Zhiwei Ren

Thermal Assisted Oxygen Annealing for High Efficiency Planar CH3NH3PbI3 Perovskite Solar Cells

We report investigations on the influences of post-deposition treatments on the performance of solution-processed methylammonium lead triiodide (CH3NH3PbI3)-based planar solar cells. The prepared films were stored in pure N2 at room temperature or annealed in pure O2 at room temperature, 45°C, 65°C and 85°C for 12 hours prior to the deposition of the metal electrodes. It is found that annealing in O2 leads to substantial increase in the power conversion efficiencies (PCEs) of the devices. Furthermore, strong dependence on the annealing temperature for the PCEs of the devices suggests that a thermally activated process may underlie the observed phenomenon. It is believed that the annealing process may facilitate the diffusion of O2 into the spiro-MeOTAD for inducing p-doping of the hole transport material. Furthermore, the process can result in lowering the localized state density at the grain boundaries as well as the bulk of perovskite. Utilizing thermal assisted O2 annealing, high efficiency devices with good reproducibility were attained. A PCE of 15.4% with an open circuit voltage (VOC) 1.04 V, short circuit current density (JSC) 23 mA/cm2, and fill factor 0.64 had been achieved for our champion device.

Perovskite Photovoltachromic Supercapacitor with All-Transparent Electrodes

Photovoltachromic cells (PVCCs) are of great interest for the self-powered smart windows of architectures and vehicles, which require widely tunable transmittance and automatic color change under photostimuli. Organolead halide perovskite possesses high light absorption coefficient and enables thin and semitransparent photovoltaic device. In this work, we demonstrate co-anode and co-cathode photovoltachromic supercapacitors (PVCSs) by vertically integrating a perovskite solar cell (PSC) with MoO3/Au/MoO3 transparent electrode and electrochromic supercapacitor. The PVCSs provide a seamless integration of energy harvesting/storage device, automatic and wide color tunability, and enhanced photostability of PSCs. Compared with conventional PVCC, the counter electrodes of our PVCSs provide sufficient balancing charge, eliminate the necessity of reverse bias voltage for bleaching the device, and realize reasonable in situ energy storage. The color states of PVCSs not only indicate the amount of energy stored and energy consumed in real time, but also enhance the photostability of photovoltaic component by preventing its long-time photoexposure under fully charged state of PVCSs. This work designs PVCS devices for multifunctional smart window applications commonly made of glass.

Efficiency enhancement by defect engineering in perovskite photovoltaic cells prepared using evaporated PbI2/CH3NH3I multilayers

We report, for the first time, on the synthesis of perovskite films by thermal annealing of evaporated lead(II) iodide (PbI2)/methylammonium iodide (CH3NH3I) multilayers. Detailed characterization of the resulting films is presented. Our work demonstrates that compact, high quality and uniform perovskite films can be grown using this technique. Optimization of the device structure was achieved by careful design of the layer thickness and the number of PbI2/CH3NH3I pairs used in the formation of the absorber layer. Utilizing additional annealing steps in a controlled atmosphere was shown to result in significant improvement in the device performance. Our experimental data indicate that O2 treatments may result in substantial reduction in the trap density of the device and thereby significant improvement in the lifetimes of the carriers. A high power conversion efficiency (PCE) of 12.5% was recorded for the champion device.

Investigation of high performance TiO2 nanorod array perovskite solar cells

In this paper, systematic investigations on the fabrication and characterization of high performance TiO2 nanorod array perovskite solar cells (NAPSCs) are reported. The TiO2 nanorods, of length around 350–400 nm, were grown by solvothermal technique directly on glass/FTO substrates. From the scanning transmission electron microscopy (STEM) we demonstrate that excellent crystallinity for the TiO2 nanorods can be produced using the solvothermal technique. Precursor consisting of a mixture of PbI2, CH3NH3I (MAI) and CH3NH3Cl (MACl) was used for the growth of perovskite thin films on the glass/FTO/TiO2 nanorod array (TiO2-NA) substrates. It is found that the morphology and quality of the perovskite layer depend strongly on the concentration of MACl in the precursor. Experimental studies on femtosecond transient absorption (fs-TA) indicate that the incorporation of TiO2-NA greatly enhances the collection efficiency of the photo-generated carriers due to substantial increase of interfacial area between the perovskite and TiO2-NA, leading to a reduction in carrier diffusion distance. It is shown to be the key factor that the proposed technique facilitates the use of a thicker perovskite absorber layer (∼500 nm) without compromising on the series resistance. Detailed J–V characterization shows that the NAPSCs exhibit negligible hysteresis with a power conversion efficiency (PCE) >19% for the champion device.

Characterization of Low-Frequency Excess Noise in CH3NH3PbI3-Based Solar Cells Grown by Solution and Hybrid Chemical Vapor Deposition Techniques

In this study, detailed investigations of low-frequency noise (LFN) characteristics of hybrid chemical vapor deposition (HCVD)- and solution-grown CH3NH3PbI3 (MAPI) solar cells are reported. It has been shown that LFN is a ubiquitous phenomenon observed in all semiconductor devices. It is the smallest signal that can be measured from the device; hence, systematic characterization of the LFN properties can be utilized as a highly sensitive nondestructive tool for the characterization of material defects in the device. It has been demonstrated that the noise power spectral densities of the devices are critically dependent on the parameters of the fabrication process, including the growth ambient of the perovskite layer and the incorporation of the mesoscopic structures in the devices. Our experimental results indicated that the LFN arises from a thermally activated trapping and detrapping process, resulting in the corresponding fluctuations in the conductance of the device. The results show that the presence of oxygen in the growth ambient of the HCVD process and the inclusion of an mp-TiO2 layer in the device structure are two important factors contributing to the substantial reduction in the density of the localized states in the MAPI devices. Furthermore, the lifetimes of the MAPI perovskite-based solar cells are strongly dependent on the material defect concentration. The degradation process is substantially more rapid for the devices with higher initial defect density compared to the devices prepared under optimized conditions and structure that exhibit substantially lower initial trap density.

Novel growth techniques for the deposition of high-quality perovskite thin films

We present investigations on the growth of high quality CH3NH3PbI3 (MAPI) thin films using both vapor and solution techniques. Recent work on perovskite film growth indicates critical dependencies of the film quality on the nucleation and crystallization steps requiring: i.) uniform distribution of nucleation sites; and ii.) optimal crystallization rate that facilitates the growth of a compact, continuous film with low density of pinholes. Our work shows that the hybrid chemical vapor deposition technique (HCVD) technique is well suited for the deposition of evenly distributed nucleation sites and the optimization of the crystallization rate of the film through detailed monitoring of the thermal profile of the growth process. Signficant reduction in the defect states is recorded by annealing the perovskite films in O2. The results are consistent with theoretical studies by Yin et al. 1 on O and Cl passivation of the shallow states at the grain boundary of MAPI. Their work provides the theoretical basis for our experimental observations on the passivation of shallow states by oxygen annealing. High quality films were achieved through detailed management of the carrier gas composition and the thermal profile of the nucleation and crystallization steps.

A Cryogenic Process for Antisolvent‐Free High‐Performance Perovskite Solar Cells

A cryogenic process is introduced to control the crystallization of perovskite layers, eliminating the need for the use of environmentally harmful antisolvents. This process enables decoupling of the nucleation and the crystallization phases by inhibiting chemical reactions in as-cast precursor films rapidly cooled down by immersion in liquid nitrogen. The cooling is followed by blow-drying with nitrogen gas, which induces uniform precipitation of precursors due to the supersaturation of precursors in the residual solvents at very low temperature, while at the same time enhancing the evaporation of the residual solvents and preventing the ordered precursors/perovskite from redissolving into the residual solvents. Using the proposed techniques, the crystallization process can be initiated after the formation of a uniform precursor seed layer. The process is generally applicable to improve the performance of solar cells using perovskite films with different compositions, as demonstrated on three different types of mixed halide perovskites. A champion power conversion efficiency (PCE) of 21.4% with open-circuit voltage (VOC ) = 1.14 V, short-circuit current density ( JSC ) = 23.5 mA cm-2 , and fill factor (FF) = 0.80 is achieved using the proposed cryogenic process.

Record high performance of perovskite/crystalline silicon four-terminal tandem solar cells

Perovskite and crystalline silicon (c-Si) with complementary absorption spectra are connected in a 4-terminal-tandem configuration for efficient utilization of the photons from the complete solar spectrum. A highly transparent electrode with low resistivity is developed by the deposition of molybdenum trioxide (MoO3)/Gold (Au)/ molybdenum trioxide (MoO3) multilayer. The thickness of constituent layer of the electrode is carefully controlled to achieve the highest light transmissivity to enhance the absorption of the bottom cell. Perovskite films with low density of bandgap states are obtained by oxygen postdeposition treatment. A record power conversion efficiency (PCE) of 23.6% for tandem device is achieved comparing to 18.1% and 19.1% of transparent perovskite solar cell and c-Si solar cell operated individually.

In2O3 based perovskite solar cells

Hybrid organic-inorganic perovskite solar cells have attracted lots of attention in recent years. Growth and properties of perovskite layer and its relationship to photovoltaic performance have been extensively studied. Comparably less attention was devoted to the research of the influence of electron transporting layer (ETL). Conventionally, TiO2 is selected as ETL. However, photocatalytic property of this transparent conductive metal oxide reduces the stability of perovskite solar cells under illumination. To realize the commercialization, the stability of perovskite solar cell must be improved. In this study, we replace TiO2 by In2O3, which is not only transparent and conductive, but also has little photocatalytic effect and it has higher electron mobility than TiO2. Investigation on different solution process methods of In2O3 as ETL is demonstrated.

In2O3based perovskite solar cells

Hybrid organic-inorganic perovskite solar cells have attracted lots of attention in recent years. Growth and properties of perovskite layer and its relationship to photovoltaic performance have been extensively studied. Comparably less attention was devoted to the research of the influence of electron transporting layer (ETL). Conventionally, TiO2 is selected as ETL. However, photocatalytic property of this transparent conductive metal oxide reduces the stability of perovskite solar cells under illumination. To realize the commercialization, the stability of perovskite solar cell must be improved. In this study, we replace TiO2 by In2O3, which is not only transparent and conductive, but also has little photocatalytic effect and it has higher electron mobility than TiO2. Investigation on different solution process methods of In2O3 as ETL is demonstrated.