A study of nitrogen incorporation in pyramidal site-controlled quantum dots
© Juska et al; licensee Springer. 2011
Received: 18 July 2011
Accepted: 26 October 2011
Published: 26 October 2011
We present the results of a study of nitrogen incorporation in metalorganic-vapour-phase epitaxy-grown site-controlled quantum dots (QDs). We report for the first time on a significant incorporation (approximately 0.3%), producing a noteworthy red shift (at least 50 meV) in some of our samples. Depending on the level of nitrogen incorporation/exposure, strong modifications of the optical features are found (variable distribution of the emission homogeneity, fine-structure splitting, few-particle effects). We discuss our results, especially in relation to a specific reproducible sample which has noticeable features: the usual pattern of the excitonic transitions is altered and the fine-structure splitting is suppressed to vanishing values. Distinctively, nitrogen incorporation can be achieved without detriment to the optical quality, as confirmed by narrow linewidths and photon correlation spectroscopy.
Quantum dots (QDs) are usually referred to as 'artificial atoms' due to the discrete nature of energetic structure and similarities in quantum properties. Application of individual QDs is envisioned in the fields of advanced optoelectronics, photonics, quantum information processing . Among the properties required to be met are certainly precise control over positioning (e.g. inside a photonic cavity or waveguide), high optical quality (i.e. low or absent spectral meandering of the excitonic features) and high uniformity as a guarantee of technological scalability. In many respects, features like tailored symmetry properties (e.g. better than C2v for entangled photon emission), customised oscillator strengths, wavelength tunability and possibly many more, depending on the applications, are a necessity.
The system of pyramidal QDs is particularly versatile. It ensures a precise spatial control over a few nanometres. Extremely high spectral purity and uniformity has also been demonstrated [2–4]. Emission wavelength control of the system can be achieved by changing the composition and/or thickness of pseudomorphically grown epitaxial QD layer [4, 5], the size and position of tetrahedral recesses , the size and distribution of QDs , and different excitonic transitions are accessible depending on the measuring geometry [8, 9]. One possible alternative for tuning the emission wavelength (possibly closer to the one of the transparent optical transmission windows used in telecommunications) can be achieved with the help of dilute nitride materials. It's widely known that incorporation of nitrogen in small quantities has a huge impact on the band structure of (In)GaAs [10, 11]. The most prominent modification is the shrinkage of the emission energy. Also, the incorporation of the small radius nitrogen atoms into InGaAs alloys grown on GaAs is expected to reduce the strain and thus enable the growth of layers that are thicker and/or have higher indium concentration.
In this study, we report the first outcomes of our investigations on growing diluted nitride quantum dots. Our study of the emission wavelength as a function of the flux of nitrogen precursor unsymmetrical dimethylhydrazine (U-DMHy) used during the metalorganic vapour phase epitaxy (MOVPE) growth process has demonstrated (for the first time in the site-controlled family) unambiguous shrinkage of the emission energy by at least 50 meV. Moreover, despite the typically reported degradation of optical properties in dilute nitride materials, we maintain relatively high quality in some of our samples, which is also proved by evidence of single-photon emission. We show that the exposure to the nitrogen precursor during the growth has a major impact on the optical properties, varying substantially excitonic linewidths, emission homogeneity and QD symmetry properties. We discuss our results comparing to a specific (reproducible) sample which demonstrated noticeable features : the usual pattern of the excitonic transitions is altered and a fine-structure splitting (FSS) is suppressed to values smaller than the measurement resolution of 4 μeV, while until now, site-controlled pyramidal QDs have always demonstrated (with the only one exception ) a FSS - an indication of broken rotational symmetry. We performed for the first time photon correlation spectroscopy on nitrogen-containing single dots, confirming few-particle attributions.
Growth parameters and optical properties of the set A QDs
T G, °C
QD thickness, nm
Averaged QD PL, meV
Growth parameters and optical properties of the set B QDs
T G, °C
QD thickness, nm
Averaged QD PL, meV
The QD samples were characterised by micro-photoluminescence spectroscopy (microPL) at cryogenic temperatures. The core of the setup consists of a tuneable pulse repetition laser diode emitting at 633 nm, a helium closed-cycle cryostat and two spectrometers equipped with a charge-coupled device (CCD) or an array of InGaAs detectors. High-resolution, polarisation-resolved measurements of the FSS were carried out by placing a half-wave retardation plate and a linear polarizer in the optical axis of the system. Due to the presence of the FSS, the spectral positions of exciton and biexciton transitions typically follow counterphase sinusoids while changing polarisation angle. The value of the FSS is obtained by subtracting the corresponding biexciton-exciton positions. The resulting sinusoid amplitude gives the value of the FSS. The actual spectral resolution of approximately 18 μeV at 870 nm wavelength combined with a peak fitting procedure  enables a total resolution of approximately 4 μeV.
Photon correlation measurements were carried out in a typical Hanbury Brown and Twiss setup, equipped with silicon avalanche photo diodes (APD) with a low rate of dark counts (approximately 50 cps). Monochromators were used as narrow band-pass filters. Time-resolved features were measured with a single APD and a photon-counting card synchronised with an optical signal. The resolution of time-resolved features is determined by the instrument response function which can be very closely approximated by the Gaussian function with a width of 530 ps.
Results and discussion
Group B was grown at lower temperature (655°C) than group A, which is in general a more favourable condition to avoid nitrogen desorption from the surface . Also, a higher flux ratio U-DMHy/AsH3 up to 5.46 was used compared to A samples, providing higher probability to trap nitrogen atoms. Nevertheless, a 35-meV energy shift has also been observed in the set A samples, even if the growth conditions were less favourable for nitrogen incorporation: a growth temperature of 730°C and the flux ratio up to 0.67. However, a good optical quality from QDs from the set A was only preserved in the sample with the smallest energy shift, while the other nitrogen containing dots showed broader linewidths, as high as 1 meV, and decreased intensity by more than one order of magnitude. Moreover, increasing U-DMHy in samples A did not trivially provide higher nitrogen incorporation. We do not have an explanation for this behaviour, and more work will be needed to clarify the exact incorporation dynamics in our samples.
Samples showing nitrogen incorporation do not show in general the uniformity of the emission properties (e.g. few milli-electron volt dispersion of emission energy, small dispersion of FSS, regular excitonic spectrum) that their counterpart without nitrogen demonstrated [2, 3, 25]. For example, a variety of few-particle effects have been observed and no constant pattern of excitonic transitions from the set B QDs has been measured, even if a significant part of them showed a biexciton emitting at lower energy (binding biexciton). It should be said, in fact, that non-uniformity should be expected in dilute nitride single QDs due to a high sensitivity of the energetic structure to small variations of the nitrogen incorporated (even a few tens of atoms correspond to a non negligible shift in emission energy and confinement energy). As a consequence, when nitrogen is significantly present, one can observe an increased non-homogeneity, which sometimes produces a free exciton emission energy distribution as broad as 30 meV (samples B2 and B3 in the Table 2).
When exciton and biexciton transitions could be identified in the samples from set A (A1, A3), negative biexciton binding energy (ΔE XX = E X − EXX) was always found to be a characteristic feature. We observe that even other QDs grown like the sample A1 but at lower temperature (700°C and 670°C, which we only discuss here in this contest), which reduces the width of self-limiting GaAs profile and thus the shape of a QD, exhibited a clear antibinding biexciton. The relevance of such modification is that generally the biexciton of counterpart QDs unexposed to U-DMHy is always binding (ΔE XX = 1.8 meV). A representative comparison of the spectra is presented in Figure 6, where the spectrum of 0.5 nm In0.25 Ga0.75As nitrogen-free QD is shown in the top part, while the typical spectrum of counterparts exposed to U-DMHy in the bottom. The relative position of biexciton transition (XX) in respect of exciton (X) indicates XX type (binding and antibinding, respectively).
In general, the change of excitonic pattern identifies a strong change of Coulomb interaction between photogenerated carriers within QD and possibly the change of geometrical properties . However, the identification of such reasons in our case still requires further work so to obtain an elucidative theoretical model. It is nevertheless clear that the nature of the observed optical modifications cannot be attributed solely and simply to the nitrogen presence in the QD material, but more likely to its non-uniform distribution and/or incorporation, and its influence to the dot formation mechanism as a whole at given growth parameters. In fact, power dependency, time-resolved and fine-structure splitting measurements confirm that the biexciton of QDs in set B, where epitaxial conditions have been varied significantly, appears at lower energy (binding) than exciton, oppositely to the set A QDs.
As we reported elsewhere , we found that the sample A1 showed an unexpected welcome feature, a vanishingly small FSS, a result of interest as small but non-negligible FSS could be found in our nitrogen-free In x Ga1−x As QDs in GaAs barriers. For example, FSS of at least 7 μeV was always found in In0.25 Ga0.75As 0.5-nm nominal thickness QDs (grown at the same conditions as set A samples without exposure to U-DMHy). In the top inset of Figure 6 an example of FSS measurement of such nitrogen-free QD is presented - the sinusoid is directly related to the energetic position of exciton and biexciton and the amplitude of it gives the value of FSS.
In conclusion, we have presented the first broad study on nitrogen incorporation in single In0.25 Ga0.75As1-δ N δ site-controlled QDs. Nitrogen incorporation was attested by photoluminescence red-shift of at least 50 meV. Single-photon emission from selected QDs was proved by auto-correlation measurements. While nitrogen incorporation in thicker QDs grown at lower temperature resulted in a broad distribution of optical properties (emission energy and transitions linewidth non-homogeneity) and fine-structure splitting as large as 90 μeV, exposure to U-DMHy of thinner QDs grown in a specific set of epitaxial conditions (higher temperature) altered the excitonic pattern (an antibinding biexciton appeared) and fine-structure splitting values were suppressed below the setup resolution of 4 μeV.
As a consequence of our results, it is clear that the exposure of QD layer to U-DMHy during the growth could be exploited not only as an emission tuning mechanism preserving good quality of optical properties but also in a particular case to improve the rotational symmetry of pyramidal site-controlled QDs - a necessary feature for the efficient generation of entangled photons.
This research was enabled by the Irish Higher Education Authority Program for Research in Third Level Institutions (2007 to 2011) via the INSPIRE programme, and by Science Foundation Ireland under grants 05/IN.1/I25 and 08/RFP/MTR/1659, and EU FP7 under the Marie Curie Reintegration Grant PERG07-GA-2010-268300. We are grateful to K. Thomas for his support with the MOVPE system.
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