Showing papers by "Xiaoming Wen published in 2017"

Unravelling charge carrier dynamics in protonated g-C3N4 interfaced with carbon nanodots as co-catalysts toward enhanced photocatalytic CO2 reduction: A combined experimental and first-principles DFT study

Abstract: In this work, we demonstrated the successful construction of metal-free zerodimensional/ two-dimensional carbon nanodot (CND)-hybridized protonated g-C3N4 (pCN) (CND/pCN) heterojunction photocatalysts by means of electrostatic attraction. We experimentally found that CNDs with an average diameter of 4.4 nm were uniformly distributed on the surface of pCN using electron microscopy analysis. The CND/pCN-3 sample with a CND content of 3 wt.% showed the highest catalytic activity in the CO2 photoreduction process under visible and simulated solar light. This process results in the evolution of CH4 and CO. The total amounts of CH4 and CO generated by the CND/pCN-3 photocatalyst after 10 h of visible-light activity were found to be 29.23 and 58.82 μmol·g catalyst −1 , respectively. These values were 3.6 and 2.28 times higher, respectively, than the amounts generated when using pCN alone. The corresponding apparent quantum efficiency (AQE) was calculated to be 0.076%. Furthermore, the CND/pCN-3 sample demonstrated high stability and durability after four consecutive photoreaction cycles, with no significant decrease in the catalytic activity. The significant improvement in the photoactivity using CND/pCN-3 was attributed to the synergistic interaction between pCN and CNDs. This synergy allows the effective migration of photoexcited electrons from pCN to CNDs via well-contacted heterojunction interfaces, which retards the charge recombination. This was confirmed by photoelectrochemical measurements, and steady-state and time-resolved photoluminescence analyses. The first-principles density functional theory (DFT) calculations were consistent with our experimental results, and showed that the work function of CNDs (5.56 eV) was larger than that of pCN (4.66 eV). This suggests that the efficient shuttling of electrons from the conduction band of pCN to CNDs hampers the recombination of electron–hole pairs. This significantly increased the probability of free charge carriers reducing CO2 to CH4 and CO. Overall, this study underlines the importance of understanding the charge carrier dynamics of the CND/pCN hybrid nanocomposites, in order to enhance solar energy conversion.

Acoustic-optical phonon up-conversion and hot-phonon bottleneck in lead-halide perovskites.

Abstract: The hot-phonon bottleneck effect in lead-halide perovskites (APbX3) prolongs the cooling period of hot charge carriers, an effect that could be used in the next-generation photovoltaics devices. Using ultrafast optical characterization and first-principle calculations, four kinds of lead-halide perovskites (A=FA+/MA+/Cs+, X=I-/Br-) are compared in this study to reveal the carrier-phonon dynamics within. Here we show a stronger phonon bottleneck effect in hybrid perovskites than in their inorganic counterparts. Compared with the caesium-based system, a 10 times slower carrier-phonon relaxation rate is observed in FAPbI3. The up-conversion of low-energy phonons is proposed to be responsible for the bottleneck effect. The presence of organic cations introduces overlapping phonon branches and facilitates the up-transition of low-energy modes. The blocking of phonon propagation associated with an ultralow thermal conductivity of the material also increases the overall up-conversion efficiency. This result also suggests a new and general method for achieving long-lived hot carriers in materials.

Consolidation of the optoelectronic properties of CH 3 NH 3 PbBr 3 perovskite single crystals

Abstract: Ultralow trap densities, exceptional optical and electronic properties have been reported for lead halide perovskites single crystals; however, ambiguities in basic properties, such as the band gap, and the electronic defect densities in the bulk and at the surface prevail. Here, we synthesize single crystals of methylammonium lead bromide (CH3NH3PbBr3), characterise the optical absorption and photoluminescence and show that the optical properties of single crystals are almost identical to those of polycrystalline thin films. We observe significantly longer lifetimes and show that carrier diffusion plays a substantial role in the photoluminescence decay. Contrary to many reports, we determine that the trap density in CH3NH3PbBr3 perovskite single crystals is 1015 cm−3 , only one order of magnitude lower than in the thin films. Our enhanced understanding of optical properties and recombination processes elucidates ambiguities in earlier reports, and highlights the discrepancies in the estimation of trap densities from electronic and optical methods. Metal halide perovskites for optoelectronic devices have been extensively studied in two forms: single-crystals or polycrystalline thin films. Using spectroscopic approaches, Wenger et al. show that polycrystalline thin films possess similar optoelectronic properties to single crystals.

Light Illumination Induced Photoluminescence Enhancement and Quenching in Lead Halide Perovskite

Abstract: It has been found that light illumination (soaking) can significantly change the optical and electronic properties of perovskites and the performance of perovskite solar cells. Here using steady state and time-resolved photoluminescence (PL) techniques, we investigate systematically the effect of light illumination on a well encapsulated CH3NH3PbI3 perovskites. Under a continuous constant illumination at low intensity, the PL exhibits either enhancement or constant; dependent on the detrapping rate and density of the defect states in the perovskite which in turn is determined by fabrication methods. Defect curing is attributed to the origin of the PL enhancement. Under a continuous higher intensity illumination, PL quenching is observed with different thresholds relevant to the sample fabrication. This is ascribed to mobile ion accumulation resulting in increased electron/ hole non-radiative recombination. We confirmed the PL enhancement and quenching under continuous illumination (light soaking) partly originate from the intrinsic contribution of the perovskite, closely correlated to the defect density therefore the fabrication. These findings provide novel insight into the carrier dynamics correlated to the defect trapping and mobile ions which helps to understand the instability of perovskite solar cells.

Inverted Hysteresis in CH3NH3PbI3 Solar Cells: Role of Stoichiometry and Band Alignment.

Abstract: J–V hysteresis in perovskite solar cells is known to be strongly dependent on many factors ranging from the cell structure to the preparation methods Here we uncover one likely reason for such sensitivity by linking the stoichiometry in pure CH3NH3PbI3 (MAPbI3) perovskite cells with the character of their hysteresis behavior through the influence of internal band offsets We present evidence indicating that in some cells the ion accumulation occurring at large forward biases causes a temporary and localized increase in recombination at the MAPbI3/TiO2 interface, leading to inverted hysteresis at fast scan rates Numerical semiconductor models including ion accumulation are used to propose and analyze two possible origins for these localized recombination losses: one based on band bending and the other on an accumulation of ionic charge in the perovskite bulk

A New Passivation Route Leading to Over 8% Efficient PbSe Quantum‐Dot Solar Cells via Direct Ion Exchange with Perovskite Nanocrystals

Abstract: Colloidal quantum dots (QDs) are promising candidate materials for photovoltaics (PV) owing to the tunable bandgap and low-cost solution processability. Lead selenide (PbSe) QDs are particularly attractive to PV applications due to the efficient multiple-exciton generation and carrier transportation. However, surface defects arising from the oxidation of the PbSe QDs have been the major limitation for their development in PV. Here, a new passivation method for chlorinated PbSe QDs via ion exchange with cesium lead halide (Br, I) perovskite nanocrystals is reported. The surface chloride ions on the as-synthesized QDs can be partially exchanged with bromide or iodide ions from the perovskite nanocrystals, hence forming a hybrid halide passivation. Consistent with the improved photoluminescence quantum yield, the champion PV device fabricated with these PbSe QDs achieves a PCE of 8.2%, compared to 7.3% of that fabricated with the untreated QDs. This new method also leads to devices with excellent air-stability, retaining at least 93% of their initial PCEs after being stored in ambient conditions for 57 d. This is considered as the first reported PbSe QD solar cell with a PCE of over 8% to date.

Spatial Distribution of Lead Iodide and Local Passivation on Organo-Lead Halide Perovskite.

Abstract: We identify nanoscale spatial distribution of PbI2 on the (FAPbI3)0.85(MAPbBr3)0.15 perovskite thin film and investigate the local passivation effect using confocal based optical microscopy of steady state and time-resolved photoluminescence (PL). Different from a typical scanning electron microscope (SEM) morphology study, confocal based PL spectroscopy and microscopy allow researchers to map the morphologies of both perovskite and PbI2 grains simultaneously, by selectively detecting their characteristic fluorescent bands using band-pass filters. In this work, we compare the perovskite samples without and with excess PbI2 incorporation and unambiguously reveal PbI2 distribution for the PbI2-rich sample. In addition, using the nanoscale time-resolved PL technique we show that the PbI2-rich regions exhibit longer lifetime due to suppressed defect trapping, compared to the PbI2-poor regions. The measurement on the PbI2-rich sample indicates that the passivation effect of PbI2 in perovskite film is effective...

Significant performance enhancement of InGaN/GaN nanorod LEDs with multi-layer graphene transparent electrodes by alumina surface passivation

Abstract: Nanotextured surfaces provide an ideal platform for efficiently capturing and emitting light. However, the increased surface area in combination with surface defects induced by nanostructuring e.g. using reactive ion etching (RIE) negatively affects the device's active region and, thus, drastically decreases device performance. In this work, the influence of structural defects and surface states on the optical and electrical performance of InGaN/GaN nanorod (NR) light emitting diodes (LEDs) fabricated by top-down RIE of c-plane GaN with InGaN quantum wells was investigated. After proper surface treatment a significantly improved device performance could be shown. Therefore, wet chemical removal of damaged material in KOH solution followed by atomic layer deposition of only 10 alumina as wide bandgap oxide for passivation were successfully applied. Raman spectroscopy revealed that the initially compressively strained InGaN/GaN LED layer stack turned into a virtually completely relaxed GaN and partially relaxed InGaN combination after RIE etching of NRs. Time-correlated single photon counting provides evidence that both treatments—chemical etching and alumina deposition—reduce the number of pathways for non-radiative recombination. Steady-state photoluminescence revealed that the luminescent performance of the NR LEDs is increased by about 50% after KOH and 80% after additional alumina passivation. Finally, complete NR LED devices with a suspended graphene contact were fabricated, for which the effectiveness of the alumina passivation was successfully demonstrated by electroluminescence measurements.

Potential of HfN, ZrN, and TiH as hot carrier absorber and Al2O3/Ge quantum well/Al2O3 and Al2O3/PbS quantum dots/Al2O3 as energy selective contacts

Abstract: The hot carrier (HC) solar cell is one of the most promising advanced photovoltaic concepts. It aims to minimise two major losses in single junction solar cells due to sub-band gap loss and thermalisation of above band gap photons by using a small bandgap absorber, and, importantly, collecting the photo-generated carriers before they thermalise. In this paper we will present recent development of the two critical components of the HC solar cell, i.e., the absorber and energy selective contacts (ESCs). For absorber, fabrication and carrier cooling rates in potential bulk materials — hafnium nitride, zirconium nitride, and titanium hydride are presented. Results of ESCs employing double barrier resonant tunneling structures Al2O3/Ge quantum well (QW)/Al2O3 and Al2O3/PbS quantum dots (QDs)/Al2O3 are also presented. These results are expected to guide further development of practical HC solar cell devices.

Difference in hot carrier cooling rate between Langmuir-Blodgett and drop cast PbS QD films due to strong electron-phonon coupling.

Abstract: The carrier dynamics of lead sulphide quantum dot (PbS QD) drop cast films and closely packed ordered Langmuir-Blodgett films are studied with ultra-fast femtosecond transient absorption spectroscopy. The photo-induced carrier temperature is extracted from transient absorption spectra and monitored as a function of time delay. The cooling dynamics of carriers in PbS QDs suggest a reduction of the carrier energy loss rate at longer time delays through the retardation of the longitudinal optical (LO) phonon decay due to partial heating of acoustic phonon modes. A slowed hot carrier cooling time up to 116 ps is observed in the drop cast film. A faster cooling rate was also observed in the highly compact Langmuir-Blodgett film due to the enhanced carrier-LO phonon coupling strength arising from the Coulombic interaction in neighboring QDs, which is verified by temperature dependent steady state PL measurements.

Hot carrier transfer processes in nonstoichiometric titanium hydride

Abstract: The absorber of the hot carrier solar cell (HCSC) needs to have a considerably reduced hot carrier thermalisation rate, in order to maintain the photo-generated hot carriers for enough time such that they can be extracted. The slow carrier cooling effect is predicted in materials in which the phononic band gap is sufficiently large to block the Klemens decay. Binary compounds with a large mass ratio between the constituent elements are likely to have large phononic band gap. Titanium hydride is one of these binary compounds that has the potential to become an absorber of the HCSC. Whilst a large phononic gap has been observed in stoichiometric TiH2, it has not been experimentally confirmed for hydrogen deficient TiH x (where x < 2). In this article, we report the phonon density of states of TiH1.65 measured using inelastic neutron scattering and presented to clearly show the phononic band gap. We also present the carrier thermalisation process of a TiH x (1< x <2) thin film by transient absorption, and estimate the carrier cooling time in this material.

Development of Absorber and Energy Selective Contacts for Hot Carrier Solar Cells

Abstract: The hot carrier solar cell is one of the most promising advanced PV concepts with theoretical efficiency of over 65% at one sun. Two crucial components of the HC solar cell are: (i) Absorber which can sufficiently reduce the rate of hot carrier cooling so that they can be collected at higher energies, and (ii) Energy selective contacts (ESCs) which allow extraction of hot carriers only through a narrow energy range. In this paper, potential of HfN and ZrN thin films as hot carrier absorber has been investigated. Al 2 O 3 /Ge QW/ Al 2 O 3 , Al 2 O 3 /Si QW/Al 2 O 3 , and Al 2 O 3 /PbS QDs/Al 2 O 3 double barrier structures have been investigated as energy selective contacts.

Nanoscale characterization of GaN/InGaN multiple quantum wells on GaN nanorods by photoluminescence spectroscopy

Abstract: GaN/InGaN multiple quantum wells (MQW) and GaN nanorods have been widely studied as a candidate material for high-performance light emitting diodes. In this study, GaN/InGaN MQW on top of GaN nanorods are characterized in nanoscale using confocal microscopy associated with photoluminescence spectroscopy, including steady-state PL, timeresolved PL and fluorescence lifetime imaging (FLIM). Nanorods are fabricated by etching planar GaN/InGaN MQWs on top of a GaN layer on a c-plane sapphire substrate. Photoluminescence efficiency from the GaN/InGaN nanorods is evidently higher than that of the planar structure, indicating the emission improvement. Time-resolved photoluminescence (TRPL) prove that surface defects on GaN nanorod sidewalls have a strong influence on the luminescence property of the GaN/InGaN MWQs. Such surface defects can be eliminated by proper surface passivation. Moreover, densely packed nanorod array and sparsely standing nanorods have been studied for better understanding the individual property and collective effects from adjacent nanorods. The combination of the optical characterization techniques guides optoelectronic materials and device fabrication.

Selective optical contacting for solar spectrum management

Abstract: Solar spectrum management using up/down conversion is an important method to improve the photovoltaic energy conversion efficiency. It asks for a monochromatic luminescence absorption at the band edge of the photovoltaic device to reduce both the sub-band-gap and over-band-gap energy losses. Here, we demonstrate an energy selective optical contacting concept to improve the luminescence transfer efficiency for spectrum management. By increasing both the luminescence emission and re-absorption ability through photonic resonance, an efficient photon transfer channel could be established between the luminescence emitter and the photovoltaic component in a near-field region. This concept is not only able to compensate the insufficient band edge absorption ability of the photovoltaic device, but also to break the far-field limitation of luminescence radiation. The energy selection on the optical spectrum naturally imposed by the mode resonance is also helpful to improve the monochromaticity of the luminescence yield. In this paper, a photonic crystal cavity is used to realize the optical contacting concept between a thin silicon film and spectrum converter. The optical power and photon flux transferred between different components are calculated analytically using the electromagnetic Green’s function. The corresponding radiative dipole moment is estimated by the fluctuation-dissipation theorem. The example shows an over 80 times enhancement in the luminescence absorbance by the silicon layer, illustrating the great potential of this concept to be applied on nano-structured photovoltaic devices.