Core/shell nanowire (NW) heterostructures based on III-V semiconductors and related alloys are attractive for optoelectronic and photonic applications owing to the ability to modify their electronic structure via bandgap and strain engineering. Post-growth thermal annealing of such NWs is often involved during device fabrication and can also be used to improve their optical and transport properties. However, effects of such annealing on alloy disorder and strain in core/shell NWs are not fully understood. In this work we investigate these effects in novel core/shell/shell GaAs/GaNAs/GaAs NWs grown by molecular beam epitaxy on (111) Si substrates. By employing polarization-resolved photoluminescence measurements, we show that annealing (i) improves overall alloy uniformity due to suppressed long-range fluctuations in the N composition; (ii) reduces local strain within N clusters acting as quantum dot emitters; and (iii) leads to partial relaxation of the global strain caused by the lattice mismatch between GaNAs and GaAs. Our results, therefore, underline applicability of such treatment for improving optical quality of NWs from highly-mismatched alloys. They also call for caution when using ex-situ annealing in strain-engineered NW heterostructures.
Organic photovoltaics are under intense development and significant focus has been placed on tuning the donor ionization potential and acceptor electron affinity to optimize open circuit voltage. Here, it is shown that for a series of regioregular-poly(3-hexylthiophene): fullerene bulk heterojunction (BHJ) organic photovoltaic devices with pinned electrodes, integer charge transfer states present in the dark and created as a consequence of Fermi level equilibrium at BHJ have a profound effect on open circuit voltage. The integer charge transfer state formation causes vacuum level misalignment that yields a roughly constant effective donor ionization potential to acceptor electron affinity energy difference at the donor-acceptor interface, even though there is a large variation in electron affinity for the fullerene series. The large variation in open circuit voltage for the corresponding device series instead is found to be a consequence of trap-assisted recombination via integer charge transfer states. Based on the results, novel design rules for optimizing open circuit voltage and performance of organic bulk heterojunction solar cells are proposed.
Room-temperature optical and spin polarization up to 35% is reported in InAs/GaAs quantum dots in zero magnetic field under optical spin injection using continuous-wave optical orientation spectroscopy. The observed strong spin polarization is suggested to be facilitated by a shortened trion lifetime, which constrains electron spin relaxation. Our finding provides experimental demonstration of the highly anticipated capability of semiconductor quantum dots as highly polarized spin/light sources and efficient spin detectors, with efficiency greater than 35% in the studied quantum dots.
Optical spin injection is studied in novel laterally-arranged self-assembled InAs/GaAs quantum dot structures, by using optical orientation measurements in combination with tunable laser spectroscopy. It is shown that spins of uncorrelated free carriers are better conserved during the spin injection than the spins of correlated electrons and holes in an exciton. This is attributed to efficient spin relaxation promoted by the electron–hole exchange interaction of the excitons. Our finding suggests that separate carrier injection, such as that employed in electrical spin injection devices, can be advantageous for spin conserving injection. It is also found that the spin injection efficiency decreases for free carriers with high momentum, due to the acceleration of spin relaxation processes.
Unambiguous experimental evidence for a significant difference in efficiency of excitonic vs. free carrier spin injection is provided in novel laterally arranged self-assembled InAs/GaAs quantum dot structures, from optical orientation and tunable laser spectroscopy. A lower efficiency of exciton spin injection as compared to free carrier spin injection from wetting layers into QDs results in a distinct feature in luminescence polarization of the QDs as a function of excitation photon energy. It is shown that this difference is not related to carrier density and state-filling effects arising from the difference in optical absorption efficiency between the excitons and free carriers. Rather, it is a genuine property for exciton spin injection that suffers stronger spin relaxation due to Coulomb exchange interaction.
We observe remarkable, complete suppression of spin generation under optical excitation in a thin InAs/GaAs wetting layer close to the light-hole excitonic resonance, leading to zero electron spin polarization as monitored by adjacent InAs quantum dots. The suppression is attributed to efficient spin relaxation/scattering at the Fano resonance between the light-hole exciton states and the heavy-hole continuum of the wetting layer. The complete suppression is found to remain effective up to temperatures exceeding 100 K.
Hanle effect in InAs/GaAs quantum dots (QDs) is studied under optical orientation as a function of temperature over the range of 150-300 K, with the aim to understand the physical mechanism responsible for the observed sharp increase of electron spin polarization with increasing temperature. The deduced spin lifetime Ts of positive trions in the QDs is found to be independent of temperature, and is also insensitive to excitation energy and density. It is argued that the measured Ts is mainly determined by the longitudinal spin flip time (T1) and the spin dephasing time (T2 *) of the studied QD ensemble, of which both are temperatureindependent over the studied temperature range and the latter makes a larger contribution. The observed sharply rising of the QD spin polarization degree with increasing temperature, on the other hand, is shown to be induced by an increase in spin injection efficiency from the barrier/wetting layer and also by a moderate increase in spin detection efficiency of the QD.
Quantum dots (QDs) are a promising building block for future spin-functional devices with applications in spintronics and quantum information processing. Essential to the success of these devices is the ability to create a desired spin orientation of charge carriers (electrons and holes) in QDs via the injection of spin-polarized carriers. Researchers have now shown that this can be done most efficiently using independent (free) carriers rather than electron-hole pairs (excitons).
Electron spin dephasing and relaxation due to hyperfine interaction with nuclear spins is studied in an InAs/GaAs quantum dot ensemble as a function of temperature up to 85 K, in an applied longitudinal magnetic field. The extent of hyperfineinduced dephasing is found to decrease, whereas dynamic nuclear polarization increases with increasing temperature. We attribute both effects to an accelerating electron spin relaxation through phonon-assisted electron-nuclear spin flip-flops driven by hyperfine interactions, which could become the dominating contribution to electron spin depolarization at high temperatures.
Effects of a longitudinal magnetic field on optical spin injection and detection in InAs/GaAs quantum dot (QD) structures are investigated by optical orientation spectroscopy. An increase in optical and spin polarization of the QDs is observed with increasing magnetic field in the range of 0-2 T, and is attributed to suppression of exciton spin depolarization within the QDs that is promoted by hyperfine interaction and anisotropic electron-hole exchange interaction. This leads to a corresponding enhancement in spin detection efficiency of the QDs by a factor of up to 2.5. At higher magnetic fields when these spin depolarization processes are quenched, electron spin polarization in anisotropic QD structures (such as double QDs that are preferably aligned along a specific crystallographic axis) still exhibits rather strong field dependence under non-resonant excitation. In contrast, such field dependence is practically absent in more "isotropic" QD structures (e.g. single QDs). We attribute the observed effect to stronger electron spin relaxation in the spin injectors (i.e. wetting layer and GaAs barriers) of the lower-symmetry QD structures, which also explains the lower spin injection efficiency observed in these structures.
Rich information on the dominant factors limiting spin injection and detection efficiency can be retrieved from optical orientation in a longitudinal magnetic field.
Charge separation dynamics after the absorption of a photon is a fundamental process relevant both for photosynthetic reaction centers and artificial solar conversion devices. It has been proposed that quantum coherence plays a role in the formation of charge carriers in organic photovoltaics, but experimental proofs have been lacking. Here we report experimental evidence of coherence in the charge separation process in organic donor/acceptor heterojunctions, in the form of low frequency oscillatory signature in the kinetics of the transient absorption and nonlinear two-dimensional photocurrent spectroscopy. The coherence plays a decisive role in the initial ~200 femtoseconds as we observe distinct experimental signatures of coherent photocurrent generation. This coherent process breaks the energy barrier limitation for charge formation, thus competing with excitation energy transfer. The physics may inspire the design of new photovoltaic materials with high device performance, which explore the quantum effects in the next-generation optoelectronic applications.
Polymers are lightweight, flexible, solution-processable materials that are promising for low-cost printed electronics as well as for mass-produced and large-area applications. Previous studies demonstrated that they can possess insulating, semiconducting or metallic properties; here we report that polymers can also be semi-metallic. Semi-metals, exemplified by bismuth, graphite and telluride alloys, have no energy bandgap and a very low density of states at the Fermi level. Furthermore, they typically have a higher Seebeck coefficient and lower thermal conductivities compared with metals, thus being suitable for thermoelectric applications. We measure the thermoelectric properties of various poly( 3,4-ethylenedioxythiophene) samples, and observe a marked increase in the Seebeck coefficient when the electrical conductivity is enhanced through molecular organization. This initiates the transition from a Fermi glass to a semi-metal. The high Seebeck value, the metallic conductivity at room temperature and the absence of unpaired electron spins makes polymer semi-metals attractive for thermoelectrics and spintronics.
The ability to convert several low-energy photons into a single higher-energy photon is of significant importance in diverse fields ranging from imaging and biological labeling to optoelectronics and photovoltaics. The possibility to realize this phenomenon on the nanoscale can provide an additional degree of freedom in engineering electronic properties of materials and would allow deliberate manipulation and optimization of the upconversion processes. The purpose of this chapter is to provide a review of physical mechanisms that govern the photon upconversion in semiconductor nanostructures. Taking into account a large number of comprehensive reviews on this topic, our main focus is on photon upconversion mediated by defects, which is far less explored so far but provides a viable and attractive alternative for achieving efficient photon upconversion without involving doping.
By using scanning electron microscopy and cathodoluminescence (CL), a decrease in radiative efficiency of GaNP alloy with increasing N content is seen due to the formation of structural defects. The defect formation is attributed to relaxation of tensile strain in the GaNP layer, which is lattice mismatched to GaP substrate. Several types of extended defects including dislocations, microcracks and pits are revealed in partly relaxed GaNxP1-x epilayers with x=1.9%, whereas coherently strained layers exhibit high crystalline quality for x up to 4%. According to the CL measurements, all extended defects act as competing, non-radiative channels leading to the observed strong decrease in the radiative efficiency. From CL mapping experiments, non-uniformity of strain distribution around the extended defects is partly responsible for the broadening of the photoluminescence (PL) spectra recorded in the macro-PL experiments. © 2001 Elsevier Science B.V. All rights reserved.
In this paper we review our recent results from in-depth investigations of physical mechanisms which govern efficiency of several processes important for future spintronic devises, such as spin alignment within diluted magnetic semiconductors (DMS), spin injection from DMS to non-magnetic spin detectors (SDs) and also spin depolarization within SD. Spin-injection structures based on II-VIs (e.g. ZnMnSe/Zn(Cd)Se) and III-Vs (e.g. GaMnN/Ga(In)N) were studied as model cases. Exciton spin relaxation within ZnMnSe DMS, important for spin alignment, was found to critically depend on Zeeman splitting of the exciton states and is largely facilitated by involvement of longitudinal optical (LO) phonons. Optical spin injection in ZnMnSe/Zn(Cd)Se was shown to be governed by (i) commonly believed tunneling of individual carriers or excitons and (ii) energy transfer via localized excitons and spatially separated localized electron-hole pairs (LEHP) located within DMS. Unexpectedly, the latter mechanism is in fact found to dominate spin injections. We shall also show that spin depolarization in the studied structures is essentially determined by efficient spin relaxation within non-magnetic spin detectors, which is an important factor limiting efficiency of spin detection. Detailed physical mechanisms leading to efficient spin depolarization will be discussed.
We review our recent results on optical characterization of MBE-grown GaNAs/GaAs quantum structures with N content up to 4.5%, by employing photoluminescence (PL), PL excitation, and time-resolved PL spectroscopies. The dominant PL mechanism has been determined as recombination of excitons trapped by potential fluctuations of the band edge, due to composition disorder and strain nonuniformity of the alloy. The estimated value of the localization potential is around 60 meV for the low-temperature grown structures and can be reduced by increasing the growth temperature or using post-growth rapid thermal annealing (RTA). © 2001 Elsevier Science S.A.
In this paper we will review our recent results from optical characterization studies of GaInNP. We will show that N incorporation in these alloys affects their structural and defect properties, as well as the electronic structure. The main structural changes include (i) increasing carrier localization due to strong compositional fluctuations, which is typical for all dilute nitrides, and (ii) N-induced long range ordering effects, specific for GaInNP. The observed degradation of radiative efficiency of the alloys upon increasing N content is attributed to formation of several defects acting as centres of efficient non-radiative recombination. One of the defects is identified as a complex involving a Ga interstitial atom. N incorporation is also found to change the band line up from the type I in the GaInP/GaAs structures to the type 11 in the GaInNP/GaAs heterojunctions with [N] > 0.5%. For the range of N compositions studied ([N] <= 2%), a conduction band offset at the GaInNP/GaAs interface is found to nearly linearly depend on [N] at -0.10 eV/%, whereas the valence band offset remains unaffected. (c) 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
This chapter analyses the impacts of alloying with nitrogen on structural properties and recombination processes in GaNAs nanowires (NW). It discusses possible innovative applications of these structures in advanced nano-emitters, where the incorporation of nitrogen induces the formation of self-assembled quantum dot-like states embedded in the NWs. The structural properties of these NWs were investigated by transmission electron microcopy. An important material parameter that affects performance of the NW-based devices is carrier lifetime. The non-radiative lifetime is largely affected by the material quality both in bulk and within near-surface regions. The contribution of the surface-related recombination is known to be especially severe in GaAs-based NW structures due to a large surface-to-volume ratio and the presence of surface states participating in the non-radiative recombination processes. The revealed optical properties of the GaNAs-based NW structures may be attractive for future optoelectronic applications in advanced nano-sized light emitters which could be integrated with silicon technology.
Hydrogen incorporation is shown to cause passivation of various N-related localized states and partial neutralization of N-induced changes in the electronic structure of the GaNxP1-x alloys with x < 0.008. According to the performed X-ray diffraction measurements, the hydrogenation is also found to cause strong expansion of the GaNP lattice which even changes from a tensile strain in the as-grown GaNP epilayers to a compressive strain in the post-hydrogenated structures with the highest H concentration. By comparing results obtained using two types of hydrogen treatments, i.e. by implantation from a Kaufman source and by using a remote dc H plasma, the observed changes are shown to be inherent to H due to its efficient complexing with N atoms, whereas possible effects of implantation damage are only marginal. (c) 2005 Elsevier B.V. All rights reserved.
cw hot photoluminescence (PL) complemented by transient PL measurements is employed to evaluate momentum and spin relaxation of heavy hole (HH) excitons in ZnMnSe CdSe superlattices. The rate of acoustic-phonon assisted momentum relaxation is concluded to be comparable to the total rate of exciton decay processes, about (2-3) × 1010 s-1, independent of applied magnetic fields. In magnetic fields when the Zeeman splitting ? of the exciton states is below the energy of the longitudinal optical (LO) phonon (?LO), a surprisingly strong suppression of spin relaxation rate from the bottom of the upper spin band is observed, which becomes comparable to that of momentum scattering via acoustic phonons. On the other hand, dramatic acceleration of the spin relaxation process by more than one order of magnitude is found for the excitons with a high momentum K. The findings are interpreted as being due to electron and hole spin flip processes via exchange interaction with isolated Mn2+ ions. Experimental evidence for the efficient interaction between the hot excitons and Mn impurities is also provided by the observation of spin flip transitions within Mn2+ - Mn2+ pairs that accompany the momentum relaxation of the hot HH excitons. In higher magnetic fields ?= ?LO, abrupt shortening of the spin flip time is observed. It indicates involvement of a new and more efficient spin relaxation process and is attributed to direct LO-assisted exciton spin relaxation with a subpicosecond spin relaxation time. © 2005 The American Physical Society.
This chapter discusses structural and optical properties of novel GaNP nanowires (NW), as well as their potential for future applications in optoelectronics and photonics. It reviews efforts devoted to the optimization of GaNP-based NWs for future applications in light-emitting devices and discusses the impacts of structural polymorphism on the radiative efficiency and band structure of the material. The chapter shows that GaNP NWs can be utilized as a source of linearly polarized light with the polarization direction that is not determined by dielectric mismatch between the NW and its surrounding. GaNP alloys are novel III–V semiconductors, which have a great potential for applications in amber-red light-emitting diodes and also as an active material in innovative intermediate the band solar cells. NWs grown under the non-optimized conditions usually suffer from various point and structural defects, which degrade the radiative efficiency.
Effects of Ga incorporation on electrical, structural and optical properties of ZnO epilayers are systematically studied by employing structural and optical characterization techniques combined with electrical and secondary ion mass spectrometry measurements. A non-monotonous dependence of free electron concentrations on Ga content is observed and is attributed to defect formation and phase separation. The former process is found to dominate for Ga concentrations of around 2-3x1020 cm-3. corresponding defects are suggested to be responsible for a broad red emission, which peaks at around 1.8 eV at K. Characteristic properties of this emission are well accounted for by assuming intracenter transitions at a deep center, of which the associated Huang-Rhys factor and mean phonon energy are determined. For higher Ga doping levels, the phase separation is found to be significant. It is that under these conditions only a minor fraction of incorporated Ga atoms form shallow donors, which leads to the observed dramatic decrease of carrier concentration.
Alloying of disordered GaInP with nitrogen is shown to lead to very efficient PLU in GaInNP/GaAs heterostructures grown by gas source molecular beam epitaxy (GS‐MBE). This is attributed to the N‐induced changes in the band alignment at the GaInNP/GaAs heterointerface from the type I for the N‐free structure to the type II in the samples with N compositions exceeding 0.5%. Based on the performed excitation power dependent measurements, a possible mechanism for the energy upconversion is suggested as being due to the two‐step two‐photon absorption. The photon recycling effect is shown to be important for the structures with N=1%, from time‐resolved PL measurements. © 2007 American Institute of Physics
The spin injection dynamics of GaMnN/InGaN multiquantum well (MQW) light emitting diodes (LEDs) grown by molecular beam epitaxy were examined using picosecond-transient and circularly polarized photoluminescence (PL) measurements. Even with the presence of a room temperature ferromagnetic GaMnN spin injector, the LEDs are shown to exhibit very low efficiency of spin injection. Based on resonant optical orientation spectroscopy, the spin loss in the structures is shown to be largely due to fast spin relaxation within the InGaN MQW, which itself destroys any spin polarization generated by optical spin orientation or electrical spin injection. Typical photoluminescence decay times were 20-40 ns in both commercial GaN MQW LEDs with emission wavelengths between 420-470 nm and in the GaMnN/InGaN multi-quantum well MQW LEDs. In the wurtzite InGaN/GaN system, biaxial strain at the interfaces give rise to large piezoelectric fields directed along the growth axis. This built-in piezofield breaks the reflection symmetry of confining potential leading to the presence of a large Rashba term in the conduction band Hamiltonian which is responsible for the short spin relaxation times.
Temperature dependent cw- and time-resolved photoluminescence combined with absorption measurements are employed to evaluate the origin of radiative recombination in ZnCdO alloys grown by molecular-beam epitaxy. The near-band-edge emission is attributed to recombination of excitons localized within band tail states likely caused by nonuniformity in Cd distribution. Energy transfer between the tail states is argued to occur via tunneling of localized excitons. The transfer is shown to be facilitated by increasing Cd content due to a reduction of the exciton binding energy and, therefore, an increase of the exciton Bohr radius in the alloys with a high Cd content. © 2007 American Institute of Physics.
Dilute nitrides are novel III-V-N semiconductor alloys promising for a great variety of applications ranging from nanoscale light emitters and solar cells to energy production via photoelectrochemical reactions and to nano-spintronics. These alloys have become available in the one-dimensional geometry only most recently, thanks to the advances in the nanowire (NW) growth utilizing molecular beam epitaxy. In this review we will summarize growth approaches currently utilized for the fabrication of such novel dilute nitride-based NWs, discuss their structural, defect-related and optical properties, as well as provide several examples of their potential applications.
This book provides an in-depth review of the rapidly developing field of spintronic semiconductors. It covers a broad range of topics, including growth and basic physical properties of diluted magnetic semiconductors based on II-VI, III-V and IV semiconductors, recent developments in theory and experimental techniques and potential device applications; its aim is to provide postgraduate students, researchers and engineers a comprehensive overview of our present knowledge and future perspectives of spintronic semiconductors.
Since their development in the 1990s, it has been discovered that diluted nitrides have intriguing properties that are not only distinct from those of conventional semiconductor materials, but also are conducive to various applications in optoelectronics and photonics. The book examines these applications and presents a broad and in-depth look at the basic electronic and optical properties of diluted nitrides.
The aim of Physics and Applications of Diluted Nitrides is to provide graduate students, researchers and engineers with a comprehensive overview of the present knowledge and future perspectives of diluted nitrides.
Co-authored by a group of leading scientists in the field, this book brings the reader up to speed on the development and current state of diluted nitride applications, as well as the technologies to be developed in the near future.
A major current challenge for semiconductor devices is to develop materials for the next generation of optical communication systems and solar power conversion applications. Recently, extensive research has revealed that an introduction of only a few percentages of nitrogen into III-V semiconductor lattice leads to a dramatic reduction of the band gap. This discovery has opened the possibility of using these material systems for applications ranging from lasers to solar cells. "Physics and Technology of Dilute III-V Nitride Semiconductors and Novel Dilute Nitride Material Systems" reviews the current status of research and development in dilute III-V nitrides, with 24 chapters from prominent research groups covering recent progress in growth techniques, experimental characterization of band structure, defects carrier transport, transport properties, dynamic behavior of N atoms, device applications, modeling of device design, novel optoelectronic integrated circuits, and novel nitrogen containing III-V materials.
Magneto-optical spectroscopy in combination with tunable laser excitation spectroscopy is employed to carry out a detailed study of spin alignment and spin injection in II-VI wide-bandgap semiconductor heterostructures, aiming at optimization of structural design for nano-scale spintronic applications. The use of tunable excitation is shown to provide a valuable opportunity to monitor separately spin relaxation and spin injection processes in the structures. Efficient spin alignment is achieved by using a diluted magnetic semiconductor (DMS) (a layer of ZnMnSe or a ZnMnSe/CdSe superlattice) as thin as 10 nm. The spin alignment efficiency is shown to depend critically on the ratio between the rates of spin relaxation and spin transport within the DMS layer. This allows the realization of spin alignment and spin switching functions by varying the structural design.
In this work we study device-relevant issues, such as doping efficiency and thermal stability, of recently proposed intrinsic modulation doping approach where intrinsic defects (PIn antisites) are used as a carrier source instead of impurity dopants. The InP/InGaAs heterostructure designed to resemble high electron mobility transistor (HEMT) structures, where all the layers were grown at a normal growth temperature 480°C except for the top InP layer which was grown at 265°C, was used as a prototype device. A comparison between the intrinsically doped structure with extrinsically doped HEMTs, which have an identical design except that the top InP layer was instead Si-doped and was grown at 480°C, reveals a high efficiency of the intrinsic doping. The thermal stability of the intrinsically doped HEMT is examined by annealing at temperatures 400-500°C relevant to possible processing steps needed in device fabrication. The observed severe reduction of the carrier concentration after annealing performed without phosphorous gas protection is attributed to the known instability of an InP surface at T>400°C. Thermal stability of the intrinsically doped HEMT is shown to be improved by using an InP cap layer grown at 480°C.
Doping efficiency and thermal stability of intrinsic modulation doping in InP/InGaAs heterostructures, where intrinsic defects (PInantisites) are used as an electron source, are investigated. A high efficiency of the intrinsic doping is demonstrated from a comparison between the intrinsically doped and conventional extrinsically doped structures. The thermal stability of the intrinsically doped heterostructures is shown to be largely affected by the thermal stability of the InP surface.