The interest in nanoscale materials stems from the fact that new properties are acquired at this length scale and, equally important, that these properties * To whom correspondence should be addressed. Phone, 404-8940292; fax, 404-894-0294; e-mail, mostafa.el-sayed@ chemistry.gatech.edu. † Case Western Reserve UniversitysMillis 2258. ‡ Phone, 216-368-5918; fax, 216-368-3006; e-mail, burda@case.edu. § Georgia Institute of Technology. 1025 Chem. Rev. 2005, 105, 1025−1102

Chemistry and properties of nanocrystals of different shapes.

Quantum dot (QD) solar cells have the potential to increase the maximum attainable thermodynamic conversion efficiency of solar photon conversion up to about 66% by utilizing hot photogenerated carriers to produce higher photovoltages or higher photocurrents. The former effect is based on miniband transport and collection of hot carriers in QD array photoelectrodes before they relax to the band edges through phonon emission. The latter effect is based on utilizing hot carriers in QD solar cells to generate and collect additional electron–hole pairs through enhanced impact ionization processes. Three QD solar cell configurations are described: (1) photoelectrodes comprising QD arrays, (2) QD-sensitized nanocrystalline TiO 2 , and (3) QDs dispersed in a blend of electron- and hole-conducting polymers. These high-efficiency configurations require slow hot carrier cooling times, and we discuss initial results on slowed hot electron cooling in InP QDs.

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Quantum dot solar cells

Recent research results pertaining to InN, GaN and AlN are reviewed, focusing on the different growth techniques of Group III-nitride crystals and epitaxial films, heterostructures and devices. The chemical and thermal stability of epitaxial nitride films is discussed in relation to the problems of deposition processes and the advantages for applications in high-power and high-temperature devices. The development of growth methods like metalorganic chemical vapour deposition and plasma-induced molecular beam epitaxy has resulted in remarkable improvements in the structural, optical and electrical properties. New developments in precursor chemistry, plasma-based nitrogen sources, substrates, the growth of nucleation layers and selective growth are covered. Deposition conditions and methods used to grow alloys for optical bandgap and lattice engineering are introduced. The review is concluded with a description of recent Group III-nitride semiconductor devices such as bright blue and white light-emitting diodes, the first blue-emitting laser, high-power transistors, and a discussion of further applications in surface acoustic wave devices and sensors.

https://iopscience.iop.org/article/10.1088/0022-3727/31/20/001/pdf

Growth and applications of Group III-nitrides

Here, we will first briefly summarize the general principles of QD synthesis using our previous work on InP as an example. Then we will focus on QDs of the IV-VI Pb chalcogenides (PbSe, PbS, and PbTe) and Si QDs because these were among the first QDs that were reported to produce multiple excitons upon absorbing single photons of appropriate energy (a process we call multiple exciton generation (MEG)). We note that in addition to Si and the Pb-VI QDs, two other semiconductor systems (III-V InP QDs(56) and II-VI core-shell CdTe/CdSe QDs(57)) were very recently reported to also produce MEG. Then we will discuss photogenerated carrier dynamics in QDs, including the issues and controversies related to the cooling of hot carriers and the magnitude and significance of MEG in QDs. Finally, we will discuss applications of QDs and QD arrays in novel quantum dot PV cells, where multiple exciton generation from single photons could yield significantly higher PV conversion efficiencies.

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Semiconductor quantum dots and quantum dot arrays and applications of multiple exciton generation to third-generation photovoltaic solar cells.

We analyze theoretically the optical properties of ideal semiconductor crystallites so small that they show quantum confinement in all three dimensions [quantum dots (QD's)]. In the limit of a QD much smaller than the bulk exciton size, the linear spectrum will be a series of lines, and we consider the phonon broadening of these lines. The lowest interband transition will saturate like a two-level system, without exchange and Coulomb screening. Depending on the broadening, the absorption and the changes in absorption and refractive index resulting from saturation can become very large, and the local-field effects can become so strong as to give optical bistability without external feedback. The small QD limit is more readily achieved with narrow-band-gap semiconductors.

Theory of the linear and nonlinear optical properties of semiconductor microcrystallites

We present experimental results concerning optical transitions and carrier dynamics (capture and relaxation) in self assembled InAs/GaAs quantum dot structures grown by metalorganic vapor phase epitaxy.Photoluminescence(PL) measurements at high excitation level reveal optical transitions above the ground state emission. These transitions are found to originate from occupied hole states by solving the quantum doteigenvalue problem. Time‐resolved studies after non‐resonant pulse excitation exhibit a relaxation ladder of the excited carriers from the GaAs barrier down to the ground state of the quantum dots. From both the continuous‐wave measurements and the PL‐decay curves we conclude that the carrier relaxation at non‐resonant excitation is mediated by Coulomb interaction (Auger effect). PL‐decay curves after resonant pulse excitation reveal a longer rise time compared to non‐resonant excitation which is a clear indication of a relaxation bottleneck inside the quantum dots. We interpret the rise time (≊ 400 ps) in this case to originate from relaxation via scattering by acoustic phonons. The PL‐decay time of the ground state emission ≊700 ps is interpreted as the excitonic lifetime of the quantum dot.

Optical transitions and carrier relaxation in self assembled InAs/GaAs quantum dots

We establish rate equations to describe Auger carrier capture kinetics in quantum dot structures, calculate Auger capture coefficients for self-assembled quantum dots, and analyze Auger capture kinetics using these equations. We show that Auger capture times can be of the order of 1–100 ps depending on barrier carrier and dot densities. Auger capture rates depend strongly on dot diameters and are greatest at dot diameters of about 10–20 nm.

Auger carrier capture kinetics in self-assembled quantum dot structures

Carrier relaxation in self-assembled quantum dots due to Coulomb interaction with two dimensional (2D) carriers is studied theoretically. Auger coefficients for carrier relaxation rates are calculated in the dipole approximation for Coulomb interaction. The dipole approximation allows one to derive selection rules for Auger relaxation in a cylindrical quantum dot, and to describe a general picture of Auger relaxation via energy levels in self-assembled quantum dots. A numerical example for InAs/GaAs self-assembled quantum dots demonstrates that the Auger effect may lead to relaxation times in the order of 1–10 ps at 2D carrier densities of 1011–1012 cm−2. This result demonstrates the possibility of fast carrier relaxation in quantum dots if the carrier density in the surrounding barrier is sufficiently high. Analytical formulas for Auger coefficients are derived for moderate temperatures of the 2D carriers.

Auger carrier relaxation in self-assembled quantum dots by collisions with two-dimensional carriers

The energy structure and the carrier relaxation in self-assembled InAs/GaAs quantum dots (SADs) is investigated by photoluminescence excitation spectroscopy (PLE) and photoluminescence (PL) at resonant excitation (below the GaAs and the wetting layer bandgap). In PLE measurements we find a clear resonance from the first excited hole state as well as resonances from a relaxation via different phonons. From a comparison of the PL-rise times in time resolved spectroscopy, we conclude on a fast electron relaxation (⩽50 ps) and a slow hole relaxation with a time constant of about 400 ps. Different relaxation paths are observed in the InAs/GaAs quantum dot system and allow us to identify the hole relaxation in the SADs as multiphonon assisted tunneling. The PL-decay time in the SADs after resonant excitation (about 600 ps) is attributed to the lifetime of the quantum dot exciton. In agreement with theoretical predictions, we find a constant lifetime of about 600 ps for temperatures below 50 K and a linear incre...

Self-assembled InAs/GaAs quantum dots under resonant excitation

Room temperature distributed‐feedback (DFB) laser operation is demonstrated with emission wavelengths ranging from 389 to 399 nm. Second‐order DFB gratings were defined by electron beam lithography and reactive ion etching in the top GaN barrier layer of a GaInN/GaN double heterostructure grown by metalorganic vapor phase epitaxy. Our data allow a precise determination of the effective refractive index neff(λ) over the whole emission range. neff(λ) is compared with previously published values for GaN and GaInN.

F. Adler

Papers

Optical transitions and carrier relaxation in self assembled InAs/GaAs quantum dots

Auger carrier capture kinetics in self-assembled quantum dot structures

Auger carrier relaxation in self-assembled quantum dots by collisions with two-dimensional carriers

Self-assembled InAs/GaAs quantum dots under resonant excitation

Realization of optically pumped second-order gainn-distributed-feedback lasers