Colloidal Quantum Dot Solar Cells Research Articles

Interfacial Heterojunction Enables High Efficient PbS Quantum Dot Solar Cells.

Colloidal quantum dots (CQDs) are promising optoelectronic materials for solution-processed thin film optoelectronic devices. However, the large surface area with abundant surface defects of CQDs and trap-assisted non-radiative recombination losses at the interface between CQDs and charge-transport layer limit their optoelectronic performance. To address this issue, an interface heterojunction strategy is proposed to protect the CQDs interface by incorporating a thin layer of polyethyleneimine (PEIE) to suppress trap-assisted non-radiative recombination losses. This thin layer not only acts as a protective barrier but also modulates carrier recombination and extraction dynamics by forming heterojunctions at the buried interface between CQDs and charge-transport layer, thereby enhancing the interface charge extraction efficiency. This enhancement is demonstrated by the shortened lifetime of carrier extraction from 0.72 to 0.46ps. As a result, the resultant PbS CQD solar cells achieve a power-conversion-efficiency (PCE) of 13.4% compared to 12.2% without the heterojunction.

Role of the ZnO electron transport layer in PbS colloidal quantum dot solar cell yield.

The development of lead sulfide (PbS) colloidal quantum dot (CQD) solar cells has led to significant power conversion efficiency (PCE) improvements in recent years, with record efficiencies now over 15%. Many of the recent advances in improving PCE have focused on improving the interface between the PbS CQD active layer and the zinc oxide (ZnO) electron transport layer (ETL). Proper optimization of the ZnO ETL also increases yield, or the percentage of functioning devices per fabrication run. Simultaneous improvements in both PCE and yield will be critical as the field approaches commercialization. This review highlights recent advances in the synthesis of ZnO ETLs and discusses the impact and critical role of ZnO synthesis conditions on the PCE and yield of PbS CQD solar cells.

Suppression of Thermally Induced Surface Traps in Colloidal Quantum Dot Solids via Ultrafast Pulsed Light.

Thermal annealing (TA) of colloidal quantum dot (CQD) films is considered an important process for recent high-performing CQD solar cells (SCs) due to its beneficial effects on CQD solids, including enhanced electrical conductivity, denser packing of CQD films, and the removal of organic residues and solvents. However, the conventional TA for CQDs, which requires several minutes, leads to hydroxylation and oxidation on the CQD surface, resulting in the formation of trap states and a subsequent decline in SC performance. To address these challenges, this study introduces a flashlight annealing (FLA) technique that significantly reduces the annealing time to the millisecond scale. Through the FLA approach, it successfully suppressed hydroxylation and oxidation, resulting in decreased trap states within the CQD solids while simultaneously preserving their charge transport properties. As a result, CQD SCs treated with FLA exhibited a notable improvement, achieving an open-circuit voltage of 0.66V compared to 0.63V in TA-treated devices, leading to an increase in power conversion efficiency from 12.71% to 13.50%.

P‐Type PbS Quantum Dot Solar Ink via Hydrogen‐Bonding Modulated Solvation for High‐Efficiency Photovoltaics

AbstractLigand modulation of the electrical properties and surface solvation plays a crucial role in the development of functionalized colloidal quantum dots (CQDs) inks for solution‐processed optoelectronics. While inorganic halide ionic ligands can facilitate the n‐type doping of PbS CQDs and establish an electrical double layer in polar solvents for stable high‐concentration n‐type CQD inks, a plausible solvation strategy is still lacking to stabilize p‐type PbS CQDs, thereby resulting in a tedious multi‐step deposition involving short‐chain dithiol molecular ligands for advanced heterojunction CQD solar cells. Here an effective hydrogen bonding solvation strategy is proposed using 2‐mercaptoethanol (ME) ligands to realize stable p‐type PbS CQD ink. This strategy enables DMSO to form a dense solvation layer surrounding the ME‐modified PbS CQDs. With this approach, the PbS‐ME CQD ink exhibits a photoluminescence quantum yield of 52.03%, which is the highest record for PbS CQD inks. Finally, one‐step deposition of a p‐type PbS‐ME layer for PbS CQD photovoltaics is successfully achieved with an impressive power conversion efficiency (PCE) of 10.91%. This p‐type solar ink facilitates the fabrication of ready‐to‐use devices, enabling extensive applications in large‐scale and flexible optoelectronic devices.

Multi‐Facet Passivation of Ternary Colloidal Quantum Dot Enabled by Quadruple‐Ligand Ensemble toward Efficient Lead‐Free Optoelectronics

AbstractSolution‐processed ternary‐compound semiconductor AgBiS2 colloidal quantum dots (CQDs) are promising light‐absorbing materials owing to their nontoxicity and high absorption coefficient (>106 cm−1). However, rational strategies to passivate multi‐facet of ternary‐compound CQDs and manufacture stable CQD inks have not yet been proposed. In this paper, a ligand passivation strategy is proposed using a solution‐phase ligand exchange method. A quadruple‐ligand ensemble is employed to demonstrate multifaceted passivation on AgBiS2 CQDs and a highly stable CQD ink. Density functional theory studies reveal the secondary cation adsorption of silver halide passivation, indicating the synergistic passivation of the ligand ensemble. This yields a low trap density in CQD solids, improving the power conversion efficiency to 8.1% by 53% in CQD solar cells. Furthermore, the proposed device exhibits the fastest response time of 400 ns among all reported AgBiS2 devices, demonstrating its potential for efficient lead‐free optoelectronics.

Organic hole transport materials for high performance PbS quantum dot solar cells.

We developed a triazatruxene-based hole transport material (HTM), 3Ka-DBT-3Ka, aiming to enhance band alignment and augment charge generation and collection in devices, as an alternative for 1,2-ethanedithiol (EDT). The PbS CQD solar cells employing 3Ka-DBT-3Ka as the HTM achieve a peak efficiency of 11.4%, surpassing devices employing the conventional PbS-EDT HTM (8.9%).

Reducing the Open-Circuit Voltage Loss of PbS Quantum Dot Solar Cells via Hybrid Ligand Exchange Treatment.

The interface VOC loss between the active layer and the hole transport layer (HTL) of lead sulfide colloidal quantum dot (PbS-CQD) solar cells is a significant factor influencing the efficiency improvement of PbS colloidal quantum dot solar cells (PbS-CQDSCs). Currently, the most advanced solar cells adopt organic P-type HTLs (PbS-EDT) via solid-state ligand exchange with 1,2-ethanedithiol (EDT) on the CQD top active layer. However, EDT is unable to altogether remove the initial ligand oleic acid from the quantum dot surface, and its high reactivity leads to cracks in the HTL film caused by volume contractions, which inevitably results in significant VOC loss. These flaws prompted this research to develop a method involving hybrid organic ligand exchange using 3-mercaptopropionic acid (MPA) and 1,2-EDT (PbS-Hybrid) to overcome these drawbacks of VOC loss. The results indicated that the new exchange strategy improved the quality of the HTL film and benefited from the enhanced passivation of the quantum dot surface and better alignment of energy levels, and the average VOC of PbS-Hybrid devices is increased by approximately 25 mV compared to control devices. With the enhanced VOC, the average power conversion efficiency (PCE) of the devices is improved by 10%, with the highest PCE reaching 13.24%.

Investigation of suitable buffer layer for PbS-TBAI/PbS-EDT colloidal quantum dot solar cell using SCAPS-1D

Colloidal quantum dots (CQD) are emerging third-generation photovoltaic technologies because of their ability to link a wider range of the light spectrum compared to those of perovskite, crystalline, and copper indium gallium selenide (CIGS) solar cells. In this work, a Lead Sulphide (PbS) CQD solar cell architecture with Ag2S, CdS, ZnSe and ZnS buffer layer is presented. The device consisting of PbS-tetrabutyle ammonium iodide (PbS-TBAI) as an absorber layer, PbS-1,2-ethanedithiol (PbS-EDT) as a hole transport layer (HTL), TiO2 as an electron transport layer (ETL), and fluorine tin oxide (FTO) as an oxide layer. The electrical performances of the solar cells were simulated using SCAPS-1D while taking into account different buffer layers with increasing bandgap values. With ZnS acting as a buffer layer, the computational modelling and analysis of architectural PbS CQD solar cell result in an efficiency of 17.12%. Additionally, the parameters of the solar cell have been studied to be affected by the thickness and bandgap of the absorber and HTL layers, the effect of acceptor concentration with various buffer layers, the impact of temperature, the effect of HTL doping density, and the effect of absorber layer defect density. This study can serve as a guide for future PbS CQD solar cells.

Photovoltaic performance enhancement on carbon counter electrode based PbS colloidal quantum dots solar cells with surface trap passivation via post-treatment process

Photovoltaic performance enhancement on carbon counter electrode based PbS colloidal quantum dots solar cells with surface trap passivation via post-treatment process

Attaining above 30% efficiency of PbS-based colloidal quantum dot solar cell using MoO3 and SnO2 as charge transport layers: a numerical approach

Attaining above 30% efficiency of PbS-based colloidal quantum dot solar cell using MoO3 and SnO2 as charge transport layers: a numerical approach

Modeling and simulation of > 19% highly efficient PbS colloidal quantum dot solar cell: A step towards unleashing the prospect of quantum dot absorber

We used the SCAPS-1D simulation tool to maximize the performance of lead sulfide (PbS) solar cells. A PbS solar cell was first modeled and then experimentally verified from past research. The ZnO electron-transport layer (ETL) was then replaced with ZnO:Al ETL material. Additionally, the fluorine-doped tin oxide work function, PbS-TBAI, ZnO:Al layer thicknesses, ZnO:Al/PbS-TBAI, PbS-TBAI/PbS-EDT defect density, PbS-TBAI defect density, ZnO:Al, and PbS-TBAI doping concentration were optimized. Results showed a greater alignment of the absorber-layer valence band with the HOMO and LUMO of ZnO:Al than that of ZnO ETL. The PbS solar cell exhibited the greatest efficiency at the optimum values of 0.4 µm, 0.04 µm, 1019 cm–3, 4.0 eV, 1017 cm–3, 1014 cm–2, 1018 cm–2, and 3.8 eV for absorber thickness, ETL thickness, ETL doping concentration, work function of front contact, PbS-TBAI doping concentration, and electron affinity of ZnO:Al, respectively. The PbS solar cell also performed best at interface defect densities of 1014 and 1018 cm–2 for ZnO:Al/PbS-TBAI and PbS-TBAI/PbS-EDT, respectively. The PCE of ZnO:Al ETL-based device also increased from 15.036% before optimization to 19.169% after. The optimized result was found to be affected by temperature. The PbS-optimized device with inorganic hole-transport layers (HTLs) demonstrated higher performance than the device with organic HTL. This finding was attributed to the low hole mobility in the organic HTL than those of inorganic ones. Therefore, the ZnO:Al ETL-based device was more efficient than the ordinary ZnO ETL-based device.

Charge Transport Layer Engineering toward Efficient and Stable Colloidal Quantum Dot Solar Cells.

Lead sulfide (PbS) colloidal quantum dot (CQD) solar cell, as a new type of solution-processed photovoltaic technology, have always attracted great interest. Early studies mainly focused on the surface passivation of CQDs and optimization of device structures. Recently, researchers further developed new charge transport layers and interfacial passivation strategies based on these foundations, which have significantly improved the device efficiency and stability. In this perspective, we summarize the important research progress in transport layer materials, structures, and interfacial passivation of CQD solar cells. We also discuss the remaining challenges and potential development directions for charge transport layers for high-performance and stable PbS CQD solar cells. We hope to draw attention to the enormous potential of charge transport layers in promoting CQD-based optoelectronics toward practical applications.

Optical engineering of PbS colloidal quantum dot solar cells via Fabry–Perot resonance and distributed Bragg reflectors

A tradeoff between light absorption and charge transport is a well-known issue in PbS colloidal quantum dot (CQD) solar cells because the carrier diffusion length in PbS CQD films is comparable to the thickness of CQD film. We reduce the tradeoff between light absorption and charge transport by combining a Fabry–Perot (FP) resonator and a distributed Bragg reflector (DBR). A FP resonance is formed between the DBR and a dielectric-metal-dielectric film as a top transparent electrode. A SiO2-TiO2 multilayer is used to form a DBR. The FP resonance enhances light absorption near the resonant wavelength of the DBR without changing the CQD film thickness. The light absorption near the FP resonance wavelength is further boosted by coupling the FP resonance with the high reflectivity of the Ag-coated DBR. When the FP resonance and DBR are combined, the power conversion efficiency (PCE) of PbS CQD solar cells increases by 54%. Moreover, the DBR assisted FP resonance enables a very thin PbS layer to absorb near infrared light four times more. The overall PCE of the thin PbS CQD solar cell increases by 24% without sacrificing the average visible transmittance (AVT). Our results show how to overcome the inherence problem of the CQD and develop a semi-transparent solar cell where the wavelength-selective absorption and the transparency for visible light are important.

Performance optimization of efficient PbS quantum dots solar cells through numerical simulation

Colloidal quantum dots (CQDs) solar cells are less efficient because of the carrier recombination within the material. The electron and hole transport layers have high impact on the performance of CQDs based solar cells which makes its investigation a very important component of the development of the more efficient devices. In this work, we have tried performance optimization in tetrabutyl ammonium iodide capped lead sulfide (PbS) CQDs (PbS-TBAI) as absorber layers based solar cells by incorporating different hole transport layers (HTLs) to achieve better power conversion efficiency (PCE) in different device architectures by SCAPS—1D numerical simulation software. It was observed from the simulation that the ITO/TiO2/PbS-TBAI/HTL/Au device architecture shows higher power conversion efficiency as compared to the conventional experimentally realized device architecture of ITO/TiO2/PbS-TBAI/PbS-EDT/HTL/Au. The influence of interface defect density (IDD) at the interface TiO2/PbS-TBAI has also been studied where IDD is varied from 1 × 1013 cm−2 to 1 × 1018 cm−2 while keeping the rest of the device parameters intact. The result shows a noteworthy reduction in the PV performance of the device at higher IDD. This modelled device structure provides a new direction toward the experimental realization in high efficiency PbS QDs solar cells.

Quantum Dot-Siloxane Anchoring on Colloidal Quantum Dot Film for Flexible Photovoltaic Cell.

Lead sulfide (PbS) colloidal quantum dots (CQDs) are promising materials for next-generation flexible solar cells because of near-infrared absorption, facile bandgap tunability, and superior air stability. However, CQD devices still lack enough flexibility to be applied to wearable devices owing to the poor mechanical properties of CQD films. In this study, a facile approach is proposed to improve the mechanical stability of CQDs solar cells without compromising the high power conversion efficiency (PCE) of the devices. (3-aminopropyl)triethoxysilane (APTS) is introduced on CQD films to strengthen the dot-to-dot bonding via QD-siloxane anchoring, and as a result, crack pattern analysis reveals that the treated devices become robust to mechanical stress. The device maintains 88% of the initial PCE under 12000 cycles at a bending radius of 8.3mm. In addition, APTS forms a dipole layer on CQD films, which improves the open circuit voltage (VOC ) of the device, achieving a PCE of 11.04%, one of the highest PCEs in flexible PbS CQD solar cells.

How to minimize voltage and fill factor losses to achieve over 20% efficiency lead chalcogenide quantum dot solar cells: Strategies expected through numerical simulation

Lead chalcogenide colloidal quantum dot solar cells (CQDSCs) have the potential to revolutionize the field of light-to-electricity conversion with their exceptional optoelectronic properties. Unfortunately, realizing their full potential has been hindered by persistent and poorly understood limitations in fill factor (FF) and open-circuit voltage (Voc) losses. In this study, we performed a systematic numerical analysis of practical PbS CQDSCs to identify the root causes of FF and Voc losses in the current development stage, and to provide a clear and feasible roadmap for achieving a PCE of more than 20% in future development stages. Our analysis revealed that the highly effective route for enhancing the current 10% device is to initially modify the internal resistances, resulting in a significant reduction in FF losses to 15%, followed by systematic optimization of surface recombination velocities in the absorber layer and the absorber/hole transfer layer (HTL) interface, which can generate a Voc improvement of 3.76%, ultimately leading to a near-15% PCE. To further elevate PCE to unprecedented heights, we identified the precise regulation of surface excess charge densities at the absorber/HTL interface and the HTL/back contact interface as critical factors. By finely tuning these performance-limiting factors, we demonstrated the feasibility of achieving over 20% PCE, with minimal Voc loss of 318.10 mV and almost negligible FF loss of 6.08% in PbS CQDSCs. Our investigation provides crucial insights into the causes of FF and Voc losses in PbS CQDSCs and offers a clear pathway for future progress in this rapidly evolving field.

Fabrication of PbSe colloidal quantum dot solar cells using low-temperature Li-doped ZnO electron transport layer

The lead selenide quantum dots (PbSe QDs) have incredible features because of their tunable bandgap and synthesis process at low temperatures. Aside from the highly effective QDs active layer, the electron transport layer (ETL) also plays a significant part in obtaining high-efficiency colloidal quantum dots solar cells (CQDSCs). Here, we introduce undoped and 1–3% lithium-doped zinc oxide (LZO) sol–gel as an ETL and utilized it in CQDSCs to achieve high efficiency. ZnO and LZO thin films are obtained by low annealing temperature whereas the PbSe QDs-based absorber layer is deposited by layer-by-layer (LBL) technique in the presence of 1-ethyl-3-methylimidazolium iodide (EMII) which is acting as a ligand exchange material. Results show that 2 wt% Li-doping on one hand can maximumly increase the conduction band minimum, and transmittance, whereas on the other hand decreases the oxygen defects densities as well as the roughness of the thin film as compared to other ETLs. Subsequently, PbSe CQDSCs with 2 wt% Li-doped ZnO ETL display the highest power conversion efficiency (PCE) of 10.80% as compared to 10.12% PCE of ZnO-based PbSe CQDSCs (7.5% higher). Similarly, 2 wt% LZO-based PbSe CQDSCs devices show long-term stability of about 40 days. Furthermore, Li-doping in ZnO offers a viable approach for low-cost, high-performance CQDSCs.

Open-Shell Diradical-Sensitized Electron Transport Layer for High-Performance Colloidal Quantum Dot Solar Cells.

The zinc oxide (ZnO) nanoparticles (NPs) are well-documented as an excellent electron transport layer (ETL) in optoelectronic devices. However, the intrinsic surface flaw of the ZnO NPs can easily result in serious surface recombination of carriers. Exploring effective passivation methods of ZnO NPs is essential to maximize the device's performance. Herein, a hybrid strategy is explored for the first time to improve the quality of ZnO ETL by incorporating stable organic open-shell donor-acceptor type diradicaloids. The high electron-donating feature of the diradical molecules can efficiently passivate the deep-level trap states and improve the conductivity of ZnO NP film. The unique advantage of the radical strategy is that its passivation effectiveness is highly correlated with the electron-donating ability of radical molecules, which can be precisely controlled by the rational design of molecular chemical structures. The well-passivated ZnO ETL is applied in lead sulfide (PbS) colloidal quantum dot solar cells, delivering a power conversion efficiency of 13.54%. More importantly, as a proof-of-concept study, this work will inspire the exploration of general strategies using radical molecules to construct high-efficiency solution-processed optoelectronic devices.

Polyethylenimine-based bifunctional interfacial layer for efficient quantum dot photovoltaics

Interface engineering, which efficiently optimizes the interfacial carrier collection and recombination, has been proven to be of importance for the emerging colloidal quantum dot solar cells (CQDSCs). Compared with the attractive modification efforts at the interface between quantum dots and the anode/electron transport layer (ETL), the interface between fluorine-doped tin-oxide (FTO) cathodes and the ETL, for which there exists a band alignment mismatch and high trap density in ZnO, has been investigated less. Herein, two kinds of ethylenimine-based polymers, branched by only ethylenimine groups (b-PEI) and by both ethylenimine/ethoxylated groups (e-PEI), respectively, are introduced as bifunctional interfacial layers (BILs) in lead sulfide (PbS) CQDSCs. PEI-based BILs were utilized to modulate the work function of an FTO cathode for optimizing the band alignment at the FTO/ZnO interface and to control the crystallinity of ZnO for reducing its traps. These BILs suppressed the interfacial carrier recombination and achieved a power conversion efficiency (PCE) of 11.28% in CQDSCs, which was much superior to the PCE of the reference device without BIL (10.29%). Also, the branched side chain of PEI-based BILs plays a crucial role in rationally modulating the Schottky barrier to gain different interface-optimization effects. Our work has laid a foundation for the commercial application of CQDSCs due to the advantage of low-temperature solution processability, low-cost, and scalable manufacturing.

A Furan‐Substituted Polymeric Hole‐Transporting Material for Energy Level Regulation and Less Planarity in Colloidal Quantum Dot Solar Cells

For efficient colloidal quantum dot (CQD) solar cells (CQD‐SCs), thiol‐passivated p‐type CQDs are generally used as a hole‐transporting material (HTM); however, there are issues with the control of optoelectrical properties, low thiol passivation rate, and poor morphology with a power conversion efficiency (PCE) of approximately 11%. Although polymeric HTMs have been introduced to address these issues, maximizing efficiency and achieving green‐solvent processability and thermal stability for commercialization is necessary. Here, we synthesize a novel benzodifuran (BDF)‐based HTM (asy‐ranPBTBDF) showing an electron‐deficient state, low steric hindrance, and low planarity compared to those of a typical benzodithiophene (BDT)‐based HTM (asy‐ranPBTBDT). BDF properties lead to deep high occupied molecular orbital (HOMO) levels, close π–π stacking, excellent solubility, and amorphous properties related to efficiency, green‐solvent processability, and thermal stability. With these benefits, the asy‐ranPBTBDF‐based CQD‐SC showed enhanced open‐circuit voltage (VOC) (0.65 V) and PCE (13.29%) compared to those of the asy‐ranPBTBDT‐based device (0.63 V and 12.22%) in toxic processes with chlorobenzene. The asy‐ranPBTBDF‐based CQD‐SC showed a PCE of 12.51% in a green‐solvent process with 2‐methylanisole and improved thermal stability at 80 °C (83.8% retaining after 24 h) owing to less lateral crystallization than the asy‐ranPBTBDT‐based device (60.8% retaining after 24 h).