Chemical Physics Letters 536 (2012) 87–91

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Chemical Physics Letters

journal homepage: www.elsevier.com/locate/cplett

Optical properties of SnO2 quantum dots synthesized by laser ablation in liquid

Manish Kumar Singh ⇑, Mohan Chandra Mathpal, Arvind Agarwal
Department of Physics, Motilal Nehru National Institute of Technology, Allahabad 211004, India

a r t i c l e i n f o a b s t r a c t

Article history: SnO2 quantum dots (QDs) were controllably synthesized by laser ablation in liquid (LAL). The HRTEM
Received 26 January 2012 image shows that the diameters of the SnO2 nanoparticles fall into a small range of 1–5 nm, with the
In final form 23 March 2012 majority being less than the exciton Bohr radius of SnO2 (2.7 nm). The Selected Area Electron Diffraction
Available online 30 March 2012
(SAED) pattern of SnO2 QDs shows tetragonal crystalline structure. The photoluminescence (PL) spectrum
of such SnO2 QDs exhibits blue and green emission peaks at 445 nm and 540 nm respectively. These QDs
have potential future applications in optoelectronics, biosensor and other modern technologies.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction In liquid environment the laser ablation of solids is a simple and

versatile method to synthesize nanoparticles [27]. The correspond-
Research on semiconductor quantum dots systems has been of ing studies are mainly focused on two subjects: (i) preparation of
great interest for the last two decades. This is mainly due to novel nanoparticles via laser ablation in liquid medium and (ii) laser-
physical and chemical properties displayed by these nanometer- induced modification of the size and shape of the nanoparticles.
scale structures. Quantum dots (QDs) are semiconducting inor- In this paper the optical properties of these nanoparticles have
ganic nanocrystallites with critical dimensions smaller than or been discussed.
comparable to the exciton Bohr radius of the material, in which
carriers or excitons are confined in all three dimensions to a nano-
2. Experimental
meter sized region [1,2]. Consequently, discrete electronic states,
unusual structural transformations, unique optical properties and
Tin pellet of 99.9% purity was placed at the bottom of a glass
a blue shift of the band edge transition energy are induced in
vessel containing 20 ml of double deionized water. The pellet
QDs [3–6]. Due to the high surface-to-volume ratio, the surface
was ablated for one hour by focused beam of 1064 nm of pulsed
atoms play a large role in the properties of QDs, which usually have
Nd: YAG laser operating at 35 mJ/pulse energy with 10 Hz repeti-
fewer adjacent coordinate atoms and can be treated as defects as
tion rate and 10 ns pulse width. The solution of colloidal nanopar-
compared with the bulk atoms. These defects induce additional
ticles was collected for characterization.
electronic states in the band gap, which can mix with the intrinsic
UV–Visible absorption spectrum of synthesized colloidal solu-
states to a substantial extent and which may also influence the
tion was recorded using Perkin Elmer, Lambda-35 double beam
spacing of the energy levels and the optical properties of QDs.
spectrometer. For HRTEM analysis, a drop of colloidal solution of
Recently, tin oxide (SnO2) has attracted great attention because
nanoparticles was placed on a carbon coated copper grid followed
of its properties in broad fields such as transparent conducting
by drying. Field emission transmission electron microscope (FE-
coating of glasses, gas sensors, solar cells, and heat mirrors [7–9].
TEM) measurements of the samples were taken on a JEOL JEM
SnO2 is an n type semiconductor crystal with direct band gap
2100 F instrument with a 200 kV accelerating voltage. Fourier
(3.6 eV at 300 K) having high excitonic binding energy (130 eV).
Transform Infrared (FTIR) spectra of SnO2 nanoparticles were re-
SnO2 with various nano and microstructures, such as nanopar-
corded by Perkin Elmer RX-IR spectrometer. The photolumines-
ticles, nanorods, nanobelts, hollow microspheres, nanoflowers,
cence (PL) and photoluminescence excitation (PLE) were
mesoporous structures [10–15], nanowhiskers [16] and nanowires
performed using a Perkin Elmer LS-55 spectrophotometer.
[17] have been prepared by different methods. Up till now various
methods such as molten-salt synthesis [18], hydrothermal method
[19,20], carbothermal reduction [21], chemical precipitation [22], 3. Results and discussion
microwave technique [23,24], sol–gel [25], sonochemical [26],
etc., have been developed to fabricate tin oxide nanostructures. 3.1. UV–Visible absorption spectrum

⇑ Corresponding author. Fax: +91 532 2545341. Figure 1a shows UV–Visible absorption spectrum of colloidal
E-mail address: maksingh4@gmail.com (M.K. Singh). solution obtained by pulsed laser ablation of tin in double

0009-2614/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cplett.2012.03.084
88 M.K. Singh et al. / Chemical Physics Letters 536 (2012) 87–91
Figure 1. (a) UV–Visible absorption spectrum of SnO2 quantum dots and (b) plot of (ahm)2 versus hm for SnO2 quantum dots synthesized by pulsed laser ablation method.
deionized water. SnO2 exciton broad band starts with a hump at
300 nm because of near band edge absorption of electron in con-
duction band and exciton broad band further increases up to
200 nm. Stronger exciton effect is an important character of quan-
tum confinement in nano-semiconductors as carriers are confined
in a very small region which makes the electron and hole to move
only in a potential well. It can enhance the coupling interaction
with each other and the exciton becomes stronger, probability of
binding increases, more exciton absorption peak may appear when
the particle size decreases. Therefore the exciton absorption is ob-
served and it shows blue shift near band edge absorption relative
to the bulk exciton absorption (345 nm or 3.6 eV) [19]. This blue
shift represents the quantum confinement property of nanoparti-
cles. In the quantum confinement range, the band gap of the parti-
cle increases as the particle size decreases resulting in the shift of
absorption edge to lower wavelength [28].
When the dimensions of nanocrystalline particles approach the
exciton Bohr radius (aB), a blueshift in energy is observed due to
the quantum confinement phenomenon. The effective mass model
is commonly used to study the size dependence of optical proper-
ties of QD systems. In this approach the exciton is treated analo-
gously to a hydrogen atom, but is limited by spatial confinement.
Therefore the energy of the system is obtained by solving the prop-
er Schrodinger equation. In this manner two regimes are defined
due to the coupling of motion of the electron and the hole in the
exciton: weak and strong confinements. In the former the particle
size is larger than aB, and the electron and the hole are treated as a
correlated pair. The blue shift of the band gap energy is described
by the following equation:
2
Eeff  p2 =2lR2  1:8e2 =eR
g ¼ Eg þ h
h the plank constant, l is the effective
where R is the particle radius, 
reduced mass, e is the charge of the electron, Eg is the bulk band gap
energy (3.60 eV), static dielectric constant e of approximately 14
and Eeff
g is the effective band gap energy. As the effective mass of
the electrons is much smaller than that of the holes (me = 0.27me),
since me  mh (me and mh are the electron and hole effective
masses respectively). The charge carrier confinement mainly affects
the energy level of the electrons [29,30].
The size dependence of the band gap energies of the quantum-
confined SnO2 particles agrees very well with the confinement re-
gime. The band gap energy Eg for SnO2 nanoparticles can also be
determined by extrapolation to the zero absorption coefficients,
which are calculated using the following equation:
ðahmÞ1=n ¼ Bðhm  Eg Þ ð2Þ
where B is a constant, a is absorption coefficient, Eg is the band gap,
hm is the photon energy and n is a value that depends on the nature
of the transition. In this case, n is equal to 1/2 for the direct allowed
transition. The band gap can be estimated from a plot of (ahm)2 ver-
sus photon energy. The estimated band gap energy is 4.37 eV for
synthesized sample Figure 1b. The increase of the band gap of
SnO2 is due to the smaller size of the particles. By applying Eq. (1)
the radius (R) of SnO2 QDs found to be 1.55 nm. This study shows
that the quantum confinement effect of SnO2 is only at particle size
below the Bohr radius (2.7 nm).
3.2. Transmission electron microscopy
The morphology, particle size and structure of the synthesized
sample were characterized by TEM and HRTEM. The TEM images
are shown in Figure 2a and b which reveals that the product is
composed of homogeneous ultrafine self assembled nanoparticles
with a diameter below 5 nm. The SAED ring pattern in Figure 2c
for SnO2 QDs shows that the particles are well crystallized [31].
The diameter of the diffraction ring in SAED pattern is proportional
to (h2 + k2 + l2)2 where (hkl) are the Miller indices of the planes cor-
responding to the ring, counting from the center. First, second and
third ring correspond to (1 1 1), (2 0 0) and (2 2 0) planes respec-
tively. Figure 2d is the HRTEM image of the SnO2 QDs, which
clearly reveals the lattice fringes with a d-spacing of about
0.176 nm, corresponding to (2 1 1) planes of SnO2 (JCPDS No. 41-
1445). Highly ordered lattice fringes, even in the surface region,
are evidence of the crystallinity of the particles.
ð1Þ From the data obtained by TEM images, the particle size distri-
bution graph shown in Figure 2e, and the mean size of the particles
can be determined. It can be seen that the diameter (2R) of the
quantum dot is from 1 nm to 5 nm, and the median diameter (taken
as average particle diameter) is about 2.5 nm. The radius (R) of QDs
calculated from absorption data is 1.55 nm. Both the results show
that the size of QDs is less than the Bohr radius (R = 2.7 nm).
Therefore, the SnO2 nanoparticles are called SnO2 quantum dots
(QDs).
3.3. FTIR spectra
The FTIR spectrum is shown in Figure 3 for SnO2 nanoparticles
synthesized by LAL in water. The spectrum was recorded of a film
coated on a glass substrate by suspending the solution drop by
 M.K. Singh et al. / Chemical Physics Letters 536 (2012) 87–91 89

Figure 2. TEM images of the SnO2 quantum dots: (a and b) TEM images at 20 nm and 5 nm scale respectively (c) HRTEM image (d) SAED pattern (e) particle size histogram
curve of SnO2 QDs.

drop at 80 °C for evaporating the water. FTIR is recorded in the
range of 1000–400 cm1 for confirmation of SnO2. A band appears
in the range of 400–700 cm1 is assigned to Sn–O antisymmetric
vibration [32,33].
3.4. Photoluminescence spectrum
The photoluminescence (PL) emission spectrum for SnO2 quan-
tum dots synthesized by PLA in water at an excitation wavelength
of 271 nm is shown in Figure 4. The peak shows three individual
peaks at 409 nm, 447 nm and 540 nm respectively indicating the
blue and green emissions. These three peaks are smaller than
the band gap of SnO2 which is 4.37 eV therefore the electron is
not directly recombining to a hole in the valance band from con-
duction band [34].
Generally, defects such as oxygen vacancies are known to be the
most common defects in oxides and usually act as radiative centers
in luminescence processes. Among the oxygen vacancies in the
oxide, only the single ionized oxygen vacancy (V 0o ) state observed
by EPR is paramagnetic, and it is expected that most oxygen vacan-
cies will be in their paramagnetic V 0o state under flat-band condi-
tions [34]. V 0o is assumed to be the recombination center for the
luminescence emission, which has an effective monovalent posi-
tive charge with respect to the regular O2 site. After such a recom-
bination the effectively neutral center V 0o (neutral charge vacancy
for oxygen) will be formed, whose energy is very close to the
conduction band edge due to the correlation energy of the two
90 M.K. Singh et al. / Chemical Physics Letters 536 (2012) 87–91

green emission band (540 nm) can be atrributed to radiative

recombination from defect such as oxygen vacancies [36]. The de-
fects may arise because of non-equilibrium process in LAL [37].
Zeng et al. have shown the presence of defects formed in highly
non-equilibrium conditions had a significant impact on the lumi-
nescence of ZnO. A detailed study about blue emissions, green
emissions and quantum confinement effect for the increase in
the band gap of ZnO and other semiconducting nanoparticles due
to smaller particle size is reported by Zeng et al. [38,39].

4. Conclusions

SnO2 quantum dots were synthesized by LAL. The estimated

band gap energy is 4.37 eV for SnO2 QDs. The increase of the band
gap of SnO2 is due to the smaller size of the particles (quantum
comfinement effect). The diameters of the SnO2 nanoparticles fall
into a small range of 1–5 nm, with the majority of them are less
than the exciton Bohr radius of SnO2 (2.7 nm). Therefore, the
Figure 3. FTIR spectrum of the SnO2 quantum dots synthesized by pulsed laser SnO2 nanoparticles are called SnO2 (QDs). The SAED ring pattern
ablation. shows that the SnO2 QDs are well crystallized. The photolumines-
cence (PL) emission spectrum shows the blue and green emission.
Blue and green emission bands occur due to the recombination of
the deep trapped charges and photogenerated electrons from the
conduction band, and also due to the defect such as oxygen
vacancies.

Acknowledgments

Authors are thankful to Dr. Gajender Saini, AIRF-JNU Delhi for

TEM facilities and Prof. Ram Gopal, University of Allahabad for
extending the facilities available with them.

References

[1] A.P. Alivisatos, Science 271 (1996) 933.

[2] A. Henglein, Chem. Rev. 89 (1989) 1861.
[3] D. Granados, J.M. Garćıa, Nanotechnology 16 (2005) S282.
[4] X. Peng, Adv. Mater. 15 (2003) 459.
[5] L. Qu, W.W. Yu, X. Peng, Nano Lett. 4 (2004) 465.
[6] C. Burda, S. Link, M. Mohamed, M. El-Sayed, J. Phys. Chem. B 105 (2001) 12286.
[7] A. Diéguez, A. Romano-Rodríguez, J.R. Morante, U. Weimar, M. Schweizer-
Figure 4. Photolumniscence spectrum of SnO2 quantum dots synthesized by pulsed Berberich, W. Göpel, Sens. Actuat. B: Chem. 31 (1996) 1.
laser ablation. [8] N. Kudo, Y. Shimazaki, H. Ohkita, M. Ohoka, S. Ito, Sol. Cell 91 (2007) 1243.
[9] C. Choudhury, H.K. Sehgal, Energy Convers. Manage. 29 (1989) 265.
[10] Q.Y. Pan, J.Q. Xu, X.W. Dong, J.P. Zhang, Sens. Actuat. B: Chem. 66 (2000) 237.
electrons at room temperature, all V 0o centers are thermally disso- [11] A.A. Firooz, A.R. Mahjoub, A.A. Khodadadi, Mater. Lett. 62 (2008) 1789.
[12] P. Andrei, L.L. Fields, J.P. Zheng, Y. Cheng, Actuat. B: Chem. 128 (2007) 226.
ciated into V 0o centers and conduction band electrons. Therefore,
[13] Q.R. Zhao, Y. Gao, X. Bai, C.Z. Wu, Y. Xie, Eur. J. Inorg. Chem. 8 (2006) 1643.
photons with an energy of 2.7 eV (445 nm) will not be emitted [14] A.C. Chen, X.S. Peng, K. Koczkur, B. Miller, Chem. Commun. 17 (2004) 1964.
through a transition of an electron from the conduction band to [15] Y.D. Wang, C.L. Ma, X.D. Sun, H. Li, Micropor. Mesopor. Mater. 49 (2001) 171.
a V 0o level, as such a transition effectively occurs between the con- [16] S.H. Luo et al., Nanotechnology 15 (2004) 1424.
[17] S. Mathur, S. Barth, H. Shen, J.C. Pyun, U. Werner, Small 1 (2005) 713.
duction band edge and the V 0o level. However, recombination of a [18] D. Wang, X.F. Chu, M.L. Gong, Sens. Actuat. B: Chem. 117 (2006) 183.
conduction band electron with a V 00o center (an oxygen vacancy [19] B. Liu, H.C. Zeng, J. Phys. Chem. B 108 (2004) 5867.
containing no electrons, having an effective divalent positive [20] H. Huang, O.K. Tan, Y.C. Lee, M.S. Tse, J. Guo, T. White, Nanotechnology 17
(2006) 3668.
charge with respect to the normal O2 site) can yield such a blue [21] S. Thanasanvorakun, P. Mangkorntong, S. Choopun, N. Mangkorntong, Ceram.
emission band. Such V 00o centers can be formed when a hole is Int. 34 (2008) 1127.
trapped at a V 0o center. Thus, a model for this blue emission of [22] Y. Dabin, W. Debao, Y. Weichao, Q. Yitai, Mater. Lett. 58 (2006) 84.
[23] T. Krishnakumar, R. Jayaprakash, N. Pinna, V.N. Singh, B.R. Mehta, A.R. Phani,
the photoexcited SnO2 nanoparticles can be proposed. The excita- Mater. Lett. 63 (2009) 242.
tion of the SnO2 nanoparticle starts with the creation of an elec- [24] T. Krishnakuma, R. Jayaprakash, M. Parthibavarman, A.R. Phani, V.N. Singh, B.R.
tron–hole pair. The electron is promoted from the valence band Mehta, Mater. Lett. 63 (2009) 896.
[25] L. Korosi, S. Papp, V. Meynen, P. Cool, E.F. Vansant, I. Dekany, Colloid Surf. A:
to the conduction band, leaving a hole in the valence band. The ac- Physicochem. Eng. Aspects 268 (2005) 147.
tive hole formed can be trapped at the V 0o center directly to form [26] H.X. Luo, Z. Ying-Ji, W. Shi-Wei, Mater. Chem. Phys. 88 (2004) 421.
the V 00o center or at the surface of the particle. Then the surface- [27] M.K. Singh, A. Agarwal, R. Gopal, R.K. Swarnkar, R.K. Kotnala, J. Mater. Chem. 21
(2011) 11074.
trapped hole may transfer back into the particle to recombine with
[28] M.A. Gondal, Q.A. Drmosh, T.A. Saleh, Appl. Surf. Sci. 256 (2010) 7067.
an electron in a deep trap (V 0o ) to form the V 00o center. Thereafter, [29] L. Brus, J. Phys. Chem. 90 (1986) 2555.
recombination of a V 00o center with a conduction band electron gives [30] E.J.H. Lee, C. Ribeiro, T.R. Giraldi, E. Longo, E.R. Leite, J.A. Varela, Appl. Phys.
rise to the blue emission. The blue emission band has been gener- Lett. 84 (2004) 1745.
[31] J. Ba, J. Polleux, M. Antonietti, M. Niederberger, Adv. Mater. 17 (2005) 2509.
ated due to the recombination of the deep trapped charges and [32] S. Emiroglu, N. Barson, V. Weimar, V. Hoffman, Thin Solid Films 391 (2001)
photogenerated electrons from the conduction band [35]. The 176.
 M.K. Singh et al. / Chemical Physics Letters 536 (2012) 87–91 91

[33] P. Shah, A.V. Ramaswamy, K. Lazar, V. Ramaswamy, Appl. Catal. A: Gen. 273
(2004) 239.
[34] K. Vanheusden, W.L. Warren, C.H. Seager, D.R. Tallant, J.A. Voigt, B.E. Gnade, J.
Appl. Phys. 79 (1996) 7983.
[35] F. Gu, S.F. Wang, M.K. Lu1, G.J. Zhou, D. Xu, D.R. Yuan, J. Phys. Chem. B 108
(2004) 8119.
[36] X. An, G. Mang, Q. Wei, X. Zhang, Y. Hao, L. Zhang, Adv. Mater. 17 (2007) 1781.
[37] H. Zeng, X.W. Du, S.C. Singh, S.A. Kulinich, S. Yang, J. He, W. Cai, Adv. Funct.
Mater. (2012), http://dx.doi.org/10.1002/adfm.201102295.
[38] H. Zeng, G. Duan, Y. Li, S. Yang, X. Xu, W. Cai, Adv. Funct. Mater. 20 (2010) 561.
[39] H. Zeng, W. Cai, P. Liu, X. Xu, H. Zhou, C. Klingshirn, H. Kalt, ACS Nano 2 (2008)
1661.