The life is known to be essentially chiral, which is why many organic drugs exist in two enantiomeric forms [1, 2]. As these forms often have profoundly different impacts on human body, drug-regulating authorities require them to be separated and tested individually on toxicity and therapeutic efficacy [3–5]. The detection of enantiomeric forms of chiral molecules is only possible through their interaction with other chiral objects [6–8]. Semiconductor nanocrystals, which are often intrinsically chiral because of the unavoidable surface and bulk defects, are objects of particular promise owing to their distinctive photoluminescence properties [9–16]. It has been recently demonstrated that CdSe/ZnS quantum dots and quantum rods can acquire chirality from screw dislocations naturally developing during their growth [17–20]. It has been also shown that when semiconductor nanocrystals of one enantiomeric form are mixed with a chiral drug, they can exhibit strong affinity to its particular enantiomer . The detection and quantification of this enantiomer are then possible from the changes in the absorption or emission spectrum of the nanocrystals, which occur due to the energy and charge transfer processes that take place upon binding of the nanocrystals to the targeted enantiomer.
The major challenge of the described detection approach is the fabrication of enantiopure semiconductor nanocrystals. The existing fabrication methods are essentially symmetric, producing mixtures of left-handed, righthanded, and achiral species [17, 18]. The detection of drug enantiomers with such mixtures is still feasible through the analysis of circular dichroism (CD) spectra, comprising the lines of both nanocrystals and drug molecules . The sensitivity of the analysis can be enhanced by strengthening the optical activity of the nanocrystals via their doping with impurity ions such as Mn2+ or Er3+. In this paper, we propose and develop a method of engineering and enhancing the optical activity of semiconductor nanocrystals with specifically positioned ionic impurities.We show that there are certain optimal impurity positions that maximize the rotatory strengths of optical transitions inside the nanocrystals, making them two orders of magnitude larger than the typical rotatory strengths of small chiral molecules. It is also found that the optimally doped quantum dots exhibit an almost total dissymmetry of their absorption upon magnetic dipole transitions.
2 Theoretical model
For a semiconductor nanocrystal to be chiral and optically active, it must lack a plane or center of symmetry. The minimal number of identical impurities required to break the mirror symmetry of a nanocrystal is the largest for a nanosphere. It is easy to see that regardless of their positions, neither one nor two impurities are sufficient to make a nanosphere chiral, because there is always a rotation axis of infinite order associated with one impurity and a mirror plane associated with two. A nanosphere may acquire chirality, provided it is doped with a minimum of three impurity ions, which form a plane that does not pass through the nanosphere’s center. Similarly, a minimum of two impurities are needed to break the mirror symmetry of a nanocylinder, and one to bring chirality to a nanocuboid.
The optical activity of doped semiconductor nanocrystals results from the perturbation of their electronic subsystems by the electric field of the impurities. Figure 1 illustrates this perturbation by the example of two electronic states and one impurity ion inside a nanocuboid. One can see that by breaking the mirror symmetry of the nanocuboid, the impurity makes the electronicwave functions essentially chiral. Thus the induced chirality shows up in the nanocrystal’s CD spectrum
where N is the concentration of the nanocrystals, c is the speed of light in vacuum, ρab(w) is the spectral lineshape of transition a → b, and the rotatory transition strength is defined as 
In order to describe the quantum states of electrons confined by a doped semiconductor nanocrystal, we apply a one-band model of bulk semiconductor and ignore the exciton effects by assuming that the characteristic size of the nanocrystal, l, is much smaller than the exciton Bohr radius
which can be considered as a small perturbation of the nanocrystal. The envelope wave functions and energy states of the confined electrons are characterized by a set of three quantum numbers n and obey the Schrodinger equation
in which the Hamiltonian of the impurity-free nanocrystal,
We next take the solution of Eq. (4) in the form of the standard perturbation expansion En = εn + Vnn and Ψn = ψn + Snn'ψn', where ψn and εn are the wave functions and energy spectrum of the unperturbed Hamiltonian
Let us focus on studying the optical activity of a semiconductor nanocuboid lx × ly × lz, whose optical activity can be achieved with a single impurity ion. By assuming that the nanocrystal is located symmetrically with respect to the three Cartesian planes and its surface is impenetrable for the confined electrons, we take
where i ≠ j ≠ k, δij and εijk are the Kronecker's delta and the Levi-Civita symbol, and
The selection rules for intraband transitions are determined by Kronecker deltas, coefficients
The obtained result leads to a simple size dependence of the rotatory strength. Suppose that the lengths of the nanocrystal edges and the coordinates of the impurities are increased by a factor of f. Then εn ∝ f-2, V ∝ f-1 and Snn' ∝ f. As the matrix element of the magnetic dipole moment does not change with f while the electric dipole moment scales as ∝ f, Eqs. (2) and (5) give Rba ∝ f2. One can see that the size dependence of the rotatory strength comes from three sources: scaling of the confinement energies, scaling of the impurity potential, and scaling of the electric dipole moment. As the nanocrystal grows bigger, the Coulomb interaction between electrons and holes more and more reduces the confinement energies, resulting in their weaker size dependence εn ∝ f-q, where 1 < q < 2. Hence, the rotatory strength in the weak confinement regime is larger than that in the strong confinement regime but has a weaker size dependence, Rba ∝ fq.
Equations (2) and (5) show that there are six types of dipole-allowed transitions, two per each Cartesian axis. In particular, the confined motion along the x-axis leads to electric dipole transitions, which change the parity of state ψ ψx and preserve states ψy and ψz, and to magnetic dipole transitions, which preserve state ψx and change the parities of states ψy and ψz. The electric dipole mo-ment is much larger than the magnetic dipole moment for the transitions of the first kind, |pab | ≫ |mba|, and the opposite relation holds for the transitions of the second kind, |mha| ≫ |Pab|.
The rotatory strength of transition
The rotatory strength is seen to be contributed only by the sums involving the matrix elements of the perturbation-induced transitions between the states with different parities of the respective quantum numbers. For a nanocrys-tal doped with one impurity ion, these matrix elements are antisymmetric with respect to each ion's coordinate, making rotatory strength vanish in case the ion is located in one of the three Cartesian planes. This conclusion also holds for other components of the dipole moments, the rotatory strengths of which can be obtained from Eq. (8) by a cyclic change of subscripts x, y, and z. As the reflection of the impurity in any of the coordinate planes changes the sign of the rotatory strength, knowing Rba for all impurity locations in the first octant of the nanocrystal allows us to find Rba in the entire nanocrystal.
3 Results and discussion
Engineering optical activity of doped nanocrystals requires knowing the optimal positions ofimpurityions that maximize the activity. The optimal positions critically depend on the transition upon which the activity is observed, and can be estimated by analyzing the dominant terms in Eq. (8). These terms correspond to the perturbation-induced transitions between the unperturbed initial state ψx, ny, nz and the unperturbed final state
The isosurfaces of Rba shown in Fig. 2 illustrate the dependence of rotatory strength on the impurity position inside the first octants of nanorod, quantum dot, and nanoplatelet of approximately equal volumes. In agreement with the above discussion, the rotatory strength upon the electric dipole transition Ψ111 → Ψ121 peaks at one point, clearly seen in panels (a)-(c). The optimal impurity positions inside the nanorod, quantum dot, and nanoplatelet are (0.50, 0.44, 0.40), (0.46, 0.44, 0.42), and (0.50, 0.42, 0.40), respectively. According to panel (d), rotatory strength R141;111 has two maximums located at points (0.46, 0.22, 0.36) and (0.46, 0.72, 0.36) along the y-axis; they come from two maximums of the wave function product cos(πuy|2)sin(2πuy). Similarly, there are two and three maximums of R124;111 and R116;111 along the z-direction, as can be seen from panels (e) and (f).
One can see that the optical activity of semiconductor nanocrystals doped with one ion of charge +e can be 10 times larger than the rotatory strengths of chiral molecules, which typically range from 10-39 to 10-38 erg × cm3 [24-26]. Using several dopants of bigger charges, optimally positioned in the third, sixths, and eighths octants, one can increase the rotatory strengths of optical transitions by another factor of 10. It should also be noted that the rotatory strength is maximal for the lowest-energy intraband transitions and steeply decreases with transition energy becouse of the decrease in the probabilities of the electric and magnetic dipole transitions, governed by the coefficients
Despite the fact that the rates of electric dipole and magnetic dipole transitions differ by a factor of 10,000 , the respective rotatory strengths are of the same order of magnitude. The large difference in the transition rates shows up in dissymmetry factor g, which is the doubled ratio of CD to the sum of absorption intensities for left- and right-handed circularly polarized light. This feature is illustrated in Table 1. The large absorption upon the electric dipole transition is seen to result in g-factors in the range from 10-4 to 10-3, which is typical for small chiral molecules . As the magnetic dipole absorption is about 104 weaker than the electric dipole one, the g-factors of the magnetic dipole transitions can be of the order of unity, indicating a strong chiroptical response. Note that the g-factors in Table 1 are not maximal, as they are calculated for the impurity position providing maximum to the rotatory strength.
Rotatory strengths (in the units of erg × cm3) and dissymmetry factors of (a) electric dipole transition (111) → (121) and (b) magnetic dipole transition (111) → (122) inside nanorod, quantum dot, and nanoplatelet with a single impurity located at optimal position u, which corresponds to the maximum of rotatory strength. All material parameters are the same as in Fig. 2.
|R(a)||-136 × 10-39||-60 × 10-39||-19 × 10-39|
|g(a)||8.1 × 10-4||2.2 × 10-4||0.4 × 10-4|
|R(b)||156 × 10-39||-59 × 10-39||7 × 10-39|
The dependence of the CD spectra of doped nanocrys-tals on the impurity position is illustrated in Fig. 3. The impurity is assumed to be in plane x = lx/4, where its positions are shown by the color dots in the insets. The optical CD spectrum of the nanorod in Fig. 3(a) has two strong peaks, corresponding to the transitions in Table 1, and a much weaker peak of transition Ψ111 → Ψ124. As the impurity is moved from left to right, the weaker peak changes its sign, while nearly disappearing when the dominant peaks have maximum intensity. The CD spectrum of the quantum dot in Fig. 3(b) consists of six equally pro-nounced dipole transitions, whose rotatory strengths were shown to exhibit almost the same dependence on the impurity position. All of the peaks are the strongest where the impurity is located about the center of the first octant. The optical CD spectrum of the nanoplatelet shown in Fig. 3(c) includes four transitions, whose intensities depend on the impurity position as it is predicted by Fig. 2(d) and (e). There are also three low-energy peaks in the spectrum, which vary with position similar to the states of the quantum dot.
We have shown that one can control and maximize the optical activity of semiconductor nanocrystals by introducing impurity ions inside them. The proposed approach allows one to achieve rotatory strengths upon intraband transitions that are 100 times larger than the typical rotatory strengths of small chiral molecules. It also enables re-alization of an almost complete dissymmetry of magnetic dipole absorption, opening a new chapter in the studies of light-matter interaction on the nanoscale.
This work was funded by Grant 14.B25.31.0002 and Government Assignment No.3.17.2014/K of the Ministry of Education and Science of the Russian Federation. A.S.B. acknowledges the Dynasty Foundation Support Program for Physicists and the scholarship of the President of the Russian Federation for young scientists. We also acknowledge the financial support from Science Foundation Ireland (Grant SFI12/IA/1300).
L. A. Nguyen, H. He, and C. Pham-Huy, “Chiral drugs: An overview,” Inter. J. Biomed. Sci. 2, 85-100 (2006).
W. H. Brooks, W. C. Guida, and K. G. Daniel, “The significance of chirality in drug design and development,” Curr. Top. Med. Chem. 11, 760-770 (2011).
B. Li and D. T. Haynie, “Chiral drug separation,” Encycl. Chem. Process. 1, 449-458 (2006).
H. Caner, E. Groner, L. Levy, and I. Agranat, “Trends in the development of chiral drugs,” Drug Discov. Today 9, 105-110 (2004).
G. Gübitz and M. G. Schmid, “Chiral separation principles in chromatographic and electromigration techniques,” Mol. Biotech. 32, 159-179 (2006).
C.J. Welch, Chiral Chromatography in Support of Pharmaceutical Process Research, Preparative Enantioselective Chromotog-raphy (ed. G. B. Cox) (Blackwell, London, UK, 2005).
S. F. Mason, Molecular Optical Activity and the Chiral Discriminations (Cambridge Univ. Press, New York, 1982).
A. Hazarika, A. Layek, S. De, A. Nag, S. Debnath, P. Mahadevan, A. Chowdhury, and D. D. Sarma, “Ultranarrow and widely tunable Mn2+-induced photoluminescence from single Mn-doped nanocrystals of ZnS-CdS alloys,” Phys. Rev. Lett. 110, 267401 (2013).
E. V. Ushakova, A. P. Litvin, P. S. Parfenov, A. V. Fedorov, M. Arte-myev, A. V. Prudnikau, I. D. Rukhlenko, and A. V. Baranov, “Anomalous size-dependent decay of low-energy luminescence from PbS quantum dots in colloidal solution,” ACS Nano 6, 8913-8921 (2012).
- Export Citation
E. V. Ushakova, A. P. Litvin, P. S. Parfenov, A. V. Fedorov, M. Arte-myev, A. V. Prudnikau, I. D. Rukhlenko, and A. V. Baranov, “Anomalous size-dependent decay of low-energy luminescence from PbS quantum dots in colloidal solution,” ACS Nano 6, 8913-8921 (2012).)| false 22971234 10.1021/nn3029106
V. K. Turkov, S. Y. Kruchinin, and A. V. Fedorov, “Intraband optical transitions in semiconductor quantum dots: Radiative electronic-excitation lifetime,” Opt. Spectrosc. 110, 740-747 (2011).
W. M. Witzel, A. Shabaev, C. S. Hellberg, V. L. Jacobs, and A. L. Efros, “Quantum simulation of multiple-exciton generation in a nanocrystal by a single photon,” Phys. Rev. Lett. 105, 137401 (2010).
R. D. Schaller, S. A. Crooker, D. A. Bussian, J. M. Pietryga, J. Joo, and V. I. Klimov, “Revealing the exciton fine structure of PbSe nanocrystal quantum dots using optical spectroscopy in high magnetic fields,” Phys. Rev. Lett. 105, 067403 (2010).
A. V. Fedorov, A. V. Baranov, I. D. Rukhlenko, T. S. Perova, and K. Berwick, “Quantum dot energy relaxation mediated by plas-mon emission in doped covalent semiconductor heterostruc-tures,” Phys. Rev. B 76, 045332 (2007).
I. D. Rukhlenko and A. V. Fedorov, “Propagation of electric fields induced by optical phonons in semiconductor heterostructures,” Opt. Spectrosc. 100, 238-244 (2006).
I. D. Rukhlenko and A. V. Fedorov, “Penetration of electric fields induced by surface phonon modes into the layers of a semicon-ductor heterostructure,” Opt. Spectrosc. 101, 253-264 (2006).
M. P. Moloney, J. Govan, A. Loudon, M. Mukhina, and Y. K. Gun'ko, “Preparation of chiral quantum dots,” Nature Protoc. 10, 558-573 (2015).
M. V. Mukhina, V. G. Maslov, A. V. Baranov, A. V. Fedorov, A. O. Orlova, F. Purcell-Milton, J. Govan, and Y. K. Gun'ko, “Intrinsic chirality of CdSe/ZnS quantum dots and quantum rods,” Nano Lett. 15, 2844-2851 (2015).
A. S. Baimuratov, I. D. Rukhlenko, R. E. Noskov, P. Ginzburg, Y. K. Gun'ko, A. V. Baranov, and A. V. Fedorov, “Giant optical activity of quantum dots, rods, and disks with screw dislocations,” Sci. Rep. 5, 14712 (2015).
A. S. Baimuratov, I. D. Rukhlenko, Y. K. Gun'ko, A. V. Baranov, and A. V. Fedorov, “Dislocation-induced chirality of semiconductor nanocrystals,” Nano Lett. 15, 1710-1715 (2015).
S. D. Elliot, M. P. Moloney, and Y. K. Gun'ko, “Chiral shells and achiral cores in CdS quantum dots,” Nano Lett. 8, 2452-2457 (2008).
N. Berova, Comprehensive Chiroptical Spectroscopy, vol. 1 (John Wiley & Sons, 2012).
L. Rosenfeld, “Quantenmechanische theorie der natürlichen optischen aktivität von flüssigkeiten und gasen,” Z. Phys. 52, 161174 (1929).
R. R. Judkins and D. J. Royer, “Optical rotatory strength of tris-bidentate cobalt(II1) complexes,” Inorganic Chem. 13, 945-950 (1974).
T. S. King, P. M. Bayley, and F. C. Yong, “Optical rotatory dispersion and circular dichroism of cytochrome oxidase,” Eur. J. Biochem. 20, 103-110 (1971).
P. M. Bayley, E. B. Nielsen, and J. A. Shellman, “The rotatory properties of molecules containing two peptide groups: The-ory,” J. Phys. Chem. 73, 228-243 (1969).
O. I. Micic, J. Sprague, Z. Lu, and A. J. Nozik, “Highly efficient band-edge emission from In P quantum dots,” Appl. Phys. Lett. 68, 3150-3152 (1996).
M. Wakabayashi, S. Yokojima, T. Fukaminato, K. Shiino, M. Irie, and S. Nakamura, “Anisotropic dissymmetry factor, g: Theoretical investigation on single molecule chiroptical spectroscopy,” J. Phys. Chem. A 118, 5046-5057 (2014).