Ho-Wa Li

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.

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.

Spectroscopic study on the impact of methylammonium iodide loading time on the electronic properties in perovskite thin films

Solution processed metal–organic halide perovskite photovoltaic devices have recently drawn tremendous attention due to their simplicity of fabrication and high efficiency. Despite numerous reports on optimizing perovskite films with different fabrication approaches, there is limited understanding on the correlation between sensitive processing conditions and the microstructural and electronic properties of perovskite films. Here we combine several opto-electrical spectroscopy techniques to investigate the methylammonium iodide (MAI) loading time effect on the doping density profile and uncoordinated ions in resulting CH3NH3PbI3 perovskite thin films. We find that even in a very short period of different loading times within two minutes, there is a significant impact on the device power conversion efficiency (PCE) from 2% to over 15%. It is found that the doping density profile is inhomogeneous across the perovskite film with too short MAI loading time, resulting in an S-shape in the current density–voltage (J–V) characteristics. On the other hand, devices with too long loading time have excess uncoordinated ions attributed to the J–V hysteresis. By using combined spectroscopy techniques to pinpoint the electronic properties in perovskite films, this work would shed light on the understanding of the controversial origins of the reported S-shape and hysteresis in perovskite photovoltaic cells.

Graphene oxide as an efficient hole-transporting material for high-performance perovskite solar cells with enhanced stability

In recently developed high-efficiency metal organometal halide perovskite solar cells (PVSCs), electron and hole transporting materials have shown key roles in determining the growth of perovskite crystals, as well as the performance and stability of the device. However, interlayer materials which can facilitate both high efficiency and stability at low cost are still limited. Here, we demonstrate that, by controlling the thickness of solution-processed graphene oxide (GO), one can achieve a balance of high work function and conductivity. Using GO with the optimized thickness as a hole-transporting material (HTM) in PVSCs, a high power conversion efficiency (PCE) of 16.5% with no hysteresis has been achieved with excellent light-soaking photocurrent stability in comparison with a commonly used organic-based HTM. Under high humidity and continuous light soaking, the encapsulated perovskite devices retained >80% of their initial efficiency for >2000 h. Detailed studies on the GO binding energy, charge transfer efficiency with perovskite, and crystal morphology shed light on the origin of the observed improvement in photovoltaic performance. Benefiting from the merits of low temperature, solution processability and low cost, the proposed GO fabrication methods could aid scalable production of PVSCs with high PCE and excellent stability.

The detrimental effect of excess mobile ions in planar CH3NH3PbI3 perovskite solar cells

The origin of the impact of mobile ions in perovskite solar cells (PVSCs) has recently become a hot topic of debate. Here, we investigate systematically the structural effect and various recombination pathways in PVSCs with different ion concentrations. By probing the transient ionic current in PVSCs, we extract mobile ion concentrations in a range of 1016 cm−3 to 1017 cm−3 depending on the processing conditions during a two-step process. The PVSC with the lowest ion concentration has both the highest efficiency over 15% and shelf-life over 1300 hours. Interestingly, in contrast to the commonly adopted models in the literature, we find that the crystal size and the bimolecular and trap-assisted recombination are not responsible for the large difference in photovoltaic performance. Instead, by using transient photocurrent and steady-state photoluminescence approaches, we find that the large reduction of short-circuit current (Jsc) in mobile ion populated devices is ascribed to the slow decay in photocurrent and the increasing amount of non-radiative recombination. In addition, we also find that the excess mobile ions trigger the deformation of perovskite to PbI2, which severely reduces the device lifetime. The results provide valuable information on the understanding of the role of excess mobile ions in the degradation mechanism of PVSCs.

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.

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.

Boosting the photovoltaic thermal stability of fullerene bulk heterojunction solar cells through charge transfer interactions

Fullerene-based bulk heterojunction organic solar cells (BHJ-OSCs) represent one of the current state-of-the-art organic solar cells. Nonetheless, most of these devices still suffer from adverse performance degradation due to thermally induced morphology changes of active layers. We herein demonstrate that the photovoltaic performance stability of BHJ-OSCs can be profoundly enhanced with an appositely functionalized 9-fluorenylidene malononitrile. The latter, through charge transfer (CT) interactions with a donor polymer, enables the formation of a “frozen” 3-dimensional mesh-like donor polymer matrix, which effectively restrains free movement of embedded fullerene molecules and suppresses their otherwise uncontrolled aggregation. 9-Fluorenylidene malononitrile derivatives with multiple CT interaction sites are particularly effective as preservation of a power conversion efficiency of over 90% under severe thermal stress has been accomplished. The generality of this novel strategy has been affirmed with several common donor polymers, manifesting it to be hitherto the most efficient approach to stabilized fullerene-based BHJ-OSCs.

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.

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.