Efficient Infrared Solar Cells Employing Quantum Dot Solids with Strong Inter-Dot Coupling and Efficient Passivation

Lead chalcogenide quantum dot (QD) infrared (IR) solar cells are promising devices for breaking through the theoretical efficiency limit of single-junction solar cells by harvesting the low-energy IR photons that cannot be utilized by common devices. However, the device performance of QD IR photovoltaic is limited by the restrictive relation between open-circuit voltages (V_OC) and short circuit current densities (J_SC), caused by the contradiction between surface passivation and electronic coupling of QD solids. Here, a strategy is developed to decouple this restriction via epitaxially coating a thin PbS shell over the PbSe QDs (PbSe/PbS QDs) combined with in situ halide passivation. The strong electronic coupling from the PbSe core gives rise to significant carrier delocalization, which guarantees effective carrier transport. Benefited from the protection of PbS shell and in situ halide passivation, excellent trap-state control of QDs is eventually achieved after the ligand exchange. By a fine control of the PbS shell thickness, outstanding IR J_SC of 6.38 mA cm⁻² and IR V_OC of 0.347 V are simultaneously achieved under the 1100 nm-filtered solar illumination, providing a new route to unfreeze the trade-off between V_OC and J_SC limited by the photoactive layer with a given bandgap.     

Core/Shell PbSe/PbS QDs TiO2 Heterojunction Solar Cell

Quasi type‐II PbSe/PbS quantum dots (QDs) are employed in a solid state high efficiency QD/TiO₂ heterojunction solar cell. The QDs are deposited using layer‐by‐layer deposition on a half‐micrometer‐thick anatase TiO₂ nanosheet film with (001) exposed facets. Theoretical calculations show that the carriers in PbSe/PbS quasi type‐II QDs are delocalized over the entire core/shell structure, which results in better QD film conductivity compared to PbSe QDs. Moreover, PbS shell permits better stability and facile electron injection from the QDs to the TiO₂ nanosheets. To complete the electrical circuit of the solar cell, a Au film is evaporated as a back contact on top of the QDs. This PbSe/PbS QD/TiO₂ heterojunction solar cell produces a light to electric power conversion efficiency (η) of 4% with short circuit photocurrent (J_sc) of 17.3 mA/cm². This report demonstrates highly efficient core/shell near infrared QDs in a QD/TiO₂ heterojunction solar cell.     

Matrix Manipulation of Directly-Synthesized PbS Quantum Dot Inks Enabled by Coordination Engineering

The direct-synthesis of conductive PbS quantum dot (QD) ink is facile, scalable, and low-cost, boosting the future commercialization of optoelectronics based on colloidal QDs. However, manipulating the QD matrix structures still is a challenge, which limits the corresponding QD solar cell performance. Here, for the first time a coordination-engineering strategy to finely adjust the matrix thickness around the QDs is presented, in which halogen salts are introduced into the reaction to convert the excessive insulating lead iodide into soluble iodoplumbate species. As a result, the obtained QD film exhibits shrunk insulating shells, leading to higher charge carrier transport and superior surface passivation compared to the control devices. A significantly improved power-conversion efficiency from 10.52% to 12.12% can be achieved after the matrix engineering. Therefore, the work shows high significance in promoting the practical application of directly synthesized PbS QD inks in large-area low-cost optoelectronic devices.     

Passivating {100} Facets of PbS Colloidal Quantum Dots via Perovskite Bridges for Sensitive and Stable Infrared Photodiodes

Solution-processed PbS colloidal quantum dots (CQDs) are promising optoelectronic materials for next-generation infrared imagers due to their monolithic integratability with silicon readout circuit and tunable bandgap controlled by CQDs size. However, large-size PbS CQDs (diameter >4 nm) for longer shortwave-infrared photodetection consist mainly of {100} facets with incomplete surface passivation and unsatisfied stability. Here, it is reported that perovskite-bridged PbS CQDs, in which the {100} facets of the CQDs are epitaxially bridged with CsPbI_3–xBr_x perovskite, can achieve improved passivation and enhanced stability in comparison with the traditional strategies. The resultant infrared CQDs photodiodes exhibit significantly reduced dark current, nearly 50% enhanced photoresponse, and improved work stability. These superior properties synergistically produce the most balanced performance (with a high −3 dB bandwidth of 42 kHz and an impressive specific detectivity of 6.2 × 10¹² Jones) among the reported CQDs photodetectors.     

Crystal growth and equilibrium crystal shapes of silicon in the melt

The crystal growth shape (CGS) and equilibrium crystal shape (ECS) of silicon in Si melt are observed using in situ observation. Fully faceted silicon CGSs, which are dominated by the {111} facets, are observed from the {112} and {110} orientation. Silicon CGS in three‐dimensional in Si melt is octahedral in shape, bounded by {111} facets. Silicon ECSs in the melt are obtained by the relaxation from the CGSs and exhibit the {111} facets separated by curved interface. Copyright © 2012 John Wiley & Sons, Ltd.     

PbS/CdS/ZnS Quantum Dots: A Multifunctional Platform for In Vivo Near‐Infrared Low‐Dose Fluorescence Imaging

Over the past decade, near‐infrared (NIR)‐emitting nanoparticles have increasingly been investigated in biomedical research for use as fluorescent imaging probes. Here, high‐quality water‐dispersible core/shell/shell PbS/CdS/ZnS quantum dots (hereafter QDs) as NIR imaging probes fabricated through a rapid, cost‐effective microwave‐assisted cation exchange procedure are reported. These QDs have proven to be water dispersible, stable, and are expected to be nontoxic, resulting from the growth of an outer ZnS shell and the simultaneous surface functionalization with mercaptopropionic acid ligands. Care is taken to design the emission wavelength of the QDs probe lying within the second biological window (1000–1350 nm), which leads to higher penetration depths because of the low extinction coefficient of biological tissues in this spectral range. Furthermore, their intense fluorescence emission enables to follow the real‐time evolution of QD biodistribution among different organs of living mice, after low‐dose intravenous administration. In this paper, QD platform has proven to be capable (ex vivo and in vitro) of high‐resolution thermal sensing in the physiological temperature range. The investigation, together with the lack of noticeable toxicity from these PbS/CdS/ZnS QDs after preliminary studies, paves the way for their use as outstanding multifunctional probes both for in vitro and in vivo applications in biomedicine.     

Controlled Fabrication of PbS Quantum‐Dot/Carbon‐Nanotube Nanoarchitecture and its Significant Contribution to Near‐Infrared Photon‐to‐Current Conversion

A solution‐processed nanoarchitecture based on PbS quantum dots (QDs) and multi‐walled carbon nanotubes (MWCNTs) is synthesized by simply mixing the pre‐synthesized high‐quality PbS QDs and oleylamine (OLA) pre‐functionalized MWCNTs. Pre‐functionalization of MWCNTs with OLA is crucial for the attachment of PbS QDs and the coverage of QDs on the surface of MWCNTs can be tuned by varying the ratio of PbS QDs to MWCNTs. The apparent photoluminescence (steady‐state emission and fluorescence lifetime) “quenching” effect indicates efficient charge transfer from photo‐excited PbS QDs to MWCNTs. The as‐synthesized PbS‐QD/MWCNT nanoarchitecture is further incorporated into a hole‐conducting polymer poly(3‐hexylthiophene)‐(P3HT), forming the P3HT:PbS‐QD/MWCNT nanohybrid, in which the PbS QDs act as a light harvester for absorbing irradiation over a wide wavelength range of the solar spectrum up to near infrared (NIR, ≈1430 nm) range; whereas, the one‐dimensional MWCNTs and P3HT are used to collect and transport photoexcited electrons and holes to the cathode and anode, respectively. Even without performing the often required “ligand exchange” to remove the long‐chained OLA ligands, the built nanohybrid photovoltaic (PV) device exhibits a largely enhanced power conversion efficiency (PCE) of 3.03% as compared to 2.57% for the standard bulk hetero‐junction PV cell made with P3HT and [6,6]‐Phenyl‐C₆₁‐Butyric Acid Methyl Ester (PCBM) mixtures. The improved performance of P3HT:PbS‐QD/MWCNT nanohybrid PV device is attributed to the significantly extended absorption up to NIR by PbS QDs as well as the effectively enhanced charge separation and transportation due to the integrated MWCNTs and P3HT. Our research results suggest that properly integrating QDs, MWCNTs, and polymers into nanohybrid structures is a promising approach for the development of highly efficient PV devices.     

Fast,Air‐Stable Infrared Photodetectors based on Spray‐Deposited Aqueous HgTe Quantum Dots

The ability to detect near‐infrared and mid‐infrared radiation has spawned great interest in colloidal HgTe quantum dots (QDs). In contrast to the studies focused on extending the spectral range of HgTe QD devices, the temporal response, another figure of merit for photodetectors, is rarely investigated. In this work, a single layer, aqueous HgTe QD based photoconductor structure with very fast temporal response (up to 1 MHz 3 dB bandwidth) is demonstrated. The device is fabricated using a simple spray‐coating process and shows excellent stability in ambient conditions. The origin of the remarkably fast time response is investigated by combining light intensity‐dependent transient photocurrent, temperature‐dependent photocurrent, and field‐effect transistor (FET) measurements. The charge carrier mobility, as well as the energy levels and carrier lifetimes associated with the trap states in the QDs, are identified. The results suggest that the temporal response is dominated by a fast bimolecular recombination process under high light intensity and by a trap‐mediated recombination process at low light intensity. Interestingly, it was found that the gain and time response of aqueous HgTe QD‐based photoconductors can be tuned by controlling the QD size and surface chemistry, which provides a versatile approach to optimize the photodetectors with selectable sensitivity and operation bandwidth.     

Capping vertically aligned InGaAs/GaAs(Sb) quantum dots with a AlGaAsSb spacer layer in intermediate‐band solar cell devices

This study demonstrated the feasibility of fabricating a highly stacked vertically aligned InGaAs/GaAs(Sb) quantum dot (QD) structure with an AlGaAsSb spacer layer for improving the device performance of QD intermediate‐band solar cell (QD‐IBSC) devices. The power‐dependent photoluminescence measurements of the proposed structure revealed a blueshift in the QD ground‐state emissions when the excitation power was increased, indicating the formation of an intermediate band inside the QD structure. Capping the InGaAs QDs with a GaAsSb layer prevented the QDs from collapsing because there was less In–Ga intermixing between the QDs and GaAsSb layer. In addition to maintaining the QD structure, the carrier lifetime was extended by tuning the energy band alignment of the InGaAs/GaAsSb QD structure. Inserting the AlGaAsSb layer into the spacer layer increased the band gap, which in turn increased the open‐circuit voltage of the QD‐IBSC. The QD‐IBSC in this work shows an extension of external‐quantum efficiency by up to 1200 nm (compared with a GaAs reference cell) through the absorption by QDs and increased the open‐circuit voltage from 0.67 to 0.70 V by adopting the AlGaAsSb spacer layer. These results confirm that adopting a columnar InGaAs/GaAs(Sb) QD structure with a AlGaAsSb spacer layer can enhance the performance of QD‐IBSC devices. Copyright © 2016 John Wiley & Sons, Ltd.     

Overcoming the Cut‐Off Charge Transfer Bandgaps at the PbS Quantum Dot Interface

Light harvesting from large size of semiconductor PbS quantum dots (QDs) with a bandgap of less than 1 eV is one of the greatest challenges precluding the development of PbS QD‐based solar cells because the interfacial charge transfer (CT) from such QDs to the most commonly used electron acceptor materials is very inefficient, if it occurs at all. Thus, an alternative electron‐accepting unit with a new driving force for CT is urgently needed to harvest the light from large‐sized PbS QDs. Here, a cationic porphyrin is utilized as a new electron acceptor unit with unique features that bring the donor–acceptor components into close molecular proximity, allowing ultrafast and efficient electron transfer for QDs of all sizes, as inferred from the drastic photoluminescence quenching and the ultrafast formation of the porphyrin anionic species. The time‐resolved results clearly demonstrate the possibility of modulating the electron transfer process between PbS QDs and porphyrin moieties not only by the size quantization effect but also by the interfacial electrostatic interaction between the positively charged porphyrin and the negatively charged QDs. This approach provides a new pathway for engineering QD‐based solar cells that make the best use of the diverse photons making up the Sun's broad irradiance spectrum.     

Two strategies to enhance efficiency of PbS quantum dot solar cells: Removing surface organic ligands and configuring a bilayer heterojunction with a new conjugated polymer

We present two novel techniques for improving the efficiency of PbS quantum dot (QD) solar cells. First, plasma was applied to QD film with the aim of removing surface organic ligands, and then the chemical and optical properties of the QDs were investigated. Second, a thin layer of conjugated polymer was then deposited on top of the plasma-treated PbS QD film as a transportation layer for holes. The charge separation and subsequent transfer dynamics were examined, as were the resultant photovoltaic characteristics, according to the kind of polymer used. The developed device, which comprises a bilayer heterojunction of plasma-treated PbS QDs and poly[2,6-(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole)-alt-4,7(2,1,3-benzothiadiazole)] (PSBTBT), showed not only broad-range absorption of the solar spectrum, but also high charge transfer efficiency prior to recombination. This results in a largely increased power conversion efficiency (PCE) of 1.76%, compared to the 0.7% value of a PbS QD-only device not subjected to plasma treatment. This indicates that the proposed techniques are very useful for improving the efficiency of inorganic QD-based solar cells.     

Below‐bandgap absorption in InAs/GaAs self‐assembled quantum dot solar cells

A new approach to derive the below‐bandgap absorption in InAs/GaAs self‐assembled quantum dot (QD) devices using room temperature external quantum efficiency measurement results is presented. The significance of incorporating an extended Urbach tail absorption in analyzing QD devices is demonstrated. This tail is used to evaluate the improvement in the photo‐generated current. The wetting layer and QD absorption contributions are separated from the tail absorption. Several absorption peaks due to QD excited states and potentially different size QDs are observed. An inhomogeneous broadening of 25 meV arising from the variance in the size of QDs is derived. Copyright © 2014 John Wiley & Sons, Ltd.     

Morphological dependence of passive epitaxial oxide films on nanoparticles of iron

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Cation‐Exchange Synthesis of Highly Monodisperse PbS Quantum Dots from ZnS Nanorods for Efficient Infrared Solar Cells

Infrared solar cells that utilize low‐bandgap colloidal quantum dots (QDs) are promising devices to enhance the utilization of solar energy by expanding the harvested photons of common photovoltaics into the infrared region. However, the present synthesis of PbS QDs cannot produce highly efficient infrared solar cells. Here, a general synthesis is developed for low‐bandgap PbS QDs (0.65–1 eV) via cation exchange from ZnS nanorods (NRs). First, ZnS NRs are converted to superlattices with segregated PbS domains within each rod. Then, sulfur precursors are released via the dissolution of the ZnS NRs during the cation exchange, which promotes size focusing of PbS QDs. PbS QDs synthesized through this new method have the advantages of high monodispersity, ease‐of‐size control, in situ passivation of chloride, high stability, and a “clean” surface. Infrared solar cells based on these PbS QDs with different bandgaps are fabricated, using conventional ligand exchange and device structure. All of the devices produced in this manner show excellent performance, showcasing the high quality of the PbS QDs. The highest performance of infrared solar cells is achieved using ≈0.95 eV PbS QDs, exhibiting an efficiency of 10.0% under AM 1.5 solar illumination, a perovskite‐filtered efficiency of 4.2%, and a silicon‐filtered efficiency of 1.1%.     

Building Quantum Dots into Solids with Well‐Defined Shapes

Quantum dots (QDs) chemically synthesized in solution at a higher temperature (85 °C) were built in situ into a variety of three‐dimensional (3D) close‐packed QD ensembles (QD solids) with well‐defined shapes: needles, disks, rods, spheres, bundles, stars, ribbons, and transition structures (TSs). Design strategies using a novel cold‐treatment (–25 to 0 °C) process immediately following the synthesis of the QDs provided control over these shapes, independently from the II–VI materials used. Transformation occurred between different shapes by the rearrangement of the QDs within the QD ensembles. The QD solids were characterized by advanced electron microscopy and photoluminescence spectroscopy. The cold treatment strategy is versatile and has been applied to several II–VI QDs (CdS, ZnS, and CdSe) and may be extended to other QD systems and other chemical approaches.     

Origins of Low Quantum Efficiencies in Quantum Dot LEDs

The promise for next generation light‐emitting device (LED) technologies is a major driver for research on nanocrystal quantum dots (QDs). The low efficiencies of current QD‐LEDs are often attributed to luminescence quenching of charged QDs through Auger‐processes. Although new QD chemistries successfully suppress Auger recombination, high performance QD‐LEDs with these materials have yet to be demonstrated. Here, QD‐LED performance is shown to be significantly limited by the electric field. Experimental field‐dependent photoluminescence decay studies and tight‐binding simulations are used to show that independent of charging, the electric field can strongly quench the luminescence of QD solids by reducing the electron and hole wavefunction overlap, thereby lowering the radiative recombination rate. Quantifying this effect for a series of CdSe/CdS QD solids reveals a strong dependence on the QD band structure, which enables the outline of clear design strategies for QD materials and device architectures to improve QD‐LED performance.     

PbS and CdS Quantum Dot‐Sensitized Solid‐State Solar Cells: “Old Concepts,New Results”

Lead sulfide (PbS) and cadmium sulfide (CdS) quantum dots (QDs) are prepared over mesoporous TiO₂ films by a successive ionic layer adsorption and reaction (SILAR) process. These QDs are exploited as a sensitizer in solid‐state solar cells with 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenylamine)‐9,9′‐spirobifluorene (spiro‐OMeTAD) as a hole conductor. High‐resolution transmission electron microscopy (TEM) images reveal that PbS QDs of around 3 nm in size are distributed homogeneously over the TiO₂ surface and are well separated from each other if prepared under common SILAR deposition conditions. The pore size of the TiO₂ films and the deposition medium are found to be very critical in determining the overall performance of the solid‐state QD cells. By incorporating promising inorganic QDs (PbS) and an organic hole conductor spiro‐OMeTAD into the solid‐state cells, it is possible to attain an efficiency of over 1% for PbS‐sensitized solid‐state cells after some optimizations. The optimized deposition cycle of the SILAR process for PbS QDs has also been confirmed by transient spectroscopic studies on the hole generation of spiro‐OMeTAD. In addition, it is established that the PbS QD layer plays a role in mediating the interfacial recombination between the spiro‐OMeTAD⁺ cation and the TiO₂ conduction band electron, and that the lifetime of these species can change by around 2 orders of magnitude by varying the number of SILAR cycles used. When a near infrared (NIR)‐absorbing zinc carboxyphthalocyanine dye (TT1) is added on top of the PbS‐sensitized electrode to obtain a panchromatic response, two signals from each component are observed, which results in an improved efficiency. In particular, when a CdS‐sensitized electrode is first prepared, and then co‐sensitized with a squarine dye (SQ1), the resulting color change is clearly an addition of each component and the overall efficiencies are also added in a more synergistic way than those in PbS/TT1‐modified cells because of favorable charge‐transfer energetics.     

Multiple Function Synchronous Optimization by PbS Quantum Dots for Highly Stable Planar Perovskite Solar Cells with Efficiency Exceeding 23%

Colloidal lead sulfide (PbS) quantum dots (QDs), which possess quantum confinement effect and processing compatibility with perovskite, are regarded as an excellent material for optimizing perovskite solar cells (PSCs). However, the existing PSCs optimized by PbS QDs are still facing the challenges of poor performance of the charge transport layers, low utilization in the near-infrared (NIR) region, and unsuitable energy level alignment, which limit the improvement of power conversion efficiency (PCE). Herein, a synchronous optimization strategy is realized via simultaneously introducing PbS QDs into SnO₂ electron transport layer and employing rare-earth-doped PbS QDs (Eu:PbS QDs) film with hydrophobic chain ligands as the NIR light-absorping layer and hole transport layer (HTL) of devices. PbS QDs effectively decrease the density of trap states by passivating defects. Eu:PbS QDs film with adjustable bandgap is employed as an absorption layer to broaden the NIR spectral absorption. The well-matched energy level between Eu:PbS QDs layer and perovskite layer implies efficient hole transfer at the interface. The successful synchronous optimization greatly elevates all photovoltaic parameters, reaching a maximum PCE of 23.27%. This PCE is the highest for PSCs utilizing PbS QDs material in recent years. The optimized PSCs retain long-term moisture and light stability.     

In‐plane coupling effect on absorption coefficients of InAs/GaAs quantum dots arrays for intermediate band solar cell

Coupled semiconductor quantum dot (QD) arrays emerged recently as promising structures for the next generation of high efficiency intermediate band solar cell (IBSC), because of their ability to facilitate the formation of minibands. The quantum coupling effect that exists between states in QDs in an array influences the electronic and optical properties of such structures. So far, great experimental and theoretical efforts have been devoted to study the vertically coupled QD arrays. We present here a method based on multi‐band k ⋅ p Hamiltonian combined with periodic boundary conditions, applied to predict the electronic and optical properties of InAs/GaAs QDs‐based lateral QD arrays. Formation of the intermediate band (IB) in all cases was achieved via delocalisation of the electron ground state (e0). We show that the IB in a laterally coupled QD‐IBSC is more robust against external electric field from the solar cell's pn junction than that in a vertically coupled arrangement. Because of symmetry of the QD array lattice and QD states itself, which are C_2v for the zinc blend QDs, the electronic and absorption structures were obtained via sampling throughout the reciprocal space in the first Brillouin zone of QD arrays. Copyright © 2014 John Wiley & Sons, Ltd.     

Band Gap Engineering Improves the Efficiency of Double Quantum Dot Upconversion Nanocrystals

Solution‐processed core/multishell semiconductor quantum dots (QDs) could be tailored to facilitate the carrier separation, promotion, and recombination mechanisms necessary to implement photon upconversion. In contrast to other upconversion schemes, upconverting QDs combine the stability of an inorganic crystalline structure with the spectral tunability afforded by quantum confinement. Nevertheless, their upconversion quantum yield (UCQY) is fairly low. Here, design rules are uncovered that enable to significantly enhance the performance of double QD upconversion systems, and these findings are leveraged to fabricate upconverting QDs with increased photon upconversion efficiency and reduced saturation intensities under pulsed excitation. The role of the intra‐QD band alignment is exemplified by comparing the upconversion process in PbS/CdS/ZnSe QDs with that of PbS/CdS/CdSe ones with variable CdSe shell thicknesses. It is shown that electron delocalization into the shell leads to a longer‐lived intermediate state in the QDs, facilitating further absorption of photons, and enhancing the upconversion process. The performance of these upconversion QDs under pulsed excitation versus continuous pumping is also compared; the reasons for the significant differences between these two regimes are discussed. The results show how one can overcome some of the limitations of previous upconverting QDs, with potential applications in biophotonics and infrared detection.