Three-photon absorption in water-soluble ZnS nanocrystals

Abstract

We report on large three-photon absorption (3PA) in glutathione-capped ZnS semiconductor nanocrystals (NCs), determined by both Z-scan and transient transmission techniques with 120-fs laser pulses. The monodispersed, water-soluble ZnS NCs are synthesized by a modified protocol with a mean diameter of 2.5 nm. Their 3PA cross-section is determined to be around 2.7x10^-78 cm^6s^2photon^-2 at an optimal wavelength of commercial Ti:sapphire femtosecond lasers. This value is nearly one order of magnitude greater than that of CdS NCs, and four to five orders of magnitude higher than those of the previously reported common UV fluorescent dyes. Comment: 15 pages, 4 figures

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Three-photon absorption in water-soluble ZnS nanocrystals

Jun He, Wei Ji,a) and Jun Mi
Department of Physics, National University of Singapore
2 Science Drive 3, Singapore 117542

Yuangang Zheng and Jackie Y. Ying
Institute of Bioengineering and Nanotechnology
31 Biopolis Way, The Nanos, Singapore 138669


We report on large three-photon absorption (3PA) in glutathione-capped ZnS
semiconductor nanocrystals (NCs), determined by both Z-scan and transient
transmission techniques with 120-fs laser pulses. The monodispersed, water-soluble
ZnS NCs are synthesized by a modified protocol with a mean diameter of 2.5 nm.
Their 3PA cross-section is determined to be ~2.7 × 10–78 cm6 s2 photon–2 at an optimal
wavelength of commercial Ti:sapphire femtosecond lasers. This value is nearly one
order of magnitude greater than that of CdS NCs, and four to five orders of magnitude
higher than those of the previously reported common UV fluorescent dyes.

Keywords: ZnS nanocrystals; three-photon absorption; Z-scan technique
PACS: 78. 67. Bf, 42. 70. Nq, 42. 65. An


a)Electronic mail: phyjiwei@nus.edu.sg

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Semiconductor nanocrystals (NCs) with large multiphoton absorption (MPA)
have been the focus of material research for multiphoton fluorescence imaging.1,2
Compared to common fluorophores, semiconductor NCs have many advantages:
broad absorption bands, but very narrow and symmetric emission bands, tunable
emission wavelength, longer emission lifetime, and enhanced brightness. While two-
photon absorption (2PA) in semiconductor NCs has been widely investigated,3,4
research effort on their three-photon absorption (3PA) is limited.5 Although high-
quality CdS NCs show strong multiphoton-excited, band-gap emission,5 the intrinsic
toxicity of cadmium places ZnS NCs in an advantageous position. ZnS and related II-
VI compounds are also attractive for applications in photonic crystal devices in the
visible and near-infrared region due to their high indices of refraction and large band
gap, which make them highly transparent in the visible region.6 Recently, multicolor
electroluminescence7 and fluorescence8 of doped ZnS NCs have been investigated.
Furthermore, Nikesh et al. have reported large 2PA in ZnS nanoparticles using
picosecond Z-scan technique.9 Here, we report on the synthesis, characterization, and
3PA measurements of water-soluble ZnS NCs.
The synthesis of ZnS NCs was based on the reaction of zinc chloride and
sodium sulfide. The freshly prepared Na2S solution was added to another solution
containing ZnCl2 and glutathione at pH 11.5 with vigorous stirring. The amounts of
ZnCl2, Na2S and GSH were 5, 2 and 6 mmol, respectively, in a total volume of 500
ml. The resulting mixture was heated to 95ºC, and the growth of GSH-capped ZnS
NCs took place immediately. The band-gap edge changed from 240 nm to 293 nm in
60 min of heating. The as-prepared NCs with band-gap edge at ~293 nm were
precipitated, and washed several times with 2-propanol. The pellet of the NCs was
vacuum dried at room temperature overnight, and the final product in the powder form

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could be redissolved in water. The elemental analysis of the water-soluble ZnS NCs
was performed on ELAN 9000/DRC ICP-MS system. Both morphology and size
distribution of the NCs were examined with a field emission high-resolution
transmission electron microscope (HRTEM) (FEI Tecnai TF-20, 200 kV). The
powder X-ray diffraction (XRD) pattern of the vacuum-dried ZnS NCs was obtained
with PANalytical X’Pert PRO. The one-photon absorption spectrum was measured on
a UV-visible spectrophotometer (Shimadzu, UV-1700). The photoluminescence (PL)
and photoluminescence excitation (PLE) spectra were collected with a Jasco FP-6300
spectrofluorometer. They were obtained before and after the pulsed laser irradiation;
no measurable difference was observed, showing the high photostability of ZnS NCs
in aqueous solution.
Figure 1(a) presents a HRTEM image of the ZnS NCs capped with GSH. The
average diameter of the ZnS NCs is 2.5 ± 0.3 nm, which is dependent on the amount
of capping agent used in the preparation. In the inset of Fig. 1(a), the higher
magnification image reveals the crystalline lattice of the NCs, with a typical lattice
spacing of ~ 3.0 Å, which corresponds to the (111) plane of ZnS. A typical XRD
pattern of the NCs is shown in Fig. 1(b), which corresponds to the cubic (zinc blende)
phase. The XRD analysis10 indicates that the ZnS NCs have a mean diameter of 2.2
nm, close to the HRTEM result.
The one-photon absorption spectrum of the GSH-capped ZnS NCs in aqueous
solution is shown in Fig. 2. A recent theoretical calculation11 shows that due to the
quantum confinement, there is a blue-shift of ~ 450 meV in the bang-gap energy of
2.5-nm-diameter ZnS NCs, in comparison to that of bulk ZnS. Since the band-gap
energy for bulk ZnS is ~3.7 eV, the lowest excitonic transition in the NCs, 1S(e)–
1S3/2(h), is calculated to be at ~298 nm, in agreement with our observation (~293 nm).

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The size of the NCs can also be estimated from the excitonic profile. Table I compares
the sizes obtained from the HRTEM and XRD measurements, as well as the
calculated values based on effective mass approximation12 and realistic tight binding
calculation.13 In addition, the narrow size distribution of the NCs is confirmed by the
sharp optical absorption edge and well-defined excitonic feature. Broadening of the
excitonic transition is primarily due to the inhomogeneity arising from size dispersion.
By the use of Gaussian fitting,14 a size distribution of ~ 11% can be estimated with the
240-meV width of the excitonic transition of 1S(e)–1S3/2(h) observed in Fig. 2,
consistent with the HRTEM analysis (~ 12%).
Figure 2 also displays a broad PL emission at 350–550 nm for the ZnS NCs.
The PL emission peak (~ 440 nm), which is red-shifted compared to the excitonic
transition (~ 293 nm), is consistent with the observation by Qu et al.15 and Sapra et
al.8 for un-doped ZnS NCs. The change of excitation wavelength only leads to the
alteration in the intensity of the emission peak. Sapra et al. attributed this strong
emission band to the carrier recombination of the defect states, which are mostly on
the surface of the NCs due to sulfur vacancies. The PLE spectrum of the ZnS NCs
(Fig. 2) gives two well-resolved excitation bands (centered at 283 nm and 306 nm,
respectively).
The room-temperature 3PA of the ZnS NCs in aqueous solution of 1-cm
optical path was investigated with standard Z-scan technique. The 1-mJ, 1 kHz, 120-fs
laser pulses were generated by a Ti:Sapphire regenerative amplifier (Quantronix,
Titan), which was seeded by an erbium-doped fiber laser (Quantronix, IMRA). The
details of the Z-scan setup can be found in Ref. 16. For comparison, similar 3PA
measurements were conducted on a 0.5-mm-thick cubic ZnS bulk crystal
(Semiconductor Wafer, Inc.) with laser polarization perpendicular to its <111> axis.

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All the Z scans reported here were performed with excitation irradiances below the
damage threshold, which was determined to ~ 130 GW/cm2 for the ZnS NC solution
by a reported method.17
Figure 3 illustrates the open-aperture (OA) Z-scan curves for the ZnS NCs and
the ZnS bulk crystal at different excitation irradiances (I00), which is defined as the
peak, on-axis irradiance at the focal point (z = 0) within the sample. By employing an
analytical method,16 the 3PA coefficients,γ , for the ZnS NC solution and the ZnS
bulk crystal are found to be 0.000045 and 0.0016 cm3/GW2, respectively. The 3PA
coefficients are related to the imaginary part of the fifth-order susceptibilities by
)
00
Im5
ελχπγ
cn
=
, where n0 is the linear refractive index, c the speed of
( )(
2
2
3
5
light in vacuum, and ε0 the dielectric constant in vacuum. Thus, the intrinsic 3PA
coefficient of the NCs,
NC
γ
, can be derived as
) /(
6
3
0
3
0
ffnn
v NCsolution solution
γ
NC
γ=
,
where ƒv is the volume fraction of the NCs in the aqueous solution, and f the local
field correction that depends on the dielectric constant of the solvent and the NCs. The
value of f is ~0.58 while ƒv (~0.89%) can be accurately determined by elemental
analysis. The intrinsic 3PA coefficient obtained for the ZnS NCs is 0.024 cm3/GW2,
which is ~15 times larger than that of the bulk ZnS. This enhancement can be
attributed to the quantum confinement effect18 in ZnS NCs since our NCs’ average
radius (~ 1.3 nm) is much smaller than the Bohr exciton radius (~ 2.2 nm). Note that
our measured 3PA coefficient for bulk ZnS is in good agreement with our recent
report.16 We can convert the 3PA coefficient of 0.000045 cm3/GW2 into the 3PA
cross-section (σ3) by the definition of
0
2
3
)(
N
γω
h
σ=
, where
ω
h
is the photon
energy, and N0 the density of ZnS NCs in the solution. By using N0 = 1.1 × 1018 cm–3,

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we find σ3 to be 2.7 × 10–78 cm6s2 photon–2 for the ZnS NCs, which is at least two
orders of magnitude larger than that of ZnS bulk crystal.19 Furthermore, this 3PA
cross-section is four to five orders of magnitude higher than those of common UV
fluorescent dyes,20 and nearly one order of magnitude larger than that of CdS NCs,5
which is one of the fluorescent semiconductor NCs for multiphoton-excited
fluorescence imaging. The comparison of CdS NCs, ZnS NCs and ZnS bulk crystal is
presented in Table I. Note that the 2PA cross-sections for ZnS NCs (~2.0 × 10–46 cm4s
photon–1) are about one order of magnitude higher than that of CdS NCs (~10–47 cm4s
photon–1).5,9
As shown in Fig. 2, there exist surface (or defect) states below the lowest
excitonic transition. These states could mediate multi-step excitation processes, which
might lead to apparently high value of the 3PA cross section. To assess the magnitude
of the 2PA, we plot Ln(1–TOA) vs. Ln(I0), as detailed in Ref. 16. By the use of linear
fit to the plots of Ln(1–TOA) vs. Ln(I0), one can find the gradient to 2 for 3PA and 1
for 2PA. As shown in the insets of Fig. 3, the slope obtained (s = 1.9) confirms the
dominance of 3PA in the ZnS NCs. In addition, we can also determine the 2PA and
3PA coefficients unambiguously with the use of a Z-scan theory recently developed
for materials that possess 2PA and 3PA simultaneously.21 Details of the calculation is
not presented here but it verifies again that the 2PA is negligible in the ZnS NCs.
In the pump-probe experiments, we employed a cross-polarized, pump-probe
configuration16 with the same laser system used for the Z scans. The intensity ratio of
the pump to the probe was kept at least 40: 1. Fig. 4 illustrates the degenerate transient
transmission signals (–∆Т) as a function of the delay time. For the bulk crystal, the
transient transmission signals are mainly dominated by the autocorrelation function of
the pump and probe pulses, which reveal that the 3PA plays a key role in the observed

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nonlinear absorption since 3PA is an instantaneous nonlinear process. When the
excitation pump irradiance is increased to ~ 200 GW/cm2, there is a long absorption
tail with a characteristic time of ~ 100 ps or longer. This slow recovery process can be
attributed to absorption of 3PA-excited free carriers in the bulk ZnS since the
amplitude of the absorption tail grows proportionally to the cube of the excitation
pump irradiance (not shown in Fig. 4). The oscillatory behavior observed at higher
excitation irradiance might be attributed to saturation of 3PA or excitation of phonon
mode.22 However, both slow recovery and oscillatory behavior do not manifest
themselves in the ZnS NCs with the excitation irradiance up to ~130 GW/cm2, which
is the photo-induced damage threshold. The main peaks in the measured dynamics
seem to be broader in the NCs than in the bulk crystal. This may be attributed to group
velocity dispersion since the ZnS-NC solution is contained in a 1-cm-thick quartz cell,
while the thickness of the ZnS bulk crystal is 0.5 mm.
In summary, our study shows that the ZnS NCs possess a larger 3PA cross
section than its bulk counterpart; and it is also nearly one order of magnitude greater
than CdS NCs. More importantly, such a large 3PA is observed at 780 nm, an optimal
wavelength of commercial Ti:sapphire femtosecond lasers.


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References
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Kumar and S. Mahamuni, Appl. Phys. Lett. 84, 4602 (2004).
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[20] C. Xu and W. W. Webb, in Nonlinear and Two-photon-induced Fluorescence,
Topics in fluorescence spectroscopy Vol. 5, edited by J. R. Lakowicz (Plenum,
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131111 (2005).



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Table I. Crystallite size, one-photon absorption, 2PA and 3PA of water-soluble ZnS NCs













aReference 12.
Calculated size (nm)

HRTEM
(nm)
XRD
(nm)
NEMAa
FP-LAPWb
Lowest one-
photon
absorption
transition
(nm)
γNC
(cm3/GW2)
3PA cross-section
(σ3)
(cm6s2 photon–2)
2PA cross-section
(σ2)
(cm4s photon–1)
ZnS NCs2.5 2.2 2.5 2.6 293 0.024 2.7×10–78
~ 2.0×10–46 c
Bulk ZnS 337 0.0016 0.6×10–80 d

CdS NCs 3.9 440e
~ 10–79 e
~ 10–47 e
bReference 13.
cReference 9
dReference 19.
eReference 5.


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Figure Captions

Fig. 1 (a) HRTEM micrograph and (b) XRD pattern (thick solid line :—) of the ZnS
NCs. Gaussian fit of the data curve (thin solid line :―), and the individual
deconvoluted peaks (dotted lines :···) are also included in (b).

Fig. 2 UV-vis absorption (solid line :―), PL (dashed line :---) and PLE (dotted
line :···) spectra of the ZnS NCs. The excitation wavelength of PL spectrum is
290 nm, while the emission wavelength of PLE spectrum is 450 nm.

Fig. 3 Open-aperture Z-scans at different excitation irradiances (I00) at 780 nm for (a)
the ZnS NCs and (b) the ZnS bulk crystal. The symbols denote the
experimental data while the solid lines are theoretically fitted curves. The
insets show the plots of ln(1–TOA) vs. Ln(I0); the solid lines represent the linear
fits to the data.

Fig. 4 Degenerate, transient transmission measurements on the ZnS NCs at 780 nm at
different excitation pump irradiances (I00). The inset shows similar
measurements on the ZnS bulk for comparison.







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2030 405060 70
500
1000
1500
2000
2500
(b)
(311)
(220)
(111)


Intensity (a.u.)
2 nm
2 nm
(a)

2θ (º)



















Fig. 1. J. He et al.


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300 400500 600
0
1
2
3
0
1
2
3
Wavelength (nm)
Absorbance
PL or PLE (a.u.)


Abs
PLE
PL















Fig. 2. J. He et al.




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-6-30369
0.7
0.8
0.9
1.0
(b)



Z position (mm)
Normalized transmittance
ZnS bulk
(I00:GW/cm
33.9
124
175
2)
345
-6
-4
-2




s=2.1
ZnS bulk
Ln(I0)
Ln(1-TOA)
-2-101234
0.8
0.9
1.0
(a)


ZnS NCs
(I00:GW/cm
82.5
91.7
108
116
2)
Normalized transmittance
Z position (cm)
3.6 4.04.44.8
-4
-3
-2
ZnS NCs
s=1.9



Ln(I0)
Ln(1-TOA)

















Fig. 3. J. He et al.




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0123
0
2
4
6
8

ZnS NCs
(I00: GW/cm
7.5
30
71
2)
Delay time (ps)
-∆ ∆T (a.u.)


0123
0
10
20
30
40



Delay time (ps)
-∆ ∆T (a.u.)
ZnS bulk (I00: GW/cm
8.5
14
22
34
210
2)













Fig. 4. J. He et al.






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