Colloidal Quantum Dot Light Emitting Diodes at Telecom Wavelength with 18% Quantum Efficiency and Over 1 MHz Bandwidth.

Developing high performance, low-cost solid-state light emitters in the telecom wavelength bandwidth is of paramount importance for infrared light-based communications. Colloidal quantum dot (CQD) based light emitting diodes (LEDs) have shown tremendous advances in recent times through improvement in synthesis chemistry, surface property, and device structures. Despite the tremendous advancements of CQD based LEDs in the visible range with efficiency reaching theoretical limits, their short-wave infrared (SWIR) counterparts mainly based on lead chalcogenide CQDs, have shown lower performance (≈8%). Here the authors report on highly efficient SWIR CQD LEDs with a recorded EQE of 11.8% enabled by the use of a binary CQD matrix comprising QD populations of different bandgaps at the emission wavelength of 1550 nm. By further optimizing the optical out-coupling via the use of a hemispherical lens to reduce optical waveguide loss, the EQE of the LED increased to 18.6%. The CQD LED has an electrical bandwidth of 2 MHz, which motivated them to demonstrate its use in the first SWIR free-space optical transmission link based entirely on CQD technology (photodetector and light emitter) opening a new window of applications for CQD optoelectronics.

Visible-Blind ZnMgO Colloidal Quantum Dot Downconverters Expand Silicon CMOS Sensors Spectral Coverage into Ultraviolet and Enable UV-Band Discrimination.

Selective spectral detection of ultraviolet (UV) radiation is highly important across numerous fields from health and safety to industrial and environmental monitoring applications. Herein, a nontoxic, visible-blind, quantum dot (QD)-based sensing scheme that expands the spectral coverage of silicon complementary metal-oxide-semiconductor (CMOS) sensors into the UV, enabling efficient UV detection without affecting the sensor performance in the visible and UV-band discrimination, is reported. This scheme uses zinc magnesium oxide (ZnMgO) QDs with compositionally tunable absorption across UV and high photoluminescence quantum yield in the visible. The efficient luminescence and large Stokes shift of these QDs are exploited herein to act as an efficient downconverting material that enhances the UV sensitivity of Si-photodetectors (Si-PDs). A Si-PD integrated with the QDs results in a ninefold improvement in photoresponsivity from 0.83 to 7.5 mA W-1 at 260 nm. Leveraging the tunability of these QDs, a simple UV-band identification scheme is further reported, which uses two distinct-bandgap ZnMgO QDs stacked in a tandem architecture whose spectral emission color depends on the UV-band excitation light. The downconverting stack enables facile discrimination of UV light using a standard CMOS image sensor (camera) or by the naked eye and avoids the use of complex optics.

Low-Threshold, Highly Stable Colloidal Quantum Dot Short-Wave Infrared Laser enabled by Suppression of Trap-Assisted Auger Recombination.

Pb-chalcogenide colloidal quantum dots (CQDs) are attractive materials to be used as tuneable laser media across the infrared spectrum. However, excessive nonradiative Auger recombination due to the presence of trap states outcompetes light amplification by rapidly annihilating the exciton population, leading to high gain thresholds. Here, a binary blend is employed of CQDs and ZnO nanocrystals in order to passivate the in-gap trap states of PbS-CQD gain medium. Using transient absorption, a fivefold increase is measured in Auger lifetime demonstrating the suppression of trap-assisted Auger recombination. By doing so, a twofold reduction is achieved in amplified spontaneous emission (ASE) threshold. Finally, by integrating the proposed binary blend to a distributed feedback (DFB) resonator, single-mode lasing emission is demonstrated at 1650 nm with a linewidth of 1.23 nm (0.62 meV), operating at a low lasing threshold of ≈385 µJ cm-2 . The Auger suppression in this system has allowed to achieve unprecedented lasing emission stability for a CQD laser with recorded continuous operation of 5 h at room temperature and ambient conditions.

Solid-State Thin-Film Broadband Short-Wave Infrared Light Emitters.

Solid-state broadband light emitters in the visible have revolutionized today's lighting technology achieving compact footprints, flexible form factors, long lifetimes, and high energy saving, although their counterparts in the infrared are still in the development phase. To date, broadband emitters in the infrared have relied on phosphor-downconverted light emitters based on atomic optical transitions in transition metal or rare earth elements in the phosphor layer resulting in limited spectral bandwidths in the near-infrared and preventing their integration into electrically driven light-emitting diodes (LEDs). Herein, phosphor-converted LEDs based on engineered stacks of multi-bandgap colloidal quantum dots (CQDs) are reported as a novel class of broadband emitters covering a broad short-wave infrared (SWIR) spectrum from 1050-1650 nm with a full-width-half-maximum of 400 nm, delivering 14 mW of optical power with a quantum efficiency of 5.4% and power conversion efficiency of 13%. Leveraging the electrical conductivity of the CQD stacks, further, the first broadband SWIR-active LED is demonstrated, paving the way toward complementary metal-oxide-semiconductor integrated broadband emitters for on-chip spectrometers and low-cost volume manufacturing. SWIR spectroscopy is employed to illustrate the practical relevance of the emitters in food and material identification case studies.

Single-Exciton Gain and Stimulated Emission Across the Infrared Telecom Band from Robust Heavily Doped PbS Colloidal Quantum Dots.

Materials with optical gain in the infrared are of paramount importance for optical communications, medical diagnostics, and silicon photonics. The current technology is based either on costly III-V semiconductors that are not monolithic to silicon CMOS technology or Er-doped fiber technology that does not make use of the full fiber transparency window. Colloidal quantum dots (CQDs) offer a unique opportunity as an optical gain medium in view of their tunable bandgap, solution processability, and CMOS compatibility. The 8-fold degeneracy of infrared CQDs based on Pb-chalcogenides has hindered the demonstration of low-threshold optical gain and lasing, at room temperature. We demonstrate room-temperature, infrared, size-tunable, band-edge stimulated emission with a line width of ∼14 meV. Leveraging robust electronic doping and charge-exciton interactions in PbS CQD thin films, we reach a gain threshold at the single exciton regime representing a 4-fold reduction from the theoretical limit of an 8-fold degenerate system, with a net modal gain in excess of 100 cm-1.

Low-Cost RoHS Compliant Solution Processed Photovoltaics Enabled by Ambient Condition Synthesis of AgBiS2 Nanocrystals.

Two major challenges exist before colloidal nanocrystal solar cells can take their place in the market: So far, these devices are based on Pb/Cd-containing nanocrystals, and second, the synthesis of these nanocrystals takes place in an inert atmosphere at elevated temperatures due to the use of air-sensitive chemicals. In this report, a room-temperature, ambient-air synthesis for nontoxic AgBiS2 nanocrystals is presented. As this method utilizes stable precursors, the need for the use of a protective environment is eliminated, enabling the large-scale production of AgBiS2 nanocrystals. The production cost of AgBiS2 NCs at room temperature and under ambient conditions reduces by ∼60% compared to prior reports based on hot injection, and the solar cells made of these nanocrystals yield a promising power conversion efficiency (PCE) of 5.5%, the highest reported to date for a colloidal nanocrystal material free of Pb or Cd synthesized at room temperature and under ambient conditions.

Origin of the Below-Bandgap Turn-On Voltage in Light-Emitting Diodes and the High VOC in Solar Cells Comprising Colloidal Quantum Dots with an Engineered Density of States.

The turn-on voltage of a light-emitting diode (LED) is an important parameter as it determines the power consumption of the LED and influences the effective power conversion efficiency. LEDs based on nanoscale engineering of the blended PbS [mixture of quantum dots (QDs) with two different bandgaps] colloidal QDs have recently shown record performance in the infrared region. One of the most intriguing findings for these blended devices is the substantially lower-than-bandgap turn-on voltage and the achievement of an open circuit voltage ( VOC), approaching the radiative limit. In this work, we provide new insight into the origin of these phenomena. We posit that the decrease in the effective density of states in the conduction and valence band of the emitter QDs in the blended structures modifies the chemical potential, which controls the turn-on voltage for LEDs through the modification of the photon flux and VOC for photovoltaic devices with quasi-Fermi level modification.

High-efficiency colloidal quantum dot infrared light-emitting diodes via engineering at the supra-nanocrystalline level.

Colloidal quantum dot (CQD) light-emitting diodes (LEDs) deliver a compelling performance in the visible, yet infrared CQD LEDs underperform their visible-emitting counterparts, largely due to their low photoluminescence quantum efficiency. Here we employ a ternary blend of CQD thin film that comprises a binary host matrix that serves to electronically passivate as well as to cater for an efficient and balanced carrier supply to the emitting quantum dot species. In doing so, we report infrared PbS CQD LEDs with an external quantum efficiency of ~7.9% and a power conversion efficiency of ~9.3%, thanks to their very low density of trap states, on the order of 1014 cm-3, and very high photoluminescence quantum efficiency in electrically conductive quantum dot solids of more than 60%. When these blend devices operate as solar cells they deliver an open circuit voltage that approaches their radiative limit thanks to the synergistic effect of the reduced trap-state density and the density of state modification in the nanocomposite.

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.

Infrared Solution-Processed Quantum Dot Solar Cells Reaching External Quantum Efficiency of 80% at 1.35 µm and Jsc in Excess of 34 mA cm-2.

Developing low-cost photovoltaic absorbers that can harvest the short-wave infrared (SWIR) part of the solar spectrum, which remains unharnessed by current Si-based and perovskite photovoltaic technologies, is a prerequisite for making high-efficiency, low-cost tandem solar cells. Here, infrared PbS colloidal quantum dot (CQD) solar cells employing a hybrid inorganic-organic ligand exchange process that results in an external quantum efficiency of 80% at 1.35 µm are reported, leading to a short-circuit current density of 34 mA cm-2 and a power conversion efficiency (PCE) up to 7.9%, which is a current record for SWIR CQD solar cells. When this cell is placed at the back of an MAPbI3 perovskite film, it delivers an extra 3.3% PCE by harnessing light beyond 750 nm.

Reducing Interface Recombination through Mixed Nanocrystal Interlayers in PbS Quantum Dot Solar Cells.

The performance of ZnO/PbS colloidal quantum dot (CQD)-based heterojunction solar cells is hindered by charge carrier recombination at the heterojunction interface. Reducing interfacial recombination can improve charge collection and the photocurrent of the device. Here we report the use of a mixed nanocrystal (MNC) buffer layer comprising zinc oxide nanocrystals and lead sulfide quantum dots at the respective heterojunction interface. Remote trap passivation of the PbS CQDs taking place within this MNC layer reduces interfacial recombination and electron back transfer which in turn improves charge collection efficiency. Upon the addition of the MNC layer, the overall power conversion efficiency increases from 9.11 to 10.16% and Short-circuit current density (JSC) increases from 23.54 to 25.23 mA/cm2. Optoelectronic characterization of the solar cells confirms that the effects underlying device improvement are reduced trap density and improved charge collection efficiency due to the presence of the MNC buffer layer.

Trap-State Suppression and Improved Charge Transport in PbS Quantum Dot Solar Cells with Synergistic Mixed-Ligand Treatments.

The power conversion efficiency of colloidal PbS-quantum-dot (QD)-based solar cells is significantly hampered by lower-than-expected open circuit voltage (VOC ). The VOC deficit is considerably higher in QD-based solar cells compared to other types of existing solar cells due to in-gap trap-induced bulk recombination of photogenerated carriers. Here, this study reports a ligand exchange procedure based on a mixture of zinc iodide and 3-mercaptopropyonic acid to reduce the VOC deficit without compromising the high current density. This layer-by-layer solid state ligand exchange treatment enhances the photovoltaic performance from 6.62 to 9.92% with a significant improvement in VOC from 0.58 to 0.66 V. This study further employs optoelectronic characterization, X-ray photoelectron spectroscopy, and photoluminescence spectroscopy to understand the origin of VOC improvement. The mixed-ligand treatment reduces the sub-bandgap traps and significantly reduces bulk recombination in the devices.