0 Up votes0 Down votes

2 views14 pagesQd for si

Jan 24, 2018

si QD paper

© © All Rights Reserved

PDF, TXT or read online from Scribd

Qd for si

© All Rights Reserved

2 views

si QD paper

Qd for si

© All Rights Reserved

- Tutorial TEM
- List of All Books
- MLab_Sci
- Maxwell Equations in a Nonlinear Kerr Medium
- Statistical analysis of measured free-space laser signal intensity over a 2.33 km optical path
- Optical Image Correlating Velocimeter for metallurgical plants
- LeicaSP2_ UserGuide
- 1808.06136.pdf
- START-HERE Ch03 Lecture
- Folleto BORGES Vf
- Innovativeapproachinmicro Electromechanicalsystemmems 140122000608 Phpapp01
- maaf lagi
- Nis Elements 2ce Mpch 1
- Descr Water Types
- Spark Detector
- Combs 3096 PDF
- Dimension Icon - B068-RevB2
- CRF-Nantech2004_extended_abstract.pdf
- Comar Catalogue Edition 7
- Fiber Optics Brochure 06

You are on page 1of 14

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,

4 chauvat@lpqm.ens-cachan.fr

5 marcin.zielinski@ens-cachan.fr

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.

1. A. P. Alivisatos, “Semiconductor Clusters, Nanocrystals, and Quantum Dots,” Science 271, 933–937 (1996).

2. V. I. Klimov, Semiconductor and Metal Nanocrystals: Synthesis and Electronic and Optical Properties (Marcel

Dekker, Inc., New York, 2004).

3. S. Kim, B. Fisher, H.-J. Eisler, and M. Bawendi, “Type-II Quantum Dots: CdTe/CdSe(Core/Shell) and

CdSe/ZnTe(Core/Shell) Heterostructures,” J. Am. Chem. Soc. 125, 11466–11467 (2003).

4. D. J. Milliron, S. M. Hughes, Y. Cui, L. Manna, J. Li, L.-W. Wang, and A. P. Alivisatos, “Colloidal nanocrystal

heterostructures with linear and branched topology,” Nature 430, 190–195 (2004).

5. X. Peng, L. Manna, W. Yang, J. Wickham, E. Scher, A. Kadavanich, and A. P. Alivisatos, “Shape control of CdSe

nanocrystals,” Nature 404, 59–61 (2000).

6. L. Manna, D. J. Millirion, A. Meisel, E. C. Scher, and A. P. Alivisatos, “Controlled growth of tetrapod-branched

inorganic nanocrystals,” Nat. Mater. 2, 382–385 (2003).

7. E. C. Scher, L. Manna, and A. P. Alivisatos, “Shape control and applications of nanocrystals,” Philosophical

Transactions of The Royal Society A 361, 241–257 (2003).

8. S. Kudera, L. Carbone, E. Carlino, R. Cingolani, P. D. Cozzoli, and L. Manna, “Synthesis routes for the growth

of complex nanostructure,” Physica E 37, 128–133 (2007).

9. H. McDaniel and M. Shim, “Size and Growth Rate Dependent Structural Diversification of Fe3 O4 /CdS

Anisotropic Nanocrystal Heterostructures,” ACS Nano 3, 434–440 (2009).

10. E. Shaviv and U. Banin, “Synergistic Effects on Second Harmonic Generation of Hybrid CdSe-Au Nanoparti-

cles,” ACS Nano 4, 1529–1538 (2010).

#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 6657

11. A. Figuerola, M. V. Huis, M. Zanella, A. Genovese, S. Marras, A. Falqui, H. W. Zandbergen, R. Cingolani, and

L. Manna, “Epitaxial CdSe-Au Nanocrystal Heterostructures by Thermal Annealing,” Nano Lett. 10, 3028–3036

(2010).

12. M. Zielinski, D. Oron, D. Chauvat, and J. Zyss, “Second-Harmonic Generation from a Single Core/Shell Quan-

tum Dot,” Small 5, 2835–2840 (2009).

13. R. L. Sutherland, Handbook of Nonlinear Optics (Marcel Dekker, Inc., New York, Basel, 2003).

14. I. Shoji, T. Kondo, A. Kitamoto, M. Shirane, and R. Ito, “Absolute scale of second-order nonlinear-optical coef-

ficients,” J. Opt. Soc. Am. B 14, 2268–2294 (1997).

15. W. R. Zipfel, R. M. Williams, and W. W. Webb, “Nonlinear magic: multiphoton microscopy in the biosciences,”

Nat. Biotechnology 21, 1369–1377 (2003).

16. G. H. Patterson and D. W. Piston, “Photobleaching in Two-Photon Excitation Microscopy,” Biophys. J. 78, 2159–

2162 (2000).

17. M. Nirmal, B. O. Dabbousi, M. G. Bawendi, J. J. Macklin, J. K. Trautman, T. D. Harris, and L. E. Brus, “Fluo-

rescence intermittency in single cadmium selenide nanocrystals,” Nature 383, 802–804 (1996).

18. P. Frantsuzov, M. Kuno, B. Jankó, and R. A. Marcus, “Universal emission intermittency in quantum dots,

nanorods and nanowires,” Nat. Phys. 4, 519–522 (2008).

19. L. Bonacina, Y. Mugnier, F. Courvoisier, R. Le Dantec, J. Extermann, Y. Lambert, V. Boutou, C. Galez, J.-P. Wolf,

“Polar Fe(IO3 )3 nanocrystals as local probes for nonlinear microscopy,” Appl. Phys. B 87, 399–403 (2007).

20. L. Le Xuan, C. Zhou, A. Slablab, D. Chauvat, C. Tard, S. Perruchas, T. Gacoin, P. Villeval, and J.-F. Roch,

“Photostable Second-Harmonic Generation from a Single KTiOPO4 Nanocrystals for Nonlinear Microscopy,”

Small 4, 1332–1336 (2008).

21. C.-L. Hsieh, Y. Pu, R. Grange, and D. Psaltis, “Second harmonic generation from nanocrystals under linearly

and circularly polarized excitations,” Opt. Express 18, 11917–11932 (2010).

22. A. V. Kachynski, A. N. Kuzmin, M. Nyk, I. Roy, and P. N. Prasad, “Zinc Oxide Nanocrystals for Nonresonant

Nonlinear Optical Microscopy in Biology and Medicine,” J. Phys. Chem. C 112, 10721–10724 (2008).

23. P. Pantazis, J. Maloney, D. Wu, and S. E. Fraser, “Second harmonic generating (SHG) nanoprobes for in vivo

imaging,” Proc. Natl. Acad. Sci. 107, 14535–14540 (2010).

24. B. K. Canfield, H. Husu, J. Laukkanen, B. Bai, M. Kuittinen, J. Turunen, M. Kauranen, “Local Field Asymmetry

Drives Second-Harmonic Generation in Noncentrosymmetric Nanodimers,” Nano Lett. 7, 1251–1255 (2007).

25. Y. Pu, R. Grange, C.-L. Hsieh, and D. Psaltis, “Nonlinear Optical Properties of Core-Shell Nanocavities for

Enhanced Second-Harmonic Generation,” Phys. Rev. Lett. 104, 207402 (2010).

26. W. W. Yu, L. Qu, W. Guo, and X. Peng, “Experimental Determination of the Extinction Coefficient of CdTe,

CdSe, and CdS Nanocrystals,” Chem. Mater. 15, 2854–2860 (2003).

27. P. Villars and L. D. Calvert, Pearson’s Handbook of Crystallographic Data for Intermetallic Phases (ASM Inter-

national, Materials Park, Ohio, 1991).

28. P. Boieriu, R. Sporken, Y. Xin, N. D. Browning, and S. Sivananthan, “Wurtzite CdS on CdTe grown by molecular

beam epitaxy,” J. Electron. Mater. 29, 718–722 (2000).

29. H. Masui, S. C. Cruz, S. Nakamura, and S. P. DenBaars, “Geometrical Characteristics and Surface Polarity of

Inclined Crystallographic Planes of the Wurtzite and Zincblende Structures,” J. Electron. Mater. 38, 756–760

(2009).

30. T. Toyama, K. Matsune, H. Oda, M. Ohta, and H. Okamoto, “X-ray diffraction study of CdS/CdTe heterostructure

for thin-film solar cell: influence of CdS grain size on subsequent growth of (111)-oriented CdTe film,” J. Phys.

D: Appl. Phys. 39, 1537–1542 (2006).

31. S. Brasselet and J. Zyss, “Multipolar molecules and multipolar fields: probing and controlling the tensorial nature

of nonlinear molecular media,” J. Opt. Soc. Am. B 15, 257–288 (1998).

32. J. Zyss, “Molecular engineering implications of rotational invariance in quadratic nonlinear optics: From dipolar

to octupolar molecules and materials,” J. Chem. Phys. 98, 6583 (1993).

33. S. Brasselet, V. Le Floc’h, F. Treussart, J.-F. Roch, J. Zyss, E. Botzung-Appert, and A. Ibanez, “In Situ Diag-

nostics of the Crystalline Nature of Single Organic Nanocrystals by Nonlinear Microscopy,” Phys. Rev. Lett. 92,

207401 (2004).

34. C.-L. Hsieh, R. Grange, Y. Pu, and D. Psaltis, “Three-dimensional harmonic holographic microcopy using

nanoparticles as probes for cell imaging,” Opt. Express 17, 2880–2891 (2009).

35. C. F. Bohren, and D. R. Huffman, Absorption and Scattering of Light by Small Particles (Wiley-VCH, 2004).

36. K. Sénéchal, O. Maury, H. L. Bozec, I. Ledoux, and J. Zyss, “Zinc(II) as a versatile template for the design of

dipolar and octupolar NLO-phores,” J. Am. Chem. Soc. 124, 4560–4561 (2002).

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].

#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 6658

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):

#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 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

2.1. 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.

(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.

#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 6660

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.

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.

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)

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.

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.

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.

#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 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.

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]:

(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).

#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 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.

#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 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

- Tutorial TEMUploaded byMartzel_Wallace
- List of All BooksUploaded byNanok
- MLab_SciUploaded byAndres Torres Villegas
- Maxwell Equations in a Nonlinear Kerr MediumUploaded byBAXZ ABCD
- Statistical analysis of measured free-space laser signal intensity over a 2.33 km optical pathUploaded byParitosh Kumar Velalam
- Optical Image Correlating Velocimeter for metallurgical plantsUploaded byЛаборатория оптоэлектронной техники
- LeicaSP2_ UserGuideUploaded byHakkı Saraylık
- 1808.06136.pdfUploaded byIanjamasimanana Roger
- START-HERE Ch03 LectureUploaded byMayara Cristina Pinto
- Folleto BORGES VfUploaded byArmando Bravo
- Innovativeapproachinmicro Electromechanicalsystemmems 140122000608 Phpapp01Uploaded bywissem
- maaf lagiUploaded byRoni Kusumah
- Nis Elements 2ce Mpch 1Uploaded byClaudio Perez
- Descr Water TypesUploaded byNikolas Hatzipolitis
- Spark DetectorUploaded byaliff3211
- Combs 3096 PDFUploaded byJosh
- Dimension Icon - B068-RevB2Uploaded byHaider Abbas
- CRF-Nantech2004_extended_abstract.pdfUploaded byKrebs_1977
- Comar Catalogue Edition 7Uploaded byRetrovi Heartly
- Fiber Optics Brochure 06Uploaded byMarco Surca
- 806002LB.pdfUploaded bySelva Rani
- BS ChemistryUploaded byawais gujjar
- Field intensity distributions and polarization orientations in.pdfUploaded bySoumen Dutt
- mmc1Uploaded byBaoz Ping
- Inventory Physics (1)Uploaded byAyene Nobleta
- Ponce4-Pulse Laser DepositionUploaded byMaría González Domínguez
- Construction of Sine and Cosine Hologram of Brain Tumor ImageUploaded byInternational Journal of Research in Engineering and Technology
- Development of the Water Absorbing-Drying Property Evaluation Method of Fabric by NIR Spectral Image Measurement SystemUploaded byTI Journals Publishing
- L6Uploaded bysuman dahal
- JBlanchard Lens Mounting With Elastomeric BondsUploaded bykndprasad01

- All About LED LightingUploaded bymica
- A Transducer is a Device, Electrical, Electronic,Uploaded bymamta108832670
- Tropospheric Ducting TDMMUploaded byMuhammad Junaid
- 212 - Problem Set #10Uploaded byeveryoneMD
- Optical computersUploaded byAnirudha M V
- Tracking DHUploaded byrajachakraborty
- Fiber Optic Cable Measurement-OTDR.pdfUploaded bymentong
- Ultrasound Quiz 3.pdfUploaded byAwadhesh Singh Yadav
- Radiation Exposure Activity1Uploaded byHaider Shah
- Communication EngineeringUploaded bysmagendiran
- ALS Blood Photography Poster Eiland_Gardner LetterUploaded byMarcos Gianetto
- AQA-7407-7408-SP-2015-V1-2.pdfUploaded bydeathgrip1235
- abi dinesh@ppt.com - Copy (1).pptxUploaded byAbhishek Agarwal
- Ambarish Srivastava the Physics Teacher at FIITJEE Faridabad_ Extra Topics in Olympiad Syllabus (as Compared to IIT JEE Syllabus)Uploaded byRishikeshKumar
- Massive MIMOUploaded byNishant Chandnani
- Light Formers ShootoutUploaded byMichael Zhang
- Microwave Lab ManualUploaded byRajendra Kumar
- Coherent Anti Stokes Raman Scattering App Note 36Uploaded bykatherine
- What is the Vertical IlluminanceUploaded byTigrillo
- GW US SubmissionsUploaded byjgecik
- Syllabus Modern OpticsUploaded byNintoku82
- Visonic TOWER20AMMCW Data SheetUploaded byJMAC Supply
- Early Detection of Corrosion Damage Under Coatings With ThermographicUploaded byRamya Mandava
- Visual Acuity TestUploaded byKamil Irsyad
- Hans de Vries- Chapter 6: The Chern-Simons electro magnetic spin densityUploaded byTellusz4532
- landscape-lighting-guide-atlanta.pdfUploaded byIonut Diaconu
- How the optical microscope became a nanoscope.pdfUploaded byabihagul
- Samsung Camera NX100 User ManualUploaded bySamsung Camera
- MWE R-09 Previous Paper QuestionsUploaded byganesh4u_p
- Slide SterilizationUploaded byBima Rizkia Ramadhan

## Much more than documents.

Discover everything Scribd has to offer, including books and audiobooks from major publishers.

Cancel anytime.