Revealing the Degradation and Self-Healing Mechanisms in Perovskite Solar Cells by Sub-Bandgap External Quantum Efficiency Spectroscopy.

Ion dissociation has been identified to determine the intrinsic stability of perovskite solar cells (PVSCs), but the underlying degradation mechanism is still elusive. Herein, by combining highly sensitive sub-bandgap external quantum efficiency (s-EQE) spectroscopy, impedance analysis, and theoretical calculations, the evolution of defect states in PVSCs during the degradation can be monitored. It is found that the degradation of PVSCs can be divided into three steps: 1) dissociation of ions from perovskite lattices, 2) migration of dissociated ions, and 3) consumption of I- by reacting with metal electrode. Importantly, step (3) is found to be crucial as it will accelerate the first two steps and lead to continuous degradation. By replacing the metal with more chemically robust indium tin oxide (ITO), it is found that the dissociated ions under light soaking will only saturate at the perovskite/ITO interface. Importantly, the dissociated ions will subsequently restore to the corresponding vacancies under dark condition to heal the perovskite and photovoltaic performance. Such shuttling of mobile ions without consumption in the ITO-contact PVSCs results in harvesting-rest-recovery cycles in natural day/night operation. It is envisioned that the mechanism of the intrinsic perovskite material degradation reported here will lead to clearer research directions toward highly stable PVSCs.

Charge transfer-induced photoluminescence in ZnO nanoparticles.

The quality of solution-processed zinc oxide (ZnO) nanoparticles (NPs) is often correlated with their photoluminescence (PL) spectral characteristics. However, the reported PL spectral characteristics lack consistency and remain controversial. Here we report that "defect-emission free" PL spectra can even be obtained in thin films composed of as-synthesized ZnO NPs. It is found that both the PL spectral line-shape and intensity are extremely sensitive to nitrogen and oxygen. By conducting time-dependent PL (t-PL) and photothermal deflection spectroscopy (PDS) measurements under vacuum and different gases, it is proposed that both inert (N2) and reactive (O2) molecules can be absorbed on the ZnO NP surface and induce charge transfer (CT). The CT states induced by N2 are non-radiative which significantly reduces the band emission. Whereas the CT states induced by O2 are radiative at the visible region, and the exciton transfer is efficient which increases the overall PL quantum yield. Owing to such effects, the previously reported correlation between defects and PL emission becomes questionable and needs to be revisited. Particularly, the visible emission from the ZnO NPs is proved to be facilitated by external effects, instead of direct recombination from defect states.

Evidence on Enhanced Exciton Polarizability in Donor/Acceptor Bulk Heterojunction Organic Photovoltaics.

Using electroabsorption spectroscopy, we explore the polarizability of Frenkel excitons in both pristine donor and D/A blend films. We observe for the first time that the polarizability of excitonic states in pristine donors can be dramatically increased by adding an n-type acceptor. By investigating the dielectric effect in different organic semiconductor systems, we find that the polarizability of Frenkel excitons has direct correlation with the measured dielectric constant of the bulk heterojunction thin films. Our results disclose the difference in the nature of Frenkel excitons in pristine donor and D/A blend systems, revealing an important role of excitonic states in charge separation process of organic photovoltaic devices.

Broadband Ce(III)-Sensitized Quantum Cutting in Core-Shell Nanoparticles: Mechanistic Investigation and Photovoltaic Application.

Quantum cutting in lanthanide-doped luminescent materials is promising for applications such as solar cells, mercury-free lamps, and plasma panel displays because of the ability to emit multiple photons for each absorbed higher-energy photon. Herein, a broadband Ce3+-sensitized quantum cutting process in Nd3+ ions is reported though gadolinium sublattice-mediated energy migration in a NaGdF4:Ce@NaGdF4:Nd@NaYF4 nanostructure. The Nd3+ ions show downconversion of one ultraviolet photon through two successive energy transitions, resulting in one visible photon and one near-infrared (NIR) photon. A class of NaGdF4:Ce@NaGdF4:Nd/Yb@NaYF4 nanoparticles is further developed to expand the spectrum of quantum cutting in the NIR. When the quantum cutting nanoparticles are incorporated into a hybrid crystalline silicon (c-Si) solar cell, a 1.2-fold increase in short-circuit current and a 1.4-fold increase in power conversion efficiency is demonstrated under short-wavelength ultraviolet irradiation. These insights should enhance our ability to control and utilize spectral downconversion with lanthanide ions.

Direct Free Carrier Photogeneration in Single Layer and Stacked Organic Photovoltaic Devices.

High performance organic photovoltaic devices typically rely on type-II P/N junctions for assisting exciton dissociation. Heremans and co-workers recently reported a high efficiency device with a third organic layer which is spatially separated from the active P/N junction; but still contributes to the carrier generation by passing its energy to the P/N junction via a long-range exciton energy transfer mechanism. In this study the authors show that there is an additional mechanism contributing to the high efficiency. Some bipolar materials (e.g., subnaphthalocyanine chloride (SubNc) and subphthalocyanine chloride (SubPc)) are observed to generate free carriers much more effectively than typical organic semiconductors upon photoexcitation. Single-layer devices with SubNc or SubPc sandwiched between two electrodes can give power conversion efficiencies 30 times higher than those of reported single-layer devices. In addition, internal quantum efficiencies (IQEs) of bilayer devices with opposite stacking sequences (i.e., SubNc/SubPc vs SubPc/SubNc) are found to be the sum of IQEs of single layer devices. These results confirm that SubNc and SubPc can directly generate free carriers upon photoexcitation without assistance from a P/N junction. These allow them to be stacked onto each other with reversible sequence or simply stacking onto another P/N junction and contribute to the photocarrier generation.

Naphthalene diimide-difluorobenzene-based polymer acceptors for all-polymer solar cells.

Regio-random (P1) and -regular (P2) difluorobenzene-naphthalene-containing polymer acceptors were developed for bulk-heterojunction all-polymer solar cells (all-PSCs). P2 exhibited significantly higher crystallinity in thin films, providing high spectral absorptivity and electron mobility than P1. When used in all-PSC devices, P2 afforded a respectably higher power conversion efficiency of over 5%.

Enhanced Self-Assembly of Crystalline, Large-Area, and Periodicity-Tunable TiO2 Nanotube Arrays on Various Substrates.

Due to their superior physical properties, titanium dioxide (TiO2) nanotube arrays are one of the most investigated nanostructure systems in materials science until now. However, it is still a great challenge to achieve damage-free techniques to realize controllable, cost-effective, and high-performance TiO2 nanotube arrays on both rigid and flexible substrates for different technological applications. In this work, we demonstrate a unique strategy to achieve self-assemble crystalline, large-area, and regular TiO2 nanotube arrays on various substrates via hybrid combination of conventional semiconductor processes. Besides the usual applications of TiO2 as carrier transport layers in thin-film electronic devices, we demonstrate that the periodic TiO2 nanotube arrays can show the effect of optical grating with large-area uniformity. Specifically, the fabricated nanotube geometries, such as the tube height, pitch, diameter, and wall thickness, as well as the crystallinity can be reliably controlled by varying the processing conditions. More importantly, utilizing these nanotube arrays in perovskite solar cells can further enhance the optical absorption, leading to improved power conversion efficiency. In contrast to other typical template-assisted fabrication approaches, we employ a soft template here, which would enable the construction of nanotube arrays without any significant damage associated with template removal. Furthermore, without the thermal restriction of underlying substrates, these crystalline nanotube arrays can be transferred to mechanically flexible substrates by a simple one-step method, which can expedite these nanotubes for potential utilization in other application domains.

Evidence of Delocalization in Charge-Transfer State Manifold for Donor:Acceptor Organic Photovoltaics.

How charge-transfer states (CTSs) assist charge separation of a Coulombically bound exciton in organic photovoltaics has been a hot topic. It is believed that the delocalization feature of a CTS plays a crucial role in the charge separation process. However, the delocalization of the "hot" and the "relaxed" CTSs is still under debate. Here, with a novel frequency dependent charge-modulated electroabsorption spectroscopy (CMEAS) technique, we elucidate clearly that both "hot" and "relaxed" CTSs are loosely bound and delocalized states. This is confirmed by comparing the CMEAS results of CTSs with those of localized polaron states. Our results reveal the role of CTS delocalization on charge separation and indicate that no substantial delocalization gradient exists in CTSs.

Probing the Energy Level Alignment and the Correlation with Open-Circuit Voltage in Solution-Processed Polymeric Bulk Heterojunction Photovoltaic Devices.

Energy level alignment at the organic donor and acceptor interface is a key to determine the photovoltaic performance in organic solar cells, but direct probing of such energy alignment is still challenging especially for solution-processed bulk heterojunction (BHJ) thin films. Here we report a systematic investigation on probing the energy level alignment with different approaches in five commonly used polymer:[6,6]-phenyl-C71-butyric acid methyl ester (PCBM) BHJ systems. We find that by tuning the weight ratio of polymer to PCBM the electronic features from both polymer and PCBM can be obtained by photoemission spectroscopy. Using this approach, we find that some of the BHJ blends simply follow vacuum level alignment, but others show strong energy level shifting as a result of Fermi level pinning. Independently, by measuring the temperature-dependent open-circuit voltage (VOC), we find that the effective energy gap (Eeff), the energy difference between the highest occupied molecular orbital of the polymer donor (EHOMO-D) and lowest unoccupied molecular orbital of the PCBM acceptor (ELUMO-A), obtained by photoemission spectroscopy in all polymer:PCBM blends has an excellent agreement with the extrapolated VOC at 0 K. Consequently, the photovoltage loss of various organic BHJ photovoltaic devices at room temperature is in a range of 0.3-0.6 V. It is believed that the demonstrated direct measurement approach of the energy level alignment in solution-processed organic BHJ will bring deeper insight into the origin of the VOC and the corresponding photovoltage loss mechanism in organic photovoltaic cells.

Chlorine Incorporation for Enhanced Performance of Planar Perovskite Solar Cell Based on Lead Acetate Precursor.

We show the effects of chlorine incorporation in the crystallization process of perovskite film based on a lead acetate precursor. We demonstrate a fabrication process for fast grain growth with highly preferred {110} orientation upon only 5 min of annealing at 100 °C. By studying the correlation between precursor composition and morphology, the growth dynamic of perovskite film in the current system is discussed. In particular, we found that both lead acetate precursor and Cl incorporation are beneficial to perovskite growth. While lead acetate allows fast crystallization process, Cl improves perovskite crystallinity. Planar perovskite solar cells with optimized parameters deliver a best power conversion efficiency of 15.0% and average efficiency of 14.0% with remarkable reproducibility and good stability.

Decomposition of Organometal Halide Perovskite Films on Zinc Oxide Nanoparticles.

Solution processed zinc oxide (ZnO) nanoparticles (NPs) with excellent electron transport properties and a low-temperature process is a viable candidate to replace titanium dioxide (TiO2) as electron transport layer to develop high-efficiency perovskite solar cells on flexible substrates. However, the number of reported high-performance perovskite solar cells using ZnO-NPs is still limited. Here we report a detailed investigation on the chemistry and crystal growth of CH3NH3PbI3 perovskite on ZnO-NP thin films. We find that the perovskite films would severely decompose into PbI2 upon thermal annealing on the bare ZnO-NP surface. X-ray photoelectron spectroscopy (XPS) results show that the hydroxide groups on the ZnO-NP surface accelerate the decomposition of the perovskite films. To reduce the decomposition, we introduce a buffer layer in between the ZnO-NPs and perovskite layers. We find that a commonly used buffer layer with small molecule [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) can slow down but cannot completely avoid the decomposition. On the other hand, a polymeric buffer layer using poly(ethylenimine) (PEI) can effectively separate the ZnO-NPs and perovskite, which allows larger crystal formation with thermal annealing. The power conversion efficiencies of perovskite photovoltaic cells are significantly increased from 6.4% to 10.2% by replacing PC61BM with PEI as the buffer layer.