ISSN 1068-3356, Bulletin of the Lebedev Physics Institute, 2017, Vol. 44, No. 12, pp. 353–356.


c Allerton Press, Inc., 2017.
Original Russian Text c M.O. Morozov, I.N. Zavestovskaya, A.V. Kabashin, V.Yu. Timoshenko, 2017, published in Kratkie Soobshcheniya po Fizike, 2017, Vol. 44,
No. 12, pp. 12–18.

Photoluminescence Properties of Silicon Nanocrystals Grown

by Nanosecond Laser Ablation of Solid-State Targets
in an Inert Gas Atmosphere
M. O. Morozova, I. N. Zavestovskayab,c, A. V. Kabashinc,d, and V. Yu. Timoshenkoa,b,c
a
Faculty of Physics, Moscow State University, Moscow, 119991 Russia
b
Lebedev Physical Institute, Russian Academy of Sciences,
Leninskii pr. 53, Moscow, 119991 Russia
c
National Research Nuclear University “MEPhI”,
Kashirskoe sh. 31, Moscow, 115409 Russia; e-mail: [email protected]
d
Aix-Marseille University, CNRS, UMR 7341 CNRS, LP3, Campus de Luminy,
Case 917, F-13288, Marseille Cedex 9, France
Received November 20, 2017

Abstract—It was found that the photoluminescence intensity decay kinetics of nanocrystalline
silicon layers formed by nanosecond laser ablation of crystalline silicon targets in a helium atmo-
sphere exhibit a power-law behavior with an exponent from 0.9 to 1.5, depending on the temperature
and luminescence photon energy in the range of 1.4–1.8 eV, which indicates photoexcited carrier
recombination controlled by dissipative tunneling processes in silicon nanocrystal ensembles in a
suboxide matrix.
DOI: 10.3103/S106833561712003X

Keywords: photoluminescence, exciton, nanocrystals, silicon, laser ablation.

Introduction. While single-crystal silicon (c-Si) remains a basic material of microelectronics and
solar power engineering, silicon nanocrystals (ns-Si) are actively studied in the last few years due to their
promising applications in photonics [1, 2] and biomedicine [3, 4]. In contrast to c-Si, various forms of nc-
Si can luminesce in visible and infrared ranges [5, 6]; therefore, they are of significant practical interest
[2]. However, despite efficient photoluminescence (PL) of nc-Si at room temperature, its mechanisms
are not completely clear [5–7]. Clear identification of the PL origin is complicated by that different growth
methods, processing procedures, and tools for studying ns-Si samples can lead to different features of
PL properties.
Among various methods for growing nc-Si, laser ablation (LA) is one of the “pure” methods for
synthesizing nanomaterials [8,9]. This method is based on solid target sputtering by intense laser
radiation with the result that its components are ejected and nanoscale clusters are formed, which can
then be fixed on the substrate and/or dispersed in liquid [9–11]. One of advantages of such an approach
is avoiding undesirable impurities, which provides final product purity. This allows using of silicon in
biomedicine, in particular, in visualizing cancer cells and tumors, and as sensitizers in photodynamic
therapy and hyperthermia [3].
The objective of this work is to experimentally study the spectra and photoluminescence decay
kinetics of nc-Si produced by laser ablation of c-Si targets in an inert gas atmosphere at various
temperatures.
Experimental technique. nc-Si layers on c-Si substrates were grown by nanosecond LA of c-Si
wafers using the technique described in [11]. The average layer thickness was 1.5 μm. An analysis of the
morphology using high-resolution transmission electron microscopy (TEM) (see Fig. 1) and the infrared
spectroscopy (see [11]) showed that the samples contain nc-Si from 2 to 10 nm in size, separated by a
silicon suboxide phase.
Sample photoluminescence was excited by nanosecond radiation of a copper vapor laser with a
wavelength of 511 nm, a pulse duration of 10 ns, and a repetition rate of 15 kHz. Laser radiation was
focused on the sample into an 1-mm-diameter spot, the maximum radiation intensity on the sample was

353
354 MOROZOV et al.

Fig. 1. TEM image of an ab-Si sample fragment. Dashed curves encircle nc-Si arrangement areas.

Fig. 2. PL spectra of the ab-Si sample at various temperatures.

Fig. 3. PL intensity decay kinetics at a temperature of 30 K at a wavelength of 750 nm for the ab-Si sample excited by
a laser pulse. The line corresponds to the experimental data approximation by formula (2) with parameter b = 1.1.

1 W/cm2 . The PL spectra were measured using a SOLAR TII ms3504i monochromator in the Czerny–
Turner geometry and a PROSCAN HS 101H CCD camera. In the case of PL spectrum measurements,
an MDR-12 monochromator was used, as well as a Hamamatsu H9858-20 photomultiplier whose
signal was digitized using an oscilloscope with a passband of 350 MHz. The response time of the
measurement system was ∼10 ns. The experiments were performed in air at a temperature of 300 K and
in a vacuum cell of an “Advanced Research Systems” closed-cycle helium cryostat in the temperature
range from 30 to 300 K.
Results and discussion. The PL spectra of the ablated layer sample (ab-Si) represented broad bands
in the wavelength range of 600–1100 nm (the photon energies are 1.13–2.07 eV). Figure 2 shows the
typical PL spectra of ab-Si samples at various temperatures. We can see that the PL spectrum maximum
corresponds to 900 nm (1.38 eV) at all studied temperatures. The PL intensity increased with decreasing
temperature.
The observed broad PL band can be attributed to excitons in silicon nanocrystals with a wide size
distribution [5, 6]. The band peak position and its sufficiently large width of the order of ∼1 eV indicate a
possible contribution of exciton transitions in the bulk of nanocrystals and at their interface with the
suboxide layer where the dominance of excitons localized on silicon–oxygen bonds is expected [7].
Measurements of ab-Si PL spectra excited by light of various intensities showed the almost linear
dependence of the PL intensity (IPL ) on the pump intensity. This argues in favor of the preferential

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 PHOTOLUMINESCENCE PROPERTIES OF SILICON NANOCRYSTALS GROWN 355

Fig. 4. Dependences of the exponent b (a) on the inverse temperature for various PL wavelengths and (b) on the PL
photon energy at various temperatures.

contribution of exciton recombination in the nanocrystal bulk, and an insignificant contribution of Auger
recombination processes.
The observed temperature quenching of PL is well described by the Arrhenius activation law
 
Ea
IPL = C · exp − , (1)
kT
where Ea is the activation energy of temperature quenching of PL, k is the Boltzmann constant, and
C is a certain constant. An analysis of the dependences showed that the activation energy is of the
order of 10 meV. On the one hand, within the singlet–triplet splitting model of exciton states, this can
point to corresponding activation energies of the exchange interaction [7]. On the other hand, Ea can
correspond to the height of energy barriers separating carriers in silicon nanocrystals from nonradiative
recombination centers in surrounding silicon suboxide [11].
To obtain additional information on the nature of emitting states, the PL decay kinetics after the
end of exciting laser pulses was measured. Figure 3 shows the typical PL kinetics measured in a wide
time range. We can see that, beginning with 20 ns, this dependence is well approximated by the power
function
IPL (t) = A · t−b , (2)
where the exponent b characterizes the PL intensity decay and A is a certain constant.
The approximation of the PL kinetics decay at various temperatures and wavelengths by formula (2)
allowed us to determine the values of the exponent b, shown in Fig. 4. We can see that b grows with
decreasing temperature for PL at long wavelengths (lower photon energies); for shorter wavelengths, a
reverse tendency is observed (Fig. 4(а)).
We note that the PL decay kinetics in layers of close-packed silicon nanocrystals in the silicon oxide
matrix are well described by the so-called stretched exponential function with average lifetimes from 2
to 20 μs [12] which are close to the exciton singlet lifetimes in silicon nanocrystals [5, 6], and the degree
of “stretching” points to exciton migration processes between nanocrystals. It seems that the observed
power-law behavior of the PL decay kinetics of silicon nanocrystals in ab-Si layers cannot be explained
only by exciton migration, and its temperature dependences most likely point to thermally activated
tunneling processes.
The data of Fig. 4 show an increase in b with decreasing temperature in the PL decay kinetics at
longer wavelengths (lower photon energies). At the same time, at temperatures below liquid-nitrogen
temperature, a decrease in b with the PL photon energy is clearly observed (Fig. 4(b)).
To explain the results obtained, it should be considered that excitons can migrate from smaller
nanocrystals into larger ones. In the general case, three processes are possible, which affect carrier
recombination in silicon nanoparticles, i.e., (i) radiative annihilation of singlet–triplet excitons at points

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356 MOROZOV et al.

of their appearance in nanocrystals, (ii) exciton migration from smaller nanocrystals into larger ones via
tunneling, and (iii) nonradiative recombination on defects in surrounding suboxide. The latter process
usually requires thermal activation and probably dominates at room temperature. Processes (i) and (ii)
can also be thermally activated. It is possible that the weak temperature dependences observed in large
nanocrystals are exactly associated with the above processes, whereas the temperature dependence of
the PL decay kinetics in the short-wavelength spectral region (caused by smaller nanocrystals due to
the quantum-size effect) is almost absent.
The power-law PL decay kinetics and its temperature dependence can point to tunneling of exciton-
composing carriers into neighboring larger nanocrystals and to electronic states in surrounding silicon
suboxide, which is accompanied by energy losses, i.e., represents dissipative tunneling [13]. These
processes will inevitably lead to spatial separation of carriers and, hence, to the time dependence of the
recombination probability. The fact that faster decay kinetics (larger b) are observed in the studied ab-Si
layers for long PL wavelengths corresponding to recombination in larger nanocrystals is well explained
by the smaller degree of localization of the carrier wave function, which will promote tunneling.
Thus, the experiments performed showed that silicon nanocrystal layers grown by laser ablation of
silicon in a helium atmosphere exhibit PL in the range of 600–1100 nm with a spectral maximum at
a wavelength of 900 nm, whose spectral shape slightly varies as the temperature is lowered from 300
to 30 K. The PL quenching activation energy was estimated as 10 meV which points to low energy
barriers bounding carriers in silicon nanocrystal layers in the silicon suboxide matrix. It was found that
the PL decay kinetics of silicon nanocrystals in the time interval from 20 ns to 10 μs obey the power
dependence with an exponent of the order of unity. The data obtained indicate the effect of dissipative
tunneling processes on carrier recombination in laser-ablated silicon nanocrystal ensembles.

ACKNOWLEDGMENTS
The authors are grateful to A. Pereira (University of Lyon) for assistance in preparing laser ablated
layer samples.
This study was supported by the Ministry of Education and Science of the Russian Federation (State
contract no. 16.2969.2017/4.6).

REFERENCES
1. Handbook of Silicon Photonics, Ed. by L. Vivien and L. Pavesi (CRC Press, Boca Raton, 2013).
2. Zh. Yuan, A. Anopchenko, N. Daldosso, et al., Proc. IEEE 97, 1250 (2009).
3. A. V. Kabashin and V. Yu. Timoshenko, Nanomedicine 11, 2247 (2016).
4. L. A. Osminkina and V. Yu. Timoshenko, Mesoporous Biomater. 3, 39 (2016).
5. P. D. J. Calcott, K. J. Nash, L. T. Canham, et al., J. Lumin. 57, 257 (1993).
6. M. L. Brongersma, P. G. Kik, A. Polman, et al., Appl. Phys. Lett. 76, 351 (2000).
7. M. V. Wolkin, J. Jorne, P. M. Fauchet, et al., Phys. Rev. Lett. 82, 197 (1999).
8. A. V. Kabashin and M. Meunier, J. Appl. Phys. 94, 7941 (2003).
9. A. V. Kabashin and M. Meunier, Laser Ablation-Based Synthesis of Nanomaterials. Recent Advances
in Laser Processing Material, Ed. by J. Perriere, E. Millon, and E. Fogarassi (Elsevier, Amsterdam, 2006),
pp. 1–36.
10. K. Abderrafi, M. Gongalsky, R. Abarques, et al., J. Phys. Chem. C 115, 5147 (2011).
11. M. B. Gongalsky, A. Pereira, A. A. Manankov, et al., Sci. Rep. 6, 24732 (2016).
12. V. Yu. Timoshenko, M. G. Lisachenko, O. A. Shalygina, et al., J. Appl. Phys. 96, 2254 (2004).
13. N. G. Kelkarab, D. Lozano, G. Edgar, and J. Patiñoa, Ann. Phys. 382, 11 (2017).

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