Formamidinium Lead Iodide Perovskite Research Articles

Pressure-Induced Phase Transformation and Band-Gap Engineering of Formamidinium Lead Iodide Perovskite Nanocrystals.

Formamidinium lead halide (FAPbX3, X = Cl, Br, I) perovskite materials have recently drawn an increased amount of attention owing to their superior optoelectronic properties and enhanced material stability as compared with their methylammonium-based (MA-based) analogues. Herein, we report a study of thepressure-induced structural and optical evolutions of FAPbI3 hybrid organic-inorganic perovskite nanocrystals (NCs) using a synchrotron-based X-ray scattering technique coupled to in situ absorption and photoluminescence spectroscopies. As a result of their unique structural stability and soft nature, FAPbI3 NCs exhibit a wide range of band-gap tunability (1.44-2.17 eV) as a function of pressure (0-13.4 GPa). The study presented here not only provides an efficient and chemically orthogonal means to controllably engineer the band gap of FAPbI3 NCs using pressure but more importantly sheds light on how to strategically design the band gaps of FA-based hybrid organic-inorganic perovskites for various optoelectronic applications.

Investigating the Role of the Organic Cation in Formamidinium Lead Iodide Perovskite Using Ultrafast Spectroscopy.

Organic cation rotation in hybrid organic-inorganic lead halide perovskites has previously been associated with low charge recombination rates and (anti)ferroelectric domain formation. Two-dimensional infrared spectroscopy (2DIR) was used to directly measure 470 ± 50 fs and 2.8 ± 0.5 ps time constants associated with the reorientation of formamidinium cations (FA+, NH2CHNH2+) in formamidinium lead iodide perovskite thin films. Molecular dynamics simulations reveal the FA+ agitates about an equilibrium position, with NH2 groups pointing at opposite faces of the inorganic lattice cube, and undergoes 90° flips on picosecond time scales. Time-resolved infrared measurements revealed a prominent vibrational transient feature arising from a vibrational Stark shift: photogenerated charge carriers increase the internal electric field of perovskite thin films, perturbing the FA+ antisymmetric stretching vibrational potential, resulting in an observed 5 cm-1 shift. Our 2DIR results provide the first direct measurement of FA+ rotation inside thin perovskite films, and cast significant doubt on the presence of long-lived (anti)ferroelectric domains, which the observed low charge recombination rates have been attributed to.

Humidity‐Induced Degradation via Grain Boundaries of HC(NH2)2PbI3 Planar Perovskite Solar Cells

AbstractThe sensitivity of organic–inorganic perovskites to environmental factors remains a major barrier for these materials to become commercially viable for photovoltaic applications. In this work, the degradation of formamidinium lead iodide (FAPbI3) perovskite in a moist environment is systematically investigated. It is shown that the level of relative humidity (RH) is important for the onset of degradation processes. Below 30% RH, the black phase of the FAPbI3 perovskite shows excellent phase stability over 90 d. Once the RH reaches 50%, degradation of the FAPbI3 perovskite occurs rapidly. Results from a Kelvin probe force microscopy study reveal that the formation of nonperovskite phases initiates at the grain boundaries and the phase transition proceeds toward the grain interiors. Also, ion migration along the grain boundaries is greatly enhanced upon degradation. A post‐thermal treatment (PTT) that removes chemical residues at the grain boundaries which effectively slows the degradation process is developed. Finally, it is demonstrated that the PTT process improves the performance and stability of the final device.

Efficient Optical Amplification in the Nanosecond Regime from Formamidinium Lead Iodide Nanocrystals

Lead halide perovskite nanocrystals (NCs) were recently found to exhibit extraordinary optical amplification properties. The great majority of such studies implemented ultrashort photon pulses in the femtosecond regime to initiate the stimulated emission process. Yet the realization of practical lasing applications based on such materials is crucially dependent on their ability to sustain optical amplification at significantly longer time scales, at which major losses associated with spontaneous emission and nonradiative recombination occur. Herein we demonstrate highly efficient amplified spontaneous emission (ASE) from close-packed films of formamidinium lead iodide perovskite (FAPbI3) NCs under excitation in the nanosecond regime. Systematic optimization of the NC processing and thermal treatment yields solids that exhibit high ASE net modal gain up to 604 cm–1 and weakly temperature sensitive ASE thresholds with room-temperature values as low as 140 μJ cm–2. The efficient optical amplification using e...

Exceptional Grain Growth in Formamidinium Lead Iodide Perovskite Thin Films Induced by the δ-to-α Phase Transformation

The annealing of fine-grained (∼0.175 μm) “yellow” δ-FAPbI3 nonperovskite thin films at 100 °C in dimethyl sulfoxide vapor for a few minutes results in exceptional grain growth (∼5 μm) induced by their transformation to the desirable “black” α-FAPbI3 perovskite phase. Mechanistic insights into this unprecedented phenomenon are provided.

Synthesis of formamidinium lead iodide perovskite bulk single crystal and its optical properties

Formamidinium lead iodide (FAPbI3) is a promising hybrid perovskite material for optoelectronic devices. We synthesized bulk single crystal FAPbI3 by a rapid solution crystallization method. X-ray diffraction (XRD) was performed to characterize the crystal structure. Temperature-dependent photoluminescence (PL) spectra of the bulk single crystal FAPbI3 were measured from 10 to 300 K to explain PL recombination mechanism. It shows that near band edge emission blueshifts with the temperature increasing from 10 to 120 K and from 140 K to room temperature, a sudden emission band redshift demonstrates near 140 K because of the phase transition from orthorhombic phase to cubic phase. From the temperature-dependent PL spectra, the temperature coefficients of the bandgap and thermal activation energies of FAPbI3 perovskite are fitted.

Stabilization of the Metastable Lead Iodide Perovskite Phase via Surface Functionalization.

Metastable structural polymorphs can have superior properties and applications to their thermodynamically stable phases, but the rational synthesis of metastable phases is a challenge. Here, a new strategy for stabilizing metastable phases using surface functionalization is demonstrated using the example of formamidinium lead iodide (FAPbI3) perovskite, which is metastable at room temperature (RT) but holds great promises in solar and light-emitting applications. We show that, through surface ligand functionalization during direct solution growth at RT, pure FAPbI3 in the cubic perovskite phase can be stabilized in nanostructures and thin films at RT without cation or anion alloying. Surface characterizations reveal that long-chain alkyl or aromatic ammonium (LA) cations bind to the surface of perovskite structure. Calculations show that such functionalization reduces the surface energy and plays a dominant role in stabilizing the metastable perovskite phase. Excellent photophysics and optically pumped lasing from the stabilized single-crystal FAPbI3 nanoplates with low thresholds were demonstrated. High-performance solar cells can be fabricated with such directly synthesized stabilized phase-pure FAPbI3 with a lower bandgap. Our results offer new insights on the surface chemistry of perovskite materials and provide a new strategy for stabilizing metastable perovskites and metastable polymorphs of solid materials in general.

Effects of Rb Incorporation and Water Degradation on the Stability of the Cubic Formamidinium Lead Iodide Perovskite Surface: A First-Principles Study

Despite the major improvements in device efficiency, perovskite solar cells (PSCs) are limited by their poor stability due to the degradation toward moisture. Recently studies have demonstrated that the perovskite materials can be stabilized by adding more inorganic elements such as Cs and Rb. However, the specific mechanism is not yet fully established. In this paper, first-principles calculations were employed to investigate the effects of Rb incorporation and water degradation on cubic formamidinium lead iodide (FAPbI3) perovskite. The termination dependence of the structural stability of the representative (100), (010), and (001) surfaces was characterized by surface energies. The PbI2-terminated (001) surface was found to be the most stable surface structure. The Rb dopants were found to be energetically favorable, existing on the surface more than staying in the inner atomic layers. Furthermore, the degradation mechanism was investigated by water adsorption on the Rb-incorporated FAPbI3 (001) surfac...

Long-Lived Hot Carriers in Formamidinium Lead Iodide Nanocrystals

The efficient harvesting of hot carrier energy in semiconductors is typically inhibited by their ultrafast thermalization process. Recently, highly promising experiments reported on the slowdown of the intraband relaxation in hybrid metal halide perovskites. In this work, we report on the presence of long-lived hot carriers in weakly confined colloidal nanocrystals (NCs) of formamidinium lead iodide perovskite (FAPbI3). The effect is apparent from the excitation-dependent lengthening of the rise time and broadening of the high-energy tail of the transient absorption bleaching signal, yielding a retardation of the carrier relaxation by 2 orders of magnitude compared to typical time scales in colloidal semiconductor NCs. Three distinct cooling stages are observed, occurring at sub-picosecond, ∼5 ps, and ∼40 ps time scales, which we attribute to scattering from LO-phonons, contribution from a hot phonon bottleneck effect and Auger heating, respectively. Thermalization appears also influenced by the FAPbI3 NC...

High-performance formamidinium-based perovskite photodetectors fabricated via doctor-blading deposition in ambient condition

High-purity black α-phase formamidinium lead iodide (FAPbI3, FA is NH2CHNH+) perovskite polycrystalline film was prepared using low-cost, high-output doctor-blading deposition technique in ambient condition without further annealing process and any additives. The resulting α-phase FAPbI3 perovskite has a large domain size over 200 μm with (00l) preferential crystallographic orientation. The photodetectors with an extremely simple structure were fabricated via doctor-blading, resulting in a responsivity as high as 11.46 AW−1, a ratio of photocurrent/dark current (Ilight/Idark) as large as 105 and a response speed as fast as 5.4 ms. The results suggest that low-cost doctor-blading technique in ambient condition potentially pave a way to eliminate the yellow δ-phase FAPbI3 and get a high-quality black α-FAPbI3 perovskite film, as well as fabricate efficient FAPbI3 perovskite optoelectronic devices.

Pressure-Induced Polymorphic, Optical, and Electronic Transitions of Formamidinium Lead Iodide Perovskite.

Formamidinium lead iodide (FAPbI3) perovskite as a superior solar cell material was investigated in two polymorphs at high pressures using in situ synchrotron X-ray diffraction, FTIR spectroscopy, photoluminescence (PL) spectroscopy, electrical conductivity (EC) measurements, and ab initio calculations. We identified two new structures (i.e., Imm2 and Immm) for α-FAPbI3 but only a structural distortion (in C2/c) for δ-FAPbI3 upon compression. A pressure-enhanced hydrogen bond plays a prominent role in structural modifications, as corroborated by FTIR spectroscopy. PL measurements and calculations consistently show the structure and pressure dependences of the band gap energies. Finally, EC measurements reveal drastically different transport properties of α- and δ-FAPbI3 at low pressures but a common trend to metallic states at high pressures. All of these observations suggest strongly contrasting structural stabilities and pressure-tuned optoelectric properties of the two FAPbI3 polymorphs.

Preparation and characterization of mixed formamidinium lead iodide/methyl ammonium lead bromide layers

In the past few years, solar cells based on layers of organo-metal halide perovskites such as formamidinium and methyl ammonium lead halides gave rise to high-efficiency and low-cost photovoltaics. Further enhancements of their performance can be achieved by chemically modifying the perovskite material. Especially, the long-term stability of these devices can be improved by mixing different components of the perovskite such as the organic cation or the halide anion. This work is focused on the mixture of the well-performing formamidinium lead iodide perovskite with the highly stable methyl ammonium lead bromide. The deposited mixed perovskite layers are investigated by X-ray diffraction, UV/Vis transmission spectroscopy, scanning electron microscopy, and confocal laser scanning microscopy. We confirm the very good miscibility of both materials and demonstrate two different methods to deposit high-quality layers.

Thermal engineering of FAPbI3 perovskite material via radiative thermal annealing and in situ XRD

Lead halide perovskites have emerged as successful optoelectronic materials with high photovoltaic power conversion efficiencies and low material cost. However, substantial challenges remain in the scalability, stability and fundamental understanding of the materials. Here we present the application of radiative thermal annealing, an easily scalable processing method for synthesizing formamidinium lead iodide (FAPbI3) perovskite solar absorbers. Devices fabricated from films formed via radiative thermal annealing have equivalent efficiencies to those annealed using a conventional hotplate. By coupling results from in situ X-ray diffraction using a radiative thermal annealing system with device performances, we mapped the processing phase space of FAPbI3 and corresponding device efficiencies. Our map of processing-structure-performance space suggests the commonly used FAPbI3 annealing time, 10 min at 170 °C, can be significantly reduced to 40 s at 170 °C without affecting the photovoltaic performance. The Johnson-Mehl-Avrami model was used to determine the activation energy for decomposition of FAPbI3 into PbI2.

Mixed-Organic-Cation (FA)x(MA)1-xPbI3 Planar Perovskite Solar Cells with 16.48% Efficiency via a Low-Pressure Vapor-Assisted Solution Process.

Compared to that of methylammonium lead iodide perovskite (MAPbI3), formamidinium lead iodide perovskite (FAPbI3) has a smaller energy band gap and greater potential efficiency. To prevent the transformation of α-FAPbI3 to δ-FAPbI3, preparation of (FA)x(MA)1-xPbI3 was regarded as an effective route. Usually, the planar (FA)x(MA)1-xPbI3 perovskite solar cells are fabricated by a solution process. Herein, we report a low-pressure vapor-assisted solution process (LP-VASP) for the growth of (FA)x(MA)1-xPbI3 perovskite solar cells that features improved electron transportation, uniform morphology, high power conversion efficiency (PCE), and better crystal stability. In LP-VASP, the (FA)x(MA)1-xPbI3 films were formed by the reaction between the PbI2 film with FAI and MAI vapor in a very simple vacuum oven. LP-VASP is an inexpensive way to batch-process solar cells, avoiding the repeated deposition solution process for PbI2 films, and the device had a low cost. We demonstrate that, with an increase in the MAI content, the (101) peak position of FAPbI3 shifts toward the (110) peak position of MAPbI3, the (FA)x(MA)1-xPbI3 perovskites are stable, and no decomposition or phase transition is observed after 14 days. The photovoltaic performance was effectively improved by the introduction of MA+ with the highest efficiency being 16.48% under conditions of 40 wt % MAI. The carrier lifetime of (FA)x(MA)1-xPbI3 perovskite films is approximately three times longer than that of pure FAPbI3. Using this process, solar cells with a large area of 1.00 cm2 were fabricated with the PCE of 8.0%.

Entropy-driven structural transition and kinetic trapping in formamidinium lead iodide perovskite.

A challenge of hybrid perovskite solar cells is device instability, which calls for an understanding of the perovskite structural stability and phase transitions. Using neutron diffraction and first-principles calculations on formamidinium lead iodide (FAPbI3), we show that the entropy contribution to the Gibbs free energy caused by isotropic rotations of the FA+ cation plays a crucial role in the cubic-to-hexagonal structural phase transition. Furthermore, we observe that the cubic-to-hexagonal phase transition exhibits a large thermal hysteresis. Our first-principles calculations confirm the existence of a potential barrier between the cubic and hexagonal structures, which provides an explanation for the observed thermal hysteresis. By exploiting the potential barrier, we demonstrate kinetic trapping of the cubic phase, desirable for solar cells, even at 8.2 K by thermal quenching.

Nonstoichiometric Adduct Approach for High-Efficiency Perovskite Solar Cells.

Since the groundbreaking report on a solid-state perovskite solar cell employing a methylammonium lead iodide-sensitized mesoporous TiO2 film and an organic hole conducting layer in 2012 by our group, the swift surge of perovskite photovoltaics opens a new paradigm in solar-cell research. As a result, ca. 1300 peer-reviewed research articles were published in 2015. In this Inorganic Chemistry Forum on Halide Perovskite, the researches with highlights of work on perovskite solar cells in my laboratory are reviewed. We have developed a size-controllable two-step spin-coating method and found that minimal nonradiative recombination in perovskite crystals could lead to high photovoltaic performance. A Lewis acid based adduct method and self-formed grain boundary process were developed for high-efficiency devices with reproducibility. A power conversion efficiency of 20.4% was achieved via grain boundary engineering based on a nonstoichiometric adduct approach. The incorporation of cesium in a formamidinium lead iodide perovskite was found to show better photostability and moisture-stability. A reduction in the dimensionality from a three-dimensitonal nanocrystal to a one-dimensional nanowire led to a hypsochromic shift of absorption and fluorescence. To enhance the charge-carrier transport and light-harvesting efficiency, a nanoarchitecture of oxide layers was proposed.

Phenylalkylamine Passivation of Organolead Halide Perovskites Enabling High-Efficiency and Air-Stable Photovoltaic Cells.

Benzylamine is introduced as a surface passivation molecule that improves the moisture-resistance of the perovskites while simultaneously enhancing their electronic properties. Solar cells based on benzylamine-modified formamidinium lead iodide perovskite films exhibit a champion efficiency of 19.2% and an open-circuit voltage of 1.12 V. The modified FAPbI3 films exhibit no degradation after >2800 h air exposure.

Lewis Acid-Base Adduct Approach for High Efficiency Perovskite Solar Cells.

Since the first report on the long-term durable 9.7% solid-state perovskite solar cell employing methylammonium lead iodide (CH3NH3PbI3), mesoporous TiO2, and 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro-MeOTAD) in 2012, following the seed technologies on perovskite-sensitized liquid junction solar cells in 2009 and 2011, a surge of interest has been focused on perovskite solar cells due to superb photovoltaic performance and extremely facile fabrication processes. The power conversion efficiency (PCE) of perovskite solar cells reached 21% in a very short period of time. Such an unprecedentedly high photovoltaic performance is due to the intrinsic optoelectronic property of organolead iodide perovskite material. Moreover, a high dielectric constant, sub-millimeter scale carrier diffusion length, an underlying ferroelectric property, and ion migration behavior can make organolead halide perovskites suitable for multifunctionality. Thus, besides solar cell applications, perovskite material has recently been applied to a variety fields of materials science such as photodetectors, light emitting diodes, lasing, X-ray imaging, resistive memory, and water splitting. Regardless of application areas, the growth of a well-defined perovskite layer with high crystallinity is essential for effective utilization of its excellent physicochemical properties. Therefore, an effective methodology for preparation of high quality perovskite layers is required. In this Account, an effective methodology for production of high quality perovskite layers is described, which is the Lewis acid-base adduct approach. In the solution process to form the perovskite layer, the key chemicals of CH3NH3I (or HC(NH2)2I) and PbI2 are used by dissolving them in polar aprotic solvents. Since polar aprotic solvents bear oxygen, sulfur, or nitrogen, they can act as a Lewis base. In addition, the main group compound PbI2 is known to be a Lewis acid. Thus, PbI2 has a chance to form an adduct by reacting with the Lewis base. Crystal growth and morphology of perovskite can be controlled by taking advantage of the weak chemical interaction in the adduct. We have successfully fabricated highly reproducible CH3NH3PbI3 perovskite solar cells with PCE as high as 19.7% via adducts of PbI2 with oxygen-donor N,N'-dimethyl sulfoxide. This adduct approach has been found to be generally adopted, where formamidinium lead iodide perovskite, HC(NH2)2PbI3 (FAPbI3), with large grain, high crystallinity, and long-lived carrier lifetime was successfully fabricated via an adduct of PbI2 with sulfur-donor thiourea as Lewis base. The adduct approach proposed in this Account is a very promising methodology to achieve high quality perovskite films with high photovoltaic performance. Furthermore, single crystal growth on the conductive substrate is expected to be possible if we kinetically control the elimination of Lewis base in the adduct.

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.

The fabrication of formamidinium lead iodide perovskite thin films via organic cation exchange.

High-quality formamidinium lead iodide (FAPbI3) perovskite thin films are fabricated via organic cation exchange. With ammonia lead iodide (NH4PbI3) as the starting material, the NH4(+) in NH4PbI3 could be gradually substituted by FA(+) in formamidine acetate (FA-Ac) and simultaneously transformed to the pure phase α-FAPbI3 at elevated temperature.