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InP/ZnS core/shell colloidal quantum dots (QDs) are promising candidates as Cd- and Pb-free emitters owing to their high photoluminescence quantum yield, narrow emission linewidth, and color tunabi...

Colloidal quantum dots are promising for low-cost optoelectronic devices such as solar cells, light-emitting diodes (LEDs), lasers, and photodetectors. InAs-based quantum dots (QDs) are well suited...

Bright, narrow spectrum infrared emitters, particularly Cd- and Pb-free materials, are of interest for bioimaging, photodetection, and telecommunications. InAs-based quantum dots (QDs) are promising emitters in this spectral range; however, efforts to increase the photoluminescence quantum yield (PLQY) tend to broaden the PL line width as a consequence of interfacial defect formation when thick shells, lattice-mismatched with the core, are employed. Here we report that developing a single-precursor complex for InZnP growth enables uniform shell growth that maintains the excellent size dispersion (6%) of the cores. The introduction of this intermediate layer is key to facilitate the subsequent growth of different shells to improve radiative recombination without sacrificing size uniformity. The growth of InAs/InZnP/ZnSe leads to a PL full-width at half-maximum (fwhm) of 100 meV at 1.12 eV with a PLQY of 14%. We then further introduce an additional GaP layer to increase the radiative/nonradiative relative rate. InAs/InZnP/GaP/ZnSe QDs reach a PLQY of 23% while maintaining a narrow fwhm.

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.

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.

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.

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 cm

Colloidal quantum dots (CQDs) are promising materials for IR light detection due to their tunable bandgap and solution processing; but to date, the time response of CQD IR photodiodes has been inferior to that provided by Si and InGaAs. We 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 could be mastered – offer a strong covalent character for low permittivity and fast operation. In initial studies, we found that existing covalent character led to imbalanced charge transport in InAs, the result of unpassivated surfaces and uncontrolled heavy doping. We report surface management using amphoteric ligand coordination and find that it 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 4x reduction in permittivity compared to PbS CQDs. The resulting photodiodes achieve a response time faster than 300 ps – a more than 100x improvement compared to the best previously-reported CQD photodiodes – combined with an external quantum efficiency (EQE) of 30% at 940 nm.

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.

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.

The external quantum efficiencies of state-of-the-art colloidal quantum dot light-emitting diodes (QLEDs) are now approaching the limit set by the out-coupling efficiency. However, the brightness of these devices is constrained by the use of poorly conducting emitting layers, a consequence of the present-day reliance on long-chain organic capping ligands. Here, we report how conductive and passivating halides can be implemented in Zn chalcogenide-shelled colloidal quantum dots to enable high-brightness green QLEDs. We use a surface management reagent, thionyl chloride (SOCl2), to chlorinate the carboxylic group of oleic acid and graft the surfaces of the colloidal quantum dots with passivating chloride anions. This results in devices with an improved mobility that retain high external quantum efficiencies in the high-injection-current region and also feature a reduced turn-on voltage of 2.5 V. The treated QLEDs operate with a brightness of 460,000 cd m−2, significantly exceeding that of all previously reported solution-processed LEDs. Green light-emitting diodes with a brightness of 460,000 cd m–2 and a low turn-on voltage of 2.5 V are enabled by the use of a chlorination treatment to provide conductive passivation of the devices.

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...

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.

Electromagnetic radiation emitted from hot objects represents a sizable source of energy, one that in most applications is not harvested efficiently. Even for a blackbody at 800 °C, the radiation intensity peaks near 2.7 μm wavelength, and this requires a semiconductor absorber having a band gap in the short-wavelength infrared and beyond to enable thermophotovoltaic (TPV) heat recovery. Here we report the first solution-processed TPV device to harvest efficiently 800 °C heat. The active layer consists of colloidal quantum dots (CQDs), infrared-absorbing nanoparticles synthesized using a scalable solution-based method, having 0.75 eV band gap. We construct rectifying junction devices based on controllably p- and n-doped CQD solids that benefit from a gradient in electron affinity that extends over the devices’ thickness. The gradient-doped architecture relies on engineered charge carrier drift and overcomes the existing limitations of small band gap CQD solids. The devices provide 2.7% efficiency in the c...

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.

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.

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.

Colloidal quantum dot (CQD) photovoltaics offer a promising approach to harvest the near-IR region of the solar spectrum, where half of the sun's power reaching the earth resides. High external quantum efficiencies have been obtained in the visible region in lead chalcogenide CQD photovoltaics. However, the corresponding efficiencies for band gap radiation in the near-infrared lag behind because the thickness of CQD photovoltaic layers from which charge carriers can be extracted is limited by short carrier diffusion lengths. Here, we investigate, using a combination of electrical and optical characterization techniques, ligand passivation strategies aimed at tuning the density and energetic distribution of charge trap states at PbS nanocrystal surfaces. Electrical and optical measurements reveal a more than 7-fold enhancement of the mobility-lifetime product of PbS CQD films treated with 3-mercaptopropionic acid (MPA) in comparison to traditional organic passivation strategies that have been examined in the literature. We show by direct head-to-head comparison that the greater mobility-lifetime products of MPA-treated devices enable markedly greater short-circuit current and higher power conversion efficiency under AM1.5 illumination. Our findings highlight the importance of selecting ligand treatment strategies capable of passivating a diversity of surface states to enable shallower and lower density trap distributions for better transport and more efficient CQD solar cells.

Colloidal quantum dots (CQDs) enable multijunction solar cells using a single material programmed using the quantum size effect. Here we report the systematic engineering of 1.6 eV PbS CQD solar cells, optimal as the front cell responsible for visible-wavelength harvesting in tandem photovoltaics. We rationally optimize each of the device's collecting electrodes-the heterointerface with electron-accepting TiO(2) and the deep-work-function hole-collecting MoO(3) for ohmic contact-for maximum efficiency. We report an open-circuit voltage of 0.70 V, the highest observed in a colloidal quantum dot solar cell operating at room temperature. We report an AM1.5 solar power conversion efficiency of 3.5%, the highest observed in1.5 eV bandgap CQD PV device.

Colloidal-quantum-dot (CQD) optoelectronics offer a compelling combination of solution processing and spectral tunability through quantum size effects. So far, CQD solar cells have relied on the use of organic ligands to passivate the surface of the semiconductor nanoparticles. Although inorganic metal chalcogenide ligands have led to record electronic transport parameters in CQD films, no photovoltaic device has been reported based on such compounds. Here we establish an atomic ligand strategy that makes use of monovalent halide anions to enhance electronic transport and successfully passivate surface defects in PbS CQD films. Both time-resolved infrared spectroscopy and transient device characterization indicate that the scheme leads to a shallower trap state distribution than the best organic ligands. Solar cells fabricated following this strategy show up to 6% solar AM1.5G power-conversion efficiency. The CQD films are deposited at room temperature and under ambient atmosphere, rendering the process amenable to low-cost, roll-by-roll fabrication.

Colloidal quantum dot (CQD) photovoltaics combine low-cost solution processibility with quantum size-effect tunability to match absorption with the solar spectrum. Recent advances in CQD photovoltaics have led to 3.6% AM1.5 solar power conversion efficiencies. Here we report CQD photovoltaic devices on transparent conductive oxides and show that our devices rely on the establishment of a depletion region for field-driven charge transport and separation. The resultant depleted-heterojunction solar cells provide a 5.1% AM1.5 power conversion efficiency. The devices employ infrared-bandgap size-effect-tuned PbS colloidal quantum dots, enabling broadband harvesting of the solar spectrum. (C) 2010 Elsevier B.V. All rights reserved.

Researchers report a colloidal quantum-dot solar cell that features two junctions, each designed to absorb and convert different spectral bands of light within the solar spectrum. The device offers a power conversion efficiency of 4.2% and an open circuit voltage of 1.06 V.

The influence of quantum confinement on the one- and two-photon absorption spectra (1PA and 2PA) of PbS and PbSe semiconductor quantum dots (QDs) is investigated. The results show 2PA peaks at energies where only 1PA transitions are predicted and 1PA peaks where only 2PA transitions are predicted by the often used isotropic k x p four-band envelope function formalism. The first experimentally identified two-photon absorption peak coincides with the energy of the first one photon allowed transition. This first two-photon peak cannot be explained by band anisotropy, verifying that the inversion symmetry of the wave functions is broken and relaxation of the parity selection rules has to be taken into account to explain optical transitions in lead-salt QDs. Thus, while the band anisotropy of the bulk semiconductor plays a role in the absorption spectra, especially for the more anisotropic PbSe QDs, a complete model of the absorption spectra, for both 1PA and 2PA, must also include symmetry breaking of the quantum confined wave functions. These studies clarify the controversy of the origin of spectral features in lead-salt QDs.

Solution-processed optoelectronic materials offer a route to low-cost photodetectors, large-area solar cells, and integrated optical sources. While significant progress has been reported in organic and polymer spin-cast optoelectronics, colloidal quantum dots offer a distinct further advantage — the convenient tuning of absorption onset via the quantum size effect. Electronic transport has recently been enhanced in sizeeffect-tuned colloidal quantum dot films using ligand exchange, resulting in ultrasensitive photodetectors in both visible and infrared wavelengths; however, solid-film ligand exchange generally results in rough film morphologies, incompatible with high-uniformity image sensors. The frequent cracking of films is attributed to the significant loss of volume during the exchange process. Here, we report a new route to visiblewavelength spin-cast PbS-nanocrystal photoconductive photodetectors with sub-1% roughness, compared to the 10% roughness obtained using previously reported approaches. The new procedure yields devices that exhibit 10 A W 1 responsivities and reveal an added significant advantage: when illumination conditions change, the photodetectors respond with a single time constant of 20 ms. This compares very favorably with the multisecond and multi-time-constant response of previously reported PbS-nanocrystal photoconductive photodetectors. To be relevant to imaging applications, a top-surface photodetector must exhibit three key traits: high sensitivity to the illumination of interest, spatial uniformity across an imaging array, and video-frame-rate speed of response. Sensitivity derives from the photoconductive gain—the number of electrical carriers collected per incident photon given at a specific light level—and the noise-equivalent power (NEP)—the lowest light level that can be distinguished from noise. Spatial uniformity better than 1% across a pixel array is sought to minimize the introduction of spatial noise, which produces an image photoresponse nonuniformity of the same order. Speed of response allowing video-capture frame rates demands sub-100 ms time constants. Large photoconductive gains, as high as thousands of electrons collected per incident photon, and large dark resistivities have recently been shown to enable record high

Solution-processed semiconductors are compatible with a range of substrates, which enables their direct integration with organic circuits, microfluidics, optical circuitry and commercial microelectronics. Ultrasensitive photodetectors based on solution-process colloidal quantum dots operating in both the visible and infrared have been demonstrated, but these devices have poor response times (on the scale of seconds) to changes in illumination, and rapid-response devices based on a photodiode architecture suffer from low sensitivity. Here, we show that the temporal response of these devices is determined by two components--electron drift, which is a fast process, and electron diffusion, which is a slow process. By building devices that exclude the diffusion component, we are able to demonstrate a >1,000-fold improvement in the sensitivity-bandwidth product of tuneable colloidal-quantum-dot photodiodes operating in the visible and infrared.

Solution-processed nanocrystal optoelectronic devices offer large-area coverage, low cost, and compatibility with a wide range of substrates. Recently, photodetectors and photovoltaics based on spin-coated nanoparticle films have shown tremendous progress in performance. However, high-performance devices reported to date have employed either Pb or Cd, raising concerns regarding environmental impact and regulatory acceptance. Herein we report a high-performance solution-processed photodetector based instead on Bi2S3 nanocrystals. The devices exhibit photoconductive gain on the order of 10 combined with temporal response on the 10 ms time scale. The resultant solution-processed Bi2S3 nanorod photoconductive photodetectors are of interest in visible and near-infrared (NIR) wavelength applications requiring video-frame-rate temporal response.

Photoconductive photodetectors fabricated using simple solution-processing have recently been shown to exhibit high gains (1000) and outstanding sensitivities ( D*10(13) Jones). One ostensible disadvantage of exploiting photoconductive gain is that the temporal response is limited by the release of carriers from trap states. Here we show that it is possible to introduce specific chemical species onto the surfaces of colloidal quantum dots to produce only a single, desired trap state having a carefully selected lifetime. In this way we demonstrate a device that exhibits an attractive photoconductive gain (10) combined with a response time ( approximately 25 ms) useful in imaging. We achieve this by preserving a single surface species, lead sulfite, while eliminating lead sulfate and lead carboxylate. In doing so we preserve the outstanding sensitivity of these devices, achieving a specific detectivity of 10(12) Jones in the visible, while generating a temporal response suited to imaging applications.

We report transient absorption saturation measurements on lead sulfide colloidal nanocrystals at the first and second exciton energies and fit the results to a model incorporating intraband and interband relaxation processes. We study in detail the Auger recombination from the first excited state, which takes place when more than one electron-hole pair is excited in a dot. We find an Auger coefficient of 4.5 x 10 -30 cm 6 /s for dots of 5.5 nm diameter, and observe saturation of the absorption bleaching when the (8-fold degenerate) first level is filled. We develop a model for the absorption dynamics using Poisson statistics and find a good fit with our experimental measurements.

One billion image sensors worldwide render optical images as digital photographs in video cameras, still cameras and camera phones. These silicon-based sensors monolithically integrate photodetection with electronic readout. However, silicon photodiodes rely on a smaller bandgap than that required for visible detection; this degrades visible-wavelength sensitivity and produces unwanted infrared sensitivity. Thin-film top-surface visible photodetectors have therefore been investigated based on amorphous1, organic2 and colloidal quantum-dot3 semiconductors. However, none of these devices has exhibited visible sensitivity approaching that of silicon. Here we report a sensitive solution-processed photodetector that, across the entire visible spectrum, exhibits D* (normalized detectivity) greater than 5 × 1012 Jones (a unit of detectivity equivalent to cm Hz1/2 W−1). A photoconductive gain of >100 has been measured, facilitating high-fidelity electronic readout, and the linear dynamic range is greater than 60 dB, as required for high-contrast applications. These photodetectors are also compatible with flexible organic-based electronics.

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.

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.

We report a method for producing colloidal crystals heavily loaded with PbS quantum dots (QDs). The approach employed uses capillary forces to load the QDs in the interstitial voids of the colloid crystals and yields highly ordered structures with a high loading of QDs. The infiltration process is qualitatively monitored using confocal fluorescence microscopy and scanning electron microscopy. The optical properties of the resulting composite structure are examined using optical spectroscopy. The shift in the stopband resulting from the infiltration of the colloid crystal shows that the PbS QDs occupy nearly 100 % of the volume of the interstitial space.

We report efficient electroluminescence in the near-infrared from PbS–MEH-PPV (poly(2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene)) large-area, solution-cast nanocomposite devices. We employ multivariate optimization of the structural and materials components that govern the radiative, energy-transfer, and bipolar-injection efficiencies into the devices. As a result, we report an external electroluminescence quantum efficiency of 0.27 %, which corresponds to an internal electroluminescence quantum efficiency of 1.9 %. The very best devices exhibit internal-radiative-efficiency-limited performance and not transport- or capture-limited performance, indicating that further gains in efficiency may be achieved if the internal radiative efficiency of the nanocrystal–polymer composite can be further increased without compromising transfer and device bipolar-injection efficiency.

We investigate the effect of film morphology and phase segregation in polymer/colloidal PbS nanocrystal films on the near-infrared photoluminescence quantum efficiency (PLQE) of the nanocrystals. A direct correlation between the size of closed packed nanocrystal phase separated domains and lower PLQE was established. Films with a near-infrared PLQE of up to 12% have been prepared.

In contrast to traditional semiconductors, conjugated polymers provide ease of processing, low cost, physical flexibility and large area coverage. These active optoelectronic materials produce and harvest light efficiently in the visible spectrum. The same functions are required in the infrared for telecommunications (1,300-1,600 nm), thermal imaging (1,500 nm and beyond), biological imaging (transparent tissue windows at 800 nm and 1,100 nm), thermal photovoltaics (1,900 nm), and solar cells (800-2,000 nm). Photoconductive polymer devices have yet to demonstrate sensitivity beyond approximately 800 nm (refs 2,3). Sensitizing conjugated polymers with infrared-active nanocrystal quantum dots provides a spectrally tunable means of accessing the infrared while maintaining the advantageous properties of polymers. Here we use such a nanocomposite approach in which PbS nanocrystals tuned by the quantum size effect sensitize the conjugated polymer poly[2-methoxy-5-(2'-ethylhexyloxy-p-phenylenevinylene)] (MEH-PPV) into the infrared. We achieve, in a solution-processed device and with sensitivity far beyond 800 nm, harvesting of infrared-photogenerated carriers and the demonstration of an infrared photovoltaic effect. We also make use of the wavelength tunability afforded by the nanocrystals to show photocurrent spectra tailored to three different regions of the infrared spectrum.

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. Colloidal quantum dots are promising materials for efficient low-cost solar cells and optoelectronics, but their performance does not improve with increased carrier mobility. Here, the authors show instead that the spacing between recombination centres controls the diffusion length.

We report photoconductivity at infrared wavelengths, 975–1300nm, from a polymer∕nanocrystal quantum dot composite. Biased films of the conjugated polymer poly[2-methoxy-5-(2′-ethylhexyloxy-p-phenylenevinylene)] (MEH-PPV) sensitized with PbS nanocrystals (∼5nm diameter) demonstrate photocurrent at wavelengths beyond the response of the polymer and corresponding to the absorption of the nanocrystals. The photocurrent is attributed to absorption in the nanocrystals with subsequent hole transfer to the polymer and had an internal quantum efficiency of ∼5×10−6to∼10−5charges∕photon at 5V bias.

We quantify experimentally the efficiency of excitation transfer from a semiconducting polymer matrix to quantum dot nanocrystals. We study 5±0.5 nm PbS nanocrystals embedded in MEH-PPV (poly[2-methoxy-5-(2′-ethylhexyloxy-p-phenylenevinylene)]) polymer. We determine the excitation transfer efficiency from normalized photoluminescence excitation measurements. When the composites are made using as-synthesized PbS nanocrystals capped by oleate ligands, the excitation transfer efficiency is about 20%. Replacing these ligands with shorter chains results in a factor-of-3 enhancement in the excitation transfer efficiency. Our findings provide guidance to the realization of efficient electroluminescent devices.

Electroluminescent devices combining two families of PbS colloidal quantum dots to achieve spectrally tailored two-color emission are reported. Depending on device structure selected—the use of two separated layers versus a mixture of nanocrystals—the structures demonstrated light emission either in two infrared frequency peaks corresponding to the spectral region 1.1–1.6 μm or in a wide band spanning this same spectral region. Separated-layer devices exhibit wide tunability in the relative intensity of the two peaks by varying excitation conditions. Replacing oleate with octodecylamine ligands increases the internal electroluminescence efficiency to 3.1%.

Semiconductors with bandgaps in the near- to mid-infrared can harvest solar light that is otherwise wasted by conventional single-junction solar cell architectures. In particular, colloidal quantum dots (CQDs) are promising materials since they are cost-effective, processed from solution, and have a bandgap that can be tuned into the infrared (IR) via the quantum size effect. These characteristics enable them to harvest the infrared portion of the solar spectrum to which silicon is transparent. To date, IR CQD solar cells have been made using a wasteful and complex sequential layer-by-layer process. Here, we demonstrate ∼1 eV bandgap solar-harvesting CQD films deposited in a single step. By engineering a fast-drying solvent mixture for metal iodide-capped CQDs, we deposited active layers greater than 200 nm in thickness having a mean roughness less than 1 nm. We integrated these films into infrared solar cells that are stable in air and exhibit power conversion efficiencies of 3.5% under illumination by t...

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.

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.

We discuss strategies to reduce midgap trap state densities in colloidal quantum dot films and requirements to control doping type and magnitude. We demonstrate that these improvements result in colloidal quantum dot solar cells with certified 7.0% efficiency.

The highest-performing colloidal quantum dot (CQD) photovoltaics (PV) reported to date have relied on high-temperature (500°C) annealing of electron-accepting TiO2. Room-temperature processing reduces energy payback time and manufacturing cost, enables flexible substrates, and permits tandem solar cells that integrate a small-bandgap back cell atop a low-thermal-budget larger-bandgap front cell. Here we report an electrode strategy that enables a depleted-heterojunction CQD PV device to be fabricated entirely at room temperature. We find that simply replacing the high-temperature-processed TiO2 with a sputtered version of the same material leads to poor performance due to the low mobility of the sputtered oxide. We develop instead a two-layer donor-supply electrode (DSE) in which a highly doped, shallow work function layer supplies a high density of free electrons to an ultrathin TiO2 layer via charge-transfer doping. Using the DSE we build all-room-temperature-processed small-bandgap (1 eV) colloidal quantum dot solar cells having 4% solar power conversion efficiency and high fill factor. These 1 eV bandgap cells are suitable for use as the back junction in tandem solar cells. The DSE concept, combined with control over TiO2 stoichiometry in sputtering, provides a much-needed tunable electrode to pair with quantum-size-effect CQD films.

Colloidal quantum dots offer broad tuning of semiconductor bandstructure via the quantum size effect. Devices involving a sequence of layers comprised of quantum dots selected to have different diameters, and therefore bandgaps, offer the possibility of funneling energy toward an acceptor. Here we report a quantum funnel that efficiently conveys photoelectrons from their point of generation toward an intended electron acceptor. Using this concept we build a solar cell that benefits from enhanced fill factor as a result of this quantum funnel. This concept addresses limitations on transport in soft condensed matter systems and leverages their advantages in large-area optoelectronic devices and systems.

Lead sulfide colloidal quantum dot (CQD) solar cells with a solar power conversion efficiency of 5.6% are reported. The result is achieved through careful optimization of the titanium dioxide electrode that serves as the electron acceptor. Metal-ion-doped sol-gel-derived titanium dioxide electrodes produce a tunable-bandedge, well-passivated materials platform for CQD solar cell optimization.

The time dynamics of the photoexcited carriers and carrier-multiplication efficiencies in PbS quantum dots (QDs) are investigated. In particular, we report on the carrier dynamics, including carrier multiplication, as a function of QD size and compare them to the bulk value. We show that the intraband 1P→1S decay becomes faster for smaller QDs, in agreement with the absence of a phonon bottleneck. Furthermore, as the size of the QDs decreases, the energy threshold for carrier multiplication shifts from the bulk value to higher energies. However, the energy threshold shift is smaller than the band-gap shift and, therefore, for the smallest QDs, the threshold approaches 2.35 Eg, which is close to the theoretical energy conservation limit of twice the band gap. We also show that the carrier-multiplication energy efficiency increases with decreasing QD size. By comparing to theoretical models, our results suggest that impact ionization is sufficient to explain carrier multiplication in QDs.

The first solution-processed depleted bulk heterojunction colloidal quantum dot solar cells are presented. The architecture allows high absorption with full depletion, thereby breaking the photon absorption/carrier extraction compromise inherent in planar devices. A record power conversion of 5.5% under simulated AM 1.5 illumination conditions is reported.