Stable Inorganic Colloidal Tin and Tin-Lead Perovskite Nanocrystals with Ultralong Carrier Lifetime via Sn(IV) Control.

Inorganic tin (Sn) perovskite nanocrystals offer a promising solution to the potential toxicity concerns associated with their established lead (Pb)-based counterparts. Yet, achieving their superior stability and optoelectronic properties remains an ongoing challenge. Here, we report a synthesis of high-symmetry α-phase CsSnI3 nanocrystals with an ultralong 278 ns carrier lifetime, exceeding previous benchmarks by 2 orders of magnitude through meticulous Sn(IV) control. The nanocrystals demonstrate excellent colloidal stability, uniform monodispersity, and a distinct exciton peak. Central to these outcomes is our designed solid-liquid antioxidation suspension of tri-n-octylphosphine (TOP) and zerovalent tin (Sn(0)) that fully addresses the unique coexisting oxygen-driven and solvent-driven Sn oxidation mechanisms in Sn perovskite nanocrystal synthesis. We uncover the largely undervalued function of TOP in mitigating oxygen-driven Sn oxidation and introduce Sn(0) powder to generate a synergistic antioxidation function with TOP, significantly reducing Sn(IV)-induced defects and distortions and contributing to enhanced optoelectronic properties. Strikingly, this approach also profoundly impacts inorganic Sn-Pb perovskite nanocrystals, boosting lifetimes by 2 orders of magnitude and increasing photoluminescence quantum yield over 100-fold to 35%. Our findings illuminate the potential of Sn-based nanocrystals for optoelectronic applications.

14.31 % Power Conversion Efficiency of Sn-Based Perovskite Solar Cells via Efficient Reduction of Sn4.

The photoelectric properties of nontoxic Sn-based perovskite make it a promising alternative to toxic Pb-based perovskite. It has superior photovoltaic performance in comparison to other Pb-free counterparts. The facile oxidation of Sn2+ to Sn4+ presents a notable obstacle in the advancement of perovskite solar cells that utilize Sn, as it adversely affects their stability and performance. The study revealed the presence of a Sn4+ concentration on both the upper and lower surfaces of the perovskite layer. This discovery led to the adoption of a bi-interface optimization approach. A thin layer of Sn metal was inserted at the two surfaces of the perovskite layer. The implementation of this intervention yielded a significant decrease in the levels of Sn4+ and trap densities. The power conversion efficiency of the device was achieved at 14.31 % through the optimization of carrier transportation. The device exhibited operational and long-term stability.

Sequential Passivation for Lead-Free Tin Perovskite Solar Cells with High Efficiency.

Lead-free tin perovskite solar cells (PKSCs) have attracted tremendous interest as a replacement for toxic lead-based PKSCs. Nevertheless, the efficiency is significantly low due to the rough surface morphology and high number of defects, which are caused by the fast crystallization and easy oxidization. In this study, a facile and universal posttreatment strategy of sequential passivation with acetylacetone (ACAC) and ethylenediamine (EDA) is proposed. The results show that ACAC can reduce the trap density and enlarge the grain size (short-circuit current (Jsc ) enhancement), while EDA can bond the undercoordinated tin and regulate the energy level (open-circuit voltage (Voc ) enhancement). A promising 13 % efficiency is achieved with better stability. In addition, other combinations of diketones or amines are selected, with similar effects. This study provides a universal strategy to enhance the crystallinity and passivate defects while fabricating stable PKSCs with high efficiency.

VOC Over 1.4 V for Amorphous Tin-Oxide-Based Dopant-Free CsPbI2Br Perovskite Solar Cells.

CsPbI2Br perovskite solar cells have attracted much attention because of the rapid development in their efficiency and their great potential as a top cell of tandem solar cells. However, the VOC outputs observed so far in most cases are far from that desired for a top cell. Up to now, with various kinds of treatments, the reported champion VOC is only 1.32 V, with a VOC deficit of 0.60 V. In this work, we found that aging of the SnCl2 precursor solution for the electron-transporting layer can promote the VOC of CsPbI2Br solar cells by employing a dopant-free-polymer hole transport material (HTM) over 1.40 V and efficiency over 15.5% with high reproducibility. With the champion VOC of 1.43 V, the VOC deficit was reduced to <0.50 V, which is achieved for the first time. This simple technique of SnCl2 solution aging forms a uniform and smooth amorphous SnOx film with pure Sn4+, elevates the conduction band of SnOx, and reduces the interfacial gaps and the trap state density of the device, resulting in enhancement in average VOC from ∼1.2 V in the nonaged case to ∼1.4 V in the aged case. Furthermore, the device using an aged SnCl2 solution also exhibits a much better long-term stability than that made of the fresh solution. These achievements in dopant/additive-free CsPbI2Br solar cells can be useful for future research on CsPbI2Br and tandem solar cells.

Near-Infrared Emission from Tin-Lead (Sn-Pb) Alloyed Perovskite Quantum Dots by Sodium Doping.

Phase-stable CsSnx Pb1-x I3 perovskite quantum dots (QDs) hold great promise for optoelectronic applications owing to their strong response in the near-infrared region. Unfortunately, optimal utilization of their potential is limited by the severe photoluminescence (PL) quenching, leading to extremely low quantum yields (QYs) of approximately 0.3 %. The ultra-low sodium (Na) doping presented herein is found to be effective in improving PL QYs of these alloyed QDs without alerting their favourable electronic structure. X-ray photoelectron spectroscopy (XPS) studies suggest the formation of a stronger chemical interaction between I- and Sn2+ ions upon Na doping, which potentially helps to stabilize Sn2+ and suppresses the formation of I vacancy defects. The optimized PL QY of the Na-doped QDs reaches up to around 28 %, almost two orders of magnitude enhancement compared with the pristine one.

Highly Efficient 17.6% Tin-Lead Mixed Perovskite Solar Cells Realized through Spike Structure.

Frequently observed high Voc loss in tin-lead mixed perovskite solar cells is considered to be one of the serious bottle-necks in spite of the high attainable Jsc due to wide wavelength photon harvesting. An amicable solution to minimize the Voc loss up to 0.50 V has been demonstrated by introducing an n-type interface with spike structure between the absorber and electron transport layer inspired by highly efficient Cu(In,Ga)Se2 solar cells. Introduction of a conduction band offset of ∼0.15 eV with a thin phenyl-C61-butyric acid methyl ester layer (∼25 nm) on the top of perovskite absorber resulted into improved Voc of 0.75 V leading to best power conversion efficiency of 17.6%. This enhancement is attributed to the facile charge flow at the interface owing to the reduction of interfacial traps and carrier recombination with spike structure as evidenced by time-resolved photoluminescence, nanosecond transient absorption, and electrochemical impedance spectroscopy measurements.

High Electrical Conductivity 2D MXene Serves as Additive of Perovskite for Efficient Solar Cells.

MXenes, a newly intriguing family of 2D materials, have recently attracted considerable attention owing to their excellent properties such as high electrical conductivity and mobility, tunable structure, and termination groups. Here, the Ti3 C2 Tx MXene is incorporated into the perovskite absorber layer for the first time, which aims for efficiency enhancement. Results show that the termination groups of Ti3 C2 Tx can retard the crystallization rate, thereby increasing the crystal size of CH3 NH3 PbI3 . It is found that the high electrical conductivity and mobility of MXene can accelerate the charge transfer. After optimizing the key parameters, 12% enhancement in device performance is achieved by 0.03 wt% amount of MXene additive. This work unlocks opportunities for the use of MXene as potential materials in perovskite solar cell applications.

All-Inorganic CsPb1-x Gex I2 Br Perovskite with Enhanced Phase Stability and Photovoltaic Performance.

Compared with organic-inorganic perovskites, all-inorganic cesium-based perovskites without volatile organic compounds have gained extensive interests because of the high thermal stability. However, they have a problem on phase transition from cubic phase (active for photo-electric conversion) to orthorhombic phase (inactive for photo-electric conversion) at room temperature, which has hindered further progress. Herein, novel inorganic CsPb1-x Gex I2 Br perovskites were prepared in humid ambient atmosphere without a glovebox. The phase stability of the all-inorganic perovskite was effectively enhanced after germanium addition. In addition, the highest power conversion efficiency of 10.8 % with high open-circuit voltage (VOC ) of 1.27 V in a planar solar cell based on CsPb0.8 Ge0.2 I2 Br perovskite was achieved. Furthermore, the highest VOC up to 1.34 V was obtained by CsPb0.7 Ge0.3 I2 Br perovskite, which is a remarkable record in the field of all-inorganic perovskite solar cells. More importantly, all the photovoltaic parameters of CsPb0.8 Ge0.2 I2 Br perovskite solar cells showed nearly no decay after 7 h measurement in 50-60 % relative humidity without encapsulation.

Colloidal Synthesis of Air-Stable Alloyed CsSn1-xPbxI3 Perovskite Nanocrystals for Use in Solar Cells.

Organic-inorganic hybrid perovskite solar cells have demonstrated unprecedented high power conversion efficiencies in the past few years. Now, the universal instability of the perovskites has become the main barrier for this kind of solar cells to realize commercialization. This situation can be even worse for those tin-based perovskites, especially for CsSnI3, because upon exposure to ambient atmosphere the desired black orthorhombic phase CsSnI3 would promptly lose single crystallinity and degrade to the inactive yellow phase, followed by irreversible oxidation into metallic Cs2SnI6. By alloying CsSnI3 with CsPbI3, we herein report the synthesis of alloyed perovskite quantum dot (QD), CsSn1-xPbxI3, which not only can be phase-stable for months in purified colloidal solution but also remains intact even directly exposed to ambient air, far superior to both of its parent CsSnI3 and CsPbI3 QDs. Ultrafast transient absorption spectroscopy studies reveal that the photoexcited electrons in the alloyed QDs can be injected into TiO2 nanocrystals at a fast rate of 1.12 × 1011 s-1, which enables a high photocurrent generation in solar cells.

Efficient near infrared fluorescence detection of elastase enzyme using peptide-bound unsymmetrical squaraine dye.

Extended wavelength analyte-responsive fluorescent probes are highly desired for the imaging applications owing to their deep tissue penetration, and minimum interference from autofluorescence by biomolecules. Near infra-red (NIR) sensitive and self-quenching fluorescent probe based on the dye-peptide conjugate (SQ 1 PC) was designed and synthesized by facile and efficient one-pot synthetic route for the detection of Elastase activity. In the phosphate buffer solution, there was an efficient quenching of fluorescence of SQ 1 PC (86%) assisted by pronounced dye-dye interaction due to H-aggregate formation. Efficient and fast recovery of this quenched fluorescence of SQ 1 PC (> 50% in 30s) was observed on hydrolysis of this peptide-dye conjugate by elastase enzyme. Presently designed NIR sensitive self-quenching substrate offers the potential application for the detection of diseases related to proteases by efficient and fast detection of their activities.

Ligand-dependent exciton dynamics and photovoltaic properties of PbS quantum dot heterojunction solar cells.

The surface chemistry of colloidal quantum dots (QDs) plays an important role in determining the photoelectric properties of QD films and the corresponding quantum dot heterojunction solar cells (QDHSCs). To investigate the effects of the ligand structure on the photovoltaic performance and exciton dynamics of QDHSCs, PbS QDHSCs were fabricated by the solid state ligand exchange method with mercaptoalkanoic acid as the cross-linking ligand. Temperature-dependent photoluminescence and ultrafast transient absorption spectra show that the electronic coupling and charge transfer rate within QD ensembles were monotonically enhanced as the ligand length decreased. However, in practical QDHSCs, the second shortest ligand 3-mercaptopropionic acid (MPA) showed higher power conversion efficiency than the shortest ligand thioglycolic acid (TGA). This could be attributed to the difference in their surface trap states, supported by thermally stimulated current measurements. Moreover, compared with the non-conjugated ligand MPA, the conjugated ligand 4-mercaptobenzoic acid (MBA) introduces less trap states and has a similar charge transfer rate in QD ensembles, but has poor photovoltaic properties. This unexpected result could be contributed by the QD-ligand orbital mixing, leading to the charge transfer from QDs to ligands instead of charge transfer between adjacent QDs. This work highlights the significant effects of ligand structures on the photovoltaic properties and exciton dynamics of QDHSCs, which would shed light on the further development of QD-based photoelectric devices.

Rapid Synthesis of D-A'-π-A Dyes through a One-Pot Three-Component Suzuki-Miyaura Coupling and an Evaluation of their Photovoltaic Properties for Use in Dye-Sensitized Solar Cells.

Twenty-four D-A'-π-A dyes were rapidly synthesized through a one-pot three-component Suzuki-Miyaura coupling reaction, which was assisted by microwave irradiation. We measured the absorption spectra, electrochemical properties, and solar-cell performance of all the synthesized dyes. The D5 πA4 dye contained our originally designed rigid and nonplanar donor and exerted the highest efficiency at 5.4 %. The short-circuit current (Jsc ) was the most important parameter for the conversion efficiency (η) in the case of the organic D-A'-π-A dyes. Optimal ranges for the D-A'-π-A dyes were observed for high values of Jsc /λmax at λ=560-620 nm, an optical-absorption edge of λ=690-790 nm, and EHOMO and ELUMO values of <1.14 and -0.56 to -0.76 V, respectively.

Mechanisms of charge accumulation in the dark operation of perovskite solar cells.

In this work, a new current peak at forward bias in the dark current-voltage curves has been identified for standard mesoscopic perovskite solar cells. This characteristic peak appears only under some specific conditions, mainly in the reverse scan (RS) direction and when the solar cells were kept for several seconds under short-circuit conditions before starting the RS measurement. This peak disappears when the above experimental conditions are not applied. It is considered that this uncommon diode shape is obtained because shallow and/or deep trap states located at the interface between either perovskite/p-type or perovskite/n-type transport materials are dynamically filled during the RS voltage scan. To corroborate this hypothesis, the response of hole transport materials (HTMs), small molecule spiro-OMeTAD and polymer P3HT, as well as both HTMs with additives, was compared. Also perovskite absorbers such as CH3NH3PbI3 and all-inorganic perovskite based on cesium (CsPbI3) were also analyzed, achieving in all cases similar trends.

Rapid Synthesis of Thiophene-Based, Organic Dyes for Dye-Sensitized Solar Cells (DSSCs) by a One-Pot, Four-Component Coupling Approach.

This one-pot, four-component coupling approach (Suzuki-Miyaura coupling/C-H direct arylation/Knoevenagel condensation) was developed for the rapid synthesis of thiophene-based organic dyes for dye-sensitized solar cells (DSSCs). Seven thiophene-based, organic dyes of various donor structures with/without the use of a 3,4-ethylenedioxythiophene (EDOT) moiety were successfully synthesized in good yields based on a readily available thiophene boronic acid pinacol ester scaffold (one-pot, 3-step, 35-61%). Evaluation of the photovoltaic properties of the solar cells that were prepared using the synthesized dyes revealed that the introduction of an EDOT structure beside a cyanoacrylic acid moiety improved the short-circuit current (Jsc) while decreasing the fill factor (FF). The donor structure significantly influenced the open-circuit voltage (Voc), the FF, and the power conversion efficiency (PCE). The use of a n-hexyloxyphenyl amine donor, and our originally developed, rigid, and nonplanar donor, both promoted good cell performance (η=5.2-5.6%).

Improved understanding of the electronic and energetic landscapes of perovskite solar cells: high local charge carrier mobility, reduced recombination, and extremely shallow traps.

The intriguing photoactive features of organic-inorganic hybrid perovskites have enabled the preparation of a new class of highly efficient solar cells. However, the fundamental properties, upon which the performance of these devices is based, are currently under-explored, making their elucidation a vital issue. Herein, we have investigated the local mobility, recombination, and energetic landscape of charge carriers in a prototype CH3NH3PbI3 perovskite (PVK) using a laser-flash time-resolved microwave conductivity (TRMC) technique. PVK was prepared on mesoporous TiO2 and Al2O3 by one or two-step sequential deposition. PVK on mesoporous TiO2 exhibited a charge carrier mobility of 20 cm(2) V(-1) s(-1), which was predominantly attributed to holes. PVK on mesoporous Al2O3, on the other hand, exhibited a 50% lower mobility, which was resolved into balanced contributions from both holes and electrons. A general correlation between crystal size and mobility was revealed irrespective of the fabrication process and underlying layer. Modulating the microwave frequency from 9 toward 23 GHz allowed us to determine the intrinsic mobilities of each PVK sample (60-75 cm(2) V(-1) s(-1)), which were mostly independent of the mesoporous scaffold. Kinetic and frequency analysis of the transient complex conductivity strongly support the superiority of the perovskite, based on a significant suppression of charge recombination, an extremely shallow trap depth (10 meV), and a low concentration of these trapped states (less than 10%). The transport mechanism was further investigated by examining the temperature dependence of the TRMC maxima. Our study provides a basis for understanding perovskite solar cell operation, while highlighting the importance of the mesoporous layer and the perovskite fabrication process.

Elucidating the structure-property relationships of donor-π-acceptor dyes for dye-sensitized solar cells (DSSCs) through rapid library synthesis by a one-pot procedure.

The creation of organic dyes with excellent high power conversion efficiency (PCE) is important for the further improvement of dye-sensitized solar cells. We wish to describe the rapid synthesis of a 112-membered donor-π-acceptor dye library by a one-pot procedure, evaluation of PCEs, and elucidation of structure-property relationships. No obvious correlations between ε, and the η were observed, whereas the HOMO and LUMO levels of the dyes were critical for η. The dyes with a more positive E(HOMO), and with an E(LUMO)<-0.80 V, exerted higher PCEs. The proper driving forces were crucial for a high J(sc), and it was the most important parameter for a high η. The above criteria of E(HOMO) and E(LUMO) should be useful for creating high PCE dyes; nevertheless, that was not sufficient for identifying the best combination of donor, π, and acceptor blocks. Combinatorial synthesis and evaluation was important for identifying the best dye.

Control of charge dynamics through a charge-separation interface for all-solid perovskite-sensitized solar cells.

The relationship between the structure of the charge-separation interface and the photovoltaic performance of all-solid dye-sensitized solar cells is reported. This cell is composed of porous a TiO2/perovskite (CH3NH3PbI(x)Cl(3-x))/p-type organic conductor. The porous titania layer was passivated with Al2O3 or Y2O3 to remove surface traps of the porous titania layer. Both passivations were effective in increasing the efficiency of the solar cell. Especially, the effect of Y2O3 passivation was remarkable. After passivation, the efficiency increased from 6.59 to 7.5%. The increase in the efficiency was discussed in terms of the electron lifetime in TiO2, the thermally stimulated current, the measurement of the microwave refractive carrier lifetime, and transition absorption spectroscopy. It was proven that surface passivation resulted in retardation of charge recombination between the electrons in the porous titania layers and the holes in the p-type organic conductors.

Charge transfer and recombination at the metal oxide/CH3NH3PbClI2/spiro-OMeTAD interfaces: uncovering the detailed mechanism behind high efficiency solar cells.

In recent years, organometal halide perovskite-based solid-state hybrid solar cells have attracted unexpected increasing interest because of their high efficiency (the record power conversion efficiency has been reported to be over 15%) and low fabrication cost. It has been accepted that the high efficiency was mainly attributed to the strong optical absorption (absorption coefficient: 15,000 cm(-1) at 550 nm) over a broader range (up to 800 nm) and the long lifetimes of photoexcited charge carriers (in the order of 10 ns - a few 100 ns) of the perovskite absorbers. However, much of the fundamental photophysical properties of perovskite relating to the high photovoltaic performance are remained to be investigated. The charge separation and recombination processes at the material interfaces are particularly important for solar cell performances. To better understand the high efficiency of perovskite solar cells, we systematically investigated the charge separation (electron and hole injection) and charge recombination dynamics of CH3NH3PbClI2 hybrid solar cells employing TiO2 nanostructures as the electron transfer material (ETM) and spiro-OMeTAD as the hole transfer material (HTM). The measurements were carried out using transient absorption (TA) techniques on a time scale from sub-picoseconds to milliseconds. We clarified the timescales of electron injection, hole injection, and recombination processes in TiO2/CH3NH3PbClI2/spiro-OMeTAD solar cells. Charge separation and collection efficiency of the perovskite-based solar cells were discussed. In addition, the effect of TiO2 size on the charge separation and recombination dynamics was also investigated. It was found that all TiO2-based perovskite solar cells possessed similar charge separation processes, but quite different recombination dynamics. Our results indicate that charge recombination was crucial to the performance of the perovskite solar cells, which could be effectively suppressed through optimising nanostructured TiO2 films and surface passivation, thus pushing these cells to even higher efficiency.

Classifying the Role of Surface Ligands on the Passivation and Stability of Cs2NaInCl6 Double Perovskite Quantum Dots.

Cs2NaInCl6 double perovskites, which have excellent photoelectric conversion properties and are non-toxic and lead-free, have recently gained significant attention. In particular, double-perovskite quantum dots (QDs) are viewed as a promising material for optoelectronic device applications. Ligands such as oleic acid (OA) and oleylamine (OAm) are essential for the synthesis of perovskite QDs, but their specific roles in double-perovskite QDs remain unclear. In this study, we have investigated the binding of OA and OAm to Cs2NaInCl6 QDs through FTIR and NMR and their effects on the surface defect reduction and stability improvement for Cs2NaInCl6 QDs. We found that only OAm was bound to the QD surfaces while OA was not. The OAm has a significant effect on the photoluminescence quantum yield (PLQY) improvement by passivating the QD surface defects. The stability of the QDs was also evaluated, and it was observed that OA played a significant role in the stability of the QDs. Our findings provide valuable insights into the roles of ligands in influencing the photophysical properties and stability of lead-free double-perovskite QDs.