J. Am. Chem. Soc.

2001, 123, 3743-3748 3743

Highly Luminescent Silicon Nanocrystals with Discrete Optical

Transitions
Justin D. Holmes,† Kirk J. Ziegler, R. Christopher Doty, Lindsay E. Pell,
Keith P. Johnston, and Brian A. Korgel*
Contribution from the Center for Nano- and Molecular Science and Technology, Department of Chemical
Engineering and Texas Materials Institute, UniVersity of Texas, Austin, Texas 78712
ReceiVed August 8, 2000. ReVised Manuscript ReceiVed February 16, 2001

Abstract: A new synthetic method was developed to produce robust, highly crystalline, organic-monolayer
passivated silicon (Si) nanocrystals in a supercritical fluid. By thermally degrading the Si precursor,
diphenylsilane, in the presence of octanol at 500 °C and 345 bar, relatively size-monodisperse sterically stabilized
Si nanocrystals ranging from 15 to 40 Å in diameter could be obtained in significant quantities. Octanol binds
to the Si nanocrystal surface through an alkoxide linkage and provides steric stabilization through the hydrocarbon
chain. The absorbance and photoluminescence excitation (PLE) spectra of the nanocrystals exhibit a significant
blue shift in optical properties from the bulk band gap energy of 1.2 eV due to quantum confinement effects.
The stable Si clusters show efficient blue (15 Å) or green (25-40 Å) band-edge photoemission with luminescence
quantum yields up to 23% at room temperature, and electronic structure characteristic of a predominantly
indirect transition, despite the extremely small particle size. The smallest nanocrystals, 15 Å in diameter,
exhibit discrete optical transitions, characteristic of quantum confinement effects for crystalline nanocrystals
with a narrow size distribution.

Introduction
Semiconductor cluster properties depend on size. For ex-
ample, quantum confinement effects lead to unique electronic
and optical properties, such as size-tunable excitation and
luminescence energies with an overall loss of energy level
degeneracy.1 By studying the discrete energetic states that
appear, these clusters can provide a test of our current
understanding of quantum mechanics. Examples of size-
dependent discrete optical transitions exist for clusters of direct
band gap semiconductors, such as CdSe1,2 and InAs.3 This loss
of energy level degeneracy, however, has not previously been
observed in the optical properties of Si nanocrystals.4-8 Why
Figure 1. (A) Brillouin zone for the diamond lattice. (B) Bulk band
is Si different? Figure 1 shows the Brillouin zone and band structure for Si. The arrows indicate the energies of the direct Γ f Γ
structure for bulk Si. In Si, the lowest lying Γ f X energetic (1) transition, and the indirect phonon-assisted Γ f L (3) and Γ f X
* To whom correspondence should be addressed. (2) transitions. Note that the direct transition at k ) 0 (the Γ f Γ
† Current address: Department of Chemistry, University College Cork,
transition) is a saddle point. Ramakrishna and Friesner21 predicted that
Cork, Ireland. the indirect transitions increase in energy with decreased quantum dot
(1) For example, see: Alivisatos, A. P. Science 1996, 271, 933 and
references contained therein.
size, with a slight red-shift in the direct transition energy. This prediction
(2) Murray, C. B.; Norris, D. J.; Bawendi, M. G. J. Am. Chem. Soc. arises from the qualitative difference between the parabolic conduction
1993, 115, 8706. band structure of a direct semiconductor and the saddle-point conduction
(3) Banin, U.; Lee, C. J.; Guzelian, A. A.; Kadavanich, A. V.; Alivisatos, band structure of the indirect semiconductor.
A. P.; Jaskolski, W.; Bryant, G. W.; Efros, A. L.; Rosen, M. J. Chem. Phys.
1998, 109, 2306. transition violates conservation of momentum; therefore, light
(4) Wilson, W. L.; Szajowski, P. F.; Brus, L. E. Science 1993, 262, 1242.
Littau, K. A.; Szajowski, P. J.; Muller, A. J.; Kortan, A. R.; Brus, L. E. J. absorption requires phonon assistance, resulting in a very low
Phys. Chem. 1993, 97, 1224. Brus, L. E.; Szajowski, P. F.; Wilson, W. L.; transition probability.9 Consequently, bulk Si photoluminescence
Harris, T. D.; Schuppler, S.; Citrin, P. H. J. Am. Chem. Soc. 1995, 117, is very weak. Quantum confinement in Si nanocrystals4-8,10 and
2915. Brus, L. J. Phys. Chem. 1994, 98, 3575.
(5) Heath, J. R. Science 1992, 258, 1131. Batson, P. E.; Heath, J. R. porous Si11 leads to enhanced luminescence efficiencies with
Phys. ReV. Lett. 1993, 71, 911. quantum yields that have reached as high as 5% at room
(6) Bley, R. A.; Kauzlarich, S. M. J. Am. Chem. Soc. 1996, 118, 12461. temperature4 and blue-shifted “band gap” energies. However,
Yang, C.-S.; Bley, R. A.; Kauzlarich, S. M.; Lee, H. W.; Delgado, G. R. J.
Am. Chem. Soc. 1999, 121, 5191. (9) Sze, S. M. Physics of Semiconductor DeVices, 2nd ed.; Wiley: New
(7) Van Buuren, T.; Dinh, L. N.; Chase, L. L.; Siekhaus, W. J.; York, 1981.
Terminello, L. J. Phys. ReV. Lett. 1998, 80, 3803. (10) Furukawa, S.; Miyasato, T. Phys. ReV. B 1988, 38, 5726. Takagi,
(8) (a) Wilcoxon, J. P.; Samara, G. A. Appl. Phys. Lett. 1999, 74, 3164. H.; Ogawa, H.; Yamzaki, Y.; Ishizaki, A.; Nakagiri, T. Appl. Phys. Lett.
(b) Wilcoxon, J. P.; Samara, G. A.; Provencio, P. N. Phys. ReV. B 1999, 1990, 56, 2379.
60, 2704. (11) Canham, L. T. Appl. Phys. Lett. 1990, 57, 1046.

10.1021/ja002956f CCC: $20.00 © 2001 American Chemical Society

Published on Web 03/28/2001
3744 J. Am. Chem. Soc., Vol. 123, No. 16, 2001 Holmes et al.

Figure 2. Illustration of sterically stabilized nanocrystals. Flexible

organic molecules, such as alkanes, provide repulsive interactions Figure 3. Schematic of the supercritical reaction apparatus used in
between other nanocrystals in solution, thus preventing uncontrolled the batch production of Si nanocrystals.
particle growth and aggregation. The crystalline semiconductor core
tends to be well-defined and faceted. the rapid reactant diffusion necessary to achieve diffusion-
limited growth for the narrowest particle size distributions
in sharp contrast to their direct band gap semiconductor possible.15 Using this method, relatively size-monodisperse,
counterparts, Si nanocrystals have not displayed discrete highly stable Si nanocrystals ranging from 15 to 40 Å in
electronic transitions in the absorbance and photoluminescence diameter are produced.
excitation (PLE) spectra.4-8 Without experimental evidence to This article presents the structural, chemical, and optical
the contrary, one might argue that even the smallest quantum characterization of the Si nanocrystals produced using this
dots of Si, with its indirect band gap, will not exhibit discrete method, with transmission electron microscopy (TEM), energy-
electronic transitions at room temperature due to the phonon- dispersive X-ray spectroscopy (EDS), Fourier transform infrared
assisted continuum occurring across the excitation spectra. This spectroscopy (FTIR), UV-visible absorbance, and luminescence
would have important implications on the development of (both PL and PLE) spectroscopy data. The Si nanocrystals
quantum electronic devices utilizing Si. consist of crystalline cores coated by hydrocarbon ligands bound
Nonlithographic strategies are required to create Si quantum through covalent alkoxide bonds with the nanocrystal surface.
dots with the necessary dimensions (<5 nm diameter) to exhibit The nanocrystals luminesce with size-tunable color, from the
quantum confinement effects at room temperature. The highly blue (15 Å diameter) to the green (25-40 Å diameter). Discrete
successful wet chemical techniques used to synthesize Group optical transitions also appear in the absorbance and PLE spectra
II-VI and III-V semiconductors have not been readily applied of the 15 Å diameter nanocrystals, which is consistent with
to Si, largely due to the high temperatures required to degrade quantum confinement effects in semiconductors.
the necessary precursors, which exceed the boiling points of
available capping solvents. Furthermore, the covalent bonding Experimental Section
of Si requires temperatures higher than the II-VI materials to Diphenylsilane and anhydrous 1-octanol and hexane, packaged under
achieve highly crystalline cores. Moderate progress has been nitrogen, were obtained from Aldrich Chemical Co. (St. Louis, MO)
made with alternative solution-phase reduction of Si salts5-8 and stored in a nitrogen glovebox.
and aerosol4 methods. These methods, however, have produced Organic-passivated Si nanocrystals were prepared by thermally
nanocrystals with extremely broad size distributions, which degrading diphenylsilane in mixtures of octanol and hexane (octanol:
would smear any discrete size-dependent optical features in the Tc ) 385 °C, Pc ) 34.5 bar; hexane: Tc ) 235 °C, Pc ) 30 bar) well
above the critical point at 500 °C and 345 bar in an inconnell high-
absorbance and PLE spectra. Furthermore, the aerosol methods
pressure cell as shown in Figure 3. The presence of Si particles was
have required a thick oxide coating to stabilize their structure,4 observed by the formation of a yellow solution; no color change was
which has been shown recently to significantly affect the observed in the absence of diphenylsilane. When diphenylsilane was
photoluminescence (PL) energies of porous Si.12 Recently, we degraded in the presence of sc-ethanol rather than sc-octanol, the
demonstrated that nanocrystal steric stabilization in a super- solution quickly turned from orange to brown and then clear as
critical solvent is possible.13 Here, we demonstrate that by using polydisperse micron-sized Si particles formed and settled on the walls
a Si surface-passivating solvent heated and pressurized above of the reaction vessel.16 This result suggests that, unlike ethanol, the
its critical point, the necessary temperatures can be reached to bound octanol chains provide sufficient steric stabilization to prevent
degrade the Si precursor while maintaining solvation of the aggregation. The sc-octanol quenches the reaction and passivates the
capping ligand to arrest particle growth (Figure 2), thus Si nanocrystal surface.
A typical preparation begins inside a glovebox. Diphenylsilane
combining the best assets of both the aerosol and wet chemical
solution (250-500 mM in octanol) is loaded into an inconnell high-
approaches. The high temperature of 500 °C promotes Si pressure cell (0.2 mL) and sealed under a nitrogen atmosphere. After
crystallization. The additional advantage of using a supercritical removing the cell from the glovebox, it is attached via a three-way
(sc) solvent over a conventional solvent is the high diffusion valve to a stainless steel high-pressure tube (∼40 cm3) equipped with
coefficient, on the order of 10-3 to 10-4 cm2 s-1,14 enabling a stainless steel piston. Deionized water is pumped into the back of
(12) Wolkin, M. V.; Jorne, J.; Fauchet, P. M.; Allan, G.; Delerue, C. (15) As diffusion-limited growth proceeds, the size distribution tight-
Phys. ReV. Lett. 1999, 82, 197. ens: Reiss, H. J. Chem. Phys. 1951, 19, 482.
(13) Shah, P. S.; Holmes, J. D.; Doty, R. C.; Johnston, K. P.; Korgel, B. (16) Previous studies have used sc-alcohols as solvents in the thermal
A. J. Am. Chem. Soc. 2000, 122, 4245. synthesis of materials. For example, homo- and heterometallic submicron
(14) McHugh, M. A.; Krukonis, V. J. Supercritical Fluids Extraction: sized powders of titanium dioxide and MgAlO4 were synthesized from
Principles and Practice, 2nd ed.; Butterworth-Heinman (Boston): Boston, alkoxide precursors in sc-ethanol at 350 °C: Barj, M.; Bocquet, J. F.; Chor,
MA, 1993. K.; Pommier, C. J. Mater. Sci. 1992, 27, 2187.
Silicon Nanocrystals with Discrete Optical Transitions J. Am. Chem. Soc., Vol. 123, No. 16, 2001 3745

Figure 4. High-resolution TEM image of a 40 Å diameter Si

nanocrystal. The lattice spacing of 3.1 Å is consistent with the (111)
separation in the Si diamond-like lattice. The adsorbed organic capping
layer is not visible in the TEM image. The faceted surface indicates
that the nanocrystals were grown in a controlled environment.

the piston with an HPLC pump (Thermoquest) to inject oxygen-free

octanol through an inlet heat exchanger and into the reaction cell to
the desired pressure, between 140 and 345 bar. The cell is covered
with heating tape (2 ft) and heated to 500 °C ((0.2 °C) within 15-20
min with use of a platinum resistance thermometer and a temperature Figure 5. TEM images of Si nanocrystals: (A) Low-resolution TEM
controller. The reaction proceeds at these conditions for 2 h. Chloroform image of an aggregate of 15 Å diameter Si nanocrystals extended out
is used to extract the Si nanoparticles from the cell upon cooling and from the edge of a carbon film. EDS of the aggregate (Figure 6)
depressurization. The nanocrystal dispersion is subsequently dried and confirmed that the nanocrystals were Si. (B) High-resolution TEM
the organic-stabilized Si nanocrystals are redispersed in hexane or image of several 15 Å diameter Si nanocrystals. (C and D) High-
chloroform. The small 15 Å diameter particles also redisperse in ethanol. resolution images of 35 and 25 Å diameter sterically stabilized Si
The larger Si nanocrystals, with slightly broader size distributions, are nanocrystals. The lattice planes are visible in the 25 Å diameter
produced by increasing the Si:octanol mole ratio with hexane as a nanocrystals.
solvent; a typical Si:octanol mole ratio is 1000:1. The reaction yield in
percent conversion of Si precursor to Si incorporated in the nanocrystals
radicals can react to form Si-Si bonds. The octanol molecules
varies from 0.5% to 5%. subsequently displace the phenyl groups and cap the Si particle
A JEOL 2010 transmission electron microscope with 1.7 Å point- surface.
to-point resolution operating with a 200 kV accelerating voltage with Size-monodisperse 15 Å diameter Si nanocrystals were
a GATAN digital photography system was used for transmission obtained by reacting diphenylsilane in pure octanol with
electron microscopy. In situ elemental analysis was performed on the subsequent redispersion in ethanol. A fraction of the sample is
nanocrystals with an Oxford energy dispersive spectrometer. Electron made up of larger Si nanocrystals that form during the reaction
diffraction images were obtained with the JEOL 2010 operating at 200 that do not resuspend in ethanol due to their hydrophobicity,
kV. Absorbance spectra were recorded with a Varian Cary 500 UV- whereas the extreme surface curvature of the 15 Å diameter
Vis-NIR spectrophotometer with Si nanocrystals dispersed in ethanol
nanocrystals provides ethanol with “access” to the polar Si-
or hexane. The extinction coefficients, , were deterimined for the
nanocrystals from the relationship between the measured absorbance
O-C capping layer termination to enable the size-selective
(A ) cl), the path length (l ) 10 cm), and the Si concentration dispersion of 15 Å diameter Si nanocrystals. The 15 Å diameter
determined from dry weights. The quantity c is the absorption nanocrystals are barely perceptible in TEM images obtained with
coefficient, R. Luminescence measurements were performed with a samples dispersed on a carbon-coated TEM grid (Figure 5). In
SPEX Fluorolog-3 spectrophotometer. The PL and PLE spectra were Figure 5A, a low-resolution image of an aggregate of these 15
corrected with quinine sulfate as a standard. Quantum yields were Å diameter nanocrystals also shows that the sample contains
calculated by comparison with 9,10-diphenylanthracene. FTIR measure- little size variation. For comparison, TEM images in Figure 5
ments were obtained with a Perkin-Elmer Spectrum 2000 FTIR of larger Si nanocrystals with diameters ranging from 25 to 35
spectrometer. FTIR spectra were acquired from dried films of silicon Å produced by performing the synthesis in sc-hexane with
nanocrystals deposited on Zinc Selenide windows.
increased Si:octanol mole ratios clearly reveal highly crystalline
Results and Discussion cores and faceted surfaces. Crystalline lattice planes are observed
in nanocrystals as small as 25 Å. Electron diffraction from these
Synthesis and Characterization. Figure 4 shows a TEM nanocrystals (Figure 6) also confirms that the nanocrystals
image of an organic-monolayer stabilized 40 Å diameter Si consist of crystalline Si cores with diamond lattice structure.
nanocrystal. The particle exhibits a crystalline core with a well- A variety of other techniques were used to characterize the
defined faceted surface. The lattice spacing is 3.1 Å, charac- Si nanocrystals, including energy-dispersive X-ray spectroscopy
teristic of the distance separating the (111) planes in diamond- (EDS), X-ray photoelectron spectroscopy (XPS), Fourier trans-
like Si. Si nanocrystal formation likely propagates through a form infrared spectroscopy (FTIR), UV-vis absorbance, and
radical mechanism as shown below:17 PL and PLE spectroscopy. In situ EDS measurements, shown
in Figure 7, of the nanocrystals imaged by TEM revealed Si in
(Ph)2SiH2 f (Ph)2SiH• (1) high abundance with the presence of oxygen and carbon as well.
A quantitative analysis of the elemental ratios was not possible
2(Ph)2SiH• f H(Ph)2Si - Si(Ph)2H (2) since the supporting substrate was carbon containing a measur-
able amount of residual oxygen. XPS, however, provides an
The benzene rings help stabilize the diphenyl silane radical elemental analysis of the particles which gives an indication of
intermediates by delocalizing the electron charge. These free how the nanocrystals are capped with the organic ligands.
(17) March, J. AdVanced Organic Chemistry: Reactions, Mechanisms, Figure 8 shows XPS data for 15 Å diameter Si nanocrystals,
and Structure, 4th ed.; Wiley: New York, 1992. which reveals that the sample contains a Si:C ratio of 0.70:1.
3746 J. Am. Chem. Soc., Vol. 123, No. 16, 2001 Holmes et al.

Figure 6. Electron diffraction images and data for Si nanocrystals:

(A) Diffraction pattern from a few Si nanocrystals with (200), (400), Figure 8. XPS of the 15 Å diameter Si nanocrystals deposited on a
and (511) orientation. (B) Diffraction of many Si nanocrystals graphite substrate: (A) Si 2p region in the spectrum (modified area is
predominantly (111) and (311) oriented (Inset: measured d spacings 592.2 counts) and (B) C 1s region (-) and its deconvoluted peaks from
of 1.6 and 3.2 Å correspond to the (311) and (111) lattice spacings in the graphite substrate (- -) and the capping ligand (- ‚‚‚ -). The
Si). modified area of the C 1s curve due to the capping ligand is 850.5
counts. The silicon-to-carbon ratio (Si:C) is 0.70:1.

value is about twice that expected for a close-packed monolayer

of ligands surrounding the nanocrystals. Therefore, XPS indi-
cates that the ligands coat the nanocrystals with approximately
50% surface coverage. An estimate of the surface coverage of
the largerst 20 Å diameter nanocrystals in the sample size
distribution gives an area per molecule of 33 Å2, for ap-
proximately 70% surface coverage.
FTIR spectra show that the nanocrystals are most likely
terminated with a combination of hydrogen and hydrocarbon
chains, bound through an alkoxide (Si-O-C) linkage. In Figure
9, the four characteristic methylene and terminal methyl
stretching modes Ṽa(CH2) ) 2928 cm-1, Ṽs(CH2) ) 2855 cm-1,
Ṽa(CH3,ip) ) 2954.5 cm-1, Ṽs(CH2,FR) ) 2871 cm-1, reveal that a
hydrocarbon steric layer has indeed adsorbed to the particle
Figure 7. EDS data of the nanocrystals imaged by TEM in Figure surface. The notable absence of the hydroxyl stretch (Ṽ(O-H) )
4A. The copper peak results from the copper TEM grid used as the 3300 cm-1) and the presence of the strong doublet corresponding
material support. to the Si-O-CH2- stretching modes, Ṽ(Si-O-CH2-) )1100-
1070 cm-1, suggests covalent alkoxide bonding to the Si
By using a shell approximation, dp ) aSi(3NSi/4π)1/3, where aSi nanocrystal surface.18 Siloxane Si-O-Si stretches typically
is the lattice constant (5.43 Å), the number of Si atoms, NSi, in occur at slightly lower wavenumber (1085 and 1020 cm-1);
a nanocrystal can be calculated. Particles with 15 Å diameter however, the presence of residual oxide on the nanocrystal
(dp) have approximately 88 atoms. The Si:C ratio determined surfaces cannot be completely excluded based on these data
from XPS can be used to calculate approximately the area alone. The absence of the very strong characteristic aryl-Si
occupied on the nanocrystal surface by each capping ligand. stretching mode, at Ṽ(Si-Ph) ) 1125-1090 cm-1, confirms
With the Si:C ratio equal to 0.7, the 15 Å cluster with 88 core precursor degradation. The lack of the strong Ṽ(Si-C-Si) ) 1080-
Si atoms has 125 C atoms surrounding it. Each ligand has 8
carbons. Therefore, each particle is surrounded by approximately (18) Pretsch, E.; Clerc, T.; Seibl, J.: Simon, W. Tables of Spectral Data
for Structure Determination of Organic Compounds: Springer-Verlag:
16 capping ligands. Dividing the particle surface area by 16 Berlin, 1942. Socrates, G. Infrared Characteristic Group Frequencies Tables
indicates that each ligand occupies an average of 44 Å2. This and Charts; John Wiley & Sons: New York, 1994.
Silicon Nanocrystals with Discrete Optical Transitions J. Am. Chem. Soc., Vol. 123, No. 16, 2001 3747

Figure 9. FTIR spectrum of Si nanocrystals on a ZnSe window. The

spectrum reveals that the sterically stabilizing hydrocarbon chains are Figure 11. Room-temperature absorbance spectra of Si nanocrystals
covalently linked to the Si surface through alkoxide linkages. These formed under supercritical conditions in the presence of octanol. The
covalent linkages give rise to highly stable optical properties in the absorbance spectra were insensitive to solvent polarity, indicating that
presence of ambient oxygen and water. the absorbance is due to an exciton state and not a charge-transfer
transition between bound ligands. Note the blue shift in the absorbance
edge, and the appearance of discrete optical transitions in the spectra
of the 15 Å diameter nanocrystals compared to the larger, more
polydisperse nanocrystals.

Figure 10. Room-temperature PL (solid lines, excitation energy

denoted by solid arrows) and PLE (dashed lines, detection energy
denoted by dashed arrows) spectra of Si nanocrystals. The spectra of
15 Å diameter nanocrystals are compared with spectra of slightly larger
particles with a broader size distribution. Figure 12. Photographic image of the luminescent Si nanocrystals
excited at 320 nm in hexane: (A) 15 Å diameter Si nanocrystals and
1040 cm-1 stretching mode eliminates the possibility that the (B) 25-40 Å diameter nanocrystals. The smaller nanocrystals emit in
nanoparticles consist of a Si-C core, or that the alkane layer is the near-UV and appear deep blue, whereas the larger particles appear
directly adsorbed to the Si surface. Strong Si TO (transverse blue-green.
optical) phonon bands occur between 450 and 520 cm-1, appear in the PLE spectra of the 15 Å diameter nanocrystals,
indicating that the particles are composed of Si only.19,20 Strong which are mirrored by a few meV in the absorbance spectra in
peaks between 750 and 850 cm-1 and subtle absorption peaks Figure 11. As shown in Figure 10, the nanocrystals exhibit size-
in the range 2100 to 2300 cm-1 can possibly be assigned to a dependent PL and PLE spectra, with the smaller nanocrystals
variety of Si-H stretching modes.18 There is also a possible (15 Å diameter) emitting in the near-UV and the larger
carbonyl stretch at Ṽ = 1700 cm-1 that could result from octanol nanocrystals (25 to 40 Å diameter) emitting green light (see
adsorption through a Si-CdO linkage if alcohol oxidation to Figure 12). For all sizes, the absorption coefficient R, was found
the aldehyde occurs. On the basis of XPS and FTIR data, the to increase quadratically with incident energy, R ∼ [hV - Eg]2,
nanocrystal surface is coated mostly by the hydrocarbon ligands. near the absorption edge (Figure 13), which is characteristic of
However, the remaining 30% to 50% of the surface is coated a predominantly indirect transition.9 Figure 13 compares the
with a combination of hydrogen, Si-CdO, and possibly a small extinction coefficients for bulk Si with those measured for the
portion of oxide. 15 Å diameter nanocrystals. The indirect Γ f X transition
Optical Properties. The Si nanocrystals photoluminesce as remains the lowest energy transition, increasing from 1.2 eV
shown in Figure 10 with overall quantum yields as high as 23% (bulk Si) to 1.9 eV due to quantum confinement. It should be
at room temperature. Several closely spaced discrete features noted that it appears that the direct Γ f Γ transition has red
(19) The TO stretching modes occur at 517, 463, and 494 cm-1 for the shifted to 3.2 eV from 3.4 eV and the L f L transition energy
Γ, X, and L critical points for bulk Si, respectively: Giannozzi, P.; de has blue-shifted from 4.4 eV to 4.7 eV, in quantitatiVe
Gironcoli, S.; Pavone, P.; Baroni, S. Phys. ReV. B 1991, 43, 7231. These agreement with empirical pseudopotential calculations by Ra-
peak assignments, however, cannot be made unequivocally because of the
possible presence of aromatic hydrocarbon impurities in the sample, which makrishna and Friesner,21 although these assignments cannot
absorb in this frequency range.18 be made conclusively. Further comparison of the extinction
(20) A sharp IR absorbance peak occurs at 480 cm-1, which may coefficients measured for the nanocrystals with values for bulk
correspond to localized TO phonons: Scholten, A. J.; Akimov, A. V.;
Dijkhuis, J. I. Phys. ReV. B 1993, 47, 13910. (21) Ramakrishna, M. V.; Friesner, R. A. J. Chem. Phys. 1992, 96, 873.
3748 J. Am. Chem. Soc., Vol. 123, No. 16, 2001 Holmes et al.

with the general perception of quantum confinement effects in

Si. The PL from Si nanocrystals, however, has been shown to
be highly sensitive to surface chemistry, especially the presence
of oxide on the nanocrystal surface.12,23 Indeed, the PL spectrum
of the 15 Å diameter nanocrystals is complicated by the presence
of two prominent peaks in the 15 Å nanocrystal spectrum as
shown in Figure 10: one at 2.95 eV (419 nm) and one at 2.65
eV (467 nm). Furthermore, the PL was found to depend on the
excitation wavelength, with 3.4 eV (363 nm) excitation yielding
the highest quantum yield and the sharpest PL. Increasing the
excitation energy from 3.4 eV to 4.4 eV (281 nm) led to a
decrease in the intensity of the highest energy feature with
respect to the low-energy “satellite” peak, and a decrease in
the overall quantum yield. Although we cannot assign these
peaks conclusively at this time, we propose that the higher
Figure 13. Extinction coefficients plotted on a log scale for bulk Si
and those measured for 15 Å Si nanocrystals formed by arrested
energy peak is intrinsic to quantum confinement in Si nano-
precipitation in supercritical octanol. The absorption edge corresponds crystals and the lower energy peak results from the presence of
to the indirect Γ f X transition and the two peaks in the bulk Si spectra oxygen on the particle surface, as proposed in ref 12 for porous
correspond to the Γ f Γ and L f L critical points at 3.4 and 4.3 eV, Si. Wolkin et al.12 calculated that the PL energy due to intrinsic
respectively. Note the apparent blue shift of the Γ f X and L f L quantum confinement in Si can in some cases differ from the
transitions in the nanocrystals due to quantum confinement and the PL energy due to surface states, specifically SidO. For
apparent red shift of the Γ f Γ transition, as predicted by Ramakrishna nanocrystals greater than 3 nm in diameter, the intrinsic and
and Friesner in ref 21. surface state emission energies are the same, with emission at
2 eV (620 nm).12 However, 15 Å diamater nanocrystals were
Si reveals an overall lifting of the critical point degeneracies predicted to give rise to intrinsic PL at 2.8 eV, and surface state
(direct transitions at k ) 0 and away from k ) 0), as predicted PL resulting from the presence of oxygen at 2.3 eV (537 nm).12
by both empirical pseudopotential21 and tight-binding22 calcula- The PL spectra of the Si nanocrystals shown in Figure 10 are
tions, and an oscillator strength enhancement. These results consistent with this interpretation. It should be noted, however,
contrast the spectra for slightly larger, more polydisperse Si that peak splitting due to separate direct and phonon-assisted
nanocrystals, ranging in size from 25 to 40 Å in diameter in absorption and emission events has been observed by Calcott
Figure 11, which exhibit monotonically increasing featureless et al.24 for porous Si and may provide an alternative explanation.
absorbance spectra. A slight exciton peak, however, does seem
to appear in the PLE spectra in Figure 10 for the larger Conclusions
nanocrystals at 2.6 eV (470 nm).
The Si nanocrystal PL was remarkably stable in the presence Sc-octanol serves as an effective capping ligand for the
of atmospheric oxygen, especially when considering the sen- synthesis of Si nanocrystals. Significant quantities of stable,
sitivity of the optical properties of porous-Si to surface well-passivated nanocrystals can be produced in a simple batch
chemistry, such as oxidation.12,23 The sc-technique provides Si reactor. The smallest size-monodisperse 15 Å diameter Si
nanocrystals with sufficiently robust surface passivation to nanocrystals exhibit previously unobserved discrete electronic
prevent strong interactions between the Si cores and the absorption and luminescence transitions due to quantum con-
surrounding solvent to enable efficient luminescence from Si. finement effects. This study also confirms that Si clusters as
Comparison between the PL and PLE spectra in Figure 10 small as 15 Å in diameter still behave as indirect semiconduc-
reveals a Stokes shift of approximately 100 meV with respect tors. This supercritical route for nanostructure formation might
to the lowest energy peak in the PLE spectra. The relatively be applied to other materials, such as Si nanowires,25 that require
broad PL peak has a characteristic lifetime of 2 ns, indicating high temperatures for crystal formation and the solvation of
that various nonradiative processes are important in the nano- capping ligands.
crystals. It is worth noting that the low-energy PL peak observed
by Brus et al.4 for ∼20 Å diameter oxide-coated Si nanocrystals Acknowledgment. B.A.K. thanks the Welch Foundation, the
at 1.6 eV was not observed in any of these samples. National Science Foundation, and DuPont for support. K.P.J.
The origin of the photoluminescence in Si nanocrystals is thanks the Department of Energy and the National Science
quite complex and remains actively debated. The PL spectrum Foundation for support.
in Figure 10 is clearly size dependent, with the larger particles JA002956F
emitting lower energy light than the smaller particles, consistent
(24) Calcott, P. D. J.; Nash, K. J.; Canham, L. T.; Kane, M. J.; Brumhead,
(22) Hill, N. A.; Whaley, K. B. Phys. ReV. Lett. 1995, 75, 1130. Hill, N. D. J. Phys.: Condens. Matter 1993, 5, L91.
A.; Whaley, K. B. J. Electron. Mater. 1996, 25, 269. (25) Holmes, J. D.; Johnston, K. P.; Doty, R. C.; Korgel, B. A. Science
(23) Lauerhaas, J. M.; Sailor, M. J. Science 1993, 261, 1567. 2000, 287, 1471.