Metal Halide Perovskites Research Articles

Bromine‐Substituted Cation Anchoring to Suppress Ion Migration in Alternating Cations Intercalation‐Type Perovskite for Stable X‐Ray Detection

Metal halide perovskites have emerged as excellent direct X‐ray detection materials owing to their large mobility‐lifetime product, strong radiation absorption, and low‐cost preparation. However, it is still a challenge to achieve stable X‐ray detection due to the limitations associated with severe ion migration under high voltage bias. Herein, based on a bromine substitution strategy to suppress ion migration, a 2D alternating cations intercalation‐type (ACI) perovskite, (R‐MPA)(BrEA)PbBr4 (1, R‐MPA = methylphenethylamm‐onium; BrEA = 2‐bromoethylamine) is reported to achieve X‐ray detection. Specifically, introducing Br atom forms additional intermolecular interactions (i.e., Br···π) and enhances hydrogen bonding interactions, greatly improving the structure stability. Based on this enhanced interaction, 1 presents a higher activation energy of ion migration (1.05 eV) than that of (R‐MPA)EAPbBr4 resulting in a lower dark current drift of 9.17 × 10−8 nA cm−1 s−1 V−1, revealing that suppression of ion migration. Consequently, the 1‐based detector shows a high sensitivity of 2653.7 μC Gy−1 cm−2 and, most importantly, outstanding operational and environmental stability, maintaining ≈91% of its initial sensitivity at 50 V bias after 90 days in the air. This work demonstrates an efficient strategy for introducing halogen interactions via ACI to suppress ion migration for stable X‐ray detection.

Minimizing Voltage Deficit in Perovskite Indoor Photovoltaics by Interfacial Engineering.

Metal halide perovskites with bandgap of ≈1.8eV are competitive candidates for indoor photovoltaic (IPV) devices, owing to their superior photovoltaic properties and ideal absorption spectra matched to most indoor light sources. However, these perovskite IPVs suffer from severe trap induced non-radiative recombination, resulting in large open-circuit voltage (VOC) losses, particularly under low light intensity. Herein, an effective approach is developed to minimizing trap density by modifying the buried interface of perovskite layer with bifunctional molecular 2-(4-Fluorophenyl)ethylamine Hydrobromide (F-PEABr). The benzene ring of F-PEABr molecules can firmly anchor at the hole transporting layer by π-π stacking interaction, and the other ends can passivate the defects on the buried interface of perovskite layer. Based on that, the F-PEABr modified perovskite IPVs achieved power conversion efficiency (PCE) of 42.3% with a remarkable VOC of 1.13V under 1000 lux illumination from a 4000K LED lamp. Finally, perovskite IPV mini-modules with area of 10.40cm2 are demonstrated with a PCE of 35.2%. This interface modification strategy paves the way for crafting high-performance perovskite IPVs, holding great potential for self-powered internet of things applications.

Natural and Nature-Inspired Biomaterial Additives for Metal Halide Perovskite Optoelectronics.

This comprehensive review meticulously categorizes and discusses the applications of diverse biomaterials, specifically natural and nature-inspired synthetic materials in metal halide perovskite optoelectronics. Applications range from solar cells to light-emitting diodes, photodetectors, and X-ray detectors. Emphasis is placed on the intricate interactions between bio-additives and perovskite crystals, highlighting their influence on the grain size, crystal orientation, grain boundaries, and surface passivation. This review also explores the advantages and disadvantages of each natural or nature-inspired material and their unique properties compared with conventional additives. Special attention is given to the mechanistic and functional viewpoints, showing how these biomaterials enhance device performance. Through additive engineering with ecofriendly biomaterials, defects in metal halide perovskite thin films can be effectively passivated, thus extending the photostability or in some cases mechanical flexibility of devices. This review provides valuable insights for selecting and designing next-generation biomaterial additives, offering new prospects for achieving high-performance perovskite layers and advancing the field of peorvskite- based optoelectronics.

Investigation of Charge Transfer Mechanism and Dielectric Relaxation in CsCdCl3 Perovskite

ABSTRACTThe exceptional optoelectronic capabilities of all‐inorganic metal halide perovskite semiconductor components open up a multitude of possible applications. Among all the metal halides, the chloride of cesium cadmium has not been investigated in great detail. Here, we describe a straightforward method for creating CsCdCl3 perovskite single crystals using the slow evaporation solution growth approach. These were investigated by utilizing X‐ray powder diffraction, and optical and impedance spectroscopies. The creation of a single‐phase with a hexagonal‐type structure was verified by the X‐ray powder diffraction (XRPD) data. The compound's semiconductor characteristics were verified by the optical measurement, indicating a direct band‐gap value of about 3.16 eV. The absorption and reflectance spectrum was also used to calculate and explain the optical extinction coefficient, Urbach energy, and skin depth as functions of the input photon's wavelength. Besides, the impedance spectroscopy technique was employed to investigate the characteristics of this component, across a frequency range of 10−1 Hz to 106 Hz and at temperatures ranging from 313 K to 453 K. The frequency behavior of the AC conductivity, σac, was analyzed using the universal Jonscher law. The outcomes of the charge transport investigation on CsCdCl3 imply that the perovskite material possessed a quantum mechanical tunneling (QMT) model for T < 363 K and a large polaron tunneling (OLPT) paradigm for T > 363 K. A correlation between the ionic conductivity and the crystal structure was established and discussed. Ultimately, the low dielectric loss and high dielectric constant of CsCdCl3 make it a promising material for energy harvesting devices.

Direct Laser Interference Patterning of Fluorine‐Doped Tin Oxide as a Pathway to Higher Efficiency in Perovskite Solar Cells

AbstractImproving light‐trapping capabilities through surface microstructuring of transparent conductive oxides is a promising approach to enhance solar cell efficiency. This study focuses on treating fluorine‐doped tin oxide (FTO) thin films using four‐beam direct laser interference patterning (DLIP) to create dot‐like periodic surface microstructures. The surface analysis using scanning electron microscopy and confocal microscopy reveals the presence of a periodic square grid of microcraters with a spatial period of ≈700 nm and an average depth ranging between 4 and 18 nm. These structures enhance the dispersion of incoming light up to 1000% in the visible and NIR spectra. When integrated into metal halide perovskite solar cells, FTO films patterned using low fluence conditions lead to a notable increase in the power conversion efficiencies (PCEs) compared to those made using untreated FTO. Importantly, preliminary stability tests on devices based on patterned FTO substrates show significantly improved stability compared to those fabricated using reference unpatterned substrates. These findings demonstrate that a DLIP treatment of FTO substrates is a promising technique that can substantially enhance the efficiency and stability of perovskite photovoltaic devices.

Enhancement of NIR‐II Emission of Er3+ by Doping Fe3+ in Double Perovskites: Multimode Luminescence for Versatile Optoelectronic Applications

AbstractErbium ions are commonly used to extend the photoelectric properties of metal halide perovskites from visible to near‐infrared range. However, achieving high‐efficiency multimode luminescence in a single system is difficult due to the weak absorption associated with forbidden 4f‐4f transitions. In this study, a unique strategy is proposed to adjust multimode luminescence and enhance the second near‐infrared region (NIR‐II) emission in Cs2NaBiCl6 by incorporating Fe3+ ions. The as‐prepared material demonstrates reversible thermochromism, driven by strong electron‐phonon coupling effect, and exhibits tunable luminescence that can be adjusted by altering excitation energy and temperature. Notably, benefitting from the charge transfer transition of Fe3+‐Cl− along with the influence of Fe3+ doping on the geometrical and electronic structures, the blue‐excitable (450 nm) NIR‐II emission around 1541 nm from Er3+ is realized for the first time, achieving an intensity 16.7 times higher and a maximum photoluminescence quantum yield (PLQY) of 22.5 %. This enhancement enables innovative applications such as two‐dimensional information encryption by the multi‐channel cooperative responses and improved NIR imaging. The study highlights the potential of Fe3+ doping in optimizing absorption and multimode luminescence in perovskites, opening avenues for advanced applications in blue‐excitable NIR light emitting diodes (LEDs), thermometer, anti‐counterfeiting, and NIR imaging.

Exciton dynamics in CsPbBr3 single crystal: LT splitting energy, exciton-polariton dispersion, and biexciton binding energy.

Metal halide perovskite materials (MHPs) are promising for several applications due to their exceptional properties. Understanding excitonic properties is essential for exploiting these materials. For this purpose, we focus on CsPbBr3 single crystals, which have higher crystal quality, are more stable, and have no Rashba effect at low temperatures compared to other 3D MHPs. We have estimated exciton energy positions, longitudinal-transverse splitting energy, and damping energy using low-temperature reflection spectra. Under high excitation intensity, two biexciton emissions (M-emission) and exciton-exciton scattering emission (P-emission) were observed. We assign the two M-emissions to the emission to the states of longitudinal and transverse excitons, i.e., ML and MT emissions. From the energy position of the MT emission, the biexciton binding energy has been estimated to be ∼2meV. By analyzing P-emission obtained from the back side of the sample, we have estimated the exciton binding energy to be 17.8-23.7meV. This estimation minimizes the influence of the wavenumber distribution in the scattering process. In addition, time-resolved transmittance measurements using pulsed white light have revealed the group velocity dispersion. Comparing experimental results with theoretical calculations using the Lorentz model clarifies that exciton dynamics in CsPbBr3 can be described with a simple Lorentz model. These insights enhance the understanding of exciton behavior and support the development of exciton-based devices using MHPs.

Microscopic mechanism of water-assisted diffusional phase transitions in inorganic metal halide perovskites.

The stability of perovskite materials is profoundly influenced by the presence of moisture in the surrounding environment. While it is well-established that water triggers and accelerates the black-yellow phase transition, leading to the degradation of the photovoltaic properties of perovskites, the underlying microscopic mechanism remains elusive. In this study, we employ classical molecular dynamics simulations to examine the role of water molecules in the yellow-black phase transition in a typical inorganic metal halide perovskite, CsPbI3. We have demonstrated, through interfacial energy calculations and classical nucleation theory, that the phase transition necessitates a crystal-amorphous-crystal two-step pathway rather than the conventional crystal-crystal mechanism. Simulations for CsPbI3 nanowires show that water molecules in the air can enter the amorphous interface between the black and yellow regions. The phase transition rate markedly increases with the influx of interfacial water molecules, which enhance ion diffusivity by reducing the diffusion barrier, thereby expediting the yellow-black phase transition in CsPbI3. We propose a general mechanism through which solvent molecules can greatly facilitate phase transitions that otherwise have prohibitively high transition energies.

Solution Processed Bilayer Metal Halide White Light Emitting Diodes.

Metal halide perovskites and perovskite-related organic metal halide hybrids (OMHHs) have recently emerged as a new class of luminescent materials for light emitting diodes (LEDs), owing to their unique and remarkable properties, including near-unity photoluminescence quantum efficiencies, highly tunable emission colors, and low temperature solution processing. While substantial progress has been made in developing monochromatic LEDs with electroluminescence across blue, green, red, and near-infrared regions, achieving highly efficient and stable white electroluminescence from a single LED remains a challenging and under-explored area. Here, a facile approach to generating white electroluminescence is reported by combining narrow sky-blue emission from metal halide perovskites and broadband orange/red emission from zero-dimensional (0D) OMHHs. For the proof of concept, utilizing TPPcarz+ passivated two-dimensional (2D) CsPbBr3 nanoplatelets (NPLs) as sky blue emitter and 0D TPPcarzSbBr4 as orange/red emitter (TPPcarz+ = triphenyl (9-phenyl-9H-carbazol-3-yl) phosphonium), white LEDs (WLEDs) with a solution processed bilayer structure have been fabricated to exhibit a peak external quantum efficiency (EQE) of 4.8% and luminance of 1507 cd m-2 at the Commission Internationale de L'Eclairage (CIE) coordinate of (0.32, 0.35). This work opens a new pathway for creating highly efficient and stable WLEDs using metal halide perovskites and related materials.

Enhancing negative thermal quenching in green-emitting perovskite microspheres via shallow trap state modulation

AbstractFor luminescent materials, negative thermal quenching (NTQ), characterized by an increase in the luminescent intensity with temperature, has a large potential in lighting and display technologies. However, leveraging NTQ in metal halide perovskites is challenging, and the mechanism is not well understood. Herein, by utilizing low-temperature photoluminescence, persistent luminescence and thermoluminescence, the origins of NTQ in CsPbBr3 microspheres are systematically studied, which pertain to the liberation of carriers from shallow trap states. Experimental and theoretical investigations reveal that the energy of these shallow defect states is approximately 0.135 eV beneath the conduction band. A rapid thermal treatment increases the density of these shallow traps and amplifies the NTQ effect, resulting in an enhancement of room-temperature photoluminescence by more than 60% compared to that at 150 K. The process also reduces the threshold for amplified spontaneous emission to about 45 W/cm2. Our findings not only provide a deeper understanding of the NTQ phenomenon in CsPbBr3 microspheres but also open new avenues for enhancing the performance of perovskite optoelectronic devices through energy state regulation.

A First-principles Investigation of the Structural, Optoelectronic, Elastic and Thermal properties ofthe p-type Half-metallic Ferromagnetic Perovskites BaFeX3(X = Cl, Br, I)

Abstract The half-metallic nature of the metal halide perovskites BaFeX3 (X=Cl, Br,I) and their physical properties were studied using Spin-polarised Density Functional Theory calculations. For each structure, ferromagnetic, antiferromagnetic and non-magnetic calculation were
performed and the ferromagnetic phase was found to have the lowest energy. The calculated band structures in addition to the electronic density of states confirmed half-metallicity, where the perovskites showed semiconducting nature in the spin up
channel and metallic in spin-down channel. The optical properties are calculated and strong absorption in the UV range was seen and the mechanical properties demonstrated mechanical stability with ductile behaviour for all perovskites. The specific heats (at
constant volume) of all of the studied perovskites levelled off to about 245 JK−1mol−1 at high temperatures. The Seebeck coefficient was also calculated as a function of temperature and found to be positive for all the structures which confirm them to be
p-type materials. These perovskites are therefore suited for thin film fabrication and bulk single crystals for applications such as UV photodetectors and energy harvesting, in addition to spintronics applications.

Numerical simulation of electrically pumped active vertical‐cavity surface‐emitting lasers diodes based on metal halide perovskite

AbstractMetal halide perovskites (MHP)‐based electrically pumped vertical‐cavity surface‐emitting lasers (EPVCSEL) are promising candidates in optoelectronics due to low‐carbon footprint solution processing method. However, significant challenges impede MHP‐EPVCSEL manufacturing: (1) Distributed Bragg Reflectors (DBRs) composed of typical electron transport layers (ETLs) and hole transport layers (HTLs) are not conductive enough. (2) Due to large mobility difference of typical ETLs and HTLs, carriers‐unbalanced injection leads to severe performance degradation. Herein, we propose a potential strategy to address such challenges using MAPbCl3 and CsSnCl3 as carrier transport layers with mobility 3 orders larger than typical ETLs and HTLs. Via transfer matrix method calculations, we find that the reflectance of DBRs composed of MAPbCl3 (130.5 nm)/CsSnCl3 (108 nm) is larger than 91% with 10 pairs of DBRs. Furthermore, the proposed EPVCSEL device simulation shows that MHP‐EPVCSEL has the potential to achieve room temperature continuous wave lasing with a threshold current density of ∼69 A cm−2 and output optical power ∼10−4 W. This work can provide a deep insight into the practical realization of MHP‐EPVCSEL.

Surface n-Doped Metal Halide Perovskite for Efficient and Stable Solar Cells through Organic Chelation.

Perovskite solar cells (PSCs) have emerged as a leading photovoltaic technology due to their high efficiency and low cost. Even though they have developed rapidly since their inception, with efficiencies of over 26%, inverted PSCs face challenges such as nonradiative recombination and ion migration. Surface treatment, especially the utilization of organic compounds, has improved efficiency and stability by optimizing the perovskite-charge transport layer interface. Herein, we report a facile and effective strategy by introducing 2,2'-bipyridyl to modify the surface of perovskite, achieving a power conversion efficiency of 24.43% with increasing open-circuit voltage and fill factor and good repeatability on multiple devices. We reveal that the 2,2'-bipyridyl molecule can chelate lead ions on the surface of perovskite, effectively suppressing nonradiative recombination. Furthermore, this modification can induce surficial n-doping to refine the energy level alignment, thereby minimizing charge transport losses. Additionally, the device maintained over 92% of the initial efficiency after 1000 h of operation at the maximum power point under continuous illumination. This surface chelation and defect passivation strategy employing 2,2'-bipyridyl offers a promising avenue for exploring the details of potential long-term degradation mechanisms and the development of commercially viable high-performance p-i-n PSCs.

White Light Emission in Europium‐Doped Inorganic Perovskite Single Matrix

AbstractThe realization of stable single‐component white light emission in metal halide perovskites is still challenging due to the fast halide ion migration and narrow luminescence bands. In this work, all‐inorganic single CsPbClxBr3−x perovskite microplates with stable red‐blue‐green triple color light emission are prepared by introducing europium ions Eu3+ as dopants. Eu doping effectively suppresses ion migration and enables two spatially separated halide phases with stable dual‐wavelength emissions. Furthermore, the incorporation of Eu3+ compensates for the absence of red‐light emission, thereby yielding a superior white emission with exceptional quality. The color rendering index of triple‐color‐emitting perovskites can be tuned successfully by controlling the halogen ratios, and the optimal microplate achieved a Commissions Internationale de l’Eclairage (CIE) coordinates of (0.32, 0.32). The results present a new enlightenment for the preparation of low‐cost single‐component white light materials.

DFT-based accurate and efficient bandgap prediction of CsSnI3-xBrx and parameter optimization for enhanced perovskite solar cell performance

This article analyzes the bandgap (Eg) of tin-based metal halide perovskites CsSnI3-xBrx (x = 0, 1, 2, 3) using density functional theory (DFT). For the first time, the study evaluates various exchange-correlation (XC) families—LDA, GGA, MGGA, and HSE—along with key DFT parameters such as pseudopotentials (PP), K-point densities, and basis sets. The investigation identifies the optimal combination of parameters that most accurately matches experimental Eg values for different mole fractions. The study reports average deviations from experimental Eg values of 6.48% for LDA, 8.08% for GGA, 3.44% for MGGA, and 3.07% for HSE. While HSE shows the smallest deviation, MGGA demonstrates better consistency across mole fractions with lower computational costs. Additionally, the band structure and Eg trends for each mole fraction are examined, providing valuable insights for future computational studies on perovskite materials.

In-situ preparation of BiOBr/Bi-doped CsPbBr3 S-scheme heterojunction for efficient photocatalytic CO2 reduction

Metal halide perovskite nanocrystals have garnered significant attention in the realm of photocatalytic CO2 reduction in recent years owing to their remarkable reducing properties and high selectivity. However, the issue of low photocatalytic activity due to severe carrier recombination phenomena in perovskite has posed a significant challenge. To address this, a one-pot in-situ preparation strategy was employed to create a BiOBr/Bi-doped perovskite nanocrystal S-scheme heterojunction, resulting in a significant improvement in the CO2 photoreduction performance. The heterojunction material exhibited a CO yield of 151.56 μmolg-1h−1, with a selectivity for CO of 93.6 %. The molar ratio of the components was modulated using an in-situ water aging strategy, yielding a photocatalyst performance that exceeded that of pure BiOBr. The synthesis strategy of one-step in-situ preparation of heterojunctions overcomes the problem of insufficient bonding caused by two-step methods. And various characterizations and DFT calculations strongly support the S-scheme mechanism of the photocatalyst. The active site effectively reduces the energy barrier for the transition from *COOH to *CO intermediate, thereby significantly improving photocatalytic activity.

Strain effect on the physical properties of novel Mg3NI3 perovskite material: First principle DFT analysis

Inorganic perovskite-based substances have become a major attraction to solar technology. Inorganic cubic perovskites have generated a heap of fascination owing to their distinctive optical, electrical, and structural features. The photovoltaic and optoelectronic industries prioritize lead-free, atomically tailored metal halide perovskites due to the need to address lead (Pb) toxicity and instability. This study assessed the optical, structural, and electrical parameters of Pb-free inorganic halide perovskites as a function of biaxial compressive and tensile strain, leveraging first-principles density-functional theory (FP-DFT). Refractive index, absorption coefficient, reflectivity, dielectric function, and tolerance factor are a few additional optical parameters that are computed and processed. The bandgap of the planar molecule is 0.412 eV (PBE) when SOC is not applied. The bandgap reduces to 0.363 eV (PBE) at its Γ(gamma) and R-point when the subjective SOC effect is taken into consideration. This compound's bandgap will narrow under tensile strain and expand under compressive strain, depending on whether the SOC effect is applied or not. Several elastic factors are anticipated, including the bulk modulus, Pugh's ratio, elastic constants, anisotropic factors, and Poisson's ratio. Electronic property calculations using band mechanism and density of states (DOS) suggest that have a bandgap that is indirect and semiconductive. The elastic properties of this material were found to be mechanically stable, anisotropic, and ductile. In the photon energy range suitable for solar cells, the spikes in the dielectric constant of are seen. Our findings point to the prospect of as a non-toxic, high-performance, low-cost material for implementation in solar cells and different semiconductor devices.

Promoting Charge-Carriers Dynamics by Relaxed Lattice Strain in A-site-doped Halide Perovskite for Photocatalytic H2 Evolution.

Because of the unique and superior optoelectronic properties, metal halide perovskites (MHPs) have attracted great interests in photocatalysis. Element doping strategy is adopted to modify perovskite materials to improve their photocatalytic performance. However, the contribution of bare doping-site onto photocatalytic efficiency, and the correlation between doping locations and activity have not yet to be demonstrated. Thispromoted us to explore the potential of A-site-doped MHPs for photocatalysis. Herein, we dope potassium (K+) into CsPbBr3 and first reveal that the occupied locations of K+ in CsPbBr3 is lattice incorporation rather than surface segregation, which would change from A-site substitution to interstitial site in lattice with the increase of K+ concentrations. Taking H2 evolution as a model reaction, photocatalytic activity of CsPbBr3 after K+ doping could be significantly improved ~11-fold with A-site substitution, which is superior to that of interstitial site doping. Moreover, other alkali metals including Li, Na, and Rb doping give the same results. The structure of photocatalysts during reaction confirmed the contribution of A-site doping onto enhanced photocatalytic activity. Mechanistic insights show it is a result of the relaxed residual lattice strain induced promoted charge-carriers dynamics and formed upward shifting of band after K+ A-site doping.

Promoting Charge‐Carriers Dynamics by Relaxed Lattice Strain in A‐site‐doped Halide Perovskite for Photocatalytic H2 Evolution

Because of the unique and superior optoelectronic properties, metal halide perovskites (MHPs) have attracted great interests in photocatalysis. Element doping strategy is adopted to modify perovskite materials to improve their photocatalytic performance. However, the contribution of bare doping‐site onto photocatalytic efficiency, and the correlation between doping locations and activity have not yet to be demonstrated. This promoted us to explore the potential of A‐site‐doped MHPs for photocatalysis. Herein, we dope potassium (K+) into CsPbBr3 and first reveal that the occupied locations of K+ in CsPbBr3 is lattice incorporation rather than surface segregation, which would change from A‐site substitution to interstitial site in lattice with the increase of K+ concentrations. Taking H2 evolution as a model reaction, photocatalytic activity of CsPbBr3 after K+ doping could be significantly improved ~11‐fold with A‐site substitution, which is superior to that of interstitial site doping. Moreover, other alkali metals including Li, Na, and Rb doping give the same results. The structure of photocatalysts during reaction confirmed the contribution of A‐site doping onto enhanced photocatalytic activity. Mechanistic insights show it is a result of the relaxed residual lattice strain induced promoted charge‐carriers dynamics and formed upward shifting of band after K+ A‐site doping.

Surface Defects Control Bulk Carrier Densities in Polycrystalline Pb-Halide Perovskites.

The (opto)electronic behavior of semiconductors depends on their (quasi-)free electronic carrier densities. These are regulated by semiconductor doping, i.e., controlled "electronic contamination". For metal halide perovskites (HaPs), the functional materials in several device types, which already challenge some of the understanding of semiconductor properties, this study shows that doping type, density and properties derived from these, are to a first approximation controlled via their surfaces. This effect, relevant to all semiconductors, and already found for some, is very evident for lead (Pb)-HaPs because of their intrinsically low electrically active bulk and surface defect densities. Volume carrier densities for most polycrystalline Pb-HaP films (<1µm grain diameter) are below those resulting from even < 0.1% of surface sites being electrically active defects. This implies and is consistent with interfacial defects controlling HaP devices in multi-layered structures with most of the action at the two HaP interfaces. Surface and interface passivation effects on bulk electrical properties are relevant to all semiconductors and are crucial for developing those used today. However, because bulk dopant introduction in HaPs at controlled ppm levels for electronic-relevant carrier densities is so difficult, passivation effects are vastly more critical and dominate, to first approximation, their optoelectronic characteristics in devices.