Dicarboxylic Acid-Assisted Surface Oxide Removal and Passivation of Indium Antimonide Colloidal Quantum Dots for Short-Wave Infrared Photodetectors.

Heavy-metal-free III-V colloidal quantum dots (CQDs) are promising materials for solution-processed short-wave infrared (SWIR) photodetectors. Recent progress in the synthesis of indium antimonide (InSb) CQDs with sizes smaller than the Bohr exciton radius enables quantum-size effect tuning of the band gap. However, it has been challenging to achieve uniform InSb CQDs with band gaps below 0.9 eV, as well as to control the surface chemistry of these large-diameter CQDs. This has, to date, limited the development of InSb CQD photodetectors that are sensitive to ≥ ${\ge }$ 1400 nm light. Here we adopt solvent engineering to facilitate a diffusion-limited growth regime, leading to uniform CQDs with a band gap of 0.89 eV. We then develop a CQD surface reconstruction strategy that employs a dicarboxylic acid to selectively remove the native In/Sb oxides, and enables a carboxylate-halide co-passivation with the subsequent halide ligand exchange. We find that this strategy reduces trap density by half compared to controls, and enables electronic coupling among CQDs. Photodetectors made using the tailored CQDs achieve an external quantum efficiency of 25 % at 1400 nm, the highest among III-V CQD photodetectors in this spectral region.

Molecular surface programming of rectifying junctions between InAs colloidal quantum dot solids.

Heavy-metal-free III-V colloidal quantum dots (CQDs) show promise in optoelectronics: Recent advancements in the synthesis of large-diameter indium arsenide (InAs) CQDs provide access to short-wave infrared (IR) wavelengths for three-dimensional ranging and imaging. In early studies, however, we were unable to achieve a rectifying photodiode using CQDs and molybdenum oxide/polymer hole transport layers, as the shallow valence bandedge (5.0 eV) was misaligned with the ionization potentials of the widely used transport layers. This occurred when increasing CQD diameter to decrease the bandgap below 1.1 eV. Here, we develop a rectifying junction among InAs CQD layers, where we use molecular surface modifiers to tune the energy levels of InAs CQDs electrostatically. Previously developed bifunctional dithiol ligands, established for II-VI and IV-VI CQDs, exhibit slow reaction kinetics with III-V surfaces, causing the exchange to fail. We study carboxylate and thiolate binding groups, united with electron-donating free end groups, that shift upward the valence bandedge of InAs CQDs, producing valence band energies as shallow as 4.8 eV. Photophysical studies combined with density functional theory show that carboxylate-based passivants participate in strong bidentate bridging with both In and As on the CQD surface. The tuned CQD layer incorporated into a photodiode structure achieves improved performance with EQE (external quantum efficiency) of 35% (>1 µm) and dark current density < 400 nA cm-2, a >25% increase in EQE and >90% reduced dark current density compared to the reference device. This work represents an advance over previous III-V CQD short-wavelength IR photodetectors (EQE < 5%, dark current > 10,000 nA cm-2).

Fast Near-Infrared Photodetection Using III-V Colloidal Quantum Dots.

Colloidal quantum dots (CQDs) are promising materials for infrared (IR) light detection due to their tunable bandgap and their solution processing; however, to date, the time response of CQD IR photodiodes is inferior to that provided by Si and InGaAs. It is reasoned that the high permittivity of II-VI CQDs leads to slow charge extraction due to screening and capacitance, whereas III-Vs-if their surface chemistry can be mastered-offer a low permittivity and thus increase potential for high-speed operation. In initial studies, it is found that the covalent character in indium arsenide (InAs) leads to imbalanced charge transport, the result of unpassivated surfaces, and uncontrolled heavy doping. Surface management using amphoteric ligand coordination is reported, and it is found that the approach addresses simultaneously the In and As surface dangling bonds. The new InAs CQD solids combine high mobility (0.04 cm2 V-1 s-1 ) with a 4× reduction in permittivity compared to PbS CQDs. The resulting photodiodes achieve a response time faster than 2 ns-the fastest photodiode among previously reported CQD photodiodes-combined with an external quantum efficiency (EQE) of 30% at 940 nm.

Ligand Exchange at a Covalent Surface Enables Balanced Stoichiometry in III-V Colloidal Quantum Dots.

III-V colloidal quantum dots (CQDs) are promising semiconducting materials for optoelectronic applications; however, their strong covalent character requires a distinct approach to surface management compared with widely investigated II-VI and IV-VI CQDs-dots, which by contrast are characterized by an ionic nature. Here we show stoichiometric reconstruction in InAs CQDs by ligand exchange. In particular, we find that indium-carboxylate ligands, which passivate as-synthesized InAs CQDs and are responsible for In-rich surfaces, can be replaced by anionic ligands such as thiols. This enables the production of inks consisting of balanced-stoichiomety CQDs; this is distinct from what is observed in II-VI and IV-VI CQDs, in which thiols replace carboxylates. The approach enables the implementation of InAs CQD solids as the active layer in photodiode detectors that exhibit an external quantum efficiency of 36% at 930 nm and a photoresponse time of 65 ns, which is 4 times shorter than that of reference PbS CQD devices.

Ligand-Assisted Reconstruction of Colloidal Quantum Dots Decreases Trap State Density.

Increasing the power conversion efficiency (PCE) of colloidal quantum dot (CQD) solar cells has relied on improving the passivation of CQD surfaces, enhancing CQD coupling and charge transport, and advancing device architecture. The presence of hydroxyl groups on the nanoparticle surface, as well as dimers-fusion between CQDs-has been found to be the major source of trap states, detrimental to optoelectronic properties and device performance. Here, we introduce a CQD reconstruction step that decreases surface hydroxyl groups and dimers simultaneously. We explored the dynamic interaction of charge carriers between band-edge states and trap states in CQDs using time-resolved spectroscopy, showing that trap to ground-state recombination occurs mainly from surface defects in coupled CQD solids passivated using simple metal halides. Using CQD reconstruction, we demonstrate a 60% reduction in trap density and a 25% improvement in charge diffusion length. These translate into a PCE of 12.5% compared to 10.9% for control CQDs.

Quantum Dot-Plasmon Lasing with Controlled Polarization Patterns.

The tailored spatial polarization of coherent light beams is important for applications ranging from microscopy to biophysics to quantum optics. Miniaturized light sources are needed for integrated, on-chip photonic devices with desired vector beams; however, this issue is unresolved because most lasers rely on bulky optical elements to achieve such polarization control. Here, we report on quantum dot-plasmon lasers with engineered polarization patterns controllable by near-field coupling of colloidal quantum dots to metal nanoparticles. Conformal coating of CdSe-CdS core-shell quantum dot films on Ag nanoparticle lattices enables the formation of hybrid waveguide-surface lattice resonance (W-SLR) modes. The sidebands of these hybrid modes at nonzero wavevectors facilitate directional lasing emission with either radial or azimuthal polarization depending on the thickness of the quantum dot film.

Engineering Directionality in Quantum Dot Shell Lasing Using Plasmonic Lattices.

We report how the direction of quantum dot (QD) lasing can be engineered by exploiting high-symmetry points in plasmonic nanoparticle (NP) lattices. The nanolaser architecture consists of CdSe-CdS core-shell QD layers conformally coated on two-dimensional square arrays of Ag NPs. Using waveguide-surface lattice resonances (W-SLRs) near the Δ point in the Brillouin zone as optical feedback, we achieved lasing from the gain in CdS shells at off-normal emission angles. Changing the periodicity of the plasmonic lattices enables other high-symmetry points (Γ or M) of the lattice to overlap with the QD shell emission, which facilitates tuning of the lasing direction. We also increased the thickness of the QD layer to introduce higher-order W-SLR modes with additional avoided crossings in the band structure, which expands the selection of cavity modes for any desired lasing emission angle.

Machine Learning Accelerates Discovery of Optimal Colloidal Quantum Dot Synthesis.

Colloidal quantum dots (CQDs) allow broad tuning of the bandgap across the visible and near-infrared spectral regions. Recent advances in applying CQDs in light sensing, photovoltaics, and light emission have heightened interest in achieving further synthetic improvements. In particular, improving monodispersity remains a key priority in order to improve solar cells' open-circuit voltage, decrease lasing thresholds, and improve photodetectors' noise-equivalent power. Here we utilize machine-learning-in-the-loop to learn from available experimental data, propose experimental parameters to try, and, ultimately, point to regions of synthetic parameter space that will enable record-monodispersity PbS quantum dots. The resultant studies reveal that adding a growth-slowing precursor (oleylamine) allows nucleation to prevail over growth, a strategy that enables record-large-bandgap (611 nm exciton) PbS nanoparticles with a well-defined excitonic absorption peak (half-width at half-maximum (hwhm) of 145 meV). At longer wavelengths, we also achieve improved monodispersity, with an hwhm of 55 meV at 950 nm and 24 meV at 1500 nm, compared to the best published to date values of 75 and 26 meV, respectively.

Ligand cleavage enables formation of 1,2-ethanedithiol capped colloidal quantum dot solids.

Colloidal quantum dots have garnered significant interest in optoelectronics, particularly in quantum dot solar cells (QDSCs). Here we report QDSCs fabricated using a ligand that is modified, following film formation, such that it becomes an efficient hole transport layer. The ligand, O-((9H-fluoren-9-yl)methyl) S-(2-mercaptoethyl) carbonothioate (FMT), contains the surface ligand 1,2-ethanedithiol (EDT) protected at one end using fluorenylmethyloxycarbonyl (Fmoc). The strategy enables deprotection following colloidal deposition, producing films containing quantum dots whose surfaces are more thoroughly covered with the remaining EDT molecules. To compare fabrication methods, we deposited CQDs onto the active layer: in one case, the traditional EDT-PbS/EDT-PbS is used, while in the other EDT-PbS/FMT-PbS is used. The devices based on the new EDT/FMT match the PCE values of EDT/EDT controls, and maintain a higher PCE over an 18 day storage interval, a finding we attribute to an increased thiol coverage using the FMT protocol.

Halide Re-Shelled Quantum Dot Inks for Infrared Photovoltaics.

Colloidal quantum dots are promising materials for tandem solar cells that complement silicon and perovskites. These devices are fabricated from solution phase; however, existing methods for making infrared-bandgap CQD inks suffer agglomeration and fusion during solution exchange. Here we develop a ligand exchange that provides robust surface protection and thereby avoids aggregation. First, we exchanged long oleic acid ligands to a mixed system comprising medium-chain ammonium and anionic chloride ligands; we then reshelled the surface using short halides and pseudohalide ligands that enabled transfer to a polar solvent. Absorbance and photoluminescence measurements reveal the retention of exciton sharpness, whereas X-ray photoelectron spectroscopy indicates halide capping. The best power conversion efficiency of these devices is 0.76 power points after filtering through silicon, which is 1.9× higher than previous single-step solution-processed IR-CQD solar cells.

Origins of Stokes Shift in PbS Nanocrystals.

Stokes shift, an energy difference between the excitonic absorption and emission, is a property of colloidal quantum dots (CQDs) typically ascribed to splitting between dark and bright excitons. In some materials, e.g., PbS, CuInS2, and CdHgTe, a Stokes shift of up to 200 meV is observed, substantially larger than the estimates of dark-bright state splitting or vibronic relaxations. The shift origin remains highly debated because contradictory signatures of both surface and bulk character were reported for the Stokes-shifted electronic state. Here, we show that the energy transfer among CQDs in a polydispersed ensemble in solution suffices to explain the excess Stokes shift. This energy transfer is primarily due to CQD aggregation and can be substantially eliminated by extreme dilution, higher-viscosity solvent, or better-dispersed colloids. Our findings highlight that ensemble polydispersity remains the primary source of the Stokes shift in CQDs in solution, propagating into the Stokes shift in films and the open-circuit voltage deficit in CQD solar cells. Improved synthetic control can bring notable advancements in CQD photovoltaics, and the Stokes shift continues to provide a sensitive and significant metric to monitor ensemble size distribution.

All-Quantum-Dot Infrared Light-Emitting Diodes.

Colloidal quantum dots (CQDs) are promising candidates for infrared electroluminescent devices. To date, CQD-based light-emitting diodes (LEDs) have employed a CQD emission layer sandwiched between carrier transport layers built using organic materials and inorganic oxides. Herein, we report the infrared LEDs that use quantum-tuned materials for each of the hole-transporting, the electron-transporting, and the light-emitting layers. We successfully tailor the bandgap and band position of each CQD-based component to produce electroluminescent devices that exhibit emission that we tune from 1220 to 1622 nm. Devices emitting at 1350 nm achieve peak external quantum efficiency up to 1.6% with a low turn-on voltage of 1.2 V, surpassing previously reported all-inorganic CQD LEDs.

Self-Assembled PbSe Nanowire:Perovskite Hybrids.

Inorganic semiconductor nanowires are of interest in nano- and microscale photonic and electronic applications. Here we report the formation of PbSe nanowires based on directional quantum dot alignment and fusion regulated by hybrid organic-inorganic perovskite surface ligands. All material synthesis is carried out at mild temperatures. Passivation of PbSe quantum dots was achieved via a new perovskite ligand exchange. Subsequent in situ ammonium/amine substitution by butylamine enables quantum dots to be capped by butylammonium lead iodide, and this further drives the formation of a PbSe nanowire superlattice in a two-dimensional (2D) perovskite matrix. The average spacing between two adjacent nanowires agrees well with the thickness of single atomic layer of 2D perovskite, consistent with the formation of a new self-assembled semiconductor nanowire:perovskite heterocrystal hybrid.

Infrared Colloidal Quantum Dot Photovoltaics via Coupling Enhancement and Agglomeration Suppression.

Materials optimized for single-junction solar spectral harvesting, such as silicon, perovskites, and large-band-gap colloidal quantum dot solids, fail to absorb the considerable infrared spectral energy that lies below their respective band gap. Here we explore through modeling and experiment the potential for colloidal quantum dots (CQDs) to augment the performance of solar cells by harnessing transmitted light in the infrared. Through detailed balance modeling, we identify the CQD band gap that is best able to augment wafer-based, thin-film, and also solution-processed photovoltaic (PV) materials. The required quantum dots, with an excitonic peak at 1.3 µm, have not previously been studied in depth for solar performance. Using computational studies we find that a new ligand scheme distinct from that employed in better-explored 0.95 µm band gap PbS CQDs is necessary; only via the solution-phase application of a short bromothiol can we prevent dot fusion during ensuing solid-state film treatments and simultaneously offer a high valence band-edge density of states to enhance hole transport. Photoluminescence spectra and transient studies confirm the desired narrowed emission peaks and reduced surface-trap-associated decay. Electronic characterization reveals that only through the use of the bromothiol ligands is strong hole transport retained. The films, when used to make PV devices, achieve the highest AM1.5 power conversion efficiency yet reported in a solution-processed material having a sub-1 eV band gap.

Record Charge Carrier Diffusion Length in Colloidal Quantum Dot Solids via Mutual Dot-To-Dot Surface Passivation.

Through a combination of chemical and mutual dot-to-dot surface passivation, high-quality colloidal quantum dot solids are fabricated. The joint passivation techniques lead to a record diffusion length for colloidal quantum dots of 230 ± 20 nm. The technique is applied to create thick photovoltaic devices that exhibit high current density without losing fill factor.

Engineering colloidal quantum dot solids within and beyond the mobility-invariant regime.

Colloidal quantum dots are attractive materials for efficient, low-cost and facile implementation of solution-processed optoelectronic devices. Despite impressive mobilities (1-30 cm2 V(-1) s(-1)) reported for new classes of quantum dot solids, it is--surprisingly--the much lower-mobility (10(-3)-10(-2) cm2 V(-1) s(-1)) solids that have produced the best photovoltaic performance. Here we show that it is not mobility, but instead the average spacing among recombination centres that governs the diffusion length of charges in today's quantum dot solids. In this regime, colloidal quantum dot films do not benefit from further improvements in charge carrier mobility. We develop a device model that accurately predicts the thickness dependence and diffusion length dependence of devices. Direct diffusion length measurements suggest the solid-state ligand exchange procedure as a potential origin of the detrimental recombination centres. We then present a novel avenue for in-solution passivation with tightly bound chlorothiols that retain passivation from solution to film, achieving an 8.5% power conversion efficiency.

Role of bond adaptability in the passivation of colloidal quantum dot solids.

Colloidal quantum dot (CQD) solids are attractive materials for photovoltaic devices due to their low-cost solution-phase processing, high absorption cross sections, and their band gap tunability via the quantum size effect. Recent advances in CQD solar cell performance have relied on new surface passivation strategies. Specifically, cadmium cation passivation of surface chalcogen sites in PbS CQDs has been shown to contribute to lowered trap state densities and improved photovoltaic performance. Here we deploy a generalized solution-phase passivation strategy as a means to improving CQD surface management. We connect the effects of the choice of metal cation on solution-phase surface passivation, film-phase trap density of states, minority carrier mobility, and photovoltaic power conversion efficiency. We show that trap passivation and midgap density of states determine photovoltaic device performance and are strongly influenced by the choice of metal cation. Supported by density functional theory simulations, we propose a model for the role of cations, a picture wherein metals offering the shallowest electron affinities and the greatest adaptability in surface bonding configurations eliminate both deep and shallow traps effectively even in submonolayer amounts. This work illustrates the importance of materials choice in designing a flexible passivation strategy for optimum CQD device performance.

All-inorganic colloidal quantum dot photovoltaics employing solution-phase halide passivation.

A new solution-phase halide passivation strategy to improve the electronic properties of colloidal quantum dot films is reported. We prove experimentally that the approach leads to an order-of-magnitude increase in mobility and a notable reduction in trap state density. We build solar cells having the highest efficiency (6.6%) reported using all-inorganic colloidal quantum dots. The improved photocurrent results from increased efficiency of collection of infrared-generated photocarriers.

Quantum junction solar cells.

Colloidal quantum dot solids combine convenient solution-processing with quantum size effect tuning, offering avenues to high-efficiency multijunction cells based on a single materials synthesis and processing platform. The highest-performing colloidal quantum dot rectifying devices reported to date have relied on a junction between a quantum-tuned absorber and a bulk material (e.g., TiO(2)); however, quantum tuning of the absorber then requires complete redesign of the bulk acceptor, compromising the benefits of facile quantum tuning. Here we report rectifying junctions constructed entirely using inherently band-aligned quantum-tuned materials. Realizing these quantum junction diodes relied upon the creation of an n-type quantum dot solid having a clean bandgap. We combine stable, chemically compatible, high-performance n-type and p-type materials to create the first quantum junction solar cells. We present a family of photovoltaic devices having widely tuned bandgaps of 0.6-1.6 eV that excel where conventional quantum-to-bulk devices fail to perform. Devices having optimal single-junction bandgaps exhibit certified AM1.5 solar power conversion efficiencies of 5.4%. Control over doping in quantum solids, and the successful integration of these materials to form stable quantum junctions, offers a powerful new degree of freedom to colloidal quantum dot optoelectronics.

Hybrid passivated colloidal quantum dot solids.

Colloidal quantum dot (CQD) films allow large-area solution processing and bandgap tuning through the quantum size effect. However, the high ratio of surface area to volume makes CQD films prone to high trap state densities if surfaces are imperfectly passivated, promoting recombination of charge carriers that is detrimental to device performance. Recent advances have replaced the long insulating ligands that enable colloidal stability following synthesis with shorter organic linkers or halide anions, leading to improved passivation and higher packing densities. Although this substitution has been performed using solid-state ligand exchange, a solution-based approach is preferable because it enables increased control over the balance of charges on the surface of the quantum dot, which is essential for eliminating midgap trap states. Furthermore, the solution-based approach leverages recent progress in metal:chalcogen chemistry in the liquid phase. Here, we quantify the density of midgap trap states in CQD solids and show that the performance of CQD-based photovoltaics is now limited by electron-hole recombination due to these states. Next, using density functional theory and optoelectronic device modelling, we show that to improve this performance it is essential to bind a suitable ligand to each potential trap site on the surface of the quantum dot. We then develop a robust hybrid passivation scheme that involves introducing halide anions during the end stages of the synthesis process, which can passivate trap sites that are inaccessible to much larger organic ligands. An organic crosslinking strategy is then used to form the film. Finally, we use our hybrid passivated CQD solid to fabricate a solar cell with a certified efficiency of 7.0%, which is a record for a CQD photovoltaic device.