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At least 37 records · Page 2

Large Polaron Screening Delays Mobility Roll-Off in Halide Perovskites under High Injection

The interplay between carrier density regimes and the various scattering processes is fundamental for understanding charge transport efficiency in high-performance semiconductors. Combining ultrafast time-resolved terahertz spectroscopy (TRTS) and transient microwave photoconductivity (TRMC), we measure carrier mobilities over 7 orders of magnitude (10 13 –10 20 carriers cm –3 ), reaching a regime where carrier–carrier scattering dominates and mobility begins to roll off. We find the Caughey–Thomas model can be effectively employed for transport modeling in 3D metal halide perovskites (MHPs), and the mobility roll-off near ∼10 19 cm –3 can be tuned by MHP composition. Carrier lifetime in MHPs starts decreasing at much lower carrier densities due to interband multi-carrier recombination, while intraband carrier mobility remains unchanged as carrier–carrier scattering is screened by the presence of polarons. The validated Caughey–Thomas model provides a practical input for device simulations, prevents overestimation of diffusion length under high injection, and suggests that MHPs are excellent candidates for unipolar device applications under high carrier densities.

14 SOLAR ENERGY↗

Charge carrier dynamics in two-dimensional hybrid perovskites: Dion–Jacobson vs. Ruddlesden–Popper phases

Two-dimensional (2D) halide perovskites are promising materials for environmentally stable next-generation optoelectronic device applications. Besides the widely investigated Ruddlesden–Popper (RP) phases, Dion–Jacobson (DJ) phases are attracting considerable attention due to their rapid emergence as efficient solar cell materials. However, there is very little atomistic understanding of the charge carrier dynamics under ambient conditions for these DJ-phases, limiting the possibilities to tune their optoelectronic performances through compositional engineering routes. In this study, by combining nonadiabatic molecular dynamics with time-domain density functional theory methods at room temperature, we compare the dominant non-radiative carrier recombination and dephasing processes in RP and DJ monolayered lead halide perovskites. Our systematic study demonstrates that performance-limiting nonradiative carrier recombination processes greatly depends on the electron–phonon interactions induced by structural fluctuations and instantaneous charge localization in these materials. The stiffer interlayer packing due to the presence of single spacer dications, which separates the lead iodide slabs, reduces the thermal fluctuations in the DJ-phase to a greater extent than that in the RP-phase 2D-perovskites. Specific electronic coupling between the closely spaced lead iodide layers enhances the delocalization of band-edge charge densities in DJ-phase systems. Compared to the RP-phase, reduced inelastic electron–phonon scattering in DJ-phase perovskites significantly limits intrinsic non-radiative recombination processes. The consequent enhancement in the photogenerated charge carrier lifetime makes DJ-phase perovskites potentially suitable for various optoelectronic devices. The computational insights gained from this study allow us to outline a set of robust design principles for DJ-phase perovskites to strategically tune their optoelectronic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tracking carrier and exciton dynamics in mixed-cation lead mixed-halide perovskite thin films

Mixed-cation lead mixed-halide perovskites simultaneously possess structural stability and high power conversion efficiency. A thorough study of both carrier and exciton dynamics is needed to understand the photophysical properties that underpin its superior photovoltaic performance. By utilizing a broadband transient absorption spectroscopy, we observe the carrier and exciton dynamics in a FA 0.85 Cs 0.15 Pb(I 0.97 Br 0.03 ) 3 (FCPIB) perovskite by simultaneously resolving the carrier and exciton contribution to the transient change of the absorption spectra, from which the carrier density and exciton oscillator strength can be determined. Our data reveal a quick and significant conversion of the photogenerated carriers to excitons, on top of the usual carrier recombination process. Moreover, the decay of carrier density shows a change of kinetics from a second-order recombination at high pump fluence to a third-order recombination at low pump fluence. Our analysis utilizes band anharmonicity, presents an independent determination of electronic temperature and quasi-Fermi energy, and reveals an interesting interplay among the processes of carrier cooling, exciton formation/decay and carrier recombination, all as a function of time after photoexcitation. Our work demonstrates the use of pump fluence as a knob to tune the relative populations of carriers and excitons in halide perovskite materials.

36 MATERIALS SCIENCE↗

“Self-trapping” in solar cell hybrid inorganic-organic perovskite absorbers

In the simplest picture, a “self-trapped” polaron forms when an excess electron or hole deforms a crystal lattice, creating a potential well with bound states. Properties of self-trapped polarons in methylammonium lead iodide perovskite (MAPbI 3 ), which is widely used as solar cell absorber, are of great interest, and are a subject of ongoing investigations and debates concerning the existence of large polarons with the co-presence of metastable self-trapping. Herein, we employ a self-interaction-free density functional theory method to investigate the stability of small polarons in tetragonal MAPbI 3 phase. The electron small polaron is found to be unstable, while the hole small polaron is found to be metastable at realistic operation temperatures of solar cells. Further, the hole polaron is found to have a hole band close to the conduction band, which in conjunction with its metastability suggests that small polarons will have an appreciable effect on charge-carrier recombinations in MAPbI 3 . Further, in this study, we posit that the existence of the metastable polarons in addition to the large polarons may explain the experimentally observed non-monotonic temperature dependence of bimolecular charge-carrier recombination rate in tetragonal MAPbI 3 phase.

14 SOLAR ENERGY↗

Ultrathin alumina passivation for improved photoelectrochemical water oxidation catalysis of tin oxide sensitized by a phosphonate-functionalized perylene diimide first without, and then with, CoOy

Previously, a photoanode composed of nanostructured SnO 2 coated with the perylene diimide dye N,N'-bis(phosphonomethyl)-3,4,9,10-perylenediimide (PMPDI) plus photoelectrochemically deposited cobalt oxide (CoO y ) was shown to photoelectrochemically oxidize water at 31 ± 7% faradaic efficiency. A non-ideal part of that prior system is that the addition of the known CoO y water oxidation catalyst (WOC) resulted in a reduction of the total photocurrent rather than the anticipated increase, due to an increase in charge-carrier recombination. Herein, we show deposition of an ultrathin alumina overlayer applied by atomic layer deposition (ALD) on the SnO 2 /PMPDI photoanode can improve the photoactivity and catalytic activity of the system; the addition a ca. 1 nm-thick AlO x layer deposited on a 4000 nm (i.e., 4 micron) thick mesoporous anode system can and does have a positive, 2.5-fold improvement in the steady-state photocurrent with 29 ± 9% faradaic efficiency vs. the control anode without alumina passivation by reducing charge-carrier recombination. Moreover, ALD-deposited AlO x layer does help support the understanding of the “anti-catalysis” of co-depositing a CoO y WOC on the SnO 2 /PMPDI DS-PECs—specifically the picture of direct CoO y –SnO 2 contact-mediated recombination—but that AlO x layer was unable to improve the photocurrent in a net SnO 2 /PMPDI/AlO x (/CoO y ) system. We attribute the lack of a performance enhancement by CoOy WOC to incomplete coverage of each SnO 2 nanoparticle by the AlO x . Overall, we find the addition of an optimized ultrathin AlOx layer (0.6 nm thick; deposited at 85 °C) improves the SnO 2 /PMPDI/AlO x system's photoactivity by a factor of up to ca. 3-fold with reduced recombination. These results document that metal-oxide passivation by low-temperature ALD can be an effective strategy for improving the water oxidation performance of even nanostructured dye sensitized-photoelectrochemical cell.

36 MATERIALS SCIENCE↗

Degradation-related defect level in weathered silicon heterojunction modules characterized by deep level transient spectroscopy

Commercial silicon heterojunction photovoltaic modules, known as amorphous-silicon-based heterojunction with intrinsic thin-film layer (HIT) modules, show average degradation after 10 years in the field. HIT modules weathered outdoors in Colorado and Florida display mostly uniform decreases in intensity when mapped with photoluminescence (PL) imaging compared to a control module. Flash-table-based current-voltage curves show that degradation is dominated by voltage loss. Samples are cored from each of the modules, and deep level transient spectroscopy (DLTS) detects three electron-trap defect states in all modules with activation energies of electron emission from the defects of 0.07, 0.16, and 0.50 eV. DLTS measurements on the weathered modules show an additional deep-level, electron-trap defect state with an activation energy of 0.51 eV and a trap density of approximately 10 12 cm –3 . The capture rate is measured using varying short filling pulse times, and the resulting capture cross section is estimated to be 1.1x10 –16 cm 2 . The development of the weathering-related defect level correlates to decreases in carrier lifetime, PL intensity, and module voltage. Various depths of the space charge region are probed with increments in applied reverse bias and filling-pulse bias. Furthermore, this DLTS depth profiling shows a trend of trap density increasing with less applied reverse bias, suggesting that the weathering-related defect increases carrier recombination toward the interface between the bulk silicon wafer and the junction-forming amorphous-silicon passivation layers.

14 SOLAR ENERGY↗

Vertical Architecture Solution-Processed Quantum Dot Photodetectors with Amorphous Selenium Hole Transport Layer

Colloidal quantum dots (CQDs) provide wide spectral tunability and high absorption coefficients owing to quantum confinement and large oscillator strengths, which along with solution processability, allow a facile, low-cost, and room-temperature deposition technique for the fabrication of photonic devices. However, many solution-processed CQD photodetector devices demonstrate low specific-detectivity and slow temporal response. To achieve improved photodetector characteristics, limiting carrier recombination and enhancing photogenerated carrier separation are crucial. In this study, we develop and present an alternate vertical-stack photodetector wherein we use a solution-processed quantum dot photoconversion layer coupled to an amorphous selenium (a-Se) wide-bandgap charge transport layer that is capable of exhibiting single-carrier hole impact ionization and is compatible with active-matrix readout circuitry. This a-Se chalcogenide transport layer enables the fabrication of high-performance and reliable solution-processed quantum dot photodetectors, with enhanced charge extraction capabilities, high specific detectivity (D* ~ 0.5–5 × 10 12 Jones), fast 3 dB electrical bandwidth (3 dB BW ~ 22 MHz), low dark current density (J D ~ 5–10 pA/cm 2 ), low noise current (i n ~ 20–25 fW/Hz 1/2 ), and high linear dynamic range (LDR ~130–150 dB) across the measured visible electromagnetic spectrum (~405–656 nm).

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Fundamental electronic mechanisms limiting the performance of solar cells

Attention is focused on distortion in the energy band, and carrier recombination and generation rates (lifetimes), as the two dominant mechanisms. Spatial dependences associated with these two mechanisms, in the direction normal to the surface illuminated by the sun and in the direction tangential to that surface, are also emphasized as crucial factors in governing the efficiency of solar cells. Electronic parameters for the set of differential equations characterizing transport, recombination, and generation of carriers, and interband and band-bound transition rates, are studied.

Lindholm, F. A.↗

Barriers to carriers: faults and recombination in non-stoichiometric perovskite scintillators

Abstract Tuning the efficiency and speed of charge carrier recombination in inorganic scintillators can potentially improve their performance in diverse applications. Recent work suggests that this maybe be achieved via a two-phase scintillator AB that naturally phase separates into A -rich and B -rich domains. In addition, a favorable electronic structure and band-edge alignment such that the charge carriers are confined or are thermodynamically driven to preferentially accumulate in one of the two domains, might lead to an improved radiative recombination rate. Here, we use density functional theory computations and ab initio molecular dynamics (AIMD), including non-adiabatic molecular dynamics (NAMD) simulations, to examine an alternative phase structure and its potential impact on recombination. Using a model perovskite SrTiO $$_3$$ 3 system with one-, two- and three-dimensional Ruddlesden–Popper (RP) phases, we demonstrate that RP faults induce band structure changes in the material that can act as barriers to carrier transport. Our AIMD/NAMD simulations indicate competing effects of a lower mean free path (potentially enhancing the desired radiative recombination and overall scintillating efficiency) and faster non-radiative recombination (undesired) due to enhanced electron–phonon coupling in the faulted system. Full exploitation of such a rational design approach would require tuning of the effective scintillation efficiency by varying the perovskite chemistry using appropriate arrangements of RP faults in the bulk material. Finally, other effects, such as the tendency of point defects to segregate at the interface, that might affect the overall performance, are briefly discussed. We expect the basic results found here to apply to other nanostructured scintillators. Graphical Abstract

36 MATERIALS SCIENCE↗

An all optical approach for comprehensive in-operando analysis of radiative and nonradiative recombination processes in GaAs double heterostructures

We demonstrate an all optical approach that can surprisingly offer the possibility of yielding much more information than one would expect, pertinent to the carrier recombination dynamics via both radiative and nonradiative processes when only one dominant deep defect level is present in a semiconductor material. By applying a band-defect state coupling model that explicitly treats the inter-band radiative recombination and Shockley–Read–Hall (SRH) recombination via the deep defect states on an equal footing for any defect center occupation fraction, and analyzing photoluminescence (PL) as a function of excitation density over a wide range of the excitation density (e.g., 5–6 orders in magnitude), in conjunction with Raman measurements of the LO-phonon plasmon (LOPP) coupled mode, nearly all of the key parameters relevant to the recombination processes can be obtained. They include internal quantum efficiency (IQE), minority and majority carrier density, inter-band radiative recombination rate (W r ), minority carrier nonradiative recombination rate (W nr ), defect center occupation fraction (f), defect center density (N t ), and minority and majority carrier capture cross-sections (σ t and σ tM ). While some of this information is thought to be obtainable optically, such as IQE and the W r /W nr ratio, most of the other parameters are generally considered to be attainable only through electrical techniques, such as current-voltage (I-V) characteristics and deep level transient spectroscopy (DLTS). Following a procedure developed herein, this approach has been successfully applied to three GaAs double-heterostructures that exhibit two distinctly different nonradiative recombination characteristics. The method greatly enhances the usefulness of the simple PL technique to an unprecedented level, facilitating comprehensive material and device characterization without the need for any device processing.

14 SOLAR ENERGY↗

Structural and immunological differences in Plasmodium falciparum sexual stage transmission-blocking vaccines comprised of Pfs25-EPA nanoparticles

Development of a malaria vaccine that blocks transmission of different parasite stages to humans and mosquitoes is considered critical for elimination efforts. A vaccine using Pfs25, a protein on the surface of zygotes and ookinetes, is under investigation as a transmission-blocking vaccine (TBV) that would interrupt parasite passage from mosquitoes to humans. The most extensively studied Pfs25 TBVs use Pichia pastoris-produced recombinant forms of Pfs25, chemically conjugated to a recombinant carrier protein, ExoProtein A (EPA). The recombinant form of Pfs25 first used in humans was identified as Pfs25H, which contained a total of 14 heterologous amino acid residues located at the amino- and carboxyl-termini including a His6 affinity tag. A second recombinant Pfs25, identified as Pfs25M, was produced to remove the heterologous amino acid residues and conjugated to EPA (Pfs25M-EPA). Here, monomeric Pfs25M was characterized biochemically and biophysically for identity, purity, and integrity including protein structure to assess its comparability with Pfs25H. Although the biological activities of Pfs25H and Pfs25M, whether generated by monomeric forms or conjugated nanoparticles, appeared similar, fine-mapping studies with two transmission-blocking monoclonal antibodies detected structural and immunological differences. In addition, evaluation of antisera generated against conjugated Pfs25H or Pfs25M nanoparticles in nonhuman primates identified polyclonal IgG that recognized these structural differences.

60 APPLIED LIFE SCIENCES↗

Probing crystallographic orientation-specific carrier lifetimes in epitaxial Ge/AlAs and InGaAs/InP heterostructures

Current silicon (Si) fin transistors rely on (100) and (110) crystallographically oriented surfaces, and the proposed alternate channel transistor technology comprises materials with higher mobility than Si. Crystallographically oriented epitaxial germanium (Ge) and indium–gallium arsenide (InGaAs) have the potential to replace Si in ultra-low power transistor applications. The higher carrier lifetime is an indication of superior material quality, which relates to the leakage current of a fin transistor. To gain insights into the carrier recombination dynamics in these crystallographically oriented epitaxial Ge and InGaAs layers, the contactless microwave photoconductive decay (μ-PCD) technique at an excitation wavelength of 1500 nm was employed to probe the orientation-specific carrier lifetimes. Highly effective carrier lifetimes >200 ns for (100)Ge/AlAs and (110)Ge/AlAs, and ~80 ns for (111)Ge/AlAs heterostructures, were extracted at room temperature. The measured carrier lifetime has a strong dependence on the surface orientation, which could be related to orientation-specific bulk trap states present within the bandgap of Ge. The (111)Ge orientation has 3 times lower carrier lifetime compared to the (100)Ge and (110)Ge surface orientations. On the other hand, the carrier lifetimes of 125 μs and 10 ns were determined from (100)InGaAs/InP and (110)InGaAs/InP heterostructures, respectively. The reduction in carrier lifetimes in both (111)Ge and (110)InGaAs was due to high electrical conductivity or higher bulk trap states present within the bandgap as well as the facet-dependent growth of the (110)InGaAs layer on InP. A surface passivating layer is indispensable for these orientation-specific epitaxial layers to improve the carrier lifetime. Therefore, the higher carrier lifetimes from technologically interesting (100)Ge and (110)Ge surfaces would offer a path for the development of Ge-based ultra-low power electronics, and optoelectronic devices based on the (100)InGaAs layer.

36 MATERIALS SCIENCE↗

Optically controlled absorption modulator based on state filling of In(x)Ga(1-x)As/GaAs quantum wells

The first demonstration of an optically controlled absorption modulator based on state filling in a periodically doped In(x)Ga(1-x)As/GaAs multiple quantum well structure is reported. Differential absorption of approximately 10,000/cm is observed in the quantum wells of the test structure at saturation pump powers. Photoluminescence and time-resolved modulation measurements confirm the predicted behavior of carrier recombination and give a measure of enhanced carrier lifetime of approximately 1 ms. These initial results show the potential for developing these structures into optically addressed spatial light modulators.

Iannelli, J. M.↗

Photocarrier-induced persistent structural polarization in soft-lattice lead halide perovskites

The success of the lead halide perovskites in diverse optoelectronics has motivated considerable interest in their fundamental photocarrier dynamics. Here, in this work, we report the discovery of photocarrier-induced persistent structural polarization and local ferroelectricity in lead halide perovskites. Photoconductance studies of thin-film single-crystal CsPbBr 3 at 10 K reveal long-lasting persistent photoconductance with an ultralong photocarrier lifetime beyond 10 6 s. X-ray diffraction studies reveal that photocarrier-induced structural polarization is present up to a critical freezing temperature. Photocapacitance studies at cryogenic temperatures further demonstrate a systematic local phase transition from linear dielectric to paraelectric and relaxor ferroelectric under increasing illumination. Our theoretical investigations highlight the critical role of photocarrier–phonon coupling and large polaron formation in driving the local relaxor ferroelectric phase transition. Our findings show that this photocarrier-induced persistent structural polarization enables the formation of ferroelectric nanodomains at low temperature, which suppress carrier recombination and offer the possibility of exploring intriguing carrier–phonon interplay and the rich polaron photophysics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Charge Carrier Lifetime Determination in Graded Absorber Solar Cells Using Time‐Resolved Photoluminescence Simulations and Measurements

Thin‐film photovoltaic device efficiencies are limited by carrier recombination, thus understanding recombination mechanisms is critical for performance improvements. Bulk minority carrier lifetime ( τ bulk ) is a critical parameter for solar cells but is difficult to determine in P–N junction devices, especially for high doping. As doping ≥10 16 cm −3 is required for efficient drift‐charge‐carrier‐collection devices, a method for τ bulk determination in doped P–N junction devices is necessary. This work utilizes time‐resolved photoluminescence (TRPL) simulations to quantify bulk and interface recombination properties in highly doped, graded absorber CdSeTe structures. The two methods developed here for τ bulk determination include utilization of an instantaneous lifetime representation to guide TRPL fitting and direct comparison between measured and simulated decays. Simulations verified that both methods are valid for state‐of‐the‐art device architectures which include graded bandgap absorbers, graded doping, and graded lifetimes. Shifts in the dominant recombination mechanism are identified for sufficiently long τ bulk , where front and back interface quality plays a more prominent role. Evaluation of surface recombination velocities and conduction band offset illustrate electro‐optical advantages of a positive conduction band offset and highlight the necessity of improved interfaces as bulk quality in photovoltaic devices improves.

14 SOLAR ENERGY↗

Fermi Level Engineering of Passivation and Electron Transport Materials for p-Type CuBi 2 O 4 Employing a High-Throughput Methodology

Metal oxide semiconductors are promising for solar photochemistry if the issues of excessive charge carrier recombination and material degradation can be resolved, which are both influenced by surface quality and interface chemistry. Coating the semiconductor with an overlayer to passivate surface states is a common remedial strategy but is less desirable than application of a functional coating that can improve carrier extraction and reduce recombination while mitigating corrosion. Here, a data-driven materials science approach utilizing high-throughput methodologies, including inkjet printing and scanning droplet electrochemical cell measurements, is used to create and evaluate multi-element coating libraries to discover new classes of candidate passivation and electron-selective contact materials for p-type CuBi 2 O 4 . The optimized overlayer (Cu 1.5 TiO z ) improves the onset potential by 110 mV, the photocurrent by 2.8×, and the absorbed photon-to-current efficiency by 15.5% compared to non-coated photoelectrodes. It is shown that these enhancements are related to reduced surface recombination through passivation of surface defect states as well as improved carrier extraction efficiency through Fermi level engineering. This work presents a generalizable, high-throughput method to design and optimize passivation materials for a variety of semiconductors, providing a powerful platform for development of high-performance photoelectrodes for incorporation into solar-fuel generation systems.

36 MATERIALS SCIENCE↗

Small Polarons and Surface Defects in Metal Oxide Photocatalysts Studied Using XUV Reflection–Absorption Spectroscopy

In photocatalytic transition metal oxides, the surface electronic structure and carrier kinetics are complicated by both charge trapping at defects and self-trapping by small polaron formation. These effects are specific to both the material and the type of defect or surface states involved. Here we review recent studies on ultrafast photoexcited charge carrier dynamics at the surfaces of alpha-Fe 2 O 3 (hematite) and NiO and at the interface of a alpha-Fe 2 O 3 /NiO heterojunction using extreme ultraviolet (XUV) reflection-absorption spectroscopy. We study dynamics of small polaron formation at hematite surfaces showing that the rate of carrier self-trapping is slower than in the bulk due to a greater lattice reorganization energy required for surface polaron formation. We also show that surface dynamics of hematite can be systematically tuned to control carrier transport properties through surface functionalization. To better understand the impact of defects on carrier events, we study charge carrier recombination of NiO. It is shown that O vacancies have no detrimental effect on carrier lifetime while grain boundaries cause fast recombination. Finally, we study a model heterojunction consisting of alpha-Fe 2 O 3 and NiO and find that interfacial charge transfer across these two materials occurs by a two-step mechanism where the interfacial electric field drives fast exciton dissociation followed by hole injection from alpha-Fe2O3 to NiO. Finally, these examples illustrate future opportunities to observe surface electron dynamics in photocatalytic materials with element and chemical state resolution using ultrafast XUV spectroscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Local Background Hole Density Drives Nonradiative Recombination in Tin Halide Perovskites

In this study, we use multimodal microscopy to study carrier recombination in semiconducting tin halide perovskite films based on PEA 0.2 FA 0.8 SnI 3 (PEA = phenethylammonium; FA = formamidinium). We use the observation of pseudo-first-order photoluminescence (PL) decay kinetics to establish a method for quantifying the hole dopant level and nonradiative recombination rate constant. We find that untreated PEA 0.2 FA 0.8 SnI 3 films exhibit large hole doping concentrations of p 0 ≈ 10 19 cm –3 , which is reduced to p 0 ≈ 10 16 cm –3 after SnF 2 treatment. While it is well-known that the radiative recombination rates are increased with p 0 , we reveal that the nonradiative rate is also increased. We find that p-type regions in untreated PEA 0.2 FA 0.8 SnI 3 films are centers for nonradiative recombination, which are diminished in films with p 0 ≈ 10 16 cm –3 . We discover significant PL heterogeneity even in PEA 0.2 FA 0.8 SnI 3 films with moderate dopant levels, suggesting that new strategies to eliminate deleterious defects in PEA 0.2 FA 0.8 SnI 3 must be developed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗