Lead Iodide Perovskite Solar Cells Research Articles

In Situ TEM Analysis of Organic-Inorganic Metal-Halide Perovskite Solar Cells under Electrical Bias.

Changes in the nanostructure of methylammonium lead iodide (MAPbI3) perovskite solar cells are assessed as a function of current-voltage stimulus by biasing thin samples in situ in a transmission electron microscope. Various degradation pathways are identified both in situ and ex situ, predominantly at the positively biased MAPbI3 interface. Iodide migrates into the positively biased charge transport layer and also volatilizes along with organic species, which triggers the nucleation of PbI2 nanoparticles and voids and hence decreases the cell performance.

The Influence of Water Vapor on the Stability and Processing of Hybrid Perovskite Solar Cells Made from Non-Stoichiometric Precursor Mixtures.

We investigated the influence of moisture on methylammonium lead iodide perovskite (MAPbI3 ) films and solar cells derived from non-stoichiometric precursor mixtures. We followed both the structural changes under controlled air humidity through in situ X-ray diffraction, and the electronic behavior of devices prepared from these films. A small PbI2 excess in the films improved the stability of the perovskite compared to stoichiometric samples. We assign this to excess PbI2 layers at the perovskite grain boundaries or to the termination of the perovskite crystals with Pb and I. In contrast, the MAI-excess films composed of smaller perovskite crystals showed increased electronic disorder and reduced device performance owing to poor charge collection. Upon exposure to moisture followed by dehydration (so-called solvent annealing), these films recrystallized to form larger, highly oriented crystals with fewer electronic defects and a remarkable improvement in photocurrent and photovoltaic efficiency.

Low-temperature operation of perovskite solar cells: With efficiency improvement and hysteresis-less

Methylammonium lead iodide perovskite solar cells (PSCs) based on a solution-processed ZnO electron transporting layer were systematically investigated at low-temperature operating conditions. The power conversion efficiency gradually improved from 14.2% to 15.5% as the temperature decreased from 298 to 253K, mainly owing to increments of short circuit current density and open circuit voltage. In addition, the improvements in photocurrent related to the high charge carrier mobility, owing to the ideal nondispersive charge transport and fast electron transport lifetime at low temperature. Strikingly, hysteresis was suppressed with decreasing temperature related to the inhibition or relatively slow of ionic migration at reversed poling direction. This finding shows promising result of PSCs working efficiently under low temperature condition.

Electric-Field-Induced Degradation of Methylammonium Lead Iodide Perovskite Solar Cells.

Perovskite solar cells have great potential for high efficiency generation but are subject to the impact of external environmental conditions such as humidity, UV and sun light, temperature, and electric fields. The long-term stability of perovskite solar cells is an important issue for their commercialization. Various studies on the stability of perovskite solar cells are currently being performed; however, the stability related to electric fields is rarely discussed. Here the electrical stability of perovskite solar cells is studied. Ion migration is confirmed using the temperature-dependent dark current decay. Changes in the power conversion efficiency according to the amount of the external bias are measured in the dark, and a significant drop is observed only at an applied voltage greater than 0.8 V. We demonstrate that perovskite solar cells are stable under an electric field up to the operating voltage.

Local Time-Dependent Charging in a Perovskite Solar Cell.

Efficient charge extraction within solar cells explicitly depends on the optimization of the internal interfaces. Potential barriers, unbalanced charge extraction, and interfacial trap states can prevent cells from reaching high power conversion efficiencies. In the case of perovskite solar cells, slow processes happening on time scales of seconds cause hysteresis in the current-voltage characteristics. In this work, we localized and investigated these slow processes using frequency-modulation Kelvin probe force microscopy (FM-KPFM) on cross sections of planar methylammonium lead iodide (MAPI) perovskite solar cells. FM-KPFM can map the charge density distribution and its dynamics at internal interfaces. Upon illumination, space charge layers formed at the interfaces of the selective contacts with the MAPI layer within several seconds. We observed distinct differences in the charging dynamics at the interfaces of MAPI with adjacent layers. Our results indicate that more than one process is involved in hysteresis. This finding is in agreement with recent simulation studies claiming that a combination of ion migration and interfacial trap states causes the hysteresis in perovskite solar cells. Such differences in the charging rates at different interfaces cannot be separated by conventional device measurements.

Carbon quantum dots as new hole transport material for perovskite solar cells

The use of carbon quantum dots (CQDs) in photovoltaic devices has not yet been fully explored. Herein, we report the use of CQDs in MAPI (methyl ammonium lead iodide) perovskite solar cells as a first attempt to implement this material in photovoltaic applications beyond its use as transparent conductive electrode.

Electron and hole drift mobility measurements on methylammonium lead iodide perovskite solar cells

We report nanosecond domain time-of-flight measurements of electron and hole photocarriers in methylammonium lead iodide perovskite solar cells. The mobilities ranged from 0.06 to 1.4 cm2/Vs at room temperature, but there is little systematic difference between the two carriers. We also find that the drift mobilities are dispersive (time-dependent). The dispersion parameters are in the range of 0.4–0.7, and they imply that terahertz domain mobilities will be much larger than nanosecond domain mobilities. The temperature-dependences of the dispersion parameters are consistent with confinement of electron and hole transport to fractal-like spatial networks within nanoseconds of their photogeneration.

Photon recycling in lead iodide perovskite solar cells

Lead-halide perovskites have emerged as high-performance photovoltaic materials. We mapped the propagation of photogenerated luminescence and charges from a local photoexcitation spot in thin films of lead tri-iodide perovskites. We observed light emission at distances of ≥50 micrometers and found that the peak of the internal photon spectrum red-shifts from 765 to ≥800 nanometers. We used a lateral-contact solar cell with selective electron- and hole-collecting contacts and observed that charge extraction for photoexcitation >50 micrometers away from the contacts arose from repeated recycling between photons and electron-hole pairs. Thus, energy transport is not limited by diffusive charge transport but can occur over long distances through multiple absorption-diffusion-emission events. This process creates high excitation densities within the perovskite layer and allows high open-circuit voltages.

Light-Induced Space-Charge Accumulation Zone as Photovoltaic Mechanism in Perovskite Solar Cells

We fabricated formamidinium lead iodide perovskite solar cell for analysis of the photovoltaic mechanism based on the interpretation of the capacitance variation under illumination. It was shown that the low-frequency capacitance increases proportional to incident light intensity, and in addition it increases proportional to absorber thickness. Furthermore, the voltage dependence of capacitance is exponential with slope 1/2 (thermal energy). We conclude that the large photovoltage and capacitance are associated with electronic accumulation zone at the interface with the metal oxide contact. While this type of accumulation capacitance is common in many devices as transistors, the perovskite solar cell shows a singular behavior in that under light the electronic carrier accumulation grows unlimited by another series capacitance, reaching values as large as 10 mF cm(-2) at one sun illumination.

Investigating relation of photovoltaic factors with properties of perovskite films based on various solvents

Methylammonium lead iodide (MAPbI3) perovskite solar cells are fabricated by two-step sequential deposition processes. The influence of the properties of PbI2 precursor film on the cell performance is investigated based on different solvents. The X-ray diffraction (XRD) patterns, Urbach energy value and scan electron microscope (SEM) images reveal that solvents have considerable influence on the crystal structure, band tail and morphology of PbI2 precursor films. The addition of a small amount of dimethyl sulfoxide (DMSO) in N,N-dimethylformamide (DMF) solvent promotes the compactness and uniformity of PbI2 precursor films, but also causes defect in band tail. The relation of the properties of perovskite film with photovoltaic parameters is explored. A high conversion efficiency of 16.6% for solar cells based on mixed solvents with 10vol% DMSO is achieved. Meanwhile, light beam-induced current (LBIC) images directly evidence the improvement of uniformity for perovskite solar cells caused by DMSO addition.

Synergistic improvements in stability and performance of lead iodide perovskite solar cells incorporating salt additives

Alkali metal halide additives chelate with Pb2+ ions during film formation promoting homogeneous nucleation, which greatly enhances the power conversion efficiency (15.08%) and stability (over 50 days) of planar perovskite solar cells.

Fullerene imposed high open-circuit voltage in efficient perovskite based solar cells

Five different commercially available fullerenes are evaluated as hole blocking/electron transporting materials in p–i–n methylammonium lead iodide perovskite solar cells using a vacuum deposited perovskite absorber layer.

Effects of Solution-Based Fabrication Conditions on Morphology of Lead Halide Perovskite Thin Film Solar Cells

We present a critical review of the effects of processing conditions on the morphology of methylammonium lead iodide (CH3NH3PbI3) perovskite solar cells. Though difficult to decouple from synthetic and film formation effects, a single morphological feature, specifically grain size, has been evidently linked to the photovoltaic performance of this class of solar cells. Herein, we discuss experimental aspects of optimizing the (a) temperature and time of annealing, (b) spin-coating parameters, and (c) solution temperature of methylammonium iodide (MAI) solution.

Silver Iodide Formation in Methyl Ammonium Lead Iodide Perovskite Solar Cells with Silver Top Electrodes

Silver is a low‐cost candidate electrode material for perovskite solar cells. However, in such cells the silver electrodes turn yellow within days of device fabrication. The color change is also accompanied by a dramatic decrease in the power conversion efficiency when compared to otherwise identical devices using gold electrodes. Here, it is shown that the color change results from silver oxidation to silver iodide, due to a reaction with iodine in methyl ammonium lead perovskite. The change in X‐ray diffraction and X‐ray photo­electron spectroscopy is discussed. Exposure to air accelerates corrosion of the Ag electrodes when compared to dry nitrogen gas exposure. However, iodine not reacted with silver is observed by X‐ray photoelectron spectroscopy even for the perovskite solar cell kept in dry nitrogen gas. It is proposed that silver iodide is formed when methyl ammonium iodide migration is facilitated by the small pinholes in the hole transport layer spiro‐MeOTAD.

Ionic transport in hybrid lead iodide perovskite solar cells.

Solar cells based on organic–inorganic halide perovskites have recently shown rapidly rising power conversion efficiencies, but exhibit unusual behaviour such as current–voltage hysteresis and a low-frequency giant dielectric response. Ionic transport has been suggested to be an important factor contributing to these effects; however, the chemical origin of this transport and the mobile species are unclear. Here, the activation energies for ionic migration in methylammonium lead iodide (CH3NH3PbI3) are derived from first principles, and are compared with kinetic data extracted from the current–voltage response of a perovskite-based solar cell. We identify the microscopic transport mechanisms, and find facile vacancy-assisted migration of iodide ions with an activation energy of 0.6 eV, in good agreement with the kinetic measurements. The results of this combined computational and experimental study suggest that hybrid halide perovskites are mixed ionic–electronic conductors, a finding that has major implications for solar cell device architectures.

The efficiency limit of CH3NH3PbI3 perovskite solar cells

With the consideration of photon recycling effect, the efficiency limit of methylammonium lead iodide (CH3NH3PbI3) perovskite solar cells is predicted by a detailed balance model. To obtain convincing predictions, both AM 1.5 spectrum of Sun and experimentally measured complex refractive index of perovskite material are employed in the detailed balance model. The roles of light trapping and angular restriction in improving the maximal output power of thin-film perovskite solar cells are also clarified. The efficiency limit of perovskite cells (without the angular restriction) is about 31%, which approaches to Shockley-Queisser limit (33%) achievable by gallium arsenide (GaAs) cells. Moreover, the Shockley-Queisser limit could be reached with a 200 nm-thick perovskite solar cell, through integrating a wavelength-dependent angular-restriction design with a textured light-trapping structure. Additionally, the influence of the trap-assisted nonradiative recombination on the device efficiency is investigated. The work is fundamentally important to high-performance perovskite photovoltaics.

(Invited) Scalable Fabrication of Moisture Resistant Perovksite Solar Cells

Organic-inorganic halide perovskites have created a breakthrough in the field of solar cells because of their low cost, low temperature processibility and excellent optoelectronic properties. However, the instability of organic-inorganic halide perovskites to moisture is currently a huge challenge in the field of perovskite solar cells and needs to be addressed to translate the perovskite technology from the laboratory bench to large scale industrial practice. Currently, all the lab scale perovskite cells are fabricated in controlled glove box atmosphere with less than 1 % relative humidity to prevent their deterioration under moisture. In this work, a novel concept of protecting the perovskite using a highly conductive composite of a layered material and a hole transporting polymer is presented.1 The excellent charge transport properties of the composite coating allow the use of thick coating on the perovskite, creating extremely high length scales for moisture diffusion through composite. The composite coating developed in our work, could be extended to lead-free organometallic perovskites that are both moisture and oxygen sensitive. In addition, we also present our results on our lamination approach for scalable assembly perovskite electrodes.2 The deposition of gold as a counter electrode for the lab scale perovskite cells is usually performed by thermal evaporation in a bell jar evaporator. This process is time consuming, energy intensive and not viable to scale up. Our approach involving lamination of individual electrodes, enables a much facile low cost process for fabricating perovskite solar cells. Our results and observation on polymer composites as protective coatings for perovskite and on laminating electrodes show high promise for the scalability and low cost fabrication of perovskite cells under atmospheric conditions (60 -70 % relative humidity). References Rajamanickam, N., Vendra, V.K., Kumari, S., Lavery, B.W., Ramachandran, K., Druffel, T., Sunkara, M.K. Moisture resistant methyl ammonium lead iodide perovskite solar cells. Submitted 2014.Vendra, V.K., Kumari, S., Lavery, B.W., Rajamanickam, N., Druffel, T., Sunkara, M.K. Atmospheric roll to roll processing in perovskite solar cells. Submitted 2014

Nanophotonic front electrodes for perovskite solar cells

In less than 3 years' time, a vast progress in power conversion efficiencies of organometal halide perovskite solar cells has been achieved by optimization of the device architecture, charge transport layers, and interfaces. A further increase in these efficiencies is expected from an improvement in the optical properties via anti-reflection coatings and nanophotonic light management concepts. In this contribution, we report on the development and implementation of a nanophotonic front electrode for perovskite solar cells. The nanostructures were replicated via the versatile and large-area compatible UV-nanoimprint lithography. The shallow design of the used transparent and conductive nanostructures enabled easy integration into our solution-based baseline process. Prototype methylammonium lead iodide perovskite solar cells show an improvement of 5% in short-circuit current density and an improvement from 9.6% to 9.9% in power conversion efficiency compared to the flat reference device.

Optoelectronic Studies of Methylammonium Lead Iodide Perovskite Solar Cells with Mesoporous TiO₂: Separation of Electronic and Chemical Charge Storage, Understanding Two Recombination Lifetimes, and the Evolution of Band Offsets during J-V Hysteresis.

Methylammonium lead iodide (MAPI) cells of the design FTO/sTiO2/mpTiO2/MAPI/Spiro-OMeTAD/Au, where FTO is fluorine-doped tin oxide, sTiO2 indicates solid-TiO2, and mpTiO2 is mesoporous TiO2, are studied using transient photovoltage (TPV), differential capacitance, charge extraction, current interrupt, and chronophotoamperometry. We show that in mpTiO2/MAPI cells there are two kinds of extractable charge stored under operation: a capacitive electronic charge (∼0.2 μC/cm(2)) and another, larger charge (40 μC/cm(2)), possibly related to mobile ions. Transient photovoltage decays are strongly double exponential with two time constants that differ by a factor of ∼5, independent of bias light intensity. The fast decay (∼1 μs at 1 sun) is assigned to the predominant charge recombination pathway in the cell. We examine and reject the possibility that the fast decay is due to ferroelectric relaxation or to the bulk photovoltaic effect. Like many MAPI solar cells, the studied cells show significant J-V hysteresis. Capacitance vs open circuit voltage (V(oc)) data indicate that the hysteresis involves a change in internal potential gradients, likely a shift in band offset at the TiO2/MAPI interface. The TPV results show that the V(oc) hysteresis is not due to a change in recombination rate constant. Calculation of recombination flux at V(oc) suggests that the hysteresis is also not due to an increase in charge separation efficiency and that charge generation is not a function of applied bias. We also show that the J-V hysteresis is not a light driven effect but is caused by exposure to electrical bias, light or dark.

Development of lead iodide perovskite solar cells using three-dimensional titanium dioxide nanowire architectures.

Three-dimensional (3D) nanowire (NW) architectures are considered as superior electrode design for photovoltaic devices compared to NWs or nanoparticle systems in terms of improved large surface area and charge transport properties. In this paper, we report development of lead iodide perovskite solar cells based on a novel 3D TiO2 NW architectures. The 3D TiO2 nanostructure was synthesized via surface-reaction-limited pulsed chemical vapor deposition (SPCVD) technique that also implemented the Kirkendall effect for complete ZnO NW template conversion. It was found that the film thickness of 3D TiO2 can significantly influence the photovoltaic performance. Short-circuit current increased with the TiO2 length, while open-circuit voltage and fill factor decreased with the length. The highest power conversion efficiency (PCE) of 9.0% was achieved with ∼ 600 nm long 3D TiO2 NW structures. Compared to other 1D nanostructure arrays (TiO2 nanotubes, TiO2-coated ZnO NWs and ZnO NWs), 3D TiO2 NW architecture was able to achieve larger amounts of perovskite loading, enhanced light harvesting efficiency, and increased electron-transport property. Therefore, its PCE is 1.5, 2.3, and 2.8 times higher than those of TiO2 nanotubes, TiO2-coated ZnO NWs, and ZnO NWs, respectively. The unique morphological advantages, together with the largely suppressed hysteresis effect, make 3D hierarchical TiO2 a promising electrode selection in designing high-performance perovskite solar cells.