Professor Jeremy Allam

Porphyrin–nanocarbon systems were used to generate a photocatalyst for the control of rhodamine B and rhodamine 6G photodegradation. Carboxylic functionalized multi-walled carbon nanotubes (o-MWCNTs) were decorated by two different porphyrin moieties: 5-(4-aminophenyl)-10,15,20-(triphenyl)­porphyrin (a-TPP) with an amine linker and 5-(4-carboxyphenyl)-10,15,20-(triphenyl)­porphyrin (c-TPP) with a carboxyl linker to the o-MWCNT, respectively, with their photocatalyst performances investigated. The optical properties of the mixed nanocomposite materials were investigated to reveal the intrinsic energy levels and mechanisms of degradation. The charge-transfer states of the o-MWCNTs were directly correlated with the performance of the complexes as well as the affinity of the porphyrin moiety to the o-MWCNT anchor, thus extending our understanding of energy-transfer kinetics in porphyrin–CNT systems. Both a-TPP and c-TPP o-MWCNT complexes offered improved photocatalytic performance for both RhB and Rh6G compared to the reference o-MWCNTs and both porphyrins in isolated form. The photocatalytic performance improved with higher concentration of o-MWCNTs in the complexed sample, indicating the presence of greater numbers of −H/–OH groups necessary to more efficient photodegradation. The large presence of the −H/–OH group in the complexes was expected and was related to the functionalization of the o-MWCNTs needed for high porphyrin attachment. However, the photocatalytic efficiency was affected at higher o-MWCNT concentrations due to the decomposition of the porphyrins and changes to the size of the CNT agglomerates, thus reducing the surface area of the reactant. These findings demonstrate a system that displays solar-based degradation of rhodamine moieties that are on par, or an improvement to, state-of-the-art organic systems.

We present optical and electrical characterization data obtained from bulk GaInNAs (lattice-matched to GaAs) diodes with varying GaInNAs composition. Good lattice-matching to GaAs, low reverse dark current and long wavelength absorption were achieved simultaneously, without the aid of post-growth annealing and use of antimony during the growth. © 2007 IEEE.

The ability to engineer a thin two-dimensional surface for light trapping across an ultra-broad spectral range is central for an increasing number of applications including energy, optoelectronics, and spectroscopy. Although broadband light trapping has been obtained in tall structures of carbon nanotubes with millimeter-tall dimensions, obtaining such broadband light–trapping behavior from nanometer-scale absorbers remains elusive. We report a method for trapping the optical field coincident with few-layer decoupled graphene using field localization within a disordered distribution of subwavelength-sized nanotexturing metal particles. We show that the combination of the broadband light–coupling effect from the disordered nanotexture combined with the natural thinness and remarkably high and wavelength-independent absorption of graphene results in an ultrathin (15 nm thin) yet ultra-broadband blackbody absorber, featuring 99% absorption spanning from the mid-infrared to the ultraviolet. We demonstrate the utility of our approach to produce the blackbody absorber on delicate opto-microelectromechanical infrared emitters, using a low-temperature, noncontact fabrication method, which is also large-area compatible. This development may pave a way to new fabrication methodologies for optical devices requiring light management at the nanoscale.

We have used time-resolved spectroscopy to measure the relaxation of spin polarizations in the narrow gap semiconductor material n-InAs as a function of temperature, doping, and pump wavelength. The results are consistent with the D'Yakonov-Perel mechanism for temperatures between 77 and 300 K. However, the data suggest that electron-electron scattering should be taken into account in determining the dependence of the spin lifetime on the carrier concentration in the range 5.2x10(16)-8.8x10(17) cm(-3). For a sample with doping of 1.22x10(17) cm(-3) the spin lifetime was 24 ps at room temperature. By applying a magnetic field in the sample plane we also observed coherent precession of the spins in the time domain, with a g factor g(*)=-13, also at room temperature.

The spin relaxation in undoped InSb films grown on GaAs has been investigated in the temperature range from 77 to 290 K. Two distinct lifetime values have been extracted, 1 and 2.5 ps, dependent on film thickness. Comparison of this data with a multilayer transport analysis of the films suggests that the longer time (~2.5 ps at 290 K) is associated with the central intrinsic region of the film, while the shorter time (~1 ps) is related to the highly dislocated accumulation region at the film-substrate interface. Whereas previous work on InAs films grown on GaAs showed that the native surface defect resulted in an additional charge accumulation layer with high conductivity but very short spin lifetime, in InSb layers the surface states introduce a depletion region. We infer that InSb could be a more attractive candidate for spintronic applications than InAs.

Optical waveguides containing high percentages of colloidal nanocrystals have been fabricated by layer-by-layer deposition on planar and patterned glass substrates. The two- and one-dimensional waveguidings in these structures are demonstrated by propagation loss experiments. The experimental results obtained for various film thicknesses and widths of the waveguide stripes together with simulations of the light propagation indicate that the losses are dominated by surface roughness. The variable stripe length method is used to determine the optical gain of 230 cm–1 from the amplified spontaneous emission. This high value makes the authors' waveguide structures very promising for applications in amplifiers and lasers with reduced threshold powers.

We have used time resolved spectroscopy to measure the relaxation of spin polarization in InSb/AlInSb quantum wells (QWs) as a function of temperature and mobility. The results are consistent with the D'yakonov–Perel (DP) mechanism for high mobility samples over the temperature range from 50 to 300 K. For low mobility samples at high temperature the Elliott–Yafet and DP mechanisms become comparable. We show that the mobility can in certain circumstances determine which mechanism is dominant, and that above 1 m2 V-1 s-1 in 20 nm wide InSb QWs it is the DP mechanism. We also give a criterion for the maximum spin lifetime in terms of mobility and temperature, and show that for our 20 nm wide QWs this corresponds to 0.5 ps at 300 K and mobility 1 m2 V-1 s-1.

We have used time-resolved spectroscopy to measure the relaxation of spin polarizations in the narrow gap semiconductor material n-InAs as a function of temperature, doping, and pump wavelength. The results are consistent with the D'Yakonov-Perel mechanism for temperatures between 77 and 300 K. However, the data suggest that electron-electron scattering should be taken into account in determining the dependence of the spin lifetime on the carrier concentration in the range 5.2×1016–8.8×1017 cm–3. For a sample with doping of 1.22×1017 cm–3 the spin lifetime was 24 ps at room temperature. By applying a magnetic field in the sample plane we also observed coherent precession of the spins in the time domain, with a g>/i> factor g*=–13, also at room temperature.

We report investigation of the spin relaxation in InAs films grown on GaAs at a temperature range from 77 K to 290 K. InAs is known to have a surface accumulation layer and the depth profile of the concentration and mobility is strongly nonuniform. We have correlated the spin relaxation with a multilayer analysis of the transport properties and find that the surface and the interface with the GaAs substrate both have subpicosecond lifetimes (due to the high carrier concentration), whereas the central semiconducting layer has a lifetime of an order of 10 ps. Even for the thickest film studied (1 micro-m, the semiconducting layer only carried 30% of the total current (with 10% through the interface layer and 60% through the surface accumulation layer). Designs for spintronic devices that utilize InAs, which is attractive due to its narrow gap and strong Rashba effect, will need to include strategies for minimizing the effects of the surface.

The spin relaxation in undoped InSb films grown on GaAs has been investigated in the temperature range from 77 to 290 K. Two distinct lifetime values have been extracted, 1 and 2.5 ps, dependent on film thickness. Comparison of this data with a multilayer transport analysis of the films suggests that the longer time (similar to 2.5 ps at 290 K) is associated with the central intrinsic region of the film, while the shorter time (similar to 1 ps) is related to the highly dislocated accumulation region at the film-substrate interface. Whereas previous work on InAs films grown on GaAs showed that the native surface defect resulted in an additional charge accumulation layer with high conductivity but very short spin lifetime, in InSb layers the surface states introduce a depletion region. We infer that InSb could be a more attractive candidate for spintronic applications than InAs.

We investigate the evolution of short-duration pulses injected into laser diodes biased above threshold with the use of spectrally and temporally resolved experimental and numerical methods. We show that stable transients may be formed as a result of spatially re-distributing the cavity energy. By controlling the phase of injected pulses with respect to the diode cavity radiation we show through simulation that it is possible to directly generate and control stable streams of pulses.

We investigate the optical and electrical characteristics of GaInNAs/GaAs long-wavelength photodiodes grown under varying conditions by molecular beam epitaxy and subjected to postgrowth rapid thermal annealing (RTA) at a series of temperatures. It is found that the device performance of the nonoptimally grown GaInNAs p-i-n structures, with nominal compositions of 10% In and 3.8% N, can be improved significantly by the RTA treatment to match that of optimally grown structures. The optimally annealed devices exhibit overall improvement in optical and electrical characteristics, including increased photoluminescence brightness, reduced density of deep-level traps, reduced series resistance resulting from the GaAs/GaInNAs heterointerface, lower dark current, and significantly lower background doping density, all of which can be attributed to the reduced structural disorder in the GaInNAs alloy.© 2012 TMS.

Optical waveguides containing high percentages of colloidal nanocrystals have been fabricated by layer-by-layer deposition on planar and patterned glass substrates. The two- and one-dimensional waveguidings in these structures are demonstrated by propagation loss experiments. The experimental results obtained for various film thicknesses and widths of the waveguide stripes together with simulations of the light propagation indicate that the losses are dominated by surface roughness. The variable stripe length method is used to determine the optical gain of 230 cm(-1) from the amplified spontaneous emission. This high value makes the authors' waveguide structures very promising for applications in amplifiers and lasers with reduced threshold powers.

We report Larmor precession in bulk InSb observed in the time domain from 77 to 300 K. The optically oriented polarization precesses coherently even at 300 K. The inferred Zeeman spin splitting is strongly nonparabolic, and the electron g factor (g*) is in good agreement with k·p theory (provided we take only the dilational contribution to the change in energy gap with temperature). We also show here that correct application of the 14-band k·p model agrees with apparently anomalous trends previously reported for GaAs and confirm that the most widely quoted formula for g* in GaAs is incomplete.

We have used time resolved spectroscopy to measure the relaxation of spin polarization in InSb/AlInSb quantum wells (QWs) as a function of temperature and mobility. The results are consistent with the D'yakonov - Perel (DP) mechanism for high mobility samples over the temperature range from 50 to 300 K. For low mobility samples at high temperature the Elliott - Yafet and DP mechanisms become comparable. We show that the mobility can in certain circumstances determine which mechanism is dominant, and that above 1 m(2) V-1 s(-1) in 20 nm wide InSb QWs it is the DP mechanism. We also give a criterion for the maximum spin lifetime in terms of mobility and temperature, and show that for our 20 nm wide QWs this corresponds to 0.5 ps at 300 K and mobility 1 m(2) V-1 s(-1).

Measurements of the THz absorption and the time-resolved photoluminescence have been performed on the same GaAs quantum well sample. The strength of the absorption at the internal 1s-2p exciton transition frequency is used as a measure of the density of excitons in the sample. When the interband pump laser is resonant with the 1s exciton frequency, induced absorption at the s-2p frequency is clearly seen. If the same density of carriers is created pumping in the continuum, no significant 1s-2p absorption is seen in a time window of 450 ps. Complementary time-resolved photoluminescence experiments, detecting the emission at the exciton energy under the same pump conditions, show the PL intensity in resonant and nonresonant cases to be similar. The counter-intuitive existence of luminescence at the exciton energy simultaneously with the absence of the s-2p absorption is consistent with the recent theoretical predictions of Kira et al., Phys. Rev. Lett. 81, 3263 (1998).

Exciton-exciton recombination in isolated semiconducting single-walled carbon nanotubes was studied using femtosecond transient absorption. Under sufficient excitation to saturate the optical absorption, we observed an abrupt transition between reaction- and diffusion- limited kinetics, arising from reactions between incoherent localized excitons with a finite probability of ~ 0.2 per encounter. This represents the first experimental observation of a crossover between classical and critical kinetics in a 1D coalescing random walk, which is a paradigm for the study of non- equilibrium systems.

Measurements of the THz absorption and the time-resolved photoluminescence have been performed on the same GaAs quantum well sample. The strength of the absorption at the internal 1s-2p exciton transition frequency is used as a measure of the density of excitons in the sample. When the interband pump laser is resonant with the Is exciton frequency, induced absorption at the 1s-2p frequency is clearly seen. If the same density of carriers is created pumping in the continuum, no significant 1s-2p absorption is seen in a time window of 450 ps. Complementary time-resolved photoluminescence experiments, detecting the emission at the exciton energy under the same pump conditions, show the PL intensity in resonant and nonresonant cases to be similar. The counter-intuitive existence of luminescence at the exciton energy simultaneously with the absence of the 1s-2p absorption is consistent with the recent theoretical predictions of Kira et al., Phys. Rev. Lett. 81, 3263 (1998).

We have made direct pump-probe measurements of spin lifetimes in intrinsic and degenerate n-InAs at 300 K. In particular, we measure remarkably long spin lifetimes (tau(s)similar to1.6 ns) for near-degenerate epilayers of n-InAs. For intrinsic material, we determine tau(s)similar to20 ps, in agreement with other workers. There are two main models that have been invoked for describing spin relaxation in narrow-gap semiconductors: the D'yakonov-Perel (DP) model and the Elliott-Yafet (EY) model. For intrinsic material, the DP model is believed to dominate in III-V materials above 77 K, in agreement with our results. We show that in the presence of strong n-type doping, the DP relaxation is suppressed both by the degeneracy condition and by electron-electron scattering, and that the EY model then dominates for the n-type material. We show that this same process is also responsible for a hitherto unexplained lengthening of tau(s) with n-type doping in our earlier measurements of n-InSb.

We report investigation of the spin relaxation in InAs films grown on GaAs at a temperature range from 77 K to 290 K. InAs is known to have a surface accumulation layer and the depth profile of the concentration and mobility is strongly nonuniform. We have correlated the spin relaxation with a multilayer analysis of the transport properties and find that the surface and the interface with the GaAs substrate both have subpicosecond lifetimes (due to the high carrier concentration), whereas the central semiconducting layer has a lifetime of an order of 10 ps. Even for the thickest film studied (1 mu m), the semiconducting layer only carried 30% of the total current (with 10% through the interface layer and 60% through the surface accumulation layer). Designs for spintronic devices that utilize InAs, which is attractive due to its narrow gap and strong Rashba effect, will need to include strategies for minimizing the effects of the surface.

Ferroelectric switching in bulk materials, at modest electric fields, is a relatively fast process, occurring on time scales of microseconds and less. A secondary retarded switching phenomenon also occurs on time scales of seconds and has previously been attributed to defect induced elevated energy barriers between polarisation states. As ferroelectric switching is a thermally activated process the barrier heights are also affected by temperature which is not constant in ferroelectric materials due to the electrocaloric effect. Here an additional EC induced retardation mechanism is proposed whereby EC induced temperature changes repeatedly temporarily prevent further FE switching during cooling cycles.

Despite the "darker than black" association attributed to carbon nanotube forests, here is shown that it is also possible to grow these structures, over heat-sensitive substrates, featuring highly transmissive characteristics from the UV to infrared wavelengths, for forest heights as high as 20 μm. The optical transmission is interpreted in terms of light propagation along channels that are self-generated by localized bundling of tubes, acting as waveguides. A good correlation is shown between the distribution of diameter sizes of these sub-wavelength voids and the transmission spectrum of the forests. For the shorter visible and near-UV wavelengths, this model shows that light propagates by channeling along individual vertical voids in the forests, which elucidates the origin for the widely-reported near-zero reflectance values observed in forests. For the longer infrared wavelengths, the mode spreads over many nanotubes and voids, and propagates along a "homogeneous effective medium". The strong absorption of the forest at the shorter wavelengths is correlated in terms of the stronger attenuation inside a waveguide cavity, according to the λ attenuation dependency of standard waveguide theory. The realization of this material can lead to novel avenues in new optoelectronic device design, where the carbon nanotube forests can be used as highly conducting "scaffolds" for optically active materials, whilst also allowing light to penetrate to significant depths into the structure, in excess of 20 μm, enabling optical functionality. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

By adopting structural conformations with sub-nanometer precision, nature creates highly concentrated pigment-protein arrays to capture solar energy with high-efficiency. Synthetic analogues of such systems exhibit concentration dependent fluorescence quenching when approaching pigment concentrations of that seen in biological systems. Here we report on systems of acid functionalised multi-walled carbon nanotubes (o-MWCNT) and aminophenyl tetraporphyrins that create a novel synthetic pigment-scaffold complex. The complex does not follow the trend of typical fluorescence quenching. Our steady-state and time-resolved data suggest an optimal concentration that offers a luminescence enhancement compared to the expected standard Stern-Volmer quenching relationship. The quenching is modified by controlling 1 the pigment-distance via agglomerate size to near the upper limit for Dex-ter transfer of 10Å10˚10Å as confirmed by dynamic light scattering measurements and chromophore-chromophore nearest neighbour calculations. Our results highlight a potential synthetic complex with facile synthesis to investigate resonant electron transfer processes that do not follow traditional luminescence self-quenching relationships.

By measuring THz absorption and time-resolved photoluminescence on the same GaAs quantum well sample we confirm the recent prediction of Kira that PL at the exciton frequency does not require a population of bound excitons.

Two issues with using InGaAsN as absorber in avalanche photodiodes (APDs) for 1310nm wavelength applications are addressed here. Firstly, we demonstrated InGaAsN p-i-n diodes with stable photoresponse around 1310nm but reverse leakage current density slightly above the acceptable limit of ~0.2mA/cm2 at 150kV/cm. We also investigated whether or not InGaAsN as absorber is compatible with Al0.8Ga0.2As (the proposed avalanche material in our separate-absorption-multiplication APD design) in terms of the relationship between α and β in InGaAsN. Our observations suggest α ~ β in InGaAsN, making it compatible with Al0.8Ga0.2As.

InGaAsN is a promising material system to enable low-cost GaAs-based detectors to operate in the telecommunication spectrum, despite the problems posed by the low growth temperature required for nitrogen incorporation. We demonstrate that InGaAsN p+-i-n+ structures with nominal In and N fraction of 10% and 3.8%, grown by molecular beam epitaxy (MBE) under non-optimal growth conditions, can be optimized by post growth thermal annealing to match the performance of optimally grown structures. We report the findings of an annealing study by comparing the photoluminescence spectra, dark current and background concentration of the as-grown and annealed samples. The dark current of the optimally annealed sample is approximately 2 μA/cm2 at an electric field of 100 kV/cm, and is the lowest reported to date for InGaAsN photodetectors with a cut-off wavelength of 1.3 μm. Evidence of lower unintentional background concentration after annealing at a sufficiently high temperature, is also presented.

We have grown a series of bulk GaInNAs p-i-n diodes and identified some of the dark current mechanisms present in our devices. With a nitrogen composition of ~4 %, the band gap can be reduced to 0.94 eV. We also demonstrate that low dark current density is achievable without compromising the absorption and hence quantum efficiency up to 1.4 mum.

Photoexcitation of carbon nanotubes generates excitons which decay by exciton-exciton annihilation at sufficient density. We examine this decay under conditions of one, few and many excitons per nanotube. A classic 1D reaction-diffusion behaviour is observed, with decay limited by diffusion for t>3ps and by reaction for t

We study exciton reactions on carbon nanotubes in the regime of many, few and one exciton per nanotube, and demonstrate classic 1-D reaction-diffusion behaviour. Dissociation occurs when exciton spacing is less than the exciton length.