CoO x is a promising hole-extracting layer (HEL) for inverted planar perovskite solar cells with device configuration ITO/CoO x /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%), NiO x (10.2%), and CuO x (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 CoO x (2.8 ns) < PEDOT:PSS (17.5 ns) < NiO x (22.8 ns) < CuO x (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 CoO x device retained PCE ≈ 12% for over 1000 h.
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.
Reduced graphene oxides (rGO) are synthesized via reduction of GO with reducing agents as a hole‐extraction layer for high‐performance inverted planar heterojunction perovskite solar cells. The best ...efficiencies of power conversion (PCE) of these rGO cells exceed 16%, much greater than those made of GO and poly(3,4‐ethenedioxythiophene):poly(styrenesulfonate) films. A flexible rGO device shows PCE 13.8% and maintains 70% of its initial performance over 150 bending cycles. It is found that the hole‐extraction period is much smaller for the GO/methylammonium lead‐iodide perovskite (PSK) film than for the other rGO/PSK films, which contradicts their device performances. Photoluminescence and transient photoelectric decays are measured and control experiments are performed to prove that the reduction of the oxygen‐containing groups in GO significantly decreases the ability of hole extraction from PSK to rGO and also retards the charge recombination at the rGO/PSK interface. When the hole injection from PSK to GO occurs rapidly, hole propagation from GO to the indium‐doped tin oxide (ITO) substrate becomes a bottleneck to overcome, which leads to a rapid charge recombination that decreases the performance of the GO device relative to the rGO device.
An anomalous charge‐extraction behavior is observed for the graphene oxide (GO) film showing more rapid hole‐extraction characteristic than that of the reduced graphene oxide (rGO) film, but the corresponding photovoltaic performances show an opposite trend. The rapid charge extraction in GO also leads to a rapid charge recombination so that the GO device shows poorer performance than the rGO device (13.8% vs 16.4%).
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 AZxFA1‐xSnI3. As AZ has a similar size to FA but a larger dipole moment, hybrid AZxFA1‐xSnI3 films exhibit variation in optical and electronic properties on increasing the proportion of AZ. Trifluoromethylbenzene (CF3C6H5) 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.
Can we mix it? Yes we can! Mixing 15 % of azetidinium (AZ) inside a FASnI3 perovskite crystal enhances the device performance to attain a power conversion efficiency of 9.6 % with excellent stability for the unencapsulated device, which retains 90 % of its initial performance for over 15 days.
Abstract
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@Cu
7
...S
4
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@Cu
7
S
4
under both visible and near infrared excitation. Combined with the advantageous features of yolk@shell nanostructures, Au@Cu
7
S
4
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.
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.
Photoluminescence (PL) of a nanocrystalline film of methylammonium lead iodide perovskite (MAPbI3) sandwiched between an electrode of a fluorine-doped tin oxide (FTO) layer and an insulating film of ...poly(methyl methacrylate) is found to increase and decrease significantly with the application of an external electric field ( F ext), depending on the direction of the applied field, based on the measurements of electrophotoluminescence (E-PL) spectra, i.e., field-induced change in PL spectra. The field-induced change in PL intensity is confirmed to originate from the field-induced change in the number of free carriers which induce radiative recombination, based on temporally resolved E-PL measurements. We propose that an internal field ( F int) exists even without application of F ext. The anisotropic behavior of the effect of F ext on PL is interpreted in terms of a synergy effect of F int and F ext; both fields are additive with the applied field direction from Ag to FTO electrode (positive direction) or subtractive with the opposite applied field direction (negative direction), where FTO is the positive electrode, resulting in an increased or decreased total electric field as well as quenching or enhancement of PL, respectively. The PL lifetime in the nanosecond region increased and decreased with an application of an electric field in the positive and negative directions, respectively, which is attributed to a field-induced change in the concentration of free carriers.
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 Cs
FA
PbBr
I
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.
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.
Who receives the electron? A thorough kinetic analysis of time‐resolved near‐ and mid‐IR spectra has clarified the mechanism of back electron transfer in the intermolecular photoinduced electron transfer reaction of pyrene and 1,4‐dicyanobenzene in acetonitrile (see figure). We found that acetonitrile plays a key role as a charge mediator between the charge carriers induced after photoexcitation and thus governs the overall charge recombination dynamics.
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 NO2 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.
The third structure: A combination of time‐resolved dispersive IR spectroscopy and DFT calculations reveals that the lowest excited triplet state of p‐nitroaniline has a partial quinoid structure, in apparent contradiction to the conventional picture based on characteristic resonance structures, such as neutral and zwitterionic charge‐transfer forms (see figure).
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