Metal halides perovskites, such as hybrid organic–inorganic CH3NH3PbI3, are newcomer optoelectronic materials that have attracted enormous attention as solution-deposited absorbing layers in solar cells with power conversion efficiencies reaching 20%. Herein we demonstrate a new avenue for halide perovskites by designing highly luminescent perovskite-based colloidal quantum dot materials. We have synthesized monodisperse colloidal nanocubes (4–15 nm edge lengths) of fully inorganic cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I or mixed halide systems Cl/Br and Br/I) using inexpensive commercial precursors. Through compositional modulations and quantum size-effects, the bandgap energies and emission spectra are readily tunable over the entire visible spectral region of 410–700 nm. The photoluminescence of CsPbX3 nanocrystals is characterized by narrow emission line-widths of 12–42 nm, wide color gamut covering up to 140% of the NTSC color standard, high quantum yields of up to 90%, and radiative lifetimes in the range of 1–29 ns. The compelling combination of enhanced optical properties and chemical robustness makes CsPbX3 nanocrystals appealing for optoelectronic applications, particularly for blue and green spectral regions (410–530 nm), where typical metal chalcogenide-based quantum dots suffer from photodegradation.
Postsynthetic chemical transformations of colloidal nanocrystals, such as ion-exchange reactions, provide an avenue to compositional fine-tuning or to otherwise inaccessible materials and morphologies. While cation-exchange is facile and commonplace, anion-exchange reactions have not received substantial deployment. Here we report fast, low-temperature, deliberately partial, or complete anion-exchange in highly luminescent semiconductor nanocrystals of cesium lead halide perovskites (CsPbX3, X = Cl, Br, I). By adjusting the halide ratios in the colloidal nanocrystal solution, the bright photoluminescence can be tuned over the entire visible spectral region (410–700 nm) while maintaining high quantum yields of 20–80% and narrow emission line widths of 10–40 nm (from blue to red). Furthermore, fast internanocrystal anion-exchange is demonstrated, leading to uniform CsPb(Cl/Br)3 or CsPb(Br/I)3 compositions simply by mixing CsPbCl3, CsPbBr3, and CsPbI3 nanocrystals in appropriate ratios.
The performance of organometallic perovskite solar cells has rapidly surpassed that of both conventional dye-sensitized and organic photovoltaics. High-power conversion efficiency can be realized in both mesoporous and thin-film device architectures. We address the origin of this success in the context of the materials chemistry and physics of the bulk perovskite as described by electronic structure calculations. In addition to the basic optoelectronic properties essential for an efficient photovoltaic device (spectrally suitable band gap, high optical absorption, low carrier effective masses), the materials are structurally and compositionally flexible. As we show, hybrid perovskites exhibit spontaneous electric polarization; we also suggest ways in which this can be tuned through judicious choice of the organic cation. The presence of ferroelectric domains will result in internal junctions that may aid separation of photoexcited electron and hole pairs, and reduction of recombination through segregation of charge carriers. The combination of high dielectric constant and low effective mass promotes both Wannier-Mott exciton separation and effective ionization of donor and acceptor defects. The photoferroic effect could be exploited in nanostructured films to generate a higher open circuit voltage and may contribute to the current–voltage hysteresis observed in perovskite solar cells.
Efficient water splitting requires highly active, earth-abundant, and robust catalysts. Monometallic phosphides such as Ni2P have been shown to be active toward water splitting. Our theoretical analysis has suggested that their performance can be further enhanced by substitution with extrinsic metals, though very little work has been conducted in this area. Here we present for the first time a novel PH3 plasma-assisted approach to convert NiCo hydroxides into ternary NiCoP. The obtained NiCoP nanostructure supported on Ni foam shows superior catalytic activity toward the hydrogen evolution reaction (HER) with a low overpotential of 32 mV at −10 mA cm–2 in alkaline media. Moreover, it is also capable of catalyzing the oxygen evolution reaction (OER) with high efficiency though the real active sites are surface oxides in situ formed during the catalysis. Specifically, a current density of 10 mA cm–2 is achieved at overpotential of 280 mV. These overpotentials are among the best reported values for non-noble metal catalysts. Most importantly, when used as both the cathode and anode for overall water splitting, a current density of 10 mA cm–2 is achieved at a cell voltage as low as 1.58 V, making NiCoP among the most efficient earth-abundant catalysts for water splitting. Moreover, our new synthetic approach can serve as a versatile route to synthesize various bimetallic or even more complex phosphides for various applications.
Lithium–sulfur (Li–S) battery system is endowed with tremendous energy density, resulting from the complex sulfur electrochemistry involving multielectron redox reactions and phase transformations. Originated from the slow redox kinetics of polysulfide intermediates, the flood of polysulfides in the batteries during cycling induced low sulfur utilization, severe polarization, low energy efficiency, deteriorated polysulfide shuttle, and short cycling life. Herein, sulfiphilic cobalt disulfide (CoS2) was incorporated into carbon/sulfur cathodes, introducing strong interaction between lithium polysulfides and CoS2 under working conditions. The interfaces between CoS2 and electrolyte served as strong adsorption and activation sites for polar polysulfides and therefore accelerated redox reactions of polysulfides. The high polysulfide reactivity not only guaranteed effective polarization mitigation and promoted energy efficiency by 10% but also promised high discharge capacity and stable cycling performance during 2000 cycles. A slow capacity decay rate of 0.034%/cycle at 2.0 C and a high initial capacity of 1368 mAh g–1 at 0.5 C were achieved. Since the propelling redox reaction is not limited to Li–S system, we foresee the reported strategy herein can be applied in other high-power devices through the systems with controllable redox reactions.
Unencapsulated, exfoliated black phosphorus (BP) flakes are found to chemically degrade upon exposure to ambient conditions. Atomic force microscopy, electrostatic force microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy are employed to characterize the structure and chemistry of the degradation process, suggesting that O2 saturated H2O irreversibly reacts with BP to form oxidized phosphorus species. This interpretation is further supported by the observation that BP degradation occurs more rapidly on hydrophobic octadecyltrichlorosilane self-assembled monolayers and on H-Si(111) versus hydrophilic SiO2. For unencapsulated BP field-effect transistors, the ambient degradation causes large increases in threshold voltage after 6 h in ambient, followed by a ∼103 decrease in FET current on/off ratio and mobility after 48 h. Atomic layer deposited AlO x overlayers effectively suppress ambient degradation, allowing encapsulated BP FETs to maintain high on/off ratios of ∼103 and mobilities of ∼100 cm2 V–1 s–1 for over 2 weeks in ambient conditions. This work shows that the ambient degradation of BP can be managed effectively when the flakes are sufficiently passivated. In turn, our strategy for enhancing BP environmental stability will accelerate efforts to implement BP in electronic and optoelectronic applications.
Chemically tuned inorganic–organic hybrid materials, based on CH3NH3(MA)Pb(I1–x Br x )3 perovskites, have been studied using UV–vis absorption and X-ray diffraction patterns and applied to nanostructured solar cells. The band gap engineering brought about by the chemical management of MAPb(I1–x Br x )3 perovskites can be controllably tuned to cover almost the entire visible spectrum, enabling the realization of colorful solar cells. We demonstrate highly efficient solar cells exhibiting 12.3% in a power conversion efficiency of under standard AM 1.5, for the most efficient device, as a result of tunable composition for the light harvester in conjunction with a mesoporous TiO2 film and a hole conducting polymer. We believe that the works highlighted in this paper represent one step toward the realization of low-cost, high-efficiency, and long-term stability with colorful solar cells.
Few-layer black phosphorus, a new elemental two-dimensional (2D) material recently isolated by mechanical exfoliation, is a high-mobility layered semiconductor with a direct bandgap that is predicted to strongly depend on the number of layers, from 0.35 eV (bulk) to 2.0 eV (single layer). Therefore, black phosphorus is an appealing candidate for tunable photodetection from the visible to the infrared part of the spectrum. We study the photoresponse of field-effect transistors (FETs) made of few-layer black phosphorus (3–8 nm thick), as a function of excitation wavelength, power, and frequency. In the dark state, the black phosphorus FETs can be tuned both in hole and electron doping regimes allowing for ambipolar operation. We measure mobilities in the order of 100 cm2/V s and a current ON/OFF ratio larger than 103. Upon illumination, the black phosphorus transistors show a response to excitation wavelengths from the visible region up to 940 nm and a rise time of about 1 ms, demonstrating broadband and fast detection. The responsivity reaches 4.8 mA/W, and it could be drastically enhanced by engineering a detector based on a PN junction. The ambipolar behavior coupled to the fast and broadband photodetection make few-layer black phosphorus a promising 2D material for photodetection across the visible and near-infrared part of the electromagnetic spectrum.
We report chemically exfoliated MoS2 nanosheets with a very high concentration of metallic 1T phase using a solvent free intercalation method. After removing the excess of negative charges from the surface of the nanosheets, highly conducting 1T phase MoS2 nanosheets exhibit excellent catalytic activity toward the evolution of hydrogen with a notably low Tafel slope of 40 mV/dec. By partially oxidizing MoS2, we found that the activity of 2H MoS2 is significantly reduced after oxidation, consistent with edge oxidation. On the other hand, 1T MoS2 remains unaffected after oxidation, suggesting that edges of the nanosheets are not the main active sites. The importance of electrical conductivity of the two phases on the hydrogen evolution reaction activity has been further confirmed by using carbon nanotubes to increase the conductivity of 2H MoS2.
To improve the performance of the polycrystalline thin film devices, it requires a delicate control of its grain structures. As one of the most promising candidates among current thin film photovoltaic techniques, the organic/inorganic hybrid perovskites generally inherit polycrystalline nature and exhibit compositional/structural dependence in regard to their optoelectronic properties. Here, we demonstrate a controllable passivation technique for perovskite films, which enables their compositional change, and allows substantial enhancement in corresponding device performance. By releasing the organic species during annealing, PbI2 phase is presented in perovskite grain boundaries and at the relevant interfaces. The consequent passivation effects and underlying mechanisms are investigated with complementary characterizations, including scanning electron microscopy (SEM), X-ray diffraction (XRD), time-resolved photoluminescence decay (TRPL), scanning Kelvin probe microscopy (SKPM), and ultraviolet photoemission spectroscopy (UPS). This controllable self-induced passivation technique represents an important step to understand the polycrystalline nature of hybrid perovskite thin films and contributes to the development of perovskite solar cells judiciously.
Organic–inorganic perovskite solar cells have recently emerged at the forefront of photovoltaics research. Power conversion efficiencies have experienced an unprecedented increase to reported values exceeding 19% within just four years. With the focus mainly on efficiency, the aspect of stability has so far not been thoroughly addressed. In this paper, we identify thermal stability as a fundamental weak point of perovskite solar cells, and demonstrate an elegant approach to mitigating thermal degradation by replacing the organic hole transport material with polymer-functionalized single-walled carbon nanotubes (SWNTs) embedded in an insulating polymer matrix. With this composite structure, we achieve JV scanned power-conversion efficiencies of up to 15.3% with an average efficiency of 10 ± 2%. Moreover, we observe strong retardation in thermal degradation as compared to cells employing state-of-the-art organic hole-transporting materials. In addition, the resistance to water ingress is remarkably enhanced. These are critical developments for achieving long-term stability of high-efficiency perovskite solar cells.
MoS2 is a promising and low-cost material for electrochemical hydrogen production due to its high activity and stability during the reaction. However, the efficiency of hydrogen production is limited by the amount of active sites, for example, edges, in MoS2. Here, we demonstrate that oxygen plasma exposure and hydrogen treatment on pristine monolayer MoS2 could introduce more active sites via the formation of defects within the monolayer, leading to a high density of exposed edges and a significant improvement of the hydrogen evolution activity. These as-fabricated defects are characterized at the scale from macroscopic continuum to discrete atoms. Our work represents a facile method to increase the hydrogen production in electrochemical reaction of MoS2 via defect engineering, and helps to understand the catalytic properties of MoS2.
High photoluminescence quantum yield, easily tuned emission colors, and high color purity of perovskite nanocrystals make this class of material attractive for light source or display applications. Here, green light-emitting devices (LEDs) were fabricated using inorganic cesium lead halide perovskite nanocrystals as emitters. By introducing a thin film of perfluorinated ionomer (PFI) sandwiched between the hole transporting layer and perovskite emissive layer, the device hole injection efficiency has been significantly enhanced. At the same time, PFI layer suppressed charging of the perovskite nanocrystal emitters thus preserving their superior emissive properties, which led to the three-fold increase in peak brightness reaching 1377 cd m–2. The full width at half-maximum of the symmetric emission peak with color coordinates of (0.09, 0.76) was 18 nm, the narrowest value among perovskite based green LEDs.
High photoluminescence quantum yield, easily tuned emission colors, and high color purity of perovskite nanocrystals make this class of material attractive for light source or display applications. Here, green light-emitting devices (LEDs) were fabricated using inorganic cesium lead halide perovskite nanocrystals as emitters. By introducing a thin film of perfluorinated ionomer (PFI) sandwiched between the hole transporting layer and perovskite emissive layer, the device hole injection efficiency has been significantly enhanced. At the same time, PFI layer suppressed. charging of the perovskite nanocrystal emitters thus preserving their superior emissive properties, which led to the three-fold increase in peak brightness reaching 1377 cd m(-2). The full width at half-maximum of the symmetric emission peak with color coordinates of (0.09, 0.76) was 18 nm, the narrowest value among perovskite based green LEDs.
Replacement of precious Pt with earth-abundant electrocatalysts for the hydrogen evolution reaction (HER) holds great promise for clean energy devices, but the development of low-cost and durable HER catalysts with Pt-like activity is still a huge challenge. In this communication, we report on the development of self-standing ternary FexCo1-xP nanowire array on carbon cloth (FexCo1-xP/CC) as a Pt-free HER catalyst with activities being strongly related to Fe substitution ratio. Electrochemical tests show that Fe0.5Co0.5P/CC not only possesses Pt-like activity with the need of overpotential of only 37 mV to drive 10 mA cm(-2), outperforming all non noble-metal HER catalysts reported to date, but demonstrates superior long-term durability in 0.5 M H2SO4. Density functional theory calculations further reveal that Fe substitution of Co in CoP leads to more optimal free energy of hydrogen adsorption to the catalyst surface. This study offers us a promising flexible monolithic catalyst for practical applications.
Newly fabricated few-layer black phosphorus and its monolayer structure, phosphorene, are expected to be promising for electronic and optical applications because of their finite direct band gaps and sizable but anisotropic electronic mobility. By first-principles simulations, we show that this unique anisotropic free-carrier mobility can be controlled by using simple strain conditions. With the appropriate biaxial or uniaxial strain (4–6%), we can rotate the preferred conducting direction by 90°. This will be useful for exploring unusual quantum Hall effects and exotic electronic and mechanical applications based on phosphorene.
We report the influence of uniaxial tensile mechanical strain in the range 0–2.2% on the phonon spectra and bandstructures of monolayer and bilayer molybdenum disulfide (MoS2) two-dimensional crystals. First, we employ Raman spectroscopy to observe phonon softening with increased strain, breaking the degeneracy in the E′ Raman mode of MoS2, and extract a Grüneisen parameter of ∼1.06. Second, using photoluminescence spectroscopy we measure a decrease in the optical band gap of MoS2 that is approximately linear with strain, ∼45 meV/% strain for monolayer MoS2 and ∼120 meV/% strain for bilayer MoS2. Third, we observe a pronounced strain-induced decrease in the photoluminescence intensity of monolayer MoS2 that is indicative of the direct-to-indirect transition of the character of the optical band gap of this material at applied strain of ∼1%. These observations constitute a demonstration of strain engineering the band structure in the emergent class of two-dimensional crystals, transition-metal dichalcogenides.
Graphene and monolayer transition metal dichalcogenides (TMDs) are promising materials for next-generation ultrathin optoelectronic devices. Although visually transparent, graphene is an excellent sunlight absorber, achieving 2.3% visible light absorbance in just 3.3 Å thickness. TMD monolayers also hold potential as sunlight absorbers, and may enable ultrathin photovoltaic (PV) devices due to their semiconducting character. In this work, we show that the three TMD monolayers MoS2, MoSe2, and WS2 can absorb up to 5–10% incident sunlight in a thickness of less than 1 nm, thus achieving 1 order of magnitude higher sunlight absorption than GaAs and Si. We further study PV devices based on just two stacked monolayers: (1) a Schottky barrier solar cell between MoS2 and graphene and (2) an excitonic solar cell based on a MoS2/WS2 bilayer. We demonstrate that such 1 nm thick active layers can attain power conversion efficiencies of up to ∼1%, corresponding to approximately 1–3 orders of magnitude higher power densities than the best existing ultrathin solar cells. Our work shows that two-dimensional monolayer materials hold yet untapped potential for solar energy absorption and conversion at the nanoscale.
Layered materials consist of molecular layers stacked together by weak interlayer interactions. They often crystallize to form atomically smooth thin films, nanotubes, and platelet or fullerene-like nanoparticles due to the anisotropic bonding. Structures that predominately expose edges of the layers exhibit high surface energy and are often considered unstable. In this communication, we present a synthesis process to grow MoS2 and MoSe2 thin films with vertically aligned layers, thereby maximally exposing the edges on the film surface. Such edge-terminated films are metastable structures of MoS2 and MoSe2, which may find applications in diverse catalytic reactions. We have confirmed their catalytic activity in a hydrogen evolution reaction (HER), in which the exchange current density correlates directly with the density of the exposed edge sites.