Improved Carrier Extraction Research Articles

Reducing oxygen vacancies of MoO3 by polyaniline functionalization for stable and efficient inorganic tri-brominated perovskite solar cells

The photovoltaic performance of perovskite solar cells (PSCs) is closely dependent on the efficient carrier extraction and transport at the interface. Here, a polyaniline (PANI) functionalized MoO3 (PANI/MoO3) hole transport material (HTM) is exploited to perfect the interface between the perovskite layer and carbon electrode in all-inorganic CsPbBr3 PSCs. After functionalization with PANI, the p-type behavior and the hole mobility and conductivity of MoO3 are improved by reducing the oxygen vacancies, which boosts the hole extraction and transport, energy level arrangement at the interface of CsPbBr3 perovskite/(PANI/MoO3) HTM. Meanwhile, the PANI/MoO3 with rich C–N and N–H groups introduced by PANI passivates the ions trap states of perovskite films by the C–N⋯Pb2+ (Cs+) Lewis acid-base coordination and the N–H⋯Br− hydrogen bonding, leading to an effective suppression of non-radiative recombination for improved carrier extraction. As a result, the PANI/MoO3 HTMs-based CsPbBr3 PSCs obtain a remarkably increased power conversion efficiency of 10.41 %, in comparison with the efficiency of the original device (6.55 %). In addition, the unencapsulated device with PANI/MoO3 HTMs shows excellent long-term stability with 93.9 % maintenance of the initial efficiency after storing in air with 85 % relative humidity and at 85 °C for 30 days.

Orientation Manipulation and Defect Passivation for Perovskite Solar Cells by a Natural Compound.

Different facets in perovskite crystals exhibit distinct atomic arrangements, influencing their electronic, physical, and chemical properties. Perovskite films incorporating tin oxide (SnO2) as the electron transport layer face challenges in facet regulation. This study reveals that tea saponin (TS), a natural compound serves as a SnO2 modifier, facilitates optimal growth of perovskite crystals on the (111) facet. The modification promotes preferential crystal orientation through hydrogen bond and Lewis coordination. TS forms a chelate with SnO2, resulting in a smoother film and n-type doping, leading to improved carrier extraction and reduced defects. The TS-modified perovskite solar cells achieve a champion efficiency of 24.2%, leveraging from an obvious enhancement of open-circuit voltage (Voc) of 1.18V and fill factor (FF) of 82.8%. The devices also demonstrate enhanced humidity tolerance and storage stability, ensuring improved stability without encapsulation.

Defect passivation in methylammonium/bromine free inverted perovskite solar cells using charge-modulated molecular bonding

Molecular passivation is a prominent approach for improving the performance and operation stability of halide perovskite solar cells (HPSCs). Herein, we reveal discernible effects of diammonium molecules with either an aryl or alkyl core onto Methylammonium-free perovskites. Piperazine dihydriodide (PZDI), characterized by an alkyl core-electron cloud-rich-NH terminal, proves effective in mitigating surface and bulk defects and modifying surface chemistry or interfacial energy band, ultimately leading to improved carrier extraction. Benefiting from superior PZDI passivation, the device achieves an impressive efficiency of 23.17% (area ~1 cm2) (low open circuit voltage deficit ~0.327 V) along with superior operational stability. We achieve a certified efficiency of ~21.47% (area ~1.024 cm2) for inverted HPSC. PZDI strengthens adhesion to the perovskite via -NH2I and Mulliken charge distribution. Device analysis corroborates that stronger bonding interaction attenuates the defect densities and suppresses ion migration. This work underscores the crucial role of bifunctional molecules with stronger surface adsorption in defect mitigation, setting the stage for the design of charge-regulated molecular passivation to enhance the performance and stability of HPSC.

Multifunctional chemical anchors achieve a boosted fill factor and mitigate ion migration of high-stability perovskite solar cells.

To date, it is urgent to produce perovskite films with comparative or even better morphologies in an open-air environment. Unfortunately, a substantial number of trap states on the grain surface, especially the grain boundaries (GBs) of a perovskite layer, can bring about significant deterioration in the performance of PSCs. Trap-induced carrier recombination directly exerts a detrimental influence on the carrier collection efficiency and electronic properties of a perovskite active film. Herein, 4(5)-iodoimidazole (4II), a small organic molecule agent, was introduced to passivate the surface and bulk traps of the active film, which resulted in a controlled morphology, improved carrier extraction and suppressed ion migration for the devices fabricated in a relatively humid and O2-containing environment. Conductive atomic force microscopy (C-AFM) and Kelvin probe force microscopy (KPFM) measurements were applied to study trap passivation and suppression of ion migration across the GBs of perovskite films. The results manifest that the -CN group preferably bonds with the less-coordinated Pb2+ and the -NH- group favorably forms hydrogen bonds with the uncoordinated I-. As a result, the champion device delivered a significantly boosted power conversion efficiency from 17.22% to 20.95%, with an improved fill factor (FF) from 70.54% to 80.40%, and improved ambient stability of the unencapsulated device. This study may probe research insight into the design of passivators with synergistic effects for morphology control and reduction of carrier recombination loss for equally efficient perovskite photovoltaics fabricated in ambient air.

Gamma-ray dose threshold for MAPbI3 solar cells.

In this work, we report on the effects observed in MAPbI3 polycrystalline films and solar cells under moderate gamma-ray doses of 3-21 kGy. We applied several instrumental techniques such as photoluminescence spectroscopy, time-resolved photoluminescence, Suns-VOC measurement, and impedance spectroscopy to characterize exposed samples. We observed a nonlinear dependency of such characteristics as PL intensity, career lifetime, ideality factor, and recombination resistance on the exposure dose. Small doses of 3-5 kGy annihilate some of the defect centers in the material, which results in improved carrier extraction and prolonged carrier lifetime, while with larger doses of 10 kGy and above, nonradiative recombination becomes predominant. In this way, we revealed a gamma-ray threshold for MAPbI3 films of around 10 kGy, above which it is not recommended to exploit this material. In space environment, yearly doses rarely exhibit 0.1 kGy (10 krad), and the MAPbI3 material has a sufficient margin of safety for space applications. Moreover, this unusual behaviour opens up the opportunity to use gamma-ray sources as an effective method to improve the quality of defective polycrystalline perovskite films before actual exploitation in an ionizing radiation-free environment.

Au Nanocluster Assisted Microstructural Reconstruction for Buried Interface Healing for Enhanced Perovskite Solar Cell Performance.

The heterogeneity of perovskite film crystallization along the vertical direction leads to voids and traps at the buried interfaces, hampering both efficiency and stability of perovskite solar cells. Here, bovine serum albumin-functionalized Au nanoclusters (ABSA), combined with heavy gravity, high surface charge density, and strong interactions with the electron transport layer, are designed to reconstruct the buried interfaces for not only high-quality crystallization, but also improved carrier transfer. The ABSA macromolecules with amine function groups and larger surface charge density interact with the perovskite to improve the crystallinity, and gradually migrate towards the buried interface, healing the defective voids, hence suppressing surface recombination velocity from 3075 to 452 cm s-1 . The healed buried interface and the higher surface potential of ABSA-modified TiO2 lead to improved carrier extraction at the interface. The resulting solar cell attains a power conversion efficiency of 25.0% with negligible hysteresis and remarkable stability, maintaining 92.9% of their initial efficiency after 3200 h of exposure to the ambient atmosphere, they also exhibit better continuous irradiation stability compared to control devices. These findings provide a new metal-protein complex to eliminate the deleterious voids and defects at the buried interface for improved photovoltaic performance and stability.

Aqueous solution processed electron-transporting layer based on organosilica nanodots for highly efficient and stable inverted organic solar cells

In this work, we synthesis a new electron-transporting layer material for inverted organic solar cells(i-OSCs) based on organosilica nanodots. The material is synthesized by a simple one-step hydrothermal reaction of 3-[2-(2-aminoethylamino)ethylamino] propyl-trimethoxysilane (AEEA) with carminic acid in water solvent (OSi-CA). Compared with ZnO-based devices, OSi-CA based devices show improved carrier extraction, higher PCE, and greatly increased device stability under UV irradiation. With PM6:Y6 as the active layer, OSi-CA based device has a PCE of 16.01 %. In addition, the OSi-CA electron-transporting layer significantly improves the photostability of OSCs. After 600 min of continuous UV lamp (5 mW cm−2) irradiation, the OSi-CA based i-OSC retained 95.5 % of its initial performance, whereas the ZnO-based device had only 71.2 %.

Optimizing the morphology of all-polymer solar cells for enhanced photovoltaic performance and thermal stability

Due to the complicated film formation kinetics, morphology control remains a major challenge for the development of efficient and stable all-polymer solar cells (all-PSCs). To overcome this obstacle, the sequential deposition method is used to fabricate the photoactive layers of all-PSCs comprising a polymer donor PTzBI-oF and a polymer acceptor PS1. The film morphology can be manipulated by incorporating amounts of a dibenzyl ether additive into the PS1 layer. Detailed morphology investigations by grazing incidence wide-angle X-ray scattering and a transmission electron microscope reveal that the combination merits of sequential deposition and DBE additive can render favorable crystalline properties as well as phase separation for PTzBI-oF:PS1 blends. Consequently, the optimized all-PSCs delivered an enhanced power conversion efficiency (PCE) of 15.21% along with improved carrier extraction and suppressed charge recombination. More importantly, the optimized all-PSCs remain over 90% of their initial PCEs under continuous thermal stress at 65 °C for over 500 h. This work validates that control over microstructure morphology via a sequential deposition process is a promising strategy for fabricating highly efficient and stable all-PSCs.

Cube-like anatase TiO2 mesocrystals as effective electron-transporting materials toward high-performance perovskite solar cells

Electron-transporting materials (ETMs) with higher carrier mobility and a suitable band gap structure play a significant role in determining the photovoltaic performance of perovskite solar cells (PSCs). Herein, cube-like mesoporous single-crystal anatase TiO2 (Meso-TiO2) nanoparticles synthesized by using a facile hydrothermal method were utilized as an efficient ETM for PSCs. The superior semiconducting properties of the Meso-TiO2 based ETM enabled the best power conversion efficiency (PCE) of 20.05% for a PSC. Moreover, the device retained 80% of its initial PCE after being stored in ambient conditions for 20 days under 25 ± 5% relative humidity. In contrast to the commercial TiO2 ETM, the Meso-TiO2 ETM based PSC showed a distinguished interface with better interfacial conditions and improved carrier extraction originating from the cube-like mesoporous single-crystal anatase TiO2 ETM.

Enhancing Photoresponse and Photocurrent of Integrated Perovskite/Organic Solar Cells via Layer-by-Layer Processing

Perovskite solar cells have developed rapidly in recent years to almost rival silicon cells. To extend the photoresponse in the near-infrared region, integrated perovskite/organic solar cells (IPOSCs) have been developed. Typically, the organic bulk heterojunction (BHJ) in IPOSCs is built by one-step coating of a mixed solution of a donor and an acceptor. Here, we prepare the BHJ by layer-by-layer (LBL) processing. Compared to the traditional one-step coated IPOSCs (TOS device), the LBL-processed device (LBL device) exhibits a distinctly improved short-circuit current density (JSC) and power conversion efficiency. The TOS device shows a high photoresponse from about 400 to 900 nm, while the LBL device shows a high photoresponse extending to about 950 nm. Further research indicates that the extending photoresponse of the LBL-device is caused by the redshift of absorption of the organic BHJ. Meanwhile, the LBL-processed BHJ exhibits slightly improved carrier extraction and recombination. The introduction of LBL processing provides an approach to broaden the optical absorption range and photoresponse of IPOSCs.

Mixed-Dimensional van der Waals Heterostructure for High-Performance and Air-Stable Perovskite Nanowire Photodetectors.

An organic-inorganic hybrid perovskite nanowire (NW), CH3NH3PbI3, shows great potential for high-performance photodetectors due to its excellent photoresponse. However, the inefficient carrier collection between the one-dimensional (1D) NWs and metallic electrodes, as well as degradation of the perovskite, limits the viability of the CH3NH3PbI3 NWs for commercial production. Here, we demonstrate a photodetector with a mixed-dimensional van der Waals heterostructure of hexagonal boron nitride (hBN)/graphene (Gr)/1D CH3NH3PbI3, which exhibits excellent responsivity and specific detectivity of up to 558 A/W and 2.3 × 1012 Jones, owing to the improved carrier extraction at the electrical contact between Gr and the NW. As for the atomic encapsulation of hBN, the device is extremely robust and maintains its outstanding performance for more than 2 months when exposed to air. Moreover, benefitting from the 1D geometry of the CH3NH3PbI3 NW, our device is highly sensitive to polarized light. The mixed-dimensional van der Waals heterostructure, hBN/Gr/1D CH3NH3PbI3, would provide a novel idea and protocol for fabricating high-performance and air-stable photoelectronic devices based on organic-inorganic hybrid perovskite NWs.

Perovskite-Type 2D Materials for High-Performance Photodetectors.

Photodetectors are light sensors in widespread use in image sensing, optical communication, and consumer electronics. In current smart optoelectronic technology, conventional semiconductors have encountered a bottleneck caused by inflexibility and opacity. With the ever-increasing demands for versatile optoelectronic applications, perovskite-type 2D materials demonstrate great potential for advanced photodetectors inspired by molecularly thin 2D materials. Through the reduction of thickness to thin or molecularly thin levels, single-crystalline 2D perovskites can exhibit superior optoelectronic performance characteristics, such as tunable absorption property by chemical design, enhanced carrier separation by remarkable photosensing capability, and improved carrier extraction by versatile band engineering. More importantly, perovskite-type 2D materials exhibit great potential for large-scale monolithic integration to achieve all-in-one sensing-memory-computing optoelectronic devices. In this Perspective, recent progress in 2D perovskite-based photodetectors is presented in detail. The focus is on growth strategies for reducing thickness, thickness-dependent optical and electrical properties, device engineering, heterojunction fabrication, and device performance. Finally, the current challenges and future prospects in this field are presented.

Manipulating the interlayer carrier diffusion and extraction process in organic-inorganic heterojunctions: from 2D to 3D structures

Interlayer carrier transfer at heterointerfaces plays a critical role in light to electricity conversion using organic and nanostructured materials. However, how interlayer carrier extraction at these interfaces is poorly understood, especially in organic-inorganic heterogeneous systems. Here, we provide a direct strategy for manipulating the interlayer carrier diffusion process, transfer rate and extraction efficiency in tetracene/MoS2 type-II band alignment heterostructure by constructing the 2D–3D organic-inorganic (O-I) system. As a result, the prolonged diffusion length (12.32 nm), enhanced electron transfer rate (9.53 × 109 s−1) and improved carrier extraction efficiency (60.9%) are obtained in the 2D O-I structure which may be due to the more sufficient charge transfer (CT) state generation. In addition, we have demonstrated that the interlayer carrier transfer behavior complied with the diffusion mechanism based on the one-dimensional diffusion model. The diffusion coefficients have varied from 0.0027 to 0.0036 cm2 s−1 as the organic layer changes from 3D to 2D structures. Apart from the relationship between the carrier injection and diffusion process, temperature-dependent time-resolved spectra measurement is used to reveal the trap-related recombination that may limit the interlayer carrier extraction. The controllable interlayer carrier transfer behavior enables O-I heterojunction to be optimized for optoelectronic applications.

Fermi Level Engineering of Passivation and Electron Transport Materials for p‐Type CuBi2O4 Employing a High‐Throughput Methodology

AbstractMetal 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. In this work, 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 CuBi2O4. The optimized overlayer (Cu1.5TiOz) 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.

Diluted nitride type-II superlattices: Overcoming the difficulties of bulk GaAsSbN in solar cells

We demonstrate type-II GaAsSb/GaAsN superlattices (SL) as a suitable structure to form the lattice-matched 1.0–1.15 eV subcell that would allow the implementation of the optimum monolithic multi-junction solar cell design. The separation of Sb and N atoms during growth leads to an improved composition homogeneity and a lower defect density than in the bulk GaAsSbN counterparts. The type-II band alignment SLs provide long radiative lifetimes that facilitate carrier collection as compared to equivalent type-I SLs. Moreover, the radiative lifetime can be controllably tuned through the period thickness, which is not possible in type-I SLs. A reduced period thickness results in enhanced absorption due to increased wavefunction overlap, as well as in a change in the transport regime from diffusive to quasiballistic, providing improved carrier extraction efficiency. As a result, the short period SL single-junction solar cells show an enhanced power conversion efficiency of 134% over the equivalent bulk devices.

Optical and electrical effects of nanobump structure combined with an undulated active layer on plasmonic organic solar cells

Abstract The effect of nanobump structure (NS) constructed with molybdenum oxide (MoO3) covering aerosol-derived Ag nanoparticles on organic solar cells is systematically explored by varying the MoO3 thickness. The amount of enhanced light absorption by the NS-induced scattering and plasmonic resonance effects increases with decreasing MoO3 thickness. Meanwhile, the oval-shape NS with fully enclosed Ag nanoparticles by MoO3 leads to significantly improved carrier extraction due to decreased ohmic loss, while the NS with partially covered Ag nanoparticles by thin MoO3 degrades device performance arising from increased recombination and leakage loss. Thus, the optimal MoO3 thickness occurs around 20 nm for 40 nm sized nanoparticles where the enhanced carrier generation and the improved carrier extraction by the NS effectively contribute to the improvement in photocurrent. Therefore, our analysis on carrier dynamics of plasmonic organic solar cells incorporating the NS would provide a clear guideline for optimizing device performance.

Thermally-stable hydroxyl radicals implanted on TiO2 electron transport layer for efficient carrier extraction in PbS quantum dot photovoltaics

The electron-transport layer (ETL) between the PbS colloidal quantum dots (CQDs) active layer and the FTO substrate plays a crucial role in the associated heterojunction photovoltaics. However, the presence of surface defects in the ETL limits the performance of the photovoltaics. Herein, we report the improved carrier extraction at the TiO2/PbS interface of planar PbS CQDs photovoltaics, which can be easily accomplished through pre-implanting thermally stable hydroxyl radicals on the surface of TiO2 nanoparticles (NPs) for constructing ETL. The pre-implantations on the surface of TiO2 NPs realized using HNO3 aqueous solution treatment under the hydrothermal condition surprisingly wouldn’t be completely removed after the annealing procedure necessary for preparing the conventional ETL, and effectively eliminate the interband trap sites of the TiO2 NPs by passivating intrinsic oxygen-deficient defects for achieving well-matched electron affinity and work function. As expected, the interfacial bimolecular recombination events are obviously suppressed thanks to the well-acceptable trap densities existing in TiO2 ETL as well as favorable interfacial band alignment for carrier extraction. Consequently, the power conversion efficiency (PCE) is pushed up to 9.31%, much better than the control competitors. Undoubtedly, this work provides another opportunity for optimizing performance of the relevant PbS CQDs photovoltaics resorting to interface engineering guideline.

P-i-n InGaN homojunctions (10–40% In) synthesized by plasma-assisted molecular beam epitaxy with extended photoresponse to 600 nm

We report the influence of the In mole fraction on the material and electrical characteristics of p-i-n InxGa1−xN homojunctions (x=0.10–0.40) synthesized by plasma-assisted molecular-beam epitaxy on GaN-on-sapphire substrates. Junctions terminated with p-InGaN present improved carrier extraction efficiency in comparison with devices capped with p-GaN, due to the deleterious effect of polarization discontinuities on the device performance. We demonstrate that the presence of Mg does not perturb the In incorporation in InGaN, and it leads to a significant reduction of the stacking fault density. p-In0.3Ga0.7N layers with a hole concentration of 3.2×1018cm−3 are demonstrated. InGaN homojunction devices show a peak EQE=14±2% in the blue-to-orange spectral region, and an extended cutoff to 600nm.

Band energy control of molybdenum oxide by surface hydration

The application of oxide buffer layers for improved carrier extraction is ubiquitous in organic electronics. However, the performance is highly susceptible to processing conditions. Notably, the interface stability and electronic structure is extremely sensitive to the uptake of ambient water. In this study we use density functional theory calculations to asses the effects of adsorbed water on the electronic structure of MoOx, in the context of polymer-fullerene solar cells based on PCDTBT. We obtain excellent agreement with experimental values of the ionization potential for pristine MoO3 (010). We find that IP and EA values can vary by as much as 2.5 eV depending on the oxidation state of the surface and that adsorbed water can either increase or decrease the IP and EA depending on the concentration of surface water.

Inverted Polymer Solar Cells

Inverted bulk heterojunction polymer solar cells have become the preferred device architecture for roll-to-roll (R2R) processing, which allows large area devices to be fabricated on flexible substrates. Significant improvements in inverted solar cell performance have been made with novel photovoltaic polymers, along with optimized blend morphology and improved carrier extraction materials. For the first time, inverted polymer solar cells display their potential for low-cost R2R processing with power conversion efficiencies exceeding 8%.