Colloidal Quantum Dot Photovoltaics Research Articles

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.

Fluoride passivation of ZnO electron transport layers for efficient PbSe colloidal quantum dot photovoltaics

Lead selenide (PbSe) colloidal quantum dots (CQDs) are suitable for the development of the next-generation of photovoltaics (PVs) because of efficient multiple-exciton generation and strong charge coupling ability. To date, the reported high-efficient PbSe CQD PVs use spin-coated zinc oxide (ZnO) as the electron transport layer (ETL). However, it is found that the surface defects of ZnO present a difficulty in completion of passivation, and this impedes the continuous progress of devices. To address this disadvantage, fluoride (F) anions are employed for the surface passivation of ZnO through a chemical bath deposition method (CBD). The F-passivated ZnO ETL possesses decreased densities of oxygen vacancy and a favorable band alignment. Benefiting from these improvements, PbSe CQD PVs report an efficiency of 10.04%, comparatively 9.4% higher than that of devices using sol-gel (SG) ZnO as ETL. We are optimistic that this interface passivation strategy has great potential in the development of solution-processed CQD optoelectronic devices.Graphical

Organic Solvent Dispersible MXene Integrated Colloidal Quantum Dot Photovoltaics

AbstractDespite recent advances in colloidal quantum dot (CQD) photovoltaics, several challenges persist and hinder further improvements. In particular, the Fermi level mismatch between the iodide‐treated photoactive and thiol‐treated hole‐transporting CQD layers creates an unfavorable energy band for hole collection. Furthermore, the numerous surface cracks in the thiol‐treated CQD layer facilitate direct contact between the photoactive CQD layer and the metal electrode, consequently leading to reduced device performance. To address these issues, a polycatechol functionalized MXene (PCA‐MXene) that can serve both as a dopant and an interlayer for CQD photovoltaics is developed. By achieving a uniformly dispersed mixture in a butylamine solvent, PCA‐MXene enables the effective combination of MXene and CQDs. This results in the modification of the work function of CQDs and the modulation of the energy band alignment, ultimately promoting enhanced hole extraction. Moreover, the PCA‐MXene employed as an interlayer effectively covers the surface cracks present in the thiol‐treated CQD layer. This coverage inhibits both metal electrode penetration and moisture intrusion into the device. Owing to these advantages, the CQD photovoltaics incorporating PCA‐MXene achieve a power conversion efficiency (PCE) of 13.6%, accompanied by enhanced thermal stability, in comparison to the reference device with a PCE of 12.8%.

Structurally Driven Ultrafast Charge Funneling in Organic Bulk Heterojunction Hole Transport Layer for Efficient Colloidal Quantum Dot Photovoltaics (Adv. Energy Mater. 20/2023)

Colloidal Quantum Dot Photovoltaics In article number 2203749, Edward H. Sargent, Hyosung Choi, and co-workers demonstrate a random-oriented, but closed-packed organic bulk heterojunction structure realized by solvent selection and compositional design. This enables excellent vertical charge conduction and ultrafast hole funneling that minimizes recombination. By integrating the film as a hole transport layer, high-performance colloidal quantum dot photovoltaics are demonstrated.

Structurally Driven Ultrafast Charge Funneling in Organic Bulk Heterojunction Hole Transport Layer for Efficient Colloidal Quantum Dot Photovoltaics

AbstractNanoscopic packing structures crucially determine the charge conduction and the consequent functionalities of organic semiconductors including bulk heterojunctions (BHJs), which are dependent on various processing parameters. Today's high‐performance colloidal quantum dot photovoltaics (CQDPVs) employ functional organic semiconductors as a hole transport layer (HTL). However, the processing of those films replicates a protocol dedicated to high‐performance organic PVs, and thus little is known about how to control the molecular packing structures to maximize the hole extraction function of the HTLs. Herein, it is uncovered that the random‐oriented, but closer‐packed BHJ crystallites, constructed by 1,2‐dichlorobenzene (o‐DCB) as a solvent, allow exceptional charge conduction vertically across the film and restrict diffusion‐driven charge transfer process, enabling ultrafast hole funneling from CQD to BHJ to be extracted. As a result, a power conversion efficiency of 13.66% with high photocurrent >34 mA cm−2 is achieved by employing o‐DCB‐processed BHJ HTL, far exceeding the performance of the CQDPV solely employing neat polymer HTL. A charge conduction mechanism associated with the BHJ HTL structure suppressing the bimolecular recombination is proposed. This works not only suggests key principles to control the packing structures of organic HTLs but also opens a new avenue to boost optoelectronic performance.

Conjugated polymers with controllable interfacial order and energetics enable tunable heterojunctions in organic and colloidal quantum dot photovoltaics

Top and bottom surfaces of polymer films are used to construct interfaces in heterojunction based devices, affecting device figure of merit significantly with their different aggregation states.

Solvent Engineering of Colloidal Quantum Dot Inks for Scalable Fabrication of Photovoltaics.

Development of colloidal quantum dot (CQD) inks enables single-step spin-coating of compact CQD films of appropriate thickness, enabling the promising performance of CQD photovoltaics (CQDPVs). Today's highest-performing CQD inks rely on volatile n-butylamine (BTA), but it is incompatible with scalable deposition methods since a rapid solvent evaporation results in irregular film thickness with an uneven surface. Here, we present a hybrid solvent system, consisting of BTA and N,N-dimethylformamide, which has a favorable acidity for colloidal stability as well as an appropriate vapor pressure, enabling a stable CQD ink that can be used to fabricate homogeneous, large-area CQD films via spray-coating. CQDPVs fabricated with the CQD ink exhibit suppressed charge recombination as well as fast charge extraction compared with conventional CQD ink-based PVs, achieving an improved power conversion efficiency (PCE) of 12.22% in spin-coated devices and the highest ever reported PCE of 8.84% among spray-coated CQDPVs.

Hybrid Surface Passivation for Retrieving Charge Collection Efficiency of Colloidal Quantum Dot Photovoltaics.

Efficient charge collection in photovoltaics is a key issue toward their high performance. Despite the promising performance of colloidal quantum dot (CQD)-based photovoltaics (CQDPVs), they suffer significant dissipation of photocurrent due to imperfect surface passivation of the CQD hole transport layer (HTL) by a single 1,2-ethaneditihol (EDT) ligand. To address the critical drawback of existing CQDPVs, we offer a hybrid passivation strategy, including both EDT and thiocyanate (SCN). The hybrid passivation leads to seamless surface passivation of CQDs, remarkably suppressing charge recombination. This strategy also augments the p-doping density of the CQD, resulting in a pronounced energy level bending at the active layer/HTL interface and facilitating efficient charge separation. Moreover, enhanced electronic coupling across the CQDs (originating from reduced inter-dot spacing) promotes rapid charge extraction. Consequently, the flawless charge collection by a hybrid-passivated HTL successfully retrieves the photocurrent, achieving an enhanced CQDPV power conversion efficiency of 12.70% compared with 11.49% for the control device.

Colloidal Quantum Dot Photovoltaics: Current Progress and Path to Gigawatt Scale Enabled by Smart Manufacturing

Colloidal quantum dots (QDs) have lately been pursued with intense vigor for optoelectronic applications such as photovoltaics (PV), flexible electronics, displays, mid-infrared photodetectors, las...

Colloidal Quantum Dot Photovoltaics Using Ultrathin, Solution-Processed Bilayer In2O3/ZnO Electron Transport Layers with Improved Stability

Solution-processed colloidal quantum dot (CQD) photovoltaics (PVs) continue to mature with improvements in device architectures and ligand exchange strategies. Carrier selective contacts extract ph...

Recent Research Progress in Surface Ligand Exchange of PbS Quantum Dots for Solar Cell Application

Colloidal quantum dots (CQDs) are considered as next-generation semiconductors owing to their tunable optical and electrical properties depending on their particle size and shape. The characteristics of CQDs are mainly governed by their surface chemistry, and the ligand exchange process plays a crucial role in determining their surface states. Worldwide studies toward the realization of high-quality quantum dots have led to advances in ligand exchange methods, and these procedures are usually carried out in either solid-state or solution-phase. In this article, we review recent advances in solid-state and solution-phase ligand exchange processes that enhance the performance and stability of lead sulfide (PbS) CQD solar cells, including infrared (IR) CQD photovoltaics.

Stabilizing Surface Passivation Enables Stable Operation of Colloidal Quantum Dot Photovoltaic Devices at Maximum Power Point in an Air Ambient.

Colloidal quantum dots (CQDs) are promising materials for photovoltaic (PV) applications owing to their size-tunable bandgap and solution processing. However, reports on CQD PV stability have been limited so far to storage in the dark; or operation illuminated, but under an inert atmosphere. CQD PV devices that are stable under continuous operation in air have yet to be demonstrated-a limitation that is shown here to arise due to rapid oxidation of both CQDs and surface passivation. Here, a stable CQD PV device under continuous operation in air is demonstrated by introducing additional potassium iodide (KI) on the CQD surface that acts as a shielding layer and thus stands in the way of oxidation of the CQD surface. The devices (unencapsulated) retain >80% of their initial efficiency following 300 h of continuous operation in air, whereas CQD PV devices without KI lose the amount of performance within just 21 h. KI shielding also provides improved surface passivation and, as a result, a higher power conversion efficiency (PCE) of 12.6% compared with 11.4% for control devices.

Spatial Collection in Colloidal Quantum Dot Solar Cells

AbstractIn thin‐film photovoltaic (PV) research and development, it is of interest to determine where the chief losses are occurring within the active layer. Herein, a method is developed and presented by which the spatial distribution of charge collection, operando, is ascertained, and its application in colloidal quantum dot (CQD) solar cells is demonstrated at a wide range of relevant bias conditions. A systematic computational method that relies only on knowledge of measured optical parameters and bias‐dependent external quantum efficiency spectra is implemented. It is found that, in CQD PV devices, the region near the thiol‐treated hole‐transport layer suffers from low collection efficiency, as a result of bad band alignment at this interface. The active layer is not fully depleted at short‐circuit conditions, and this accounts for the limited short‐circuit current of these CQD solar cells. The high collection efficiency outside of the depleted region agrees with a diffusion length on the order of hundreds of nanometers. The method provides a quantitative tool to study the operating principles and the physical origins of losses in CQD solar cells, and can be deployed in thin‐film solar cell device architectures based on perovskites, organics, CQDs, and combinations of these materials.

Improving Charge Collection from Colloidal Quantum Dot Photovoltaics by Single-Walled Carbon Nanotube Incorporation.

Improving charge collection is one of the key issues for high-performance PbS colloidal quantum dot photovoltaics (CQDPVs) due to the considerable charge loss resulting from the low mobility and large defect densities of the 1,2-ethanedithiol-treated PbS quantum dot hole-transporting layer (HTL). To overcome these limitations, single-walled carbon nanotubes (SWNTs) and C60-encapsulated SWNTs (C60@SWNTs) are incorporated into the HTL in CQDPVs. SWNT-incorporated CQDPV demonstrates a significantly improved short-circuit current density (JSC), and C60@SWNT-incorporated CQDPV exhibits an even higher JSC than that of pristine SWNT. Both result in improved power-conversion efficiencies. Hole-selective, photoinduced charge extraction with linearly increasing voltage measurements demonstrates that SWNT or C60@SWNT incorporation improves hole-transporting behavior, rendering suppressed charge recombination and enhanced mobility of the HTL. The enhanced p-type characteristics and the improved hole diffusion lengths of SWNT- or C60@SWNT-incorporated HTL bring improvement of the entire hole-transporting length and enable lossless hole collection, which results in the JSC enhancement of the CQDPVs.

A Small-Molecule "Charge Driver" enables Perovskite Quantum Dot Solar Cells with Efficiency Approaching 13.

Halide perovskite colloidal quantum dots (CQDs) have recently emerged as a promising candidate for CQD photovoltaics due to their superior optoelectronic properties to conventional chalcogenides CQDs. However, the low charge separation efficiency due to quantum confinement still remains a critical obstacle toward higher-performance perovskite CQD photovoltaics. Available strategies employed in the conventional CQD devices to enhance the carrier separation, such as the design of type-Ⅱ core-shell structure and versatile surface modification to tune the electronic properties, are still not applicable to the perovskite CQD system owing to the difficulty in modulating surface ligands and structural integrity. Herein, a facile strategy that takes advantage of conjugated small molecules that provide an additional driving force for effective charge separation in perovskite CQD solar cells is developed. The resulting perovskite CQD solar cell shows a power conversion efficiency approaching 13% with an open-circuit voltage of 1.10 V, short-circuit current density of 15.4 mA cm-2 , and fill factor of 74.8%, demonstrating the strong potential of this strategy toward achieving high-performance perovskite CQD solar cells.

Building Solar Cells from Nanocrystal Inks

The use of solution-processed photovoltaics is a low cost, low material-consuming way to harvest abundant solar energy. Organic semiconductors based on perovskite or colloidal quantum dot photovoltaics have been well developed in recent years; however, stability is still an important issue for these photovoltaic devices. By combining solution processing, chemical treatment, and sintering technology, compact and efficient CdTe nanocrystal (NC) solar cells can be fabricated with high stability by optimizing the architecture of devices. Here, we review the progress on solution-processed CdTe NC-based photovoltaics. We focus particularly on NC materials and the design of devices that provide a good p–n junction quality, a graded bandgap for extending the spectrum response, and interface engineering to decrease carrier recombination. We summarize the progress in this field and give some insight into device processing, including element doping, new hole transport material application, and the design of new devices.

Oxygen annealing of the ZnO nanoparticle layer for the high-performance PbS colloidal quantum-dot photovoltaics

Though numerous researches regarding the influence of annealing atmospheric condition of ZnO have been carried out, the impact of annealing atmosphere on the carrier transporting properties and the performance of the ZnO-based optoelectronics has not been well-established. Here, the effects of annealing atmosphere (i.e., N2, ambient air, and O2) used to generate ZnO nanoparticle (NP) layers are elucidated. The chemical nature of ZnO layers, especially the amount of oxygen vacancies in ZnO NPs, is modulated by the annealing atmosphere. As the composition of O2 gas increases in the annealing atmosphere, a notable reduction of oxygen vacancies of ZnO NPs and electron mobility enhancement are observed, indicating that O2 gas contributes to a reduction of surface defects on ZnO NPs during the annealing process. In addition, trap-filling by reduced oxygen vacancies of air- and O2-annealed ZnO layers, induces the enhanced built-in potential in colloidal quantum-dot photovoltaic (CQDPV) devices. As expected, PbS CQDPVs with an air- and O2-annealed ZnO layer demonstrate significantly improved power conversion efficiencies than CQDPVs with an N2-annealed ZnO layer. Further analysis shows that the interfacial recombination is reduced for CQDPVs with an air- and O2-annealed ZnO layer due to the reduced trap states of ZnO NPs.

Solution processed infrared- and thermo-photovoltaics based on 0.7 eV bandgap PbS colloidal quantum dots.

Harnessing low energy photons is of paramount importance for multi-junction high efficiency solar cells as well as for thermo-photovoltaic applications. However, semiconductor absorbers with the bandgap lower than 0.8 eV have been limited to III-V (InGaAs) or IV (Ge) semiconductors that are characterized by high manufacturing costs and complicated lattice matching requirements in their growth and integration with higher bandgap cells. Here, we have developed solution processed low bandgap photovoltaic devices based on PbS colloidal quantum dots (CQDs) with a bandgap of 0.7 eV suited for both thermo-photovoltaics and low energy solar photon harvesting. By matching the spectral response of those cells to that of the infrared solar spectrum, we report a record high short circuit current (JSC) of 37 mA cm-2 under the full solar spectrum and 5.5 mA cm-2 when placed at the back of a silicon wafer resulting in power conversion efficiencies (PCEs) of 6.4% and 0.7%, respectively. Moreover, the device reached an above bandgap PCE of ∼6% as a thermo-photovoltaic cell recorded under a 1000 °C blackbody radiator.

Surface and Interface Chemistry in Colloidal Quantum Dots for Solar Applications Studied by X-Ray Photoelectron Spectroscopy.

Control of the surface and interface chemistry of colloidal quantum dots (CQDs) is critical to achieving a product with good air stability and high performing optoelectronic devices. Through various surface passivation treatments, vast improvements have been made in fields such as CQD photovoltaics; however devices have not currently reached commercial standards. We show how X-ray photoelectron spectroscopy (XPS) can provide a better understanding of exactly how surface treatments act on CQD surfaces, and the effect of surface composition on air stability and device performance.. We illustrate this with PbS-based CQDs, using XPS to measure oxidation processes, and to quantify the composition of the topmost surface layer after different surface treatments. We also demonstrate the use of synchrotron radiation-excited depth-profiling XPS, a powerful technique for determining the surface composition, chemistry and structure of CQDs. This review describes our recent progress in characterization of CQD surfaces using SR-excited depth profiling XPS and other photoemission techniques.

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.