Determining the internal quantum efficiency of PbSe nanocrystal solar cells with the aid of an optical model

We determine the internal quantum efficiency (IQE) of the active layer of PbSe nanocrystal (NC) back-contact Schottky solar cells by combining external quantum efficiency (EQE) and total reflectance measurements with an optical model of the device stack. The model is parametrized with the complex index of refraction of each layer in the stack as calculated from ellipsometry data. Good agreement between the experimental and modeled reflectance spectra permits a quantitative estimate of the fraction of incident light absorbed by the NC films at each wavelength, thereby yielding well-constrained QE spectra for photons absorbed only by the NCs. Using a series of devices fabricated from 5.1+/-0.4 nm diameter PbSe NCs, we show that thin NC cells achieve an EQE and an active layer IQE as high as 60+/-5% and 80+/-7%, respectively, while the QE of devices with NC layers thicker than about 150 nm falls, particularly in the blue, because of progressively greater light absorption in the field-free region of the films and enhanced recombination overall. Our results demonstrate that interference effects must be taken into account in order to calculate accurate optical generation profiles and IQE spectra for these thin film solar cells. The mixed modeling/experimental approach described here is a rigorous and powerful way to determine if multiple exciton generation (MEG) photocurrent is collected by devices with EQE<100%. On the basis of the magnitudes and shapes of the IQE spectra, we conclude that the 1,2-ethanedithiol treated NC devices studied here do not produce appreciable MEG photocurrent.     

Low-temperature approach to high-yield and reproducible syntheses of high-quality small-sized PbSe colloidal nanocrystals for photovoltaic applications

Small-sized PbSe nanocrystals (NCs) were synthesized at low temperature such as 50-80 °C with high reaction yield (up to 100%), high quality, and high synthetic reproducibility, via a noninjection-based one-pot approach. These small-sized PbSe NCs with their first excitonic absorption in wavelength shorter than 1200 nm (corresponding to size < ～3.7 nm) were developed for photovoltaic applications requiring a large quantity of materials. These colloidal PbSe NCs, also called quantum dots, are high-quality, in terms of narrow size distribution with a typical standard deviation of ～7-9%, excellent optical properties with high quantum yield of ～50-90% and small full width at half-maximum of ～130-150 nm of their band-gap photoemission peaks, and high storage stability. Our synthetic design aimed at promotion of the formation of PbSe monomers for fast and sizable nucleation with the presence of a large number of nuclei at low temperature. For formation of the PbSe monomer, our low-temperature approach suggests the existence of two pathways of Pb-Se (route a) and Pb-P (route b) complexes. Either pathway may dominate, depending on the method used and its experimental conditions. Experimentally, a reducing/nucleation agent, diphenylphosphine, was added to enhance route b. The present study addresses two challenging issues in the NC community, the monomer formation mechanism and the reproducible syntheses of small-sized NCs with high yield and high quality and large-scale capability, bringing insight to the fundamental understanding of optimization of the NC yield and quality via control of the precursor complex reactivity and thus nucleation/growth. Such advances in colloidal science should, in turn, promote the development of next-generation low-cost and high-efficiency solar cells. Schottky-type solar cells using our PbSe NCs as the active material have achieved the highest power conversion efficiency of 2.82%, in comparison with the same type of solar cells using other PbSe NCs, under Air Mass 1.5 global (AM 1.5G) irradiation of 100 mW/cm(2).     

Improved photovoltaic performances by post-deposition acidic treatments on tetrapod shaped colloidal nanocrystal solids

The ligand exchange reaction with pyridine is the standard procedure for the integration of colloidal semiconductor nanocrystals (NCs) in photovoltaic devices; however, for large sized and irregularly shaped branched NCs, such as CdSe@CdTe tetrapods, this procedure can lead to a considerable waste of materials and the aggregation of NCs in the colloidal solution, therefore resulting in the formation of an inhomogeneous film and low device performances. Here, we report on alternative post-deposition treatments with carboxylic acids on films of CdSe@CdTe tetrapod shaped NCs. This approach guarantees the removal of the insulating surfactant, necessary to obtain good charge transport among NCs, while preserving the film integrity. We perform a complete characterization of the nanocrystalline films treated with different carboxylic acids and demonstrate the successful integration of such films in photovoltaic devices, showing a doubled efficiency with respect to the standard ligand exchange procedure. Our approach represents a general route towards the development of NC based devices with improved performances and minimized waste of material.     

Remarkable Electrical Conductivity Increase and Pure Metallic Properties from Semiconducting Colloidal Nanocrystals by Cation Exchange for Solution-Processable Optoelectronic Applications

The authors report a strategic approach to achieve metallic properties from semiconducting Cu Fe S colloidal nanocrystal (NC) solids through cation exchange method. An unprecedentedly high electrical conductivity is realized by the efficient generation of charge carriers onto a semiconducting Cu S NC template via minimal Fe exchange. An electrical conductivity exceeding 10 500 S cm⁻¹ (13 400 S cm⁻¹ at 2 K) and a sheet resistance of 17 Ω/sq at room temperature, which are among the highest values for solution-processable semiconducting NCs, are achieved successfully from bornite-phase Cu Fe S NC films possessing 10% Fe atom. The temperature dependence of the corresponding films exhibits pure metallic characteristics. Highly conducting NCs are demonstrated for a thermoelectric layer exhibiting a high power factor over 1.2 mW m⁻¹K⁻² at room temperature, electrical wires for switching on light emitting diods (LEDs), and source–drain electrodes for p- and n-type organic field-effect transistors. Ambient stability, eco-friendly composition, and solution-processability further validate their sustainable and practical applicability. The present study provides a simple but very effective method for significantly increasing charge carrier concentrations in semiconducting colloidal NCs to achieve metallic properties, which is applicable to various optoelectronic devices.     

Crafting Semiconductor Organic−Inorganic Nanocomposites via Placing Conjugated Polymers in Intimate Contact with Nanocrystals for Hybrid Solar Cells

Semiconductor organic?inorganic hybrid solar cells incorporating conjugated polymers (CPs) and nanocrystals (NCs) offer the potential to deliver efficient energy conversion with low‐cost fabrication. The CP‐based photovoltaic devices are complimented by an extensive set of advantageous characteristics from CPs and NCs, such as lightweight, flexibility, and solution‐processability of CPs, combined with high electron mobility and size‐dependent optical properties of NCs. Recent research has witnessed rapid advances in an emerging field of directly tethering CPs on the NC surface to yield an intimately contacted CP?NC nanocomposite possessing a well‐defined interface that markedly promotes the dispersion of NCs within the CP matrix, facilitates the photoinduced charge transfer between these two semiconductor components, and provides an effective platform for studying the interfacial charge separation and transport. In this Review, we aim to highlight the recent developments in CP?NC nanocomposite materials, critically examine the viable preparative strategies geared to craft intimate CP?NC nanocomposites and their photovoltaic performance in hybrid solar cells, and finally provide an outlook for future directions of this extraordinarily rich field.     

Air stable, photosensitive, phase pure iron pyrite nanocrystal thin films for photovoltaic application

Iron pyrite (FeS(2)) is a naturally abundant and nontoxic photovoltaic material that can potentially make devices as efficient as silicon-based ones; however existing iron pyrite photovoltaic devices contain thermodynamically unstable FeS(2) film surfaces that lead to low open circuit voltages. We report the rational synthesis of phase pure, highly crystalline cubic FeS(2) nanocrystals (NCs) using a trioctylphosphine oxide (TOPO) assisted hot-injection method. The synthesized pyrite NC films have excellent air stability over one year. In contrast, obvious surface decomposition was observed on the surface of FeS(2) NCs synthesized without TOPO. A high carrier mobility of 80 cm(2)/(V s) and a strong photoconductivity were observed for the first time for pyrite films at room temperature. Our results indicate that TOPO passivates both iron and sulfur atoms on FeS(2) NC surfaces, efficiently inhibiting surface decomposition.     

Low-temperature noninjection approach to homogeneously-alloyed PbSe(x)S(1-x) colloidal nanocrystals for photovoltaic applications

Homogeneously alloyed PbSe(x)S(1-x) nanocrystals (NCs) with their excitonic absorption peaks in wavelength shorter than 1200 nm were developed for photovoltaic (PV) applications. Schottky-type solar cells fabricated with our PbSe?.?S?.? NCs as their active materials reached a high power conversion efficiency (PCE) of 3.44%, with an open circuit voltage (V(oc)) of 0.49 V, short circuit photocurrent (J(sc)) of 13.09 mA/cm2, and fill factor (FF) of 0.54 under Air Mass 1.5 global (AM 1.5G) irradiation of 100 mW/cm2. The syntheses of the small-sized colloidal PbSe(x)S(1-x) NCs were carried out at low temperature (60 °C) with long growth periods (such as 45 min) via a one-pot noninjection-based approach in 1-octadecene (ODE), featuring high reaction yield, high product quality, and high synthetic reproducibility. This low-temperature approach employed Pb(oleate)? as a Pb precursor and air-stable low-cost thioacetamide (TAA) as a S source instead of air-sensitive high-cost bis(trimethylsilyl)sulfide ((TMS)?S), with n-tributylphosphine selenide (TBPSe) as a Se precursor instead of n-trioctylphosphine selenide (TOPSe). The reactivity difference of TOPSe made from commercial TOP 90% and TBPSe made from commercial TBP 97% and TBP 99% was addressed with in situ observation of the temporal evolution of NC absorption and with 31P nuclear magnetic resonance (NMR). Furthermore, the addition of a strong reducing/nucleation agent diphenylphosphine (DPP) promoted the reactivity of the Pb precursor through the formation of a Pb-P complex, which is much more reactive than Pb(oleate)?. Thus, the reactivity of TBPSe was increased more than that of TAA. The larger the DPP-to-Pb feed molar ratio, the more the Pb-P complex, the higher the Se amount in the resulting homogeneously alloyed PbSe(x)S(1-x) NCs. Therefore, the use of DPP allowed reactivity match of the Se and S precursors and led to sizable nucleation at low temperature so that long growth periods became feasible. The present study brings insight into the formation mechanism of monomers, nucleation/growth of colloidal composition-tunable NCs, and materials design and synthesis for next-generation low-cost and high-efficiency solar cells.     

Water-soluble germanium(0) nanocrystals: cell recognition and near-infrared photothermal conversion properties

Surfactant-passivated germanium nanocrystals (Ge(0) NCs) 3-5 nm in diameter were synthesized and encapsulated with functionalized phospholipids to yield water-soluble Ge(0) NCs. Upon encapsulation, the NCs retained their cubic crystalline phase and displayed good resistance to oxidation, as determined by transmission electron microscopy and X-ray photoelectron spectroscopy. As a test of their cell compatibility, the ability of carboxyfluorescein (CF)-labeled dinitrophenyl (DNP)-functionalized Ge(0) NCs to crosslink dinitrophenol-specific immunoglobulin E antibodies on the surface of mast cells (RBL-2H3) was examined in vitro. Treatment with a multivalent DNP antigen (i.e., DNP-Ge(0) NCs or CF-DNP-Ge(0) NCs) caused crosslinking of FcepsilonRI receptors and cellular responses, which were evaluated with morphological and colorimetric assays and live-cell fluorescence microscopy. Incubation of RBL-2H3 cells with Ge(0) NCs for approximately 24 h gave less than a 2 % increase in cell death as compared to DNP-functionalized bovine serum albumin. When irradiated with near-infrared (NIR) radiation (lambda(exc)=770 nm, 1.1 W cm(-2)) from a continuous-wave Ti:sapphire laser, the bulk-solution temperature of a toluene solution containing 20 mg mL(-1) Ge(0) NCs increased by approximately 35 degrees C within 5 min. Phospholipid-encapsulated water-soluble Ge(0) NCs at concentrations of 1.0 mg mL(-1) also displayed stable photothermal behavior under repetitive and prolonged NIR laser exposures in water, to yield a temperature increase of approximately 20 degrees C within 5 min (lambda(exc)=770 nm, 0.9 W cm(-2)). The photothermal efficiency of water-soluble Ge(0) NCs compares favorably with a recent report for Au nanoshells.     

Surfactant ligand removal and rational fabrication of inorganically connected quantum dots

A novel method is reported to create inorganically connected nanocrystal (NC) assemblies for both II-VI and IV-VI semiconductors by removing surfactant ligands using (NH4)2S. This surface modification process differs from ligand exchange methods in that no new surfactant ligands are introduced and the post-treated NC surfaces are nearly bare. The detailed mechanism study shows that the high reactivity between (NH4)2S and metal-surfactant ligand complexes enables the complete removal of surfactant ligands in seconds and converts the NC metal-rich shells into metal sulfides. The post-treated NCs are connected through metal-sulfide bonding and form a larger NCs film assembly, while still maintaining quantum confinement. Such "connected but confined" NC assemblies are promising new materials for electronic and optoelectronic devices.     

Multiscale periodic assembly of striped nanocrystal superlattice films on a liquid surface

Self-assembly of nanocrystals (NCs) into periodically ordered structures on multiple length scales and over large areas is crucial to the manufacture of NC-based devices. Here, we report an unusual yet universal approach to rapidly assembling hierarchically organized NC films that display highly periodic, tunable microscale stripe patterns over square centimeter areas while preserving the local superlattice structure. Our approach is based on a drying-driven dynamic assembly process occurring on a liquid surface with the stripe pattern formed by a new type of contact-line instability. Periodic ordering of NCs is realized on microscopic and nanoscopic scales simultaneously without the need of any specialized equipment or the application of external fields. The striped NC superlattice films obtained can be readily transferred to arbitrary substrates for device fabrication. The periodic structure imparts interesting modulation and anisotropy to the properties of such striped NC assemblies. This assembly approach is applicable to NCs with a variety of compositions, sizes, and shapes, offering a robust, inexpensive route for large-scale periodic patterning of NCs.     

Hybrid nanocomposites based on luminescent colloidal nanocrystals in poly(methyl methacrylate): spectroscopical and morphological studies

We report on preparation process and optical characterization of a nanocomposite material obtained dispersing colloidal semiconductor nanocrystals (NCs), namely CdS and CdSe@ZnS core-shell system in poly(methyl methacrylate) (PMMA). Such method allows a large flexibility on nanocrystal materials and on the choice of the polymer characteristics. Nanocomposite thin films were extensively investigated by means optical and morphological techniques. The effects on NC composition, concentration, size, and surface chemistry on the spectroscopical and structural behaviour of the nanocomposite properties were studied. The NC size dependent optical properties of the nanocomposites are mainly accounted by the NC composition and size, while the morphology of the films is explained on the base of the NC surface characteristics and their concentration in the nanocomposites.     

Nanocrystals of PbSe core, PbSe/PbS, and PbSe/PbSxS(1-x) core/shell as saturable absorbers in passively Q-switched near-infrared lasers

The saturable optical absorption properties of PbSe core nanocrystals (NCs), and their corresponding PbSe/PbScore/shell and PbSe/PbSexS(1-x) core/alloyed-shell NCs, were examined at lambda = 1.54 microm. Saturation intensities of approximately 100 MW/cm2 were obtained. The NCs act as passive Q switches in near-infrared pulsed lasers. Q-switched output pulse energies up to 3 mJ, with a pulse duration of 40-55 ns were demonstrated. Analysis of the optical transmission versus pulse light intensity was carried out according to a model that includes ground-state as well as excited-state absorption. For pulses approximately 10 ns long, the NCs act as fast saturable absorbers. The theoretical fits yield a ground-state absorption cross section of 10-16-10-15 cm2, an excited-state absorption cross section of sigma(es) is congruent to 10(-16) cm2, and an effective lifetime of tau(eff) is congruent to 5 x 10(-12) s.     

In situ gas-phase hydrosilylation of plasma-synthesized silicon nanocrystals

Surface passivation of semiconductor nanocrystals (NCs) is critical in enabling their utilization in novel optoelectronic devices, solar cells, and biological and chemical sensors. Compared to the extensively used liquid-phase NC synthesis and passivation techniques, gas-phase routes provide the unique opportunity for in situ passivation of semiconductor NCs. Herein, we present a method for in situ gas-phase organic functionalization of plasma-synthesized, H-terminated silicon (Si) NCs. Using real-time in situ attenuated total reflection Fourier transform IR spectroscopy, we have studied the surface reactions during hydrosilylation of Si NCs at 160 °C. First, we show that, during gas-phase hydrosilylation of Si NCs using styrene (1-alkene) and acetylene (alkyne), the reaction pathways of the alkenes and alkynes chemisorbing onto surface SiH(x) (x = 1-3) species are different. Second, utilizing this difference in reactivity, we demonstrate a novel pathway to enhance the surface ligand passivation of Si NCs via in situ gas-phase hydrosilylation using the combination of a short-chain alkyne (acetylene) and a long-chain 1-alkene (styrene). The quality of surface passivation is further validated through IR and photoluminescence measurements of Si NCs exposed to air.     

Shape‐Controlled Synthesis of High‐Quality Cu7S4 Nanocrystals for Efficient Light‐Induced Water Evaporation

Copper sulfides (Cu_2–xS), are a novel kind of photothermal material exhibiting significant photothermal conversion efficiency, making them very attractive in various energy conversion related devices. Preparing high quality uniform Cu_2‐xS nanocrystals (NCs) is a top priority for further energy‐and sustainability relevant nanodevices. Here, a shape‐controlled high quality Cu₇S₄ NCs synthesis strategy is reported using sulfur in 1‐octadecene as precursor by varying the heating temperature, as well as its forming mechanism. The performance of the Cu₇S₄ NCs is further explored for light‐driven water evaporation without the need of heating the bulk liquid to the boiling point, and the results suggest that as‐synthesized highly monodisperse NCs perform higher evaporation rate than polydisperse NCs under the identical morphology. Furthermore, disk‐like NCs exhibit higher water evaporation rate than spherical NCs. The water evaporation rate can be further enhanced by assembling the organic phase Cu₇S₄ NCs into a dense film on the aqueous solution surface. The maximum photothermal conversion efficiency is as high as 77.1%.     

Dispersing solvent effect on halide perovskite nanocrystals-based films and devices

Journal of Materials Science - Halide perovskite (HP) nanocrystals (NCs) are promising materials for application in optoelectronic devices. Smooth and compact films, which are obtained by spin...     

Low voltage, hysteresis free, and high mobility transistors from all-inorganic colloidal nanocrystals

High-mobility solution-processed all-inorganic solid state nanocrystal (NC) transistors with low operation voltage and near-zero hysteresis are demonstrated using high-capacitance ZrO(x) and hydroxyl-free Cytop gate dielectric materials. The use of inorganic capping ligands (In(2)Se(4)(2-) and S(2-)) allowed us to achieve high electron mobility in the arrays of solution-processed CdSe nanocrystals. We also studied the hysteresis behavior and switching speed of NC-based field effect devices. Collectively, these analyses helped to understand the charge transport and trapping mechanisms in all-inorganic NCs arrays. Finally, we have examined the rapid thermal annealing as an approach toward high-performance solution-processed NCs-based devices and demonstrated transistor operation with mobility above 30 cm(2)/(V s) without compromising low operation voltage and hysteresis.     

Characteristics of Al-doped ZnO films grown by atomic layer deposition for silicon nanowire photovoltaic device

We report the structural, electrical, and optical characteristics of Al-doped ZnO (ZnO:Al) films deposited on glass by atomic layer deposition (ALD) with various Al2O3 film contents for use as transparent electrodes. Unlike films fabricated by a sputtering method, the diffraction peak position of the films deposited by ALD progressively moved to a higher angle with increasing Al2O3 film content. This indicates that Zn sites were effectively replaced by Al, due to layer-by-layer growth mechanism of ALD process which is based on alternate self-limiting surface chemical reactions. By adjusting the Al2O3 film content, a ZnO:Al film with low electrical resistivity (9.84 x 10(-4) Omega cm) was obtained at an Al2O3 film content of 3.17%, where the Al concentration, carrier mobility, optical transmittance, and bandgap energy were 2.8 wt%, 11.20 cm2 V(-1) s(-1), 94.23%, and 3.6 eV, respectively. Moreover, the estimated figure of merit value of our best sample was 8.2 m7Omega(-1). These results suggest that ZnO:Al films deposited by ALD could be useful for electronic devices in which especially require 3-dimensional conformal deposition of the transparent electrode and surface passivation.     

Ligand effects on electronic and optoelectronic properties of two-dimensional PbS necking percolative superlattices

The inter-nanocrystal (NC) distance,necking degree,ordering level,and NC surface ligands all affect the electronic and optoelectronic properties of NC solids.Herein,we introduce a unique PbS structure of necking percolative superlattices to exclude the morphological factors and study the effect of ligands on the NC properties.X-ray photoelectron spectroscopy data indicate that 1,2-ethanedithiol (EDT),oxalic acid,mercaptopropionic acid,and NH4SCN (SCN)ligands were attached to the surface of NCs by substrate-supported ligand exchange.Field-effect transistors were tested and photodetector measurements were performed to compare these NC solids.An SCN-treated film had the highest mobility and responsivity under high-power intensity irradiation owing to its high carrier density,whereas an EDT-treated film had the lowest mobility,photocurrent,and dark current.These findings introduce new avenues for choosing suitable ligands for NC applications.     

A new route to size and population control of silver clusters on colloidal TiO₂ nanocrystals

Formation of hybrid Ag-TiO(2) nanocrystals (NCs) in which Ag clusters are uniformly deposited on individual TiO(2) NC surface has been achieved by using hydrophobic surfactant-capped TiO(2) NCs in combination with a photodeposition technique. The population of Ag clusters on the individual TiO(2) NC surface can be controlled by the degree of hydrophobicity (e.g., the number of vacant sites) on the TiO(2) NC surface while their size may be altered simply by varying irradiation time. A reversible change in color of the resulting hybrid Ag-TiO(2) NCs is induced by alternating UV light and visible-light illumination; however, the size and population of Ag clusters on TiO(2) NCs are almost unchanged. Furthermore, these materials also exhibit much higher photocatalytic performance as compared to that of Ag supported on commercial TiO(2)-P25.     

Facile synthesis of CdSe nanocrystals for bulk-heterojunction solar cells

Oleic acid (OA)-capped cadmium selenide (CdSe) nanocrystals (NCs) have been synthesized via a new high-scale route. X-ray diffraction and transmission electron microscopy confirmed that rod-like hexagonal (wurtzite) CdSe NCs with an average size of 10 nm were obtained via this new route. The obtained CdSe NCs were treated individually with pyridine and tert-butylamine (t-BA) for ligand exchange. Fourier transform infrared spectra of the as-synthesized and treated CdSe NCs confirmed the removal of OA ligands from the surface of CdSe NCs after treatments with pyridine and t-BA. Bulk-heterojunction (BHJ) solar cell devices were prepared using untreated and surface treated CdSe NCs blended with poly (3-hexylthiophene-2,5-diyl) (P3HT) polymer. BHJ solar cell devices made from P3HT:(surface treated CdSe NCs) blends showed greater improvement in photovoltaic performances compared to P3HT:(untreated CdSe NCs) blend. The improvement in photovoltaic performances was due to the increase of electron mobility in P3HT:(CdSe NCs) blends after surface treatment of CdSe NCs.