Efficient Generation of Long-Lived Triplet Excitons in 2D Hybrid Perovskite.

Triplet excitons form in quasi-2D hybrid inorganic-organic perovskites and diffuse over 100 nm before radiating with >11% photoluminescence quantum efficiency (PLQE) at low temperatures.

Employing Lead Thiocyanate Additive to Reduce the Hysteresis and Boost the Fill Factor of Planar Perovskite Solar Cells.

Lead thiocyanate in the perovskite precursor can increase the grain size of a perovskite thin film and reduce the conductivity of the grain boundaries, leading to perovskite solar cells with reduced hysteresis and enhanced fill factor. A planar perovskite solar cell with grain boundary and interface passivation achieves a steady-state efficiency of 18.42%.

Photovoltaic Properties of Two-Dimensional (CH3NH3)2Pb(SCN)2I2 Perovskite: A Combined Experimental and Density Functional Theory Study.

We explore the photovoltaic-relevant properties of the 2D MA2Pb(SCN)2I2 (where MA = CH3NH3(+)) perovskite using a combination of materials synthesis, characterization and density functional theory calculation, and determine electronic properties of MA2Pb(SCN)2I2 that are significantly different from those previously reported in literature. The layered perovskite with mixed-anions exhibits an indirect bandgap of ∼2.04 eV, with a slightly larger direct bandgap of ∼2.11 eV. The carriers (both electrons and holes) are also found to be confined within the 2D layers. Our results suggest that the 2D MA2Pb(SCN)2I2 perovskite may not be among the most promising absorbers for efficient single-junction solar cell applications; however, use as an absorber for the top cell of a tandem solar cell may still be a possibility if films are grown with the 2D layers aligned perpendicular to the substrates.

The identification and characterization of defect states in hybrid organic-inorganic perovskite photovoltaics.

Thin film photovoltaic cells based on hybrid halide perovskite absorbers have emerged as promising candidates for next generation photovoltaics. Here, we have characterized and identified the defect energy distribution in the CH3NH3PbI3 perovskite using admittance spectroscopy, which reveals a deep defect state ∼0.16 eV above the valence band. According to theoretical calculations, the defect state is possibly attributed to iodine interstitials (Ii), which can become the non-radiative recombination centers in the absorber.

Spatial element distribution control in a fully solution-processed nanocrystals-based 8.6% Cu2ZnSn(S,Se)4 device.

A fully solution-processed high performance Cu2ZnSn(S,Se)4 (CZTSSe, kesterite) device has been demonstrated. It is based on the rational engineering of elemental spatial distributions in the bulk and particularly near the surface of the film from nanocrystal precursors. The nanocrystals are synthesized through a modified colloidal approach, with excellent solubility over a large compositional window, followed by a selenization process to form the absorber. The X-ray photoluminescence (XPS) depth profiling indicates an undesirable Sn-rich surface of the selenized film. An excessive Zn species was quantitatively introduced through nanocrystals precursor to correct the element distribution, and accordingly a positive correlation between the spatial composition in the bulk/surface film and the resulting device parameter is established. The enhanced device performance is associated with the reduced interfacial recombination. With a Zn content 1.6 times more than the stoichiometry; the optimized device, which is fabricated by employing a full solution process from the absorber to the transparent top electrode, demonstrates a performance of 8.6%. This composition-control approach through stoichiometric adjustments of nanocrystal precursors, and the developed correlation between the spatial composition and device performance may also benefit other multielement-based photovoltaics.

Photovoltaics. Interface engineering of highly efficient perovskite solar cells.

Advancing perovskite solar cell technologies toward their theoretical power conversion efficiency (PCE) requires delicate control over the carrier dynamics throughout the entire device. By controlling the formation of the perovskite layer and careful choices of other materials, we suppressed carrier recombination in the absorber, facilitated carrier injection into the carrier transport layers, and maintained good carrier extraction at the electrodes. When measured via reverse bias scan, cell PCE is typically boosted to 16.6% on average, with the highest efficiency of ~19.3% in a planar geometry without antireflective coating. The fabrication of our perovskite solar cells was conducted in air and from solution at low temperatures, which should simplify manufacturing of large-area perovskite devices that are inexpensive and perform at high levels.

Controllable self-induced passivation of hybrid lead iodide perovskites toward high performance solar cells.

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.

Nanoscale Joule heating and electromigration enhanced ripening of silver nanowire contacts.

Solution-processed metallic nanowire thin film is a promising candidate to replace traditional indium tin oxide as the next-generation transparent and flexible electrode. To date however, the performance of these electrodes is limited by the high contact resistance between contacting nanowires; so improving the point contacts between these nanowires remains a major challenge. Existing methods for reducing the contact resistance require either a high processing power, long treatment time, or the addition of chemical reagents, which could lead to increased manufacturing cost and damage the underlying substrate or device. Here, a nanoscale point reaction process is introduced as a fast and low-power-consumption way to improve the electrical contact properties between metallic nanowires. This is achieved via current-assisted localized joule heating accompanied by electromigration. Localized joule heating effectively targets the high-resistance contact points between nanowires, leading to the automatic removal of surface ligands, welding of contacting nanowires, and the reshaping of the contact pathway between the nanowires to form a more desirable geometry of low resistance for interwire conduction. This result shows the interplay between thermal and electrical interactions at the highly reactive nanocontacts and highlights the control of the nanoscale reaction as a simple and effective way of turning individual metallic nanowires into a highly conductive interconnected nanowire network. The temperature of the adjacent device layers can be kept close to room temperature during the process, making this method especially suitable for use in devices containing thermally sensitive materials such as polymer solar cells.

Planar heterojunction perovskite solar cells via vapor-assisted solution process.

Hybrid organic/inorganic perovskites (e.g., CH3NH3PbI3) as light absorbers are promising players in the field of third-generation photovoltaics. Here we demonstrate a low-temperature vapor-assisted solution process to construct polycrystalline perovskite thin films with full surface coverage, small surface roughness, and grain size up to microscale. Solar cells based on the as-prepared films achieve high power conversion efficiency of 12.1%, so far the highest efficiency based on CH3NH3PbI3 with the planar heterojunction configuration. This method provides a simple approach to perovskite film preparation and paves the way for high reproducibility of films and devices. The underlying kinetic and thermodynamic parameters regarding the perovskite film growth are discussed as well.

Rational defect passivation of Cu2ZnSn(S,Se)4 photovoltaics with solution-processed Cu2ZnSnS4:Na nanocrystals.

An effective defect passivation route has been demonstrated in the rapidly growing Cu2ZnSn(S,Se)4 (CZTSSe) solar cell device system by using Cu2ZnSnS4:Na (CZTS:Na) nanocrystals precursors. CZTS:Na nanocrystals are obtained by sequentially preparing CZTS nanocrystals and surface decorating of Na species, while retaining the kesterite CZTS phase. The exclusive surface presence of amorphous Na species is proved by X-ray photoluminescence spectrum and transmission electron microscopy. With Na-free glasses as the substrate, CZTS:Na nanocrystal-based solar cell device shows 50% enhancement of device performance (∼6%) than that of unpassivated CZTS nanocrystal-based device (∼4%). The enhanced electrical performance is closely related to the increased carrier concentration and elongated minority carrier lifetime, induced by defect passivation. Solution incorporation of extrinsic additives into the nanocrystals and the corresponding film enables a facile, quantitative, and versatile approach to tune the defect property of materials for future optoelectronic applications.

Molecular solution approach to synthesize electronic quality Cu2ZnSnS4 thin films.

Successful implementation of molecular solution processing from a homogeneous and stable precursor would provide an alternative, robust approach to process multinary compounds compared with physical vapor deposition. Targeting deposition of chemically clear, high quality crystalline films requires specific molecular structure design and solvent selection. Hydrazine (N2H4) serves as a unique and powerful medium, particularly to incorporate selected metallic elements and chalcogens into a stable solution as metal chalcogenide complexes (MCC). However, not all the elements and compounds can be easily dissolved. In this manuscript, we demonstrate a paradigm to incorporate previously insoluble transitional-metal elements into molecular solution as metal-atom hydrazine/hydrazine derivative complexes (MHHD), as exemplified by dissolving of the zinc constituent as Zn(NH2NHCOO)2(N2H4)2. Investigation into the evolution of molecular structure reveals the hidden roadmap to significantly enrich the variety of building blocks for soluble molecule design. The new category of molecular structures not only set up a prototype to incorporate other elements of interest but also points the direction for other compatible solvent selection. As demonstrated from the molecular precursor combining Sn-/Cu-MCC and Zn-MHHD, an ultrathin film of copper zinc tin sulfide (CZTS) was deposited. Characterization of a transistor based on the CZTS channel layer shows electronic properties comparable to CuInSe2, confirming the robustness of this molecular solution processing and the prospect of earth abundant CZTS for next generation photovoltaic materials. This paradigm potentially outlines a universal pathway, from individual molecular design using selected chelated ligands and combination of building blocks in a simple and stable solution to fundamentally change the way multinary compounds are processed.

Novel solution processing of high-efficiency Earth-abundant Cu2 ZnSn(S,Se)4 solar cells.

A novel solution-based approach is presented to process earth-abundant Cu(2)ZnSn(S,Se)(4) absorbers using fully dissolved CZTS precursors in which each of the elemental constituents intermix on a molecular scale. This method enables the low-temperature processing of chemically clean kesterite films with excellent homogeneity. The high performance of resulting optoelectronic devices represents a chance to extend the impact of CZTS into the next chapter of thin-film solar cells.

Silver nanowire composite window layers for fully solution-deposited thin-film photovoltaic devices.

A silver nanowire-indium tin oxide nanoparticle composite and its successful application to fully solution processed CuInSe(2) solar cells as a window layer are demonstrated, effectively replacing the traditionally sputtered both intrinsic zinc oxide and indium tin oxide layers. The devices utilizing the nanocomposite window layer demonstrate photovoltaic parameters equal to or even beyond those with sputtered intrinsic zinc oxide and indium tin oxide contacts.

Photophysics of heteroleptic iridium(III) complexes of current interest; a closer look on relaxation dynamics.

The excited-state dynamics of heteroleptic iridium(III) complexes have been investigated using femto-nanosecond time-resolved luminescence and transient absorption spectroscopy. Two prototypical examples illustrated here are iridium(III) bis[2-(2,4-difluorophenyl)pyridinato-N,C(2')] quinaldinate (1) and iridium(III) bis[2-(2,4-difluorophenyl)pyridinato-N,C(2')][2-(6-methylbenzoxazol-2-yl)phenolate] (2). Upon photoexcitation at, for example, 400 nm, the emission decay, monitored at the region of phosphorescence, for both 1 and 2 consists of a system response limited rise (<300 ps) and a single exponential decay. Further single wavelength as well as full spectrum of femto-picosecond transient absorption acquired in CH(2)Cl(2) at room temperature reveals an ultrafast S(1) --> T(n) intersystem crossing (<1 ps) and a rapid T(n) --> T(1) internal conversion/vibrational relaxation within a time period of <10 ps. The results lead us to conclude that following Franck-Condon excitation, the time scale required to populate the lowest triplet state should be <10 ps.

Cyano analogues of 7-azaindole: probing excited-state charge-coupled proton transfer reactions in protic solvents.

The interplay between excited-state charge and proton transfer reactions in protic solvents is investigated in a series of 7-azaindole (7AI) derivatives: 3-cyano-7-azaindole (3CNAI), 5-cyano-7-azaindole (5CNAI), 3,5-dicyano-7-azaindole (3,5CNAI) and dicyanoethenyl-7-azaindole (DiCNAI). Similar to 7AI, 3CNAI and 3,5CNAI undergo methanol catalyzed excited-state double proton transfer (ESDPT), resulting in dual (normal and proton transfer) emission. Conversely, ESDPT is prohibited for 5CNAI and DiCNAI in methanol, as supported by a unique normal emission with high quantum efficiency. Instead, the normal emission undergoes prominent solvatochromism. Detailed relaxation dynamics and temperature dependent studies are carried out. The results conclude that significant excited-state charge transfer (ESCT) takes place for both 5CNAI and DiCNAI. The charge-transfer specie possesses a different dipole moment from that of the proton-transfer tautomer species. Upon reaching the equilibrium polarization, there exists a solvent-polarity induced barrier during the proton-transfer tautomerization, and ESDPT is prohibited for 5CNAI and DiCNAI during the excited-state lifespan. The result is remarkably different from 7AI, which is also unique among most excited-state charge/proton transfer coupled systems studied to date.