Charge photogeneration dynamics in non-fullerene polymer solar cells with fluorinated and non-fluorinated acceptors.

In this work, charge photogeneration and recombination processes of PM6:IDIC-4F and PM6:IDIC blend films were investigated by the steady-state and time-resolved spectroscopies, as well as the time-dependent density functional theory calculations. The peaks in absorption and photoluminescence (PL) spectra of IDIC and IDIC-4F solutions were assigned by combining the experiment and the simulation of UV-vis absorption and PL spectra. For neat acceptor films, the exciton diffusion length of neat IDIC and IDIC-4F films was estimated as ∼28.9 and ∼19.9 nm, respectively. For PM6-based blend films, we find that the fluorine substitution engineering on the IDIC acceptor material can increase the phase separate size of acceptor material in blend films, resulting in the reduction of dissociation efficiencies of acceptor excitons. In addition, we find that the charge recombination in PM6:IDIC-4F is dominated by bimolecular recombination, in comparison to geminate type carrier recombination in PM6:IDIC blend films. In addition, we find that thermal annealing treatment has a weak influence on carrier recombination but slightly reduces the exciton dissociation efficiency of acceptor in PM6:IDIC blend films, leading to a slightly reduced power conversion efficiency of PM6:IDIC solar cells. These results may shed light on the design of high-performance semiconductor molecules for application in solar cells.

Can photoluminescence quenching be a predictor for perovskite solar cell efficiencies?

Bromide-based perovskites have large bandgaps, making them attractive for tandem solar cells developed to overcome the Shockley-Queisser limit. A perovskite solar cell architecture employs transporting layers to improve charge extraction and transport. Due to the wide variety of materials and preparation methods, it is critical to devise fast screening methods to rank transporting layers. Herein, we evaluate perovskite fluorescence quenching followed by time- and energy-resolved photoluminescence (TER-PL) and analyse the intensity dependence as a potential method to qualify charge-transporting layers rapidly. The capability of the technique was evaluated with TiO2/FAPbBr3 and SnO2/FAPbBr3, the most commonly used electron transporting layers, which were prepared using standard protocols to make best-performing devices. The results revealed that TiO2 is the most effective quencher due to the higher density of states in the conduction band, consistent with Marcus-Gerischer's theory. However, record-performance devices use SnO2 as the electron transport layer. This shows that the relationship between photoluminescence quenching and device performance is not bidirectional. Therefore, additional measurements like conductivity are also needed to provide reliable feedback for device performance.

Ultrafast Infrared-to-Visible Photon Upconversion on Plasmon/TiO2 Solid Films.

Optical upconversion via a multiphoton absorption process converts incoherent low-energy photons to shorter wavelengths. In this contribution, we report a solid-state thin film for infrared-to-visible upconversion composed of plasmonic/TiO2 interfaces. When excited at λ = 800 nm, three photons are absorbed, leading to the excitation of TiO2 trap states into an emissive state in the visible domain. The plasmonic nanoparticle enhances the light absorption capabilities of the semiconductor, increasing emission efficiency by 20 times. We demonstrate that the plasmonic nanoparticle only changes the optical absorption of the semiconductor; i.e., the process is purely photonic. The process occurs in the ultrafast domain (<10 ps), contrasting with molecular triplet-triplet exciton annihilation, the commonly used method in photon upconversion, in the nano- to microsecond time scales. The process utilizes pre-existing trap states within the semiconductor bandgap and involves three-photon absorption.

Carrier Dynamics in Solution-Processed CuI as a P-Type Semiconductor: The Origin of Negative Photoconductivity.

There is an urgent need for efficient solution-processable p-type semiconductors. Copper(I) iodide (CuI) has attracted attention as a potential candidate due to its good electrical properties and ease of preparation. However, its carrier dynamics still need to be better understood. Carrier dynamics after bandgap excitation yielded a convoluted signal of free carriers (positive signal) and a negative feature, which was also present when the material was excited with sub-bandgap excitation energies. This previously unseen feature was found to be dependent on measurement temperature and attributed to negative photoconductivity. The unexpected signal relates to the formation of polarons or strongly bound excitons. The possibility of coupling CuI to plasmonic sensitizers is also tested, yielding positive results. The outcomes mentioned above could have profound implications regarding the applicability of CuI in photocatalytic and photovoltaic systems and could also open a whole new range of possible applications.

Photoinduced Polaron Formation in a Polymerized Electron-Acceptor Semiconductor.

Polymerized small molecular acceptor (PSMA) based all-polymer solar cells (all-PSC) have achieved power conversion efficiencies (PCE) over 16%, and the PSMA is considered to hold great promise for further improving the performance of all-PSC. Yet, in comparison with that of the polymer donor, the photophysics of a polymerized acceptor remains poorly understood. Herein, the excited state dynamics in a polymerized acceptor PZT810 was comprehensively investigated under various pump intensities and photon energies. The excess excitation energy was found to play a key role in excitons dissociation into free polarons for neat PSMA films, while free polarons cannot be generated from the polaron pairs in neat acceptor films. This work reveals an in-depth understanding of relaxation dynamics for PSMAs and that the underlying photophysical origin of PSMA can be mediated by excitation energies and intensities. These results would benefit the realization of the working mechanism for all-PSC and the designing of new PSMAs.

Morphology-Dependent One- and Two-Photon Absorption Properties in Blue Emitting CsPbBr3 Nanocrystals.

The linear and nonlinear optical parameters and morphologic dependence of CsPbBr3 nanocrystals (NCs) are crucial for device engineering. In particular, such information in asymmetric nanocrystals is still insufficient. We characterized the OPLA (σ1) and TPA cross sections (σ2) of a series CsPbBr3 nanocrystals with various aspect ratios (AR) using femtosecond transient absorption spectroscopy (TAS). The σ1 presents a linear volume dependence of all the samples, which agrees with the previous behavior in CsPbBr3 QDs. However, the σ2 values do not exhibit conventional power dependency of the crystal volume but are also modulated by the shape-dependent local field factors. In addition, the local field effect in CsPbBr3 NCs is contributed by their asymmetric morphologies and polar ionic lattices, which is more pronounced than in conventional semiconductor NCs. Finally, we revealed that the lifetimes of photogenerated multiexcitonic species of those nanocrystals feature identical morphology independence in both OPLA and TPA.

Optimizing the quasi-equilibrium state of hot carriers in all-inorganic lead halide perovskite nanocrystals through Mn doping: fundamental dynamics and device perspectives.

Hot carrier (HC) cooling accounts for the significant energy loss in lead halide perovskite (LHP) solar cells. Here, we study HC relaxation dynamics in Mn-doped LHP CsPbI3 nanocrystals (NCs), combining transient absorption spectroscopy and density functional theory (DFT) calculations. We demonstrate that Mn2+ doping (1) enlarges the longitudinal optical (LO)-acoustic phonon bandgap, (2) enhances the electron-LO phonon coupling strength, and (3) adds HC relaxation pathways via Mn orbitals within the bands. The spectroscopic study shows that the HC cooling process is decelerated after doping under band-edge excitation due to the dominant phonon bandgap enlargement. When the excitation photon energy is larger than the optical bandgap and the Mn2+ transition gap, the doping accelerates the cooling rate owing to the dominant effect of enhanced carrier-phonon coupling and relaxation pathways. We demonstrate that such a phenomenon is optimal for the application of hot carrier solar cells. The enhanced electron-LO phonon coupling and accelerated cooling of high-temperature hot carriers efficiently establish a high-temperature thermal quasi-equilibrium where the excessive energy of the hot carriers is transferred to heat the cold carriers. On the other hand, the enlarged phononic band-gap prevents further cooling of such a quasi-equilibrium, which facilitates the energy conversion process. Our results manifest a straightforward methodology to optimize the HC dynamics for hot carrier solar cells by element doping.

In situpassivation of GaxIn(1-x)P nanowires using radial AlyIn(1-y)P shells grown by MOVPE.

GaxIn(1-x)P nanowires with suitable bandgap (1.35-2.26 eV) ranging from the visible to near-infrared wavelength have great potential in optoelectronic applications. Due to the large surface-to-volume ratio of nanowires, the surface states become a pronounced factor affecting device performance. In this work, we performed a systematic study of GaxIn(1-x)P nanowires' surface passivation, utilizing AlyIn(1-y)P shells grownin situby using a metal-organic vapor phase epitaxy system. Time-resolved photoinduced luminescence and time-resolved THz spectroscopy measurements were performed to study the nanowires' carrier recombination processes. Compared to the bare Ga0.41In0.59P nanowires without shells, the hole and electron lifetime of the nanowires with the Al0.36In0.64P shells are found to be larger by 40 and 1.1 times, respectively, demonstrating effective surface passivation of trap states. When shells with higher Al composition were grown, both lifetimes of free holes and electrons decreased prominently. We attribute the acceleration of PL decay to an increase in the trap states' density due to the formation of defects, including the polycrystalline and oxidized amorphous areas in these samples. Furthermore, in a separate set of samples, we varied the shell thickness. We observed that a certain shell thickness of approximately ∼20 nm is needed for efficient passivation of Ga0.31In0.69P nanowires. The photoconductivity of the sample with a shell thickness of 23 nm decays 10 times slower compared with that of the bare core nanowires. We concluded that both the hole and electron trapping and the overall charge recombination in GaxIn(1-x)P nanowires can be substantially passivated through growing an AlyIn(1-y)P shell with appropriate Al composition and thickness. Therefore, we have developed an effectivein situsurface passivation of GaxIn(1-x)P nanowires by use of AlyIn(1-y)P shells, paving the way to high-performance GaxIn(1-x)P nanowires optoelectronic devices.

Free Carriers versus Self-Trapped Excitons at Different Facets of Ruddlesden-Popper Two-Dimensional Lead Halide Perovskite Single Crystals.

The physical origin of sub-band gap photoluminescence in Ruddlesden-Poppers two-dimensional (2D) lead halide perovskites (LHPs) is still under debate. In this paper, we studied the photoluminescence features from two different facets of 2D LHP single crystals: the in-plane facet (IF) containing the 2D inorganic layers and the facet perpendicular to the 2D layers (PF). At the IF, the free carriers (FCs) dominate due to the weak electron-phonon coupling in a symmetric lattice. At the PF, the strain accumulation along the 2D layers enhances the electron-phonon coupling and facilitates self-trapped exciton (STE) formation. The time-resolved PL studies indicate that free carriers (FCs) at the IF can move freely and display the trapping by the intrinsic defects. The STEs at the PF are not likely trapped by the defects due to the reduced mobility. However, with increasing STE density, the STE transport is promoted, enabling the trapping of STE by the intrinsic defects.

Ground- and excited-state characteristics in photovoltaic polymer N2200.

As a classical polymer acceptor material, N2200 has received extensive attention and research in the field of polymer solar cells (PSCs). However, the intrinsic properties of ground- and excited-states in N2200, which are critical for the application of N2200 in PSCs, remain poorly understood. In this work, the ground- and excited-state properties of N2200 solution and film were studied by steady-state and time-resolved spectroscopies as well as time-dependent density functional theory (TD-DFT) calculations. The transition mechanism of absorption peaks of N2200 was evaluated through the natural transition orbitals (NTOs) and hole-electron population analysis by TD-DFT. Time-resolved photoluminescence (TRPL) study shows that the lifetimes of singlet excitons in N2200 chlorobenzene solution and film are ∼90 ps and ∼60 ps, respectively. Considering the absolute quantum yield of N2200 film, we deduce that the intrinsic lifetime of singlet exciton can be as long as ∼20 ns. By comparing the TRPL and transient absorption (TA) kinetics, we find that the decay of singlet excitons in N2200 solution is dominated by a fast non-radiative decay process, and the component induced by intersystem crossing is less than 5%. Besides that, the annihilation radius, annihilation rate and diffusion length of singlet excitons in N2200 film were evaluated as 3.6 nm, 2.5 × 10-9 cm3 s-1 and 4.5 nm, respectively. Our work provides comprehensive information on the excited states of N2200, which is helpful for the application of N2200 in all-PSCs.

An Insight into the Excitation States of Small Molecular Semiconductor Y6.

Y6 is a new type of non-fullerene acceptor, which has led to power conversion efficiencies of single-junction polymer solar cells over 17% when combined with a careful choice of polymeric donors. However, the excited state characteristics of Y6, which is closely correlated with its opto-electronic applications, are not clear yet. In this work, we studied the excited state properties of the Y6 solution and Y6 film, by using steady-state and time-resolved spectroscopies as well as time-dependent density functional theory (TD-DFT) calculations. UV-Vis absorption and fluorescence simulation, natural transition orbitals (NTOs) and hole-electron distribution analysis of Y6 solution were performed for understanding the excitation properties of Y6 by using TD-DFT calculations. The lifetimes of the lowest singlet excited state in Y6 solution and film were estimated to be 0.98 and 0.8 ns, respectively. Combining the exciton lifetime and photoluminescence (PL) quantum yield, the intrinsic radiative decay lifetimes of Y6 in the solution and film were estimated, which were 1.3 and 10.5 ns for the Y6 solution and film, respectively. Long exciton lifetime (~0.8 ns) and intrinsic radiative decay lifetime (~10.5 ns) of Y6 film enable Y6 to be a good acceptor material for the application of polymer solar cells.

Carrier Recombination Processes in GaAs Wafers Passivated by Wet Nitridation.

As one of the successful approaches to GaAs surface passivation, wet-chemical nitridation is applied here to relate the effect of surface passivation to carrier recombination processes in bulk GaAs. By combining time-resolved photoluminescence and optical pump-THz probe measurements, we found that surface hole trapping dominates the decay of photoluminescence, while photoconductivity dynamics is limited by surface electron trapping. Compared to untreated sample dynamics, the optimized nitridation reduces hole- and electron-trapping rate by at least 2.6 and 3 times, respectively. Our results indicate that under ambient conditions, recovery of the fast hole trapping due to the oxide regrowth at the deoxidized GaAs surface takes tens of hours, while it is effectively inhibited by surface nitridation. Our study demonstrates that surface nitridation stabilizes the GaAs surface via reduction of both electron- and hole-trapping rates, which results in chemical and electronical passivation of the bulk GaAs surface.

Photodetector Based on Spontaneously Grown Strongly Coupled MAPbBr3/N-rGO Hybrids Showing Enhanced Performance.

Recently, metal-halide perovskites have emerged as a candidate for optoelectronic applications such as photodetectors. However, the poor device performance and instability have limited their future commercialization. Herein, we report the spontaneous growth of perovskite/N-rGO hybrid structures using a facile solution method and their applications for photodetectors. In the hybrid structures, perovskites were homogeneously wrapped by N-rGO sheets through strong hydrogen bonding. The strongly coupled N-rGOs facilitate the charge carrier transportation across the perovskite crystals but also distort the surface lattice of the perovskite creating a potential barrier for charge transfer. We optimize the addition of N-rGO in the hybrid structures to balance interfacial structural distortion and the intercrystal conductivity. High-performance photodetection up to 3 × 104 A/W, external quantum efficiency exceeding 105%, and detectivity up to 1012 Jones were achieved in the optimal device with the weight ratio between perovskites and N-rGO to be 8:1.5. The underlying mechanism behind the optimal N-rGO addition ratio in the hybrids has also been rationalized via time-resolved spectroscopic studies as a reference for future applications.

Effect of hydrogen chloride etching on carrier recombination processes of indium phosphide nanowires.

Introduction of in situ HCl etching to an epitaxial growth process has been shown to suppress radial growth and improve the morphology and optical properties of nanowires. In this paper, we investigate the dynamics of photo-generated charge carriers in a series of indium phosphide nanowires grown with varied HCl fluxes. Time resolved photo-induced luminescence, transient absorption and time resolved terahertz spectroscopy were employed to investigate charge trapping and recombination processes in the nanowires. Since the excitation photons generate charges predominantly in less than a half length of the nanowires, we can selectively assess the charge carrier dynamics at their top and bottom. We found that the photoluminescence decay is dominated by the decay of the mobile hole population due to trapping, which is affected by the HCl etching. The hole trapping rate is in general faster at the top of the nanowires than at the bottom. In contrast, electrons remain highly mobile until they recombine non-radiatively with the trapped holes. The slowest hole trapping as well as the least efficient non-radiative recombination was recorded for etching using the HCl molar fraction of χHCl = 5.4 × 10-5.

Effect of Post-Thermal Annealing on the Performance and Charge Photogeneration Dynamics of PffBT4T-2OD/PC71BM Solar Cells.

In this work, we studied influence of post thermal annealing on the performance and charge photogeneration processes of PffBT4T-2OD/PC71BM solar cells. As-prepared device exhibits a high-power conversion efficiency of 9.5%, much higher than that after thermal annealing. To understand this phenomenon, we studied charge photogeneration processes in these solar cells by means of time resolved spectroscopy. We associate the degradation of solar cell performance with the reduction of exciton dissociation efficiency and with increased bimolecular recombination of photogenerated charges as a result of annealing. We correlate the generation of localized PffBT4T-2OD polarons observed via spectro-electrochemical measurements with enhancement of the bimolecular charge recombination of annealed solar cells.

Photostability and Photodegradation Processes in Colloidal CsPbI3 Perovskite Quantum Dots.

All-inorganic CsPbI3 perovskite quantum dots (QDs) have attracted intense attention for their successful application in photovoltaics (PVs) and optoelectronics that are enabled by their superior absorption capability and great photoluminescence (PL) properties. However, their photostability remains a practical bottleneck and further optimization is highly desirable. Here, we studied the photostability of as-obtained colloidal CsPbI3 QDs suspended in hexane. We found that light illumination does induce photodegradation of CsPbI3 QDs. Steady-state spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and transient absorption spectroscopy verified that light illumination leads to detachment of the capping agent, collapse of the CsPbI3 QD surface, and finally aggregation of surface Pb0. Both dangling bonds containing surface and Pb0 serve as trap states causing PL quenching with a dramatic decrease of PL quantum yield. Our work provides a detailed insight about the correlation between the structural and photophysical consequences of the photodegradation process in CsPbI3 QDs and may lead to the optimization of such QDs toward device applications.

Carrier Recombination Processes in Gallium Indium Phosphide Nanowires.

Understanding of recombination and photoconductivity dynamics of photogenerated charge carriers in GaxIn1-xP NWs is essential for their optoelectronic applications. In this letter, we have studied a series of GaxIn1-xP NWs with varied Ga composition. Time-resolved photoinduced luminescence, femtosecond transient absorption, and time-resolved THz transmission measurements were performed to assess radiative and nonradiative recombination and photoconductivity dynamics of photogenerated charges in the NWs. We conclude that radiative recombination dynamics is limited by hole trapping, whereas electrons are highly mobile until they recombine nonradiatively. We also resolve gradual decrease of mobility of photogenerated electrons assigned to electron trapping and detrapping in a distribution of trap states. We identify that the nonradiative recombination of charges is much slower than the decay of the photoluminescence signal. Further, we conclude that trapping of both electrons and holes as well as nonradiative recombination become faster with increasing Ga composition in GaxIn1-xP NWs. We have estimated early time electron mobility in GaxIn1-xP NWs and found it to be strongly dependent on Ga composition due to the contribution of electrons in the X-valley.

Luminescence materials for pH and oxygen sensing in microbial cells - structures, optical properties, and biological applications.

Luminescence including fluorescence and phosphorescence sensors have been demonstrated to be important for studying cell metabolism, and diagnosing diseases and cancer. Various design principles have been employed for the development of sensors in different formats, such as organic molecules, polymers, polymeric hydrogels, and nanoparticles. The integration of the sensing with fluorescence imaging provides valuable tools for biomedical research and applications at not only bulk-cell level but also at single-cell level. In this article, we critically reviewed recent progresses on pH, oxygen, and dual pH and oxygen sensors specifically for their application in microbial cells. In addition, we focused not only on sensor materials with different chemical structures, but also on design and applications of sensors for better understanding cellular metabolism of microbial cells. Finally, we also provided an outlook for future materials design and key challenges in reaching broad applications in microbial cells.

Ultrafast, superhigh gain visible-blind UV detector and optical logic gates based on nonpolar a-axial GaN nanowire.

Nonpolar a-axial GaN nanowire (NW) was first used to construct the MSM (metal-semiconductor-metal) symmetrical Schottky contact device for application as visible-blind ultraviolet (UV) detector. Without any surface or composition modifications, the fabricated device demonstrated a superior performance through a combination of its high sensitivity (up to 10(4) A W(-1)) and EQE value (up to 10(5)), as well as ultrafast (<26 ms) response speed, which indicates that a balance between the photocurrent gain and the response speed has been achieved. Based on its excellent photoresponse performance, an optical logic AND gate and OR gate have been demonstrated for performing photo-electronic coupled logic devices by further integrating the fabricated GaN NW detectors, which logically convert optical signals to electrical signals in real time. These results indicate the possibility of using a nonpolar a-axial GaN NW not only as a high performance UV detector, but also as a stable optical logic device, both in light-wave communications and for future memory storage.

Enhanced photovoltaic performance of organic/silicon nanowire hybrid solar cells by solution-evacuated method.

A method has been developed to fabricate organic-inorganic hybrid heterojunction solar cells based on n-type silicon nanowire (SiNW) and poly (3,4-ethylenedioxythiophene):poly (styrenesulfonate) (PEDOT:PSS) hybrid structures by evacuating the PEDOT:PSS solution with dip-dropping on the top of SiNWs before spin-coating (solution-evacuating). The coverage and contact interface between PEDOT:PSS and SiNW arrays can be dramatically enhanced by optimizing the solution-evacuated time. The maximum power conversion efficiency (PCE) reaches 9.22% for a solution-evacuated time of 2 min compared with 5.17% for the untreated pristine device. The improvement photovoltaic performance is mainly attributed to better organic coverage and contact with an n-type SiNW surface.