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Nanoengineering the second order

susceptibility in semiconductor quantum


dot heterostructures
Marcin Zielinski,1,2,5 Shoshana Winter,3 Radoslaw Kolkowski,1
Claude Nogues,2 Dan Oron,3 Joseph Zyss,1,2 and
Dominique Chauvat1,2,4
1 Laboratoirede Photonique Quantique et Moléculaire, Ecole Normale Supérieure de Cachan,
Cachan, 94230 CEDEX, France
2 D’Alembert Institute, Laboratoire Européen Associé NABI, CNRS-Weizmann, France
3 Department of Physics of Complex Systems, Weizmann Institute of Science,

Rehovot, 76100, Israel


4 chauvat@lpqm.ens-cachan.fr
5 marcin.zielinski@ens-cachan.fr

Abstract: We study second-harmonic generation from single CdTe/CdS


core/shell rod-on-dot nanocrystals with different geometrical parameters,
which allow to fine tune the nonlinear properties of the nanostructure. These
hybrid semiconductor-semiconductor nanoparticles exhibit extremely
strong and stable second-harmonic emission, although the size of CdTe
core is still within the strong quantum confinement regime. The orientation
sensitive polarization response is analyzed by means of a pointwise additive
model of the third-order tensors associated to the nanoparticle components.
These findings prove that engineering of semiconducting complex het-
erostructures at the single nanoparticle scale can lead to extremely bright
nanometric nonlinear light sources.
© 2011 Optical Society of America
OCIS codes: (190.2620) Harmonic generation and mixing; (160.4236) Nanomaterials.

References and links


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1. Introduction
The optical properties of semiconductor quantum dots (SC QDs) can be tailored by control
of their size, shape and material composition. This ability is a result of quantum confinement
effects, which strongly determine the density of states and hence QDs optical features [1, 2].

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Over the last decade, significant advances in the field of nanoparticle synthesis has enabled
fabrication of increasingly complex nanoparticles (NPs) such as various core/shell heterostruc-
tures [3,4], anisotropically shaped or branched nanoparticles containing different semiconduct-
ing materials [5–8] metal oxide - semiconducting quantum rods (QR) [9], and semiconductor-
metal nanocrystal heterostructures [10, 11]. The production of such composite NPs that also
retain quantum confinement makes these materials interesting in nonlinear optics.
Second-harmonic generation (SHG) from single dot-shaped CdTe/CdS core-shell QDs
was recently observed by the authors using a two-photon scanning microscopy technique
(TPSM) [12]. The strong second-order nonlinearity of the CdTe core with a large nonlinear
coefficient d14 of up to 200 pmV−1 and its non-centrosymmetric, tetrahedral zinc-blende crys-
talline lattice [13, 14] allowed for downsizing QDs to 10-15 nm diameter, while maintaining
a strong second-harmonic (SH) emission, in the range of 105 cts/s from a single QD. This
was achieved with standard 100 fs pulses of near infrared (NIR) Ti-Sapphire laser light at 80
MHz repetition rate. The observed SH emission is polarization-sensitive, tunable and photo-
stable out of the one-photon resonance [12]. It shows reduced photobleaching under strong
excitation intensity, which is known as a main limitation of many organic fluorophores [15,16],
and eliminated emission intermittency (’blinking’) as is commonly observed for luminescent
QDs [17, 18]. These semiconducting QDs widen the range of applications of other nonlinearly
active inorganic nanoparticles [19–23], especially for high spatial resolution in optical near-
field probing or biological applications, such as nanolabeling.
The state-of-the-art techniques in developments of complex nanoscale objects provide the
possibility of engineering the nonlinear properties of these structures. These properties would
reflect the combination of tensorial optical responses from different materials as well as the
precise structural engineering of hybrid heterostructures, obtained by applying different sym-
metries together:
(2) (2) (2) (2)
χhybrid = χsym1 + χsym2 + χsym3 + ... (1)
(2)
where χhybrid is third rank tensor of second-order nonlinear susceptibility of the whole hy-
brid heterostructure, composed of susceptibilities corresponding to different materials and their
(2)
symmetries χsym1(2,3,...) . It would be of interest for matching the emission of a nonlinear nano-
metric sized source, e.g. its electromagnetic radiation, to any particular application in high
resolution optical microscopy. Some work on that field have been already reported, e.g. struc-
turing material with a focused ion beam for tailoring SHG properties of metallic nanoemitters
has been carried out with some success [24]. Enhancement of the SHG from an inorganic
BaTiO3 NP covered by a gold shell was also recently demonstrated [25]. Additionally, cou-
pling of gold nanorods attached to SC QDs has been investigated showing a synergistic effect
on the SHG in Hyper-Rayleigh scattering (HRS) ensemble experiment [10]. In a different ap-
proach, it is tempting to adapt well developed methodologies of SC QDs colloidal synthesis
to explore semiconductor-semiconductor hybrid nanostructures in order to tailor their optical
nonlinearities at the single NP scale.
Herein we propose an ’artificial’ nanosource for the controlled character of the nonlinear
scattering from single hybrid SC QD, where the nonlinear emission is controlled through the
choice of QD materials and geometrical parameters. As a proof-of-principle experiment we
consider a rod-on-dot (RD) quantum confined heterostructure made of two semiconducting
materials: CdTe and CdS- each having a different crystalline structure (zinc blende correspond-
ing to the 4̄3m and wurtzite 6mm point group symmetry, respectively), nonlinear susceptibility
tensor and spatial geometry (QD and quantum rod (QR), respectively):

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(C) 2011 OSA 11 April 2011 / Vol. 19, No. 8 / OPTICS EXPRESS 6659
(2) (2) (2)
χRD = χ4̄3m + χ6mm (2)
Our idea, based on the pointwise additive model of coupled SHG fields, is confirmed by the
experimental findings, allowing for accurate extraction of the three-dimensional orientation of
a single RD QD heterostructure as well as the CdS QR length

2. Materials and methods


2.1. Characterization of RD QD heterostructures
One-pot synthesis of rod-on-dot CdTe/CdS hybrids was conducted via modified standard proce-
dures [26]. 60mg tetradecyl phosphonic acid (PCI synthesis) and 13 mg Cadmium oxide were
added to 5mL octadecene (ODE) and heated up to 260oC under an Argon atmosphere, until
full dissolution of the Cadmium oxide. At this point, 0.013 g of elemental Tellurium in 2ml
trioctylphosphine (TOP) was swiftly injected into the flask and the temperature was lowered to
210oC. After several minutes the temperature was raised to 250oC and alternate injections of
0.1M Cadmium oleate in ODE and 0.1M TOP:Te, separated by 10 minutes, were performed.
When the size of the QDs reached 6 nm, the TOP:Te was replaced by elemental Sulfur dis-
solved in a 1:1 mixture of ODE and TOP. Three consecutive injections were performed at
increasing temperatures starting from 210oC and ending at 250oC. Following this, emission
had shifted from 708 nm to 713 nm. At this stage, a more reactive sulfur precursor was used
(0.1M Bis(trimethylsilyl)sulfide in ODE). Injections were carried out at temperatures varying
from 180oC to 230oC. During these injections, the emission slowly red-shifted until reaching a
final value of 720nm. The absorption and emission curves of both the CdTe cores and the final
CdTe/CdS hybrids are given in Fig. 1.

Fig. 1. (a) Absorption and (b) emission curves for the CdTe cores (dashed lines) and the
CdTe/CdS hybrid structures (solid lines). The CdTe/CdS absorption curve is vertically
shifted for clarity.

The QD geometrical features were investigated using transmission electron microscopy


(TEM) (Fig. 2a) and by atomic force microscopy (AFM) (Fig. 2b, 2c). Size determination
is quite important since SHG is expected to scale as the squared volume of the scatterer, mak-
ing it especially critical when applied to complex structures composed of at least two different
types of materials requiring a strong necessity for dimension characterization for further SHG
studies. The size of spherical CdTe cores was determined from the absorption spectrum during
their growth to 5.9 nm [26]. For the case of geometrically complex structures, such as RD QDs,
dimensions are best obtained directly from the TEM images. The size distribution of forty iso-
lated RD QDs, directly obtained from the TEM images, is shown in the histograms in Figure
2d-f. Size dispersion varies in a range between 5.7 - 6.2 nm diameter of the CdTe core (consis-
tent with the optical measurements), and 2.4 - 3.6 nm diameter of the CdS rod. The length of
the CdS rod is dispersed over a wider range, from 6.0 -16.0 nm, with a mean value of 11.0 nm.

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The complexity of the RD QDs leads to several implications, arising from a new geometry
and new physical features of such-formed hybrid NPs. This consequently impacts on described
SHG studies. Indeed, analysis of the SHG polarization dependency requires a precise definition
of the mutual orientations of the CdTe cubic zinc-blende lattice, which belongs to the 4̄3m point
group symmetry, with respect to that of the CdS rod structure. In this particular case, synthesis
conditions of RD QDs imposed growth of the CdS rod into the hexagonal wurtzite form, cor-
responding to a 6mm point group symmetry. To describe the relative lattice orientations of the
two crystal structures at the interface we used the convention described in the literature [27–
29]. The epitaxial relationships are therefore characterized by the [011̄0] axis of CdS oriented
parallel to the [112̄] axis of CdTe, and the CdS [0001] axis oriented parallel to the [111] axis of
CdTe, which means that the 6-fold axis of symmetry (parallel to [0001]) is oriented along the
rod’s growth direction. This orientation comes from the epitaxial constraint compatibility of the
zinc-blende +/ − (111) and wurtzite +/ − (0001) facets at the interface [6, 28]. For two differ-
ent materials such as CdTe and CdS, it minimizes the mismatch between two lattices down to
9.8% [30]. Thus, the rotation angle of the CdS rod around its [0001] axis relative to the CdTe is
fixed.

Fig. 2. a) TEM image of the rod-on-dot quantum heterostructures; CdTe cores and CdS
rods are clearly distinguishable. b - c) AFM topographical and phase scans (obtained with
a tapping mode (TM)) of a single and well isolated RD QD immersed within a ≈ 30 nm
thick PMMA host-matrix. d - f) TEM based histograms of the effective size distribution,
characterizing the CdTe core and CdS rod dimensions.

2.2. Sample preparation


A dilute sample containing CdTe/CdS hybrid RD QDs was prepared following a similar pro-
cedures to that described in Ref. [12], and previously used for single dot studies. Before de-
position, prepared colloidal solution of RD QDs in anisole (2.0 mg per 5 mL of the solvent)

#137305 - $15.00 USD Received 27 Oct 2010; revised 29 Nov 2010; accepted 30 Nov 2010; published 24 Mar 2011
(C) 2011 OSA 11 April 2011 / Vol. 19, No. 8 / OPTICS EXPRESS 6661
was sonicated for 1 hour to avoid aggregation. In order to obtain ≈ 30nm thick poly(methyl
methacrylate) (PMMA) host-matrix layer (MicroChem 4% 495K in anisole, diluted to 2%
MW), measured with a DEKTAK 3ST surface profiler, prepared solution containing RD QDs
was spin coated (4000 rpm, 1000 acc., 45 s) on glass cover slips (#1, cleaned before with oxy-
gen plasma) and held at 180oC for 1 min. The quality of the sample was checked by taking
several AFM scans (Veeco, Nanoscope V) using tapping mode to confirm the presence of well
dispersed monocrystals. The characteristic shape of the rod and the core are distinguishable in
Figure 2b-c, despite the presence of the PMMA host-matrix layer.

2.3. Nonlinear scanning polarization microscopy


The nonlinear optical response was measured with the same TPSM setup, equipped with Nikon
Eclipse TE2000-U inverted confocal microscope, that was previously used to study SH emit-
ting spherical CdTe/CdS core/shell QDs [12]. NPs were excited with a Spectra-Physics Mai-Tai
HP Ti-Sapphire oscillator, emitting 100 fs pulses at a repetition rate of 80 MHz. SHG photons
were detected in the epi-direction via a high numerical aperture oil-immersion objective (Nikon
X100 PA IR, NA = 1.4), and well separated spectrally from the NIR excitation beam (dichroic
mirror with a cutoff wavelength at 700 nm), as well as from eventual two-photon excited lumi-
nescence (TPEL) by a set of BG38-39 band-pass filters and short-pass Semrock SP561 filter.
Polarization analysis was achieved by precise rotation of the achromatic half-wave plate in the
excitation optical path. In the detection channel, the SHG signal was decomposed into x and y
polarization components by a polarizing beam splitter, and detected by two silicon avalanche
photodiodes (APDs, Perkin-Elmer SPCM-AQR-14) working in the photon counting regime.
The emission spectrum was obtained with an Oriel Multispec 7740 spectrometer (160 nm nar-
row slit), equipped with an Andor Technology DV420-OE CCD camera. Measurements of the
SHG excitation wavelength dependence were performed using APDs with an integration time
of 1s, while the excitation wavelength was automatically tuned using the Mai-Tai scanning
mode with a step of 1 nm/sec. The raw data was corrected by the laser output power and
transmission characteristics of all optical components of the setup, as well as by the quantum
efficiency of the APDs (see Supplementary Information for Ref. [12]).

Fig. 3. (a) Graphical illustration and (b) analytical analysis of the polarization response
of decomposed total SHG field EscatSHG , calculated for a single RD QD (b). Polarization

plots show contributions of the CdTe core, CdS rod and the interference term (positive and
SHG .
negative) into Itot

#137305 - $15.00 USD Received 27 Oct 2010; revised 29 Nov 2010; accepted 30 Nov 2010; published 24 Mar 2011
(C) 2011 OSA 11 April 2011 / Vol. 19, No. 8 / OPTICS EXPRESS 6662
3. Results and discussion
3.1. Theoretical model: SHG emission from RD heterostructure
In order to obtain the direct expression of the second-harmonic polarization response from a
hybrid RD QD consisting of two different materials, we use a linear combination of components
of the CdTe and the CdS second-order susceptibility tensors, assuming the contribution of each
(2) (2) (2)
of them to be proportional to its volume in the whole structure: χRD ∝ χCdTe + VCdSVCdTe−1
χCdS .
The volumes of the spherical CdTe core and of the cylindrical CdS rod are characterized by
considering the shape of each part, and the size distribution including the diameter of the CdTe
core assumed as DCdTe = 6.0 nm and the diameter of the CdS rod DCdS = 3.0 nm. The length of
the rod is a variable, which has a strong impact on the total SHG response, as analyzed below.
The contribution of SH fields generated from both materials into the total SHG field emitted by
SHG ∝ ∂ 2 P(2) requires consideration of coupling and appearance of the
a single RD scatterer: Escat ∂ t 2 SHG
interference effect occurring between SHG fields from both sources. Thus the SHG intensity
SHG ∝ E SHG 2 , resulting from a linear combination of the second-harmonic fields, can be

Itot scat
expressed as:

f erence i ∝
SHG SHG SHG SHG
 
Itot i
= ICdTe + ICdS + Iinter (3)

∑ E ωj Ekω Elω ∗ Emω ∗


h  i
(2)CdTe (2)CdTe∗ (2)CdS (2)CdS∗ (2)CdTe (2)CdS∗
∝ χi jk χilm + ν 2 χi jk χilm +ν χi jk χilm + c.c.
jklm

where ν = VCdSVCdTe−1 2 3
−1
= 3DCdS LCdS 2DCdTe is the volume ratio between CdS and CdTe, of
the order of unity for our RD QDs.
This pointwise additive model, when applied separately to both x and y polarization compo-
nents, allows for quantitative analysis of the SHG field terms described by Eq. (3) accounting
for the total SHG field emitted by the whole hybrid crystalline structure. Figure 3 shows an
example of such an analysis, conducted for one of the experimentally obtained results. The
signal intensities are plotted as a function of the polarization angle of the pump relative to the
laboratory x-axis for both x-polarized and y-polarized SH in the lab frame. We fit the relative
orientation of the QD in the lab frame and the relative volume via the length of the rod, while
other parameters (diameter of the CdTe core and width of the CdS rod) are kept fixed at the
mean values obtained from TEM images.

3.2. Theoretical model: SHG dependence on the CdS rod length


Detailed studies of the CdS rod length dependence give evidence of the significant contribution
of this feature to the overall SHG response. The polarization pattern of the SHG emission
from the zinc-blende-like CdTe core displays characteristic fourfold cloverleaf response [12], as
expected from its octupolar 4̄3m symmetry [31, 32], progressively changing into a dominantly
dipolar-like pattern as the CdS rod grows. Appearance of the rod leads to a progressive loss
of additional maxima for each component, which is imposed by the dipolar 6mm symmetry
of the hexagonal form of the CdS crystalline lattice. Thus the character of the SHG emission
can be tuned between different symmetries by control over the geometrical features of the SC
heterostructure. The pointwise additive model has been used to visualize the transformation
of total SHG field dependence on the CdS rod length. In Fig. 4 we present calculations for a
single RD QD for five cases: a CdTe core with approximately 6 nm diameter, RD QD with
different lengths of the CdS rod: 4, 8, 13 nm (corresponding to the experimental data), and 20
nm, where the SHG emission pattern is aligned along the CdS rod [0001] axis, and without
visible contribution of the CdTe core to SHG response. It is clear that the appearance of even a

#137305 - $15.00 USD Received 27 Oct 2010; revised 29 Nov 2010; accepted 30 Nov 2010; published 24 Mar 2011
(C) 2011 OSA 11 April 2011 / Vol. 19, No. 8 / OPTICS EXPRESS 6663
short CdS rod, e.g. 4 nm long, changes the SHG pattern in a drastic manner as compared to the
fourfold cloverleaf response of the core. Further growth of the CdS rod significantly reduces
the relative CdTe contribution, leading to approximately equal contributions of both materials
for 8 nm long rod (which gives VCdS ≈ 57nm3 versus VCdTe ≈ 113nm3), while 13 nm long rods
(VCdS ≈ 92nm3) are enough for the dipolar character of the SHG polarization response to prevail
over the octupolar core contribution. An overgrown 20 nm long rod completely transforms the
SHG field into quasi dipolar-like.

Fig. 4. a) Rod-on-dot QD cross-sections illustrating growth of the CdS QR in a range from


4 - 20 nm on a 6 nm diameter CdTe core. b) Calculated polarization responses of the SHG
emission, obtained for a single RD QD during progressive growth of its rod.

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(C) 2011 OSA 11 April 2011 / Vol. 19, No. 8 / OPTICS EXPRESS 6664
Taking into account two facts, primarily that the number of emitted SHG photons is propor-
tional to the volume squared of the emitter and, secondly, comparable nonlinearities of CdTe
and CdS (here for CdTe we assume the low value of d14 = 64.0pmV−1) [13, 14], it appears
that the interference term has a strong constructive or destructive contribution, and based on the
model (expression (3)) it changes linearly with a linear growth of the CdS quantum rod.

3.3. Polarization analysis of the experimental results


One of the distinct advantages arising from the SHG process of nanoscale scatterers is un-
doubtedly its high sensitivity to the polarization of the incident optical electromagnetic field
Ē ω . This enables probing of the spatial orientation of the scatterer relative to the laboratory
frame. Such experiments have been successfully conducted with both single-material inorganic
and organic nanocrystals, where the SHG response was determined by the regular crystalline
lattice (where it is relatively easy to process experimental polarization analysis from a theoret-
ical model) [12, 19, 20, 33, 34].
Decomposition of the x and y components of the optical polarization components of the
emitted SHG field is achieved as a function of the rotation angle of the incident electromagnetic
field Ē ω at the fundamental frequency ω . This model neglects depolarization and propagation
effects due to the embedding dielectric host material [35]. The RD QDs response can thus be
specified by a single P̄2ω dipole oscillating at the 2ω frequency [13]:

Pi (2ω ) = ε0 ∑ χi jk (−2ω ; ω , ω )E j (ω )Ek (ω )


(2) (2)
(4)
j,k

where ε0 is the permittivity of the vacuum; E j(k) (ω ) is the amplitude of the j (resp. k) component
of the excitation field at the frequency ω ; i, j and k are the components of the second-order
(2)
nonlinear optical susceptibility tensor χi jk , associated with the x, y and z axes of the Cartesian
(2)
laboratory frame. Pi (2ω ) is obtained by rotation of the second-order nonlinear susceptibility
(2)
tensor χRD of the overall RD QD structure in the (X, Y, Z) crystalline axes by the Euler set
of angles (α , β , γ ) in the laboratory frame using the z-y-x convention. In z-y-x convention, the
angle α describes the rotation around the Z axis and can be visualized as the rotation of the CdS
rod around the CdTe core, performed in the x, y plane. The second rotation angle - β , describes
the rotation around the Y axis. Because the Y axis is perpendicular to the rod, we can use the
value of β as a measure of the amount by which the rod sticks out from x, y plane, which is
the plane of the spin coated PMMA host-matrix of the sample. The last angle γ describes the
(2)
rotation around the rod axis. In the simplest approximation, χRD results from the rotation of
two tensors:
 
0 0 0 d14 0 0
(2)
χCdTe = 2  0 0 0 0 d14 0  (5)
0 0 0 0 0 d14
 
0 0 0 0 d15 0
(2)
χCdS = 2  0 0 0 d15 0 0  (6)
d31 d31 d33 0 0 0
assigned to the 4̄3m and 6mm symmetry point groups respectively, where we assume
d14 = 64.0pmV−1, d15 = 44.0pmV−1, d31 = 40.2pmV−1 and d33 = 77.9pmV−1 [13]. In order
to fit the experimental data we have used the pointwise additive model described by expression
(3).

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(C) 2011 OSA 11 April 2011 / Vol. 19, No. 8 / OPTICS EXPRESS 6665
Fig. 5. a) Experimentally obtained polarization analysis of the SH emission observed for
three RD QDs (QD 1-3). Open scattered points represent the raw data, while line traces
show smoothed functions (SF). b) Calculated fits of the experimental data smoothed traces.
c) 3D projections of RD QD crystalline lattices, characterizing the orientations of experi-
mentally studied RD NPs by Euler sets of angles.

Analysis of the experimental data obtained for three differently oriented RD QDs (Fig. 5a)
(2)
show very high sensitivity of the polarization response with respect to the orientation of the χRD
tensor, determined by the spatial position of the hybrid lattice. The excellent agreement between
the fits (see Fig. 5b) and the raw data is firstly, proof of the single dot origin of the harmonic
signal, ruling out the occurrence of complex crystalline multiple QD clusters or aggregates, thus
opening possibilities for precise determination of the corresponding spatial orientation of both
the CdTe core and CdS rod structures. The fit obtained for QD1 experimental result (first row of
Fig. 5) has been used to illustrate decomposition of the total SHG field based on the pointwise
additive model into contributions of each part of the heterostructure and the interference term,
presented in Fig. 3. The impact of the different lengths of the CdS QR on the SHG polarization
pattern (Fig. 4) corresponds to the same experimental result.
In order to obtain their orientations we have taken into account the mutual relations be-
tween both lattices, and used the model described in previous subsections. Generated three-
dimensional projections (Fig. 5c) of hybrid RD QD lattices corresponding to the orientations of
experimentally scanned RD QDs, seen in the x,y,z laboratory frame, show the mutual positions
of the CdTe and CdS lattices. It is clear that the orientation of the dipole is determined by the
[0001] axis of CdS oriented along the QR. In each case, the out-of-plane deviation (described
by the angle β between the CdS [0001] axis and the x, y plane) is lower than 45o , which to some
extent was forced by the spin coating conditions resulted in ≈ 30nm thick PMMA host-matrix,
where the RD QDs were expected to lie on the surface. However, our model can also efficiently
support less frequently occuring NPs with vertically oriented rods.

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(C) 2011 OSA 11 April 2011 / Vol. 19, No. 8 / OPTICS EXPRESS 6666
Fig. 6. a) SHG emission spectra, recorded with the same incident power of about 3.0 mW, at
six different excitation wavelengths (intensities without correction, given in arbitrary units).
The inset shows a diffraction limited scan of a single RD QD with respect to the laboratory
axis frame. b) SHG quadratic dependency on the incident power of the excitation light,
evidencing a two-photon process. The inset contains the same data plotted on a logarithmic
scale. c) Photostability of the SHG signal scattering from a single RD QD, recorded as two
polarization components along x (red trace) and y (blue trace), respectively.

#137305 - $15.00 USD Received 27 Oct 2010; revised 29 Nov 2010; accepted 30 Nov 2010; published 24 Mar 2011
(C) 2011 OSA 11 April 2011 / Vol. 19, No. 8 / OPTICS EXPRESS 6667
3.4. Spectral dependence of the SHG: influence of the quantum confinement effect
An example of the diffraction limited and well-contrasted SHG spot obtained by scanning a
single RD QD is shown in the inset of Fig. 6a (together with its orientation in reference to the
laboratory axis). The full width half maximum (FWHM) of the observed spot is approximately
290 nm. Typically, scans were obtained with the excitation wavelength set at 890 nm and with
an incident power of 3.0 mW, leading to a focused pulsed peak intensity of about 95GWcm−2 .
Examples of emission spectra recorded at various excitation frequencies between 850 - 950
nm and showing about 7 nm narrow line-width peaks of SHG, with a high signal-to-background
ratio, are presented in Fig. 6a as uncorrected raw data traces in arbitrary units. SHG emission,
however, even without correcting for the transmission of optical components is clearly dom-
inant over the whole range of excitation. The second-order character of the SH emission is
confirmed by the quadratic dependence on the incident power of the excitation laser light (Fig.
6b). Signals obtained from purely SHG emitting RD QDs (e.g. Fig. 6c) show a high degree
of photo-stability, even when doubling the intensity of the excitation in comparison with the
used excitation conditions. We observe, however, an inverse correlation between the intensity
of two-photon luminescence from these QDs and their photostability. We believe that the re-
duced photo-stability of QDs exhibiting stronger band-edge luminescence is due to induced
excited state absorption at the excitation frequency. For RD QDs exhibiting low luminescence
quantum yield (studied in this work) the excited state population completely decays nonradia-
tively within the 12 ns time interval between consecutive excitation pulses, eliminating such
possible effects.
As can be seen in Fig. 6c, under ’standard conditions’ (890 nm of excitation wavelength, with
the polarization of the incident optical electric field oriented along the dipole moment of the
single RD QD) we have observed approximately 7 · 104cts/s SHG signal count rate, which is as
strong as typical luminescence from bright QDs, despite the relatively low quantum efficiency
of the APDs of ≈24% at 445 nm. Taking into account the transmission of the collection optics as
well as the collection efficiencies, this corresponds to a SHG cross section of the order of 50GM.
It is important to point out, that this count rate was obtained from hybrid RD QD with 12nm
long rods, which corresponds to a volume of about 113nm3 for the CdTe core and 85nm3 for
the CdS rod, such that the total volume was nearly 6 times less than that of spherical CdTe/CdS
QDs (with a mean diameter about 13 nm) previously observed in single-dot studies [12]. In
this particular case, however, excitation at 890 nm does not provide the highest possible SHG
cross-section. The blue curve in Figure 7 shows that the optimal excitation wavelength at 925
nm instead of 890 nm (for this size of RD QD) would result in a nearly one and half times
higher count rate of about 1.1 · 105cts/s. SHG obtained with that excitation frequency would be
also detected with higher efficiency by the Silicon-based APDs.
(2) 2
 
The SHG emission reflects an effective nonlinear coefficient χRD corresponding to the
ef f
second-order nonlinear optical susceptibility squared, measured at a high level of the emission
photostability in the range from 800 to 990 nm (no phase-matching requirement). The raw data
was corrected for the excitation laser power, detector response and transmission of the various
optical components [12]. This results in the curves presented in Fig. 7. The blue excitation
spectrum trace corresponds to the typical sized RD QD. As can be expected from a system with
a discrete energy level spectrum, it exhibits multiple peaks. As for previously studied spherical
QDs (see the open black scattered trace) [12], there is an optimal excitation wavelength for
SHG at about 925 nm. It is, nevertheless, significantly blue-shifted with respect to the peak
positions for larger spherical CdTe/CdS QDs (970 nm) as could be expected due to the stronger
carrier confinement regime in agreement with the larger band gap of the smaller QD. RD QDs
which were identified as having a shorter CdS rod (thus having an increased confinement of

#137305 - $15.00 USD Received 27 Oct 2010; revised 29 Nov 2010; accepted 30 Nov 2010; published 24 Mar 2011
(C) 2011 OSA 11 April 2011 / Vol. 19, No. 8 / OPTICS EXPRESS 6668
Fig. 7. Excitation spectra showing the wavelength dependence of the SHG intensity ob-
served from two different single RD QDs (red and blue traces). The open black scattered
trace, placed for comparison, shows this dependency for spherical CdTe/CdS QDs, reported
in Ref. [12]. All curves reflect changes of the SHG cross-section with respect to the quan-
tum size confinement effect (cross-sections of QDs are scaled with a real ratio with respect
to size differences).

the electron) exhibit, in accordance with this observation, an even further blue shift in the SHG
excitation spectrum, as can be seen in the red trace. A more thorough evaluation of the χ (2)
excitation spectra is proposed in Ref. [12] and is currently under further study.

4. Conclusions
In summary, this work demonstrates a new approach for the engineering of the second-order
nonlinearity of semiconducting hybrid rod-on-dot heterostructures at the single nanoparticle
scale for efficient and photostable SHG emission. These hybrid nanoparticles exhibit extremely
strong and stable emission (with size dependent optimal SHG cross-section) although their vol-
ume is reduced by at least a factor of five from the previous smallest SHG scattering probes.
Moreover, it emphasizes the structural relationship between the CdTe core and CdS rod and
contributions of their respective χ (2) tensors on the SH field. The pointwise additive model
allows for comprehensive simulation of the polarization response, showing quantitative contri-
butions of the CdTe core and the CdS rod, as well as that of their interference term into the total
SH emission. The high degree of agreement between the simulation and the experimentally ob-
served results is not circumstantial and can be considered as evidence for the single crystalline
nature of the investigated QD sample. It permits precise determination of the spatial orientation
of the crystalline structure. It also shows that the hybrid system can be adequately decomposed
into a sum of its constituents in the case of semiconductor-semiconductor hybrids. This simple
result is not trivial and is even surprising since it does not hold for metal-semiconductor hybrid
particles [10]. Still, coupling of the two semiconductor parts may affect the relative magnitude
of the χ (2) coefficient, and will be investigated in a future work. Simulation analysis show that
the SHG response strongly depends on the CdS rod length and transforms from the four clover-
leaf shape characteristic of the octupolar zinc-blende symmetry of the CdTe core into a typically
dipolar response oriented along the CdS rod and imposed by the main polar axis of its hexago-
nal symmetry point group. The conceptual as well as practical possibility to fine tune at will the
balance between dipolar and octupolar contributions by adequate stoichiometry-based molec-

#137305 - $15.00 USD Received 27 Oct 2010; revised 29 Nov 2010; accepted 30 Nov 2010; published 24 Mar 2011
(C) 2011 OSA 11 April 2011 / Vol. 19, No. 8 / OPTICS EXPRESS 6669
ular engineering considerations has already been demonstrated in the case of organo-metallic
compounds for nonlinear optics (NLO) [36]. Extending such an approach from molecular to
nanoscale and from organo-metallics to semiconducting materials requires a very different ap-
proach which is proposed and demonstrated here for the first time, to the best of our knowledge.
Moreover, maintaining control over this delicate multipolar balance at the scale of nanolabels
while minimizing the size of RD QDs paves the way towards very efficient and precise orien-
tation monitoring in original bio-imaging applications.

Acknowledgements
We thank Dr. L. Manna for fruitful discussion about the crystalline structure relationships. We
are grateful to J. Lautru and to Dr. M. Buckle for technical support, and to Dr. R. Popovitz-Biro
for her help with TEM studies, conducted at the Irving and Cherna Moskowitz Center for Nano
and Bio-Nano Imaging at the Weizmann Institute of Science. We gratefully acknowledge finan-
cial support from the Israeli Ministry of Science ”Tashtiyot” program and from the ”Laboratoire
Européen Associé” NaBi between CNRS and the Weizmann Institute of Science.

#137305 - $15.00 USD Received 27 Oct 2010; revised 29 Nov 2010; accepted 30 Nov 2010; published 24 Mar 2011
(C) 2011 OSA 11 April 2011 / Vol. 19, No. 8 / OPTICS EXPRESS 6670