Project description:Wide-bandgap (WBG) perovskite solar cells (PSCs) are employed as top cells of tandem cells to break through the theoretical limits of single-junction photovoltaic devices. However, WBG PSCs exhibit severe open-circuit voltage (Voc) loss with increasing bromine content. Herein, inhomogeneous halogen-phase distribution is pointed out to be the reason, which hinders efficient extraction of carriers. We thus propose to form homogeneous halogen-phase distribution to address the issue. With the help of density functional theory, we construct a double-layer structure (D-2P) based on 2-(9H-Carbazol-9-yl)ethyl]phosphonic acid molecules to provide nucleation sites for perovskite crystallization. Homogeneous perovskite phase is achieved through bottom-up templated crystallization of halogen component. The efficient carrier extraction reduces the Shockley-Read-Hall recombination, resulting in a high Voc of 1.32 V. As a result, D-2P-treated device (1.75 eV) achieves a record power conversion efficiency of 20.80% (certified 20.70%), which is the highest value reported for WBG (more than 1.74 eV) PSCs.
Project description:Electrically driven light sources are essential in a wide range of applications, from indication and display technologies to high-speed data communication and quantum information processing. Wide-bandgap semiconductors promise to advance solid-state lighting by delivering novel light sources. However, electrical pumping of these devices is still a challenging problem. Many wide-bandgap semiconductor materials, such as SiC, GaN, AlN, ZnS, and Ga2O3, can be easily n-type doped, but their efficient p-type doping is extremely difficult. The lack of holes due to the high activation energy of acceptors greatly limits the performance and practical applicability of wide-bandgap semiconductor devices. Here, we study a novel effect which allows homojunction semiconductor devices, such as p-i-n diodes, to operate well above the limit imposed by doping of the p-type material. Using a rigorous numerical approach, we show that the density of injected holes can exceed the density of holes in the p-type injection layer by up to four orders of magnitude depending on the semiconductor material, dopant, and temperature, which gives the possibility to significantly overcome the doping problem. We present a clear physical explanation of this unexpected feature of wide-bandgap semiconductor p-i-n diodes and closely examine it in 4H-SiC, 3C-SiC, AlN, and ZnS structures. The predicted effect can be exploited to develop bright-light-emitting devices, especially electrically driven nonclassical light sources based on color centers in SiC, AlN, ZnO, and other wide-bandgap semiconductors.
Project description:A line defect with metallic characteristics has been found in optically transparent BaSnO3 perovskite thin films. The distinct atomic structure of the defect core, composed of Sn and O atoms, was visualized by atomic-resolution scanning transmission electron microscopy (STEM). When doped with La, dopants that replace Ba atoms preferentially segregate to specific crystallographic sites adjacent to the line defect. The electronic structure of the line defect probed in STEM with electron energy-loss spectroscopy was supported by ab initio theory, which indicates the presence of Fermi level-crossing electronic bands that originate from defect core atoms. These metallic line defects also act as electron sinks attracting additional negative charges in these wide-bandgap BaSnO3 films.
Project description:Bandgap tuning is a crucial characteristic of metal-halide perovskites, with benchmark lead-iodide compounds having a bandgap of 1.6 eV. To increase the bandgap up to 2.0 eV, a straightforward strategy is to partially substitute iodide with bromide in so-called mixed-halide lead perovskites. Such compounds are prone, however, to light-induced halide segregation resulting in bandgap instability, which limits their application in tandem solar cells and a variety of optoelectronic devices. Crystallinity improvement and surface passivation strategies can effectively slow down, but not completely stop, such light-induced instability. Here we identify the defects and the intragap electronic states that trigger the material transformation and bandgap shift. Based on such knowledge, we engineer the perovskite band edge energetics by replacing lead with tin and radically deactivate the photoactivity of such defects. This leads to metal halide perovskites with a photostable bandgap over a wide spectral range and associated solar cells with photostable open circuit voltages.
Project description:Defect engineering is an exciting tool for customizing semiconductors' structural and optoelectronic properties. Elaborating programmable methodologies to circumvent energy constraints in multievent inversions expands our understanding of the mechanisms governing the functionalization of nanomaterials. Herein, we introduce a novel strategy based on defect incorporation and solution rationalization, which triggers energetically unfavorable cation exchange reactions in extended solids. Using Sb2X3 + Ag (I) → Ag: Sb2X3 (X= S, Se) as a system to model, we demonstrate that incorporating chalcogen vacancies and AgSbVX complex defects into initial thin films (TFs) is crucial for activating long-range solid-state ion diffusion. Additional regulation of the Lewis acidity of auxiliary chemicals provides an exceptional conversion yield of the Ag precursor into a solid-state product up to 90%, simultaneously transforming upper matrix layers into AgSbX2. The proposed strategy enables tailoring radiative recombination processes, offers efficiency to invert TFs at moderate temperatures quickly, and yields structures of large areas with substantial antibacterial activity in visible light for a particular inversion system. Similar customization can be applied to most sulfides/selenides with controlled reaction yields.
Project description:Efficient wide-bandgap perovskite solar cells (PSCs) enable high-efficiency tandem photovoltaics when combined with crystalline silicon and other low-bandgap absorbers. However, wide-bandgap PSCs today exhibit performance far inferior to that of sub-1.6-eV bandgap PSCs due to their tendency to form a high density of deep traps. Here, we show that healing the deep traps in wide-bandgap perovskites-in effect, increasing the defect tolerance via cation engineering-enables further performance improvements in PSCs. We achieve a stabilized power conversion efficiency of 20.7% for 1.65-eV bandgap PSCs by incorporating dipolar cations, with a high open-circuit voltage of 1.22 V and a fill factor exceeding 80%. We also obtain a stabilized efficiency of 19.1% for 1.74-eV bandgap PSCs with a high open-circuit voltage of 1.25 V. From density functional theory calculations, we find that the presence and reorientation of the dipolar cation in mixed cation-halide perovskites heals the defects that introduce deep trap states.
Project description:The exciton photoluminescence of carbon nanotube semiconductors has been intensively exploited for bioimaging, anticounterfeiting, photodetection, and quantum information science. However, at high concentrations, photoluminescence is lost to self-quenching because of the nearly complete overlap of the absorption and emissive states (∼10 meV Stokes shift). Here we show that by introducing sparse fluorescent quantum defects via covalent chemistry, self-quenching can be efficiently bypassed by means of the new emission route. The defect photoluminescence is significantly red-shifted by 190 meV for p-nitroaryl tailored (6,5)-single-walled carbon nanotubes (SWCNTs) from the native emission of the nanotube. Notably, the defect photoluminescence is more than 34 times brighter than the native photoluminescence of unfunctionalized SWCNTs in the most concentrated nanotube solution tested (2.7 × 1014 nanotubes/mL). Moreover, we show that defect photoluminescence is more resistant to self-quenching than the native state in a dense film, which is the upper limit of concentration. Our findings open opportunities to harness nanotube excitons in highly concentrated systems for applications where photoluminescence brightness and light-collecting efficiency are mutually important.
Project description:Organic photodetectors displaying efficient photoelectric response in the near-infrared are typically based on narrow bandgap active materials. Unfortunately, the latter require complex molecular design to ensure sufficient light absorption in the near-infrared region. Here, we show a method combining an unconventional device architecture and ad-hoc supramolecular self-assembly to trigger the emergence of opto-electronic properties yielding to remarkably high near-infrared response using a wide bandgap material as active component. Our optimized vertical phototransistors comprising a network of supramolecular nanowires of N,N'-dioctyl-3,4,9,10-perylenedicarboximide sandwiched between a monolayer graphene bottom-contact and Au nanomesh scaffold top-electrode exhibit ultrasensitive light response to monochromatic light from visible to near-infrared range, with photoresponsivity of 2 × 105 A/W and 1 × 102 A/W, at 570 nm and 940 nm, respectively, hence outperforming devices based on narrow bandgap materials. Moreover, these devices also operate as highly sensitive photoplethysmography tool for health monitoring.
Project description:Three supramolecular bromostannates(IV) with "trapped" diiodine molecules, Cat2{[SnBr6](I2)} (Cat = Me4N+ (1), 1-MePy+ (2) and 4-MePyH (3)), were synthesized. In all cases, I2 linkers are connected with bromide ligands via halogen···halogen non-covalent interactions. Articles 1-3 were studied using Raman spectroscopy, thermogravimetric analysis, and diffuse reflectance spectroscopy. The latter indicates that 1-3 are narrow band gap semiconductors.
Project description:Organic photovoltaics (OPVs) have attracted tremendous attention in the field of thin-film solar cells due to their wide range of applications, especially for semitransparent devices. Here, we synthesize a dithiaindacenone-thiophene-benzothiadiazole-thiophene alternating donor copolymer named poly{[2,7-(5,5-didecyl-5H-1,8-dithia-as-indacenone)]-alt-[5,5-(5',6'-dioctyloxy-4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)]} (PDTIDTBT), which shows a relatively wide bandgap of 1.82 eV, good mobility, and high transmittance and ambient stability. In this work, we fabricate an OPV device using monolayer graphene as top electrode. Due to the stability of PDTIDTBT in air and water, we use a wet transfer technique for graphene to fabricate semitransparent OPVs. We demonstrate OPVs based on the PDTIDTBT:Phenyl-C61/71-butyric acid methyl ester (PCBM) blend with maximum power conversion efficiencies (PCEs) of 6.1 and 4.75% using silver and graphene top electrodes, respectively. Our graphene-based device shows a high average visible transmittance (AVT) of 55%, indicating the potential of PDTIDTBT for window application and tandem devices. Therefore, we also demonstrate tandem devices using the PDTIDTBT:Phenyl-C61-butyric acid methyl ester (PC60BM) blend in both series and parallel connections with average PCEs of 7.3 and 7.95%, respectively. We also achieve a good average PCE of 8.26% with an average open circuit voltage (Voc) of 1.79 V for 2-terminal tandem OPVs using this blend. Based on tandem design, an OPV with PCE of 6.45% and AVT of 38% is demonstrated. Moreover, our devices show improved shelf life and ultraviolet (UV) stability (using CdSe/ZnS core shell quantum dots [QDs]) in ambient with 45% relative humidity.