets of mixed PSi and aerogel . Some basic questions must be answered before applications of such composites can be addressed. Is it possible to prepare a silica aerogel with embedded nanoscale or PSi particles by conventional aerogel synthesis routes? Does the resulting NP concentration depend upon the starting proportions in a controllable way, and can it be determined conveniently? What is the oxidation state of the PSi particles after preparation? How are the optical properties of the composite related to those of the independent materials? Here, we consider these questions.
Metallurgical grade silicon grains of typical size around 4 microns were made porous via stain etching  to produce grains with a bulk silicon core and a porous silicon nanoparticle shell (we label these PSi NPs) with initially hydride-terminated surfaces. These were stored for several months in ambient conditions, and a significant amount of the surface will have oxidised, but as we shall show, they still display efficient energy transfer to oxygen, which demonstrates that some hydride-terminated surface remains , and we label these LH. A batch of these PSi NPs was deliberately oxidised to produce fully oxide-terminated surfaces (labelled LO); in both cases, we mean by oxidised that there is at least a monolayer of oxygen atoms back-bonded to the silicon atoms at the surface .
Nanoscale spherical silicon particles (Si NS) were produced in a microwave-supported plasma reactor  followed by etching to reduce their sizes to the point where quantum confinement effects lead to visible photoluminescence ; those used here had predominantly oxide-terminated surfaces (labelled SO).
Silica aerogels were prepared by a conventional one-step base-catalyst sol–gel process (described in more detail elsewhere ) so as to obtain a hydrophilic surface, and they were dried in supercritical CO2. PSi NPs or Si NSs in colloidal suspension were introduced into the mixture before the gel formation stage in concentrations from zero to 0.34 mg/ml. The potential problem of particle aggregation has also been considered for the case of Au particles ; we observe, however, that Si NP aggregation in ethanol is less severe than the case of Au. Blocks of aerogels were produced with dimensions of approximately 10 × 10 × 20 mm and were highly transparent if prepared without Si NPs. Aerogels containing particles of LO type were brown in colour, indicating a broad absorption spectrum in the visible range and, therefore, suggesting the presence of PSi. On the other hand, aerogels containing particles of LH type were grey black, hinting that much of the porous structure had been oxidised in preparation (the starting powder was brown coloured). Samples containing Si NSs were pale yellow to brown (with the exact colour depending on concentration), indicating again that Si NSs were present in the final composite.
Photoluminescence (PL) measurements were carried out at room temperature in vacuum, with continuous wave 325-nm excitation; low excitation densities in macro-sampling were used, and the PL was detected using a low-resolution single-grating spectrometer and CCD detector. It was also possible to cool the samples to liquid nitrogen temperatures (approximately 80 K) and to admit oxygen gas (O2) in order to look for the quenching of the PL by the energy transfer to adsorbed O2.
Raman scattering measurements were made in a macroscopic sampling mode in the back-scattering geometry using 532-nm excitation at powers low enough to avoid the well-known problems due to heating . The scattered light was detected using a triple-grating spectrometer with a tunable subtractive double first stage which provided rejection of the elastically scattered light; the Raman-scattered light was dispersed in a final 1-m focal length stage with a 600-groove/mm grating and was detected using a liquid nitrogen-cooled CCD. Fourier transform infrared (FTIR) transmission measurements were made using a diamond attenuated total reflection (ATR) stage mounted on an FTIR spectrometer. The rather fragile aerogels could only be subjected to a modest mounting pressure in the ATR stage, and so the comparison of the relative strength of a given band from sample to sample was not reliable (relative peak intensities within a single spectrum are of course still meaningful). For this reason, ATR-FTIR did not provide the best means to measure any type of particle concentration; we expect that measurements of diffuse reflectance or even bulk transmission in the IR may be more appropriate, and this work is in progress.
Results and discussion
At the top of Figure 1, we show also the PL spectrum of a sample of the LH particles in powder form with and without oxygen present (the arrow shows how the spectrum drops on the introduction of oxygen); this demonstrates the typical degree of quenching of the luminescence due to the energy transfer process. Detailed discussions of the evidence for this quenching mechanism have been given elsewhere . By contrast, when oxygen is admitted into the aerogel samples containing Si NPs, there is no detectable change in the PL. Thus, incorporation in aerogel brings about a change in the surface state of these particles that reduces the efficiency of the energy transfer process. This is likely to be oxidation of the hydrogen-terminated surface, leading to an increased spatial separation between the confined exciton of the nanoparticle and the oxygen orbitals and, therefore, a reduction in their coupling; further work is, however, needed to quantify this. It is not yet known at which stage of the aerogel preparation this surface oxidation takes place.
Raman scattering and FTIR
Although the colour change of the composites already indicates the state of the Si NPs after incorporation, Raman scattering is useful as a quantitative tool and because, as is usually assumed, quantum confinement and relaxation of momentum selection rules produce a shift of the frequency of the silicon Γ-point phonon mode from its bulk value of 521 cm−1. This shift allows one to estimate where the peak of the size distribution of the NPs lies [17, 22–25]. We note that the influence of the nanocrystal surface provides an alternative physical explanation of the Raman peak shift , though in that model, the quantitative relationship between NP diameter and Raman shift is not altered.
On the other hand, the aerogels containing LO particles show a Raman band that is clearly asymmetric and is shifted to lower frequency (peak at 515.5 cm−1, FWHM 31 cm−1). On the basis of these two facts and following earlier work, e.g. , we could attribute this to Raman scattering from Si NPs of diameter around 4 nm. However, bearing in mind the core-shell structure of these particles, we modelled the lineshape instead using a contribution at the bulk Si phonon frequency (intensity and FWHM varied but position fixed at 521 cm−1) and a second peak due to the nanoparticles; the fit then gives a position of 510 cm−1 for the second band (and FWHM 23 cm−1), which then implies a slightly smaller mean diameter of 2.3 nm for the nanoparticles in the remaining shell. A representative fit and its components (including the aerogel peak) are shown for one LO aerogel in Figure 2: the band arising from the porous shell is clearly dominant. Finally, the SO particles are solid and approximately spherical and so are rather analogous to Si NPs grown by ion-implantation in bulk silicon; in aerogel, we obtain a mean diameter of 2.5 to 3 nm if we interpret their Raman peaks (at 505.5 cm−1, FWHM 23 cm−1) according to the same model .
We now consider the concentration-dependence of the Raman scattering bands. Clearly, as the nanoparticle concentration increases and the resulting composites change from highly transmitting to opaque at the excitation energy, the penetration depth of the excitation light and the total scattering volume reduce dramatically. However, the well-defined aerogel Raman D2 band at 620 cm−1 provides a convenient means of comparing peak intensities, because it must arise from scattering within the same macroscopic volume of sample as the silicon Raman band. By taking the ratio of the integrated intensity of the silicon band (treated here, for simplicity, as a single band for any given nanoparticle type) to the aerogel D2 band, we should obtain a quantity proportional to the nanoparticle concentration. The validity of this normalisation depends on the structure of the silica aerogel itself not being modified by the presence of the embedded material. This may not be true; it is known, for example, that the ratio of the D1 to D2 bands gives an indication of water content in silica aerogels  and is modified after the UV-induced formation of CdS crystallites ; however, we do not expect the introduction of silicon into silica to be as dramatic a modifier of the Si-O network as water.
We have demonstrated that silicon-silica aerogel composites can be produced by conventional aerogel synthesis with the addition of either nanoscale silicon particles or macroscopic porous silicon grains. Substantial oxidation of the silicon takes place if its surface is partially hydride terminated, and this can be severe enough to remove a large fraction of the porous silicon structure, though a solid crystalline silicon core remains. For oxide-terminated porous silicon grains, however, more of the porous silicon structure survives, though it is (as expected) not active in energy transfer to adsorbed oxygen.
JA, BG, SP, MR and MDWG were postgraduate research students at the University of Bath during this work; DW is a senior lecturer in Physics at the University of Bath with a special interest in optical spectroscopy, and TAB and DK are professors of Physics at the University of Bath with interests in photonics and porous silicon, respectively.
This work was supported by the Engineering and Physical Sciences Research Council (UK) under grants EP/F018622/1 and EP/J007552/1. We thank Hartmut Wiggers of the Institute for Combustion and Gas Dynamics, Duisburg-Essen University for the supply of silicon nanospheres.
- Raulin K, Turrell S, Capoen B, Kinowski C, Thanh Tran VT, Bouazaoui M, Cristini O: Raman characterization of localized CdS nanostructures synthesized by UV irradiation in sol–gel silica matrices. Journal of Raman Spectroscopy 2011, 42: 1366–1372. 10.1002/jrs.2844View Article
- Grogan MDW, Rollings MD, Xiao LM, Wadsworth WJ, England R, Maier SA, Birks TA: Plasmonic aerogel doped with gold nanoparticles, Quantum Electronics and Laser Science Conference, OSA Technical Digest. Optical Society of America 2010. paper JThE21 paper JThE21
- Costela A, García Moreno I, Gómez C, García O, Sastre R, Roig A, Molins E: Polymer-filled nanoporous silica aerogels as hosts for highly stable solid-state dye lasers. J Phys Chem B 2005, 109: 4475–4480. 10.1021/jp040714mView Article
- Morris CA, Anderson ML, Stroud RM, Merzbacher CI, Rolison DR: Silica sol as a nanoglue: flexible synthesis of composite aerogels. Science 1999, 284: 622–624. 10.1126/science.284.5414.622View Article
- Polisski S, Goller B, Wilson K, Kovalev D, Zaikowskii V, Lapkin A: In situ synthesis and catalytic activity in CO oxidation supported on porous nanocrystalline silicon. J Catal 2010, 271: 59–66. 10.1016/j.jcat.2010.02.002View Article
- Konorov SO, Mitrokhin VP, Smirnova IV, Fedotov AB, Sidorov-Biryukov DA, Zheltikov AM: Gas- and condensed-phase sensing by coherent anti-Stokes Raman scattering in a mesoporous silica aerogel host. Chem Phys Lett 2004, 394: 1–4. 10.1016/j.cplett.2004.05.114View Article
- Canham LT: Silicon quantum wire array fabrication by electrochemical and chemical dissolution of wafers. Appl Phys Lett 1990, 57: 1046–1048. 10.1063/1.103561View Article
- Limaye S, Subramanian S, Goller B, Diener J, Kovalev D: Scaleable synthesis route for silicon nanocrystal assemblies. Physica Status Solidi a-Applications and Materials Science 2007, 204: 1297–1301. 10.1002/pssa.200674320View Article
- Sailor MJ: Porous Silicon in Practice: Preparation, Characterization and Applications. Weinheim: Wiley-VCH; 2011.View Article
- Kovalev D, Heckler H, Polisski G, Koch F: Optical properties of Si nanocrystals. Physica Status Solidi B-Basic Research 1999, 215: 871–932. 10.1002/(SICI)1521-3951(199910)215:2<871::AID-PSSB871>3.0.CO;2-9View Article
- Song JH, Sailor MJ: Quenching of photoluminescence from porous silicon by aromatic molecules. J Am Chem Soc 1997, 119: 7381–7385. 10.1021/ja971209oView Article
- Kovalev D, Gross E, Kunzner N, Koch F, Timoshenko VY, Fujii M: Resonant electronic energy transfer from excitons confined in silicon nanocrystals to oxygen molecules. Phys Rev Lett 2002, 89: 137401.View Article
- Goller B, Polisski S, Kovalev D: Spin-flip excitation of molecules mediated by photoexcited silicon nanocrystals. Phys Rev B 2007, 75: 073403.View Article
- Borsella E, Falconieri M, Botti S, Martelli S, Bignoli F, Costa L, Grandi S, Sangaletti L, Allieri B, Depero L: Optical and morphological characterization of Si nanocrystals: silica composites prepared by sol–gel processing. Materials Sci and Eng 2001, B79: 55–62.View Article
- Karlash AY, Yu EZ, Skryshevsky VA, Tsiganova AI, Kuznetsov GV: Photoluminescence properties of silica aerogel/porous silicon nanocomposites. J Physics D: Applied Physics 2010, 43: 335405. 10.1088/0022-3727/43/33/335405View Article
- Kovalev D, Fujii M: Silicon nanocrystals: photosensitizers for oxygen molecules. Adv Mater 2005, 17: 2531–2544. 10.1002/adma.200500328View Article
- Cullis AG, Canham LT, Calcott PDJ: The structural and luminescence properties of porous silicon. J Appl Phys 1997, 82: 909–965. 10.1063/1.366536View Article
- Knipping J, Wiggers H, Rellinghaus B, Roth P, Konjhodzic D, Meier C: Synthesis of high purity silicon nanoparticles in a low pressure microwave reactor. J Nanosci Nanotechnol 2004, 4: 1039–1044. 10.1166/jnn.2004.149View Article
- Goller B, Polisski S, Wiggers H, Kovalev D: Freestanding spherical silicon nanocrystals: a model system for studying confined excitons. Appl Phys Lett 2010, 97: 041110. 10.1063/1.3470103View Article
- Grogan MDW, Heck SC, Xiao LM, England R, Maier SA, Birks TA: Control of nanoparticle aggregation in aerogel hosts. J Non-Cryst Solids 2012, 358: 241–245. 10.1016/j.jnoncrysol.2011.09.018View Article
- Ayers MR, Hunt AJ: Visibly photoluminescent silica aerogels. J Non-Cryst Solids 1997, 217: 229–235. 10.1016/S0022-3093(97)00126-9View Article
- Sui Z, Leong PP, Herman IP, Higashi GS, Temkin H: Raman analysis of light-emitting porous silicon. Applied physics letters 1992, 60: 2086–2088. 10.1063/1.107097View Article
- Kanemitsu Y, Uto H, Masumoto Y, Matsumoto T, Futagi T, Mimura H: Microstructure and optical properties of free-standing porous silicon films: size dependence of absorption spectra in Si nanometer-sized crystallites. Phys Rev B 1993, 48: 2827–2830. 10.1103/PhysRevB.48.2827View Article
- Zi J, Buscher H, Falter C, Ludwig W, Zhang K, Xie X: Raman shifts in Si nanocrystals. Appl Phys Lett 1996, 69: 200–202. 10.1063/1.117371View Article
- Khoo KH, Zayak AT, Kwak H, Chelikowsky JR: First-principles study of confinement effects on the Raman spectra of Si nanocrystals. Phys Rev Lett 2010, 105: 115504.View Article
- Riegel B, Hartmann I, Kiefer W, Gross J, Fricke J: Raman spectroscopy on silica aerogels. J Non-Cryst Solids 1997, 211: 294–298. 10.1016/S0022-3093(96)00639-4View Article
- Brodsky MH, Cardona M, Cuomo JJ: Infrared and Raman spectra of the silicon-hydrogen bonds in amorphous silicon prepared by glow discharge and sputtering. Physical Review B 1977, 16: 3556–3571. 10.1103/PhysRevB.16.3556View Article
- Al-Oweini R, El-Rassy H: Synthesis and characterization by FTIR spectroscopy of silica aerogels prepared using several Si(OR)4 and R’Si(OR’)3 precursors. J Mol Struct 2009, 919: 140–145. 10.1016/j.molstruc.2008.08.025View Article
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.