Co-Cation Engineering via Mixing of Acetamidinium and Rubidium in FASnI3 for Tin Perovskite Solar Cells to Attain 14.5% Efficiency.

Tin perovskite solar cells (TPSCs) were developed by adding the co-cations acetamidinium (AC) and rubidium (Rb) in varied proportions based on the FASnI3 structure (E1). We found that adding 10% AC and 3% Rb can optimize the device (E1AC10Rb3) to attain an efficiency of power conversion of 14.5% with great shelf- and light-soaking stability. The films at varied AC and Rb proportions were characterized using XPS, SEM, AFM, GIWAXS, XRD, TOPAS, TOF-SIMS, UV-vis, PL, TCSPC, and femtosecond TAS techniques to show the excellent optoelectronic properties of the E1AC10Rb3 film in comparison to those of the other films. AC was found to have the effect of passivating the vacancy defects on the surface and near the bottom of the film, while Rb plays a pivotal role in passivating the bottom interface between perovskite and PEDOT:PSS. Therefore, the E1AC10Rb3 device with a band gap of 1.43 eV becomes a promising candidate as a narrow band gap device for tandem lead-free perovskite solar cell development.

Dual-plasmonic Au@Cu7S4 yolk@shell nanocrystals for photocatalytic hydrogen production across visible to near infrared spectral region.

Near infrared energy remains untapped toward the maneuvering of entire solar spectrum harvesting for fulfilling the nuts and bolts of solar hydrogen production. We report the use of Au@Cu7S4 yolk@shell nanocrystals as dual-plasmonic photocatalysts to achieve remarkable hydrogen production under visible and near infrared illumination. Ultrafast spectroscopic data reveal the prevalence of long-lived charge separation states for Au@Cu7S4 under both visible and near infrared excitation. Combined with the advantageous features of yolk@shell nanostructures, Au@Cu7S4 achieves a peak quantum yield of 9.4% at 500 nm and a record-breaking quantum yield of 7.3% at 2200 nm for hydrogen production in the absence of additional co-catalysts. The design of a sustainable visible- and near infrared-responsive photocatalytic system is expected to inspire further widespread applications in solar fuel generation. In this work, the feasibility of exploiting the localized surface plasmon resonance property of self-doped, nonstoichiometric semiconductor nanocrystals for the realization of wide-spectrum-driven photocatalysis is highlighted.

Highly Efficient HTM-Free Tin Perovskite Solar Cells with Outstanding Stability Exceeding 10000 h.

The bottleneck in the rapid development of tin-based perovskite solar cells (TPSCs) is the inherent chemical instability. Although this is being addressed continuously, the device performance has not improved further due to the use of PEDOT:PSS as the hole-transport material (HTM), which has poor long-term stability. Herein we have applied commercial ITO nanoparticles over ITO glass substrates and altered the surface chemistry of the ITO electrode via a simple two-step thermal annealing, followed by a UV-ozone treatment. These surface-modified ITO electrodes display promising interfacial characteristics, such as a suitable band alignment owing to significantly reduced surface carbon contamination, increased In-O bonding, and reduced oxygen vacancies, that enabled fabrication of an HTM-free TPSC device according to a two-step method. The fabricated device possessed an outstanding power conversion efficiency (PCE) of 9.7%, along with a superior long-term stability by retaining over 90% of the initial PCE upon shelf storage in a glovebox for a period of over 10000 h. The application of ITO nanoparticles led to effective interfacial passivation, whose impacts on the long-term durability were assessed using electrochemical impedance spectroscopy, time-resolved photoluminescence decay profiles, and femtosecond transient absorption spectroscopy techniques.

Effect of Acidic Strength of Surface Ligands on the Carrier Relaxation Dynamics of Hybrid Perovskite Nanocrystals.

Perovskite nanocrystals (PeNCs) are known for their use in numerous optoelectronic applications. Surface ligands are critical for passivating surface defects to enhance the charge transport and photoluminescence quantum yields of the PeNCs. Herein, we investigated the dual functional abilities of bulky cyclic organic ammonium cations as surface-passivating agents and charge scavengers to overcome the lability and insulating nature of conventional long-chain type oleyl amine and oleic acid ligands. Here, red-emitting hybrid PeNCs of the composition CsxFA(1-x)PbBryI(3-y) are chosen as the standard (Std) sample, where cyclohexylammonium (CHA), phenylethylammonium (PEA) and (trifuluoromethyl)benzylamonium (TFB) cations were chosen as the bifunctional surface-passivating ligands. Photoluminescence decay dynamics showed that the chosen cyclic ligands could successfully eliminate the shallow defect-mediated decay process. Further, femtosecond transient absorption spectral (TAS) studies uncovered the rapidly decaying non-radiative pathways; i.e., charge extraction (trapping) by the surface ligands. The charge extraction rates of the bulky cyclic organic ammonium cations were shown to depend on their acid dissociation constant (pKa) values and actinic excitation energies. Excitation wavelength-dependent TAS studies indicate that the exciton trapping rate is slower than the carrier trapping rate of these surface ligands.

Energy and Charge Transfer Dynamics in Red-Emitting Hybrid Organo-Inorganic Mixed Halide Perovskite Nanocrystals.

We report time-resolved spectral properties of highly stable and efficient red-emitting hybrid perovskite nanocrystals with the composition FA0.5MA0.5PbBr0.5I2.5 (FAMA PeNC) synthesized by using the hot-addition method. The PL spectrum of the FAMA PeNC shows a broad asymmetric band covering 580 to 760 nm with a peak at 690 nm which can be deconvoluted into two bands corresponding to the MA and FA domains. The interactions between the MA and FA domains are shown to affect the relaxation dynamics of the PeNCs from the subpicosecond to tens of nanoseconds scale. Time-correlated single-photon counting (TCSPC), femtosecond PL optical gating (FOG), and femtosecond transient absorption spectral (TAS) techniques were employed to study the intercrystal energy transfer (photon recycling) and intracrystal charge transfer processes between the MA and the FA domains of the crystals. These two processes are shown to increase the radiative lifetimes for the PLQYs exceeding 80%, which may play a key role in enhancing the performance of PeNC-based solar cells.

Retarded Charge Recombination to Enhance Photocatalytic Performance for Water-Free CO2 Reduction Using Perovskite Nanocrystals as Photocatalysts.

Femtosecond transient absorption spectral (TAS) investigations were performed to understand the carrier relaxation mechanism for perovskite nanocrystals Cs1-xFAxPbBr3 (CF, x = 0.45) and CsPbBr3 (CS), which served as efficient photocatalysts for splitting of CO2 into CO and O2 in the absence of water. Upon light irradiation for 12 h, formation of deep trap states was found for both CS and CF samples with spectral characteristics of the TAS photobleach (PB) band showing a long spectral tail extending to the long wavelength region. The charge recombination rates at the shallow surface states, bulk states, and deep-trapped surface state were found to be significantly retarded for the CF sample than for the CS sample, in agreement with the photocatalytic performances for CO product yields of the CF catalyst being greater by a factor of 3 compared to those of the CS catalyst.

Interface-Enhanced Charge Recombination in the Heterojunction between Perovskite Nanocrystals and BiOI Nanosheets Serves as an S-Scheme Photocatalyst for CO2 Reduction.

We designed an S-heterojunction system with a perovskite nanocrystal, Cs1-xFAxPbBr3 (CF), coupled with a bismuth oxyiodide (BiOI) nanosheet to form a perovskite heterojunction (PHJ) photocatalyst. On the basis of femtosecond transient absorption measurements, the pristine CF sample has two charge recombination periods, 100 and 900 ps, corresponding to surface and bulk trap-state relaxations, respectively. When CF was in contact with BiOI to form an S-heterojunction, rapid interfacial charge recombination occurred to show two decay components with time coefficients 1 and 35 ps, responsible for the electron-hole recombination in the surface and bulk states, respectively. We observed a new photoinduced absorption band on the blue side of the photobleach band of PHJ that gives relaxation more rapid than that of pristine CF, presumably due to doping of bismuth cations creating defect states to enhance the charge recombination that leads to photocatalytic performance for the PHJ catalyst poorer than for the pristine CF sample.

Femtosecond Exciton and Carrier Relaxation Dynamics of Two-Dimensional (2D) and Quasi-2D Tin Perovskites.

The dynamics of exciton and free-carrier relaxation of low-dimensional tin iodide perovskites, BA2FAn-1SnnI3n+1, where n = 1 (N1), 2 (N2), 5 (N5), and 10 (N10), were investigated with femtosecond transient absorption spectra (TAS). The absorption and photoluminescence spectra of N1 and N2 show exciton characteristics due to quantum confinement, whereas N5 and N10 display a free-carrier nature, the same as for bulk three-dimensional (3D) films. The TAS profiles were fitted according to a global kinetic model with three time coefficients representing the interactions of biexcitons, trions, and excitons for N1 and N2 and hot carriers, cold carriers, and shallow trap carriers for N5 and N10. The carrier relaxation dynamics of N5 and N10 were similar to those of 3D FASnI3 except for the absence of surface recombination in the deep-trap states due to passivation of the grain surfaces by the long alkyl chain for these quasi-2D samples (N5/N10 vs 3D).

Mixing of Azetidinium in Formamidinium Tin Triiodide Perovskite Solar Cells for Enhanced Photovoltaic Performance and High Stability in Air.

Overcoming the issue of the stability of tin-based perovskites is a major challenge for the commercial development of lead-free perovskite solar cells. To attack this problem, a new organic cation, azetidinium (AZ), is incorporated into the crystal structure of formamidinium tin triiodide (FASnI3 ) to form the mixed-cation perovskite AZx FA1-x SnI3 . As AZ has a similar size to FA but a larger dipole moment, hybrid AZx FA1-x SnI3 films exhibit variation in optical and electronic properties on increasing the proportion of AZ. Trifluoromethylbenzene (CF3 C6 H5 ) serves as antisolvent to fabricate smooth and uniform perovskite films for the devices with an inverted planar heterojunction structure. The device performance is optimized to produce the greatest efficiency at x=0.15 (AZ15), for which a power conversion efficiency of 9.6 % is obtained when the unencapsulated AZ15 device is stored in air for 100 h. Moreover, the device retains 90 % of its initial efficiency for over 15 days. The significant performance and stability of this device reveal that the concept of mixed cations is a promising approach to stabilize tin-based perovskite solar cells for future commercialization.

Femtosecond Transient Absorption Spectra and Dynamics of Carrier Relaxation of Tin Perovskites in the Absence and Presence of Additives.

The effects of additives SnF2 (10%) and EDAI2 (1%) on the dynamics of carrier relaxation of formamidinium tin triiodide (FASnI3) perovskite were studied using femtosecond transient absorption spectra (TAS) with excitation at 600 and 870 nm. The TAS were analyzed according to a parallel sequential kinetic model with a global fit through singular-value decomposition. For excitation at 600 nm, two relaxation paths were found: one involved hot and cold carriers in the bulk state undergoing shallow bulk-defect-mediated charge recombination; the other involved trap carriers in the surface state undergoing deep surface-defect-mediated charge recombination. For excitation at 870 nm, only cold carriers were subjected to the bulk-state relaxation channel. Our spectral results indicate significant effects of the additives on retarding charge recombination in both bulk and surface states as well as decreasing the bandgap renormalization energy, the bandwidth of the photobleaching (PB) band, and the Stokes shift between the PB and photoluminescence bands, explaining how the device performance of FASnI3 solar cells became enhanced in the presence of SnF2 and EDAI2.

Development of Hybrid Pseudohalide Tin Perovskites for Highly Stable Carbon-Electrode Solar Cells.

Tin-based perovskites degrade rapidly upon interaction with water and oxygen in air because Sn-I bonds are weak. To address this issue, we developed novel tin perovskites, FASnI(3-x)(SCN)x (x = 0, 1, 2, or 3), by employing a pseudohalide, thiocyanate (SCN-), as a replacement for halides and as an inhibitor to suppress the Sn2+/Sn4+ oxidation. The structural and electronic properties of pseudohalide tin perovskites in this series were explored with quantum-chemical calculations by employing the plane-wave density functional theory (DFT) method; the corresponding results are consistent with the experimental results. Carbon-based perovskite devices fabricated with tin perovskite FASnI(SCN)2 showed about a threefold enhancement of the device efficiency (2.4%) relative to that of the best FASnI3-based device (0.9%), which we attribute to the improved suppression of the formation of Sn4+, retarded charge recombination, enhanced hydrophobicity, and stronger interactions between Sn and thiocyanate for FASnI(SCN)2 than those for FASnI3. After the incorporation of phenylethyleneammonium iodide (PEAI, 10%) and ethylenediammonium diiodide (EDAI2, 5%) as coadditives, the FASnI(SCN)2 device gave the best photovoltaic performance with JSC = 20.17 mA cm-2, VOC = 322 mV, fill factor (FF) = 0.574, and overall efficiency of power conversion PCE = 3.7%. Moreover, these pseudohalide-containing devices display negligible photocurrent-voltage hysteresis and great stability in ambient air conditions.

Interfacial Investigation on Printable Carbon-Based Mesoscopic Perovskite Solar Cells with NiOx/C Back Electrode.

Solar cells with high efficiency, low cost, and high stability are the target for the new generation of solar cells. A fully printable perovskite (CH3NH3PbI3) solar cell (PSC) with device architecture FTO/TiO2/Al2O3/NiOx/C is fabricated in the current research as a low-cost and relatively stable structure and is investigated to determine how different fabrication factors such as the thickness of the insulating spacer layer (Al2O3) or treatments such as heat and UV-O3 treatments can affect the interfacial properties of this multilayer mesoporous structure. X-ray photoelectron spectra (XPS) show that UV-O3 treatment increases the Ni3+(Ni2O3) phase on the surface of the black nickel oxide layer leading to better charge extraction and increasing open-circuit voltage (VOC) up to 0.945 V. We observe improved CH3NH3PbI3 formation inside the mesoporous layers by the PbI2 penetration at a higher temperature. Impedance spectral together with current-voltage measurements show the effect of thickness for the insulator layer in the internal and interfacial resistances and photovoltaic characteristics of the cell. The best performance of the carbon-based PSC attains power conversion efficiency of 12.1% with the thickness of the Al2O3 layer at 450 nm.

Cobalt Oxide (CoOx) as an Efficient Hole-Extracting Layer for High-Performance Inverted Planar Perovskite Solar Cells.

CoOx is a promising hole-extracting layer (HEL) for inverted planar perovskite solar cells with device configuration ITO/CoOx/CH3NH3PbI3/PCBM/Ag. The devices fabricated according to a simple solution procedure showed the best photovoltaic performance attaining power conversion efficiency (PCE) of 14.5% under AM 1.5 G 1 sun irradiation, which is significantly superior to those of materials fabricated with a traditional HEL such as PEDOT:PSS (12.2%), NiOx (10.2%), and CuOx (9.4%) under the same experimental conditions. We characterized the chemical compositions with XPS, crystal structures with XRD, and film morphology with SEM/AFM techniques. Photoluminescence (PL) spectra and the corresponding PL decays for perovskite deposited on varied HEL films were recorded to obtain the hole-extracting characteristics, for which the hole-extracting times show the order CoOx (2.8 ns) < PEDOT:PSS (17.5 ns) < NiOx (22.8 ns) < CuOx (208.5 ns), consistent with the trend of their photovoltaic performances. The reproducibility and enduring stability of those devices were examined to show the outstanding long-term stability of the devices made of metal oxide HEL, for which the CoOx device retained PCE ≈ 12% for over 1000 h.

Simultaneous Observation of an Intraband Transition and Distinct Transient Species in the Infrared Region for Perovskite Solar Cells.

Solar cells based on organometal-halide perovskites such as CH3NH3PbI3 have emerged as a promising next-generation photovoltaic system, but the underlying photophysics and photochemistry remain to be established because of the limited availability of methods to implement the simultaneous and direct measurement of various charge carriers and ions that play a crucial role in the operating device. We used nanosecond time-resolved infrared (IR) spectroscopy to investigate, with high molecular specificity, distinct transient species that are formed in perovskite solar cells after photoexcitation. In CH3NH3PbI3 planar-heterojuction solar cells, we simultaneously observed infrared spectral signatures that are associated with an intraband transition of conduction-band electrons, Fano resonance, and the spiro-OMeTAD cation having an exceptionally short lifetime of 1.0 µs (at ∼1485 cm(-1)). The present results show that the time-resolved IR method offers a unique capability to elucidate these important transients in perovskite solar cells and their dynamic interplay in a comprehensive manner.

Direct observation of the solvent effects on the low-lying nπ* and ππ* excited triplet states of acetophenone derivatives in thermal equilibrium.

Low-lying excited triplet states of aromatic carbonyl compounds exhibit diverse photophysical and photochemical properties of fundamental importance. Despite tremendous effort in studying those triplet states, the effects of substituents and solvents on the energetics of the triplet manifold and on photoreactivity remain to be fully understood. We have recently studied the ordering of the low-lying nπ* and ππ* excited triplet states and its substituent dependence in acetophenone derivatives using nanosecond time-resolved near-IR (NIR) spectroscopy. Here we address the other important issue, the solvent effects, by directly observing the electronic bands in the NIR that originate from the lowest nπ* and ππ* states of acetophenone derivatives in four solvents of different polarity (n-heptane, benzene, acetonitrile, and methanol). The two transient NIR bands decay synchronously in all the solvents, indicating that the lowest nπ* and ππ* states are in thermal equilibrium irrespective of the solvent polarity studied here. We found that the ππ* band increases in intensity relative to the nπ* band as solvent polarity increases. These results are compared with the photoreduction rate constant for the acetophenone derivatives in the solvents to which 2-propanol was added as a hydrogen-atom donor. Based on the present findings, we present a comprehensive, solvent- and substituent-dependent energy level diagram of the low-lying nπ* and ππ* excited triplet states.

Mechanism of back electron transfer in an intermolecular photoinduced electron transfer reaction: solvent as a charge mediator.

Back electron transfer (BET) is one of the important processes that govern the decay of generated ion pairs in intermolecular photoinduced electron transfer reactions. Unfortunately, a detailed mechanism of BET reactions remains largely unknown in spite of their importance for the development of molecular photovoltaic structures. Here, we examine the BET reaction of pyrene (Py) and 1,4-dicyanobenzene (DCB) in acetonitrile (ACN) by using time-resolved near- and mid-IR spectroscopy. The Py dimer radical cation (Py2(·+)) and DCB radical anion (DCB(·-)) generated after photoexcitation of Py show asynchronous decay kinetics. To account for this observation, we propose a reaction mechanism that involves electron transfer from DCB(·-) to the solvent and charge recombination between the resulting ACN dimer anion and Py2(·+). The unique role of ACN as a charge mediator revealed herein could have implications for strategies that retard charge recombination in dye-sensitized solar cells.

Is our way of thinking about excited states correct? Time-resolved dispersive IR study on p-nitroaniline.

Low-lying excited electronic states of an important class of molecules known as push-pull chromophores are central to understanding their potential nonlinear optical properties. Here we report that a combination of high-sensitivity nanosecond time-resolved dispersive IR spectroscopy and DFT calculations on p-nitroaniline (PNA), a prototypical push-pull molecule, reveals that PNA in the lowest excited triplet state has a partial quinoid structure. In this structure, the quinoid configuration is restricted to a part of the phenyl ring adjacent to the NO(2) group. The partial quinoid structure of PNA cannot be explained by a commonly used hybrid of a neutral form and a zwitterionic charge-transfer form. Our findings not only cast doubt on the general applicability of the classical way of looking at excited states, based exclusively on characteristic resonance structures, but also provide deeper insights into excited-state structure of highly polarizable molecular systems.