Formamidinium Cations Research Articles

Enhancing Hole Transport Uniformity for Efficient Inverted Perovskite Solar Cells through Optimizing Buried Interface Contacts and Suppressing Interface Recombination.

[4-(3,6-dimethyl-9H-carbazol-9yl)butyl]phosphonic acid (Me-4PACz) self-assembly material has been recognized as a highly effective approach for mitigating nickel oxide (NiOx) surface-related challenges in inverted perovskite solar cells (IPSCs). However, its uneven film generation and failure to effectively passivate the buried interface defects limit the device's performance improvement potential. Herein, p-xylylenediphosphonic acid (p-XPA) containing bilateral phosphate groups (-PO3H2) is introduced as an interface layer between the NiOx/Me-4PACz and the perovskite layer. P-XPA can flatten the surface of hole transport layer and optimize interface contact. Meanwhile, p-XPA achieves better energy level alignment and promotes interfacial hole transport. In addition, the bilateral -PO3H2 of p-XPA can chelate with Pb2+ and form hydrogen bond with FA+ (formamidinium cation), thereby suppressing buried interface non-radiative recombination loss. Consequently, the IPSC with p-XPA buried interface modification achieves champion power conversion efficiency of 25.87 % (certified at 25.45 %) at laboratory scale (0.0448 cm2). The encapsulated target device exhibits better operational stability. Even after 1100 hours of maximum power point tracking at 50 °C, its efficiency remains at an impressive 82.7 % of the initial efficiency. Molecules featuring bilateral passivation groups optimize interfacial contact and inhibit interfacial recombination, providing an effective approach to enhancing the stability and efficiency of devices.

Enhancing Hole Transport Uniformity for Efficient Inverted Perovskite Solar Cells through Optimizing Buried Interface Contacts and Suppressing Interface Recombination

Abstract[4‐(3,6‐dimethyl‐9H‐carbazol‐9yl)butyl]phosphonic acid (Me‐4PACz) self‐assembly material has been recognized as a highly effective approach for mitigating nickel oxide (NiOx) surface‐related challenges in inverted perovskite solar cells (IPSCs). However, its uneven film generation and failure to effectively passivate the buried interface defects limit the device‘s performance improvement potential. Herein, p‐xylylenediphosphonic acid (p‐XPA) containing bilateral phosphate groups (−PO3H2) is introduced as an interface layer between the NiOx/Me‐4PACz and the perovskite layer. P‐XPA can flatten the surface of hole transport layer and optimize interface contact. Meanwhile, p‐XPA achieves better energy level alignment and promotes interfacial hole transport. In addition, the bilateral −PO3H2 of p‐XPA can chelate with Pb2+ and form hydrogen bond with FA+ (formamidinium cation), thereby suppressing buried interface non‐radiative recombination loss. Consequently, the IPSC with p‐XPA buried interface modification achieves champion power conversion efficiency of 25.87 % (certified at 25.45 %) at laboratory scale (0.0448 cm2). The encapsulated target device exhibits better operational stability. Even after 1100 hours of maximum power point tracking at 50 °C, its efficiency remains at an impressive 82.7 % of the initial efficiency. Molecules featuring bilateral passivation groups optimize interfacial contact and inhibit interfacial recombination, providing an effective approach to enhancing the stability and efficiency of devices.

Reactive Passivation of Wide-Bandgap Organic-Inorganic Perovskites with Benzylamine.

While amines are widely used as additives in metal-halide perovskites, our understanding of the way amines in perovskite precursor solutions impact the resultant perovskite film is still limited. In this paper, we explore the multiple effects of benzylamine (BnAm), also referred to as phenylmethylamine, used to passivate both FA0.75Cs0.25Pb(I0.8Br0.2)3 and FA0.8Cs0.2PbI3 perovskite compositions. We show that, unlike benzylammonium (BnA+) halide salts, BnAm reacts rapidly with the formamidinium (FA+) cation, forming new chemical products in solution and these products passivate the perovskite crystal domains when processed into a thin film. In addition, when BnAm is used as a bulk additive, the average perovskite solar cell maximum power point tracked efficiency (for 30 s) increased to 19.3% compared to the control devices 16.8% for a 1.68 eV perovskite. Under combined full spectrum simulated sunlight and 65 °C temperature, the devices maintained a better T80 stability of close to 2500 h while the control devices have T80 stabilities of <100 h. We obtained similar results when presynthesizing the product BnFAI and adding it directly into the perovskite precursor solution. These findings highlight the mechanistic differences between amine and ammonium salt passivation, enabling the rational design of molecular strategies to improve the material quality and device performance of metal-halide perovskites.

Stabilization of Organic Cations in Lead Halide Perovskite Solar Cells Using Phosphine Oxides Derivatives.

Preventing ion migration in perovskite photovoltaics is key to achieving stable and efficient devices. The activation energy for ion migration is affected by the chemical environment surrounding the ions. Thus, the migration of organic cations in lead halide perovskites can be mitigated by engineering their local interactions, for example through hydrogen bonding. Ion migration also leads to ionic losses via interfacial reactions. Undesirable reactivities of the organic cations can be eliminated by introducing protecting groups. In this work, we report bis(2-oxo-3-oxazolidinyl) phosphinic chloride (BOP-Cl) as a perovskite ink additive with the following benefits: (1) The phosphoryl and two oxo groups form six-membered intermolecular hydrogen-bonded rings with the formamidinium cation (FA), mitigating ion migrations. (2) The hydrogen bonding reduces the electrophilicity of the ammonium protons by donating electron density, therefore reducing its reactivity with the surface oxygen on the metal oxide. Furthermore, the molecule can react to form a protecting group on the nucleophilic oxygen at the tin oxide transport layer surface through the elimination of chlorine. As a result, we achieve perovskite solar cells with an efficiency of 25.0% and improved MPP stability T93 = 1200 h at 40-45 °C compared to a control device (T86 = 550 h). In addition, we show a negative correlation between the strength of hydrogen bonding of different phosphine oxide derivatives to the organic cations and the degree of metastable behavior (e.g., initial burn-in) of the device.

Identification and Suppression of Point Defects in Bromide Perovskite Single Crystals Enabling Gamma-Ray Spectroscopy.

Methylammonium lead tribromide (MAPbBr3) stands out as the most easily grown wide-band-gap metal halide perovskite. It is a promising semiconductor for room-temperature gamma-ray (γ-ray) spectroscopic detectors, but no operational devices are realized. This can be largely attributed to a lack of understanding of point defects and their influence on detector performance. Here, through a combination of crystal growth design and defect characterization, including positron annihilation and impedance spectroscopy, the presence of specific point defects are identified and correlated to detector performance. Methylammonium (MA) vacancies, MA interstitials, and Pb vacancies are identified as the dominant charge-trapping defects in MAPbBr3 crystals, while Br vacancies caused doping. The addition of excess MABr reduces the MA and Br defects and so enables the detection of energy-resolved γ-ray spectra using a MAPbBr3 single-crystal device. Interestingly, the addition of formamidinium (FA) cations, which converted to methylformamidinium (MFA) cations by reaction with MA+ during crystal growth further reduced MA defects. This enabled an energy resolution of 3.9% for the 662keV 137Cs line using a low bias of 100V. The work provides direction toward enabling further improvements in wide-bandgap perovskite-based device performance by reducing detrimental defects.

Hole Localization in Bulk and 2D Lead-Halide Perovskites Studied by Time-Resolved Infrared Spectroscopy.

Scattering and localization dynamics of charge carriers in the soft lattice of lead-halide perovskites impact polaron formation and recombination, which are key mechanisms of material function in optoelectronic devices. In this study, we probe the photoinduced lattice and carrier dynamics in perovskite thin films (CsFAPbX3, X = I, Br) using time-resolved infrared spectroscopy. We examine the CN stretching mode of formamidinium (FA) cations located within the lead-halide octahedra of the perovskite structure. Our investigation reveals the formation of an infrared mode due to spatial symmetry breaking within a hundred picoseconds in 3D perovskites. Experiments at cryogenic temperatures show much-reduced carrier localization, in agreement with a localization mechanism that is driven by the dynamic disorder. We extend our analysis to 2D perovskites, where the precise nature of charge carriers is uncertain. Remarkably, the signatures of charge localization we found in bulk perovskites are not observed for 2D Ruddlesden-Popper perovskites ((HexA)2FAPb2I7). This observation implies that the previously reported stabilization of free charge carriers in these materials follows different mechanisms than polaron formation in bulk perovskites. Through the exploration of heterostructures with electron/hole excess, we provide evidence that holes drive the formation of the emerging infrared mode.

Enhanced Charge Transfer in Quasi-2D Perovskite by Formamidinium Cation Gradient Incorporation for Efficient and Stable Solar Cells.

Quasi-2D perovskites have attracted much attention in perovskite photovoltaics due to their excellent stability. However, their photoelectric conversion efficiency (PCE) still lags 3D counterparts, particularly with high short-circuit current (JSC) loss. The quantum confinement effect is pointed out to be the sole reason, which introduces widened bandgap and poor exciton dissociation, and undermines the light capture and charge transport. Here, the gradient incorporation of formamidinium (FA) cations into quasi-2D perovskite is proposed to address this issue. It is observed that FA prefers to incorporate into the larger n value phases near the film surface compared to the smaller n value phases in the bulk, resulting in a narrow bandgap and gradient structure within the film. Through charge dynamic analysis using in situ light-dark Kelvin probe force microscopy and transient absorption spectroscopy, it is demonstrated that incorporating 10% FA significantly facilitates efficient charge transfer between low n-value phases in the bulk and high n-value nearby film surface, leading to reduced charge accumulation. Ultimately, the device based on (AA)2(MA0.9FA0.1)4Pb5I16, where AA represents n-amylamine renowned for its exceptional environmental stability as a bulky organic ligand, achieves an impressive power conversion efficiency (PCE) of 18.58% and demonstrates enhanced illumination and thermal stability.

Significance of Formamidinium Incorporation in Perovskite Composition and Its Impact on Solar Cell Efficiency: A Mini‐Review

Perovskite solar cells (PSCs) have gained tremendous research interest recently owing to several advantages, including low material cost, facile solution processability, bandgap tunability, and alluring device efficiency. The organic formamidinium (FA) cation‐based perovskites are mainly considered as one of the potential candidates for charge carrier generation due to their excellent properties, such as bandgap and thermal stability than traditional perovskites. However, the inevitable unfavorable polymorphism (i.e., α to δ) at room temperature still forms the basis for numerous research works to allow the fabrication of a high‐quality absorber and enhances the PSCs performance. The studies to resolve the polymorphism and several contemporary techniques (e.g., passivation strategy) with several recent novel fabrication methods presented in this review form the essence of the improvements in PSCs. The absorber morphology also influences the charge‐transfer behavior and the device's lifetime. Therefore, understanding these properties is essential to improve the absorber quality and avoid many defects. This review focuses on the structure and properties of pure and mixed FA perovskites with various halides, mainly the FA cation's role in the absorber composition. And a comprehensive overview of recent FA cation‐based double, triple, and quadrupole PSCs results with proper scientific explanations to understand the device physics.

Boosting optoelectronic performance of (FA)X(MA)1-XPbI3 perovskite solar cells: Via FAI post-treatment engineering

Complex composition engineering of mixed-cations perovskite (FAxMA1-xPbI3) has recently supported rapid progress in perovskite solar cells (PSCs). Nevertheless, it is insufficient to embed and accommodate formamidinium (FA) cation into the MAPbI3 lattice structure via existing methods, leaving behind masses of FA or lead halide content and deteriorating photovoltaic performance. Herein, we present facile surface engineering via post-treated methodology, the surface of CH3NH3PbI3 (MAPbI3) films post-treated with formamidinium iodide (FAI) solution and that results get mixed-cation FAxMA1-xPbI3 perovskite films. The mixed-cation-based FAXMA1-XPbI3 perovskite with significant and large grain size, uniform and compact morphology, highly crystallization, and consequently reducing defect density of the perovskite films can be produced via the present method. It is observed that the film, post-treated with FAI-2, shows results in a very stable and highly crystalline lattice structure with attributes such as extended carrier lifetime, better electron transport, and decreased defect density. The optimized device demonstrates a promising power conversion efficiency (PCE) of 21.89%, and higher than that of the non-treated (19.08%) devices. Furthermore, the devices based on the novel FAI-post-treatment engineering exhibit significantly enhanced stability compared to non-treated devices. Therefore, this approach provides a novel methodology that offers a simple method for producing superior mixed perovskite films, potentially paving the way for the future exploitation of the boosted performance of perovskite solar cells.

Triisocyanate Derived Interlayer and High-Melting-Point Doping Promoter Boost Operational Stability of Perovskite Solar Cells.

Formamidinium lead triiodide serves as the optimal light-absorbing layer in single-junction perovskite solar cells. However, achieving operational stability of high-efficiency n-i-p type devices at elevated temperatures remains challenging. In this work, we implemented effective surface modifications on microcrystalline perovskite films. This involved the nucleophilic addition of formamidinium cations and coordination of residual PbI2 with triphenylmethane triisocyanate as well as subsequent polymerization. The in situ growth of a cross-linking network chemically anchored on the perovskite film in this approach effectively reduced trap densities, favorably altered surface work function, suppressing interface charge recombination and thus enhancing cell efficiency. Coupled with a high-melting-point air-doping promoter, we fabricated n-i-p type perovskite solar cells surpassing 25 % efficiency, demonstrating excellent operational stability at 65 °C.

Triisocyanate Derived Interlayer and High‐Melting‐Point Doping Promoter Boost Operational Stability of Perovskite Solar Cells

AbstractFormamidinium lead triiodide serves as the optimal light‐absorbing layer in single‐junction perovskite solar cells. However, achieving operational stability of high‐efficiency n‐i‐p type devices at elevated temperatures remains challenging. In this work, we implemented effective surface modifications on microcrystalline perovskite films. This involved the nucleophilic addition of formamidinium cations and coordination of residual PbI2 with triphenylmethane triisocyanate as well as subsequent polymerization. The in situ growth of a cross‐linking network chemically anchored on the perovskite film in this approach effectively reduced trap densities, favorably altered surface work function, suppressing interface charge recombination and thus enhancing cell efficiency. Coupled with a high‐melting‐point air‐doping promoter, we fabricated n‐i‐p type perovskite solar cells surpassing 25 % efficiency, demonstrating excellent operational stability at 65 °C.

Atomic Structure and Dynamics of Organic-Inorganic Hybrid Perovskite Formamidinium Lead Iodide.

The atomic dynamic behaviors of formamidinium lead iodide [HC(NH2)2PbI3] are critical for understanding and improving photovoltaic performances. However, they remain unclear. Here, we investigate the structural phase transitions and the reorientation dynamics of the formamidinium cation [HC(NH2)2+, FA+] of FAPbI3 using neutron scattering techniques. Two structural phase transitions occur with decreasing temperature, from cubic to tetragonal phase at 285 K and then to another tetragonal at 140 K, accompanied by gradually frozen reorientation of FA cations. The nearly isotropic reorientation in the cubic phase is suppressed to reorientation motions involving a two-fold (C2) rotation along the N···N axis and a four-fold (C4) rotation along the C-H axis in the tetragonal phase, and eventually to local disordered motion as a partial C4 along the C-H axis in another tetragonal phase, thereby indicating an intimate interplay between lattice and orientation degrees of freedom in the hybrid perovskite materials. The present complete atomic structure and dynamics provide a solid standing point to understand and then improve photovoltaic properties of organic-inorganic hybrid perovskites in the future.

Optical and scintillation properties of hybrid manganese(II) bromides with formamidinium and acetamidinium cations.

In recent years, hybrid manganese(II) halides (HMHs) have attracted wide attention due to their impressive optical properties, low toxicity, and facile synthetic processibility. Being effective reabsorption-free phosphors, these compounds demonstrate the potential to be used as low-cost solution-processable scintillators. However, most of the HMHs studied to date contain bulk organic cations and, as a result, are characterized by low density and low X-ray stopping power. For this reason, we studied manganese(II) bromides with compact organic cations such as formamidinium (FA+) and acetamidinium (AcA+). In particular, we synthesized four new phases, two of which are characterized by octahedral coordination of manganese ions ((FA)MnBr3 and (AcA)MnBr3) and red emission, whereas the other two have tetrahedrally coordinated Mn2+ ions ((FA)3MnBr5 and (AcA)2MnBr4) and green emission. Photoluminescence (PL) and radioluminescence measurements demonstrated high PL quantum yields and reasonable scintillation light yields of acetamidinium-based compounds. In addition, unlike most known HMH-based scintillators, the discovered materials have a relatively high density due to the small fraction of the volume occupied by organic cations, so their X-ray attenuation coefficients are comparable to the well-known oxide scintillators.

Pyrolytic fragmentation-induced defect formation in formamidinium lead halide perovskite thin films and photovoltaic performance limits

Defect formation through the fragmented formamidinium cation in lead iodide perovskite leads to the widening charge inversion layer and limited solar cell performance.

Tailored Succinic Acid-Derived Molecular Structures toward 25.41%-Efficiency and Stable Perovskite Solar Cells.

Minimizing interfacial charged traps in perovskite films is crucial for reducing the non-radiative recombination and improving device performance. In this study, succinic acid (SA) derivatives varying active sites and spatial configurations are designed to modulate defects and crystallization in perovskite film. The SA derivative with two symmetric Br atoms, dibromosuccinic acid (DBSA), exhibits the optimal spatial arrangement for defect passivation. Experimental and theoretical results indicate that the carboxyl group and atomic Br in DBSA synergistically interact with the under-coordinated Pb2+ . Moreover, the strong electronegativity of Br efficiently stabilizes the formamidinium cation via electrostatic interaction. Consequently, film quality is significantly improved and non-radiative recombination is markedly depressed, resulting in a photoluminesence lifetime of exceeding 4µs of and a carrier diffusion length of 3µm. An exceptional efficiency of 25.41% (certified at 25.00%) along with a high fill factor of 84.39% and excellent long-term operational stability have been achieved finally.

Ultrafast vibrational control of organohalide perovskite optoelectronic devices using vibrationally promoted electronic resonance

Vibrational control (VC) of photochemistry through the optical stimulation of structural dynamics is a nascent concept only recently demonstrated for model molecules in solution. Extending VC to state-of-the-art materials may lead to new applications and improved performance for optoelectronic devices. Metal halide perovskites are promising targets for VC due to their mechanical softness and the rich array of vibrational motions of both their inorganic and organic sublattices. Here, we demonstrate the ultrafast VC of FAPbBr3 perovskite solar cells via intramolecular vibrations of the formamidinium cation using spectroscopic techniques based on vibrationally promoted electronic resonance. The observed short (~300 fs) time window of VC highlights the fast dynamics of coupling between the cation and inorganic sublattice. First-principles modelling reveals that this coupling is mediated by hydrogen bonds that modulate both lead halide lattice and electronic states. Cation dynamics modulating this coupling may suppress non-radiative recombination in perovskites, leading to photovoltaics with reduced voltage losses.

Interface Engineering with Formamidinium Salts for Improving Ambient-Processed Inverted CsPbI3 Photovoltaic Performance: Intermediate- vs Post-Treatment.

Inverted all-inorganic perovskite solar cells (PSCs) have attracted increasing attention owing to excellent thermal stability, easy fabrication, and adaptable application as top cell in tandem solar cells. Apart from efficiency, ambient processing is desirable for practical production. To avoid water invasion in ambient air, surface engineering for perovskites is reported as a valid approach. However, most were performed by post-treatment, which hardly regulates the formation process of perovskite crystals. This work demonstrates a simple but effective surface intermediate-treatment strategy to stabilize CsPbI3 perovskites fabricated in ambient air and compares the different effects yielded on the inverted PSCs. By using formamidinium (FA) salts for intermediate-treatment, the strong interaction between FA cation and [PbI6]4- octahedron improves the moisture resistance, and compared with the post-treatment strategy, the accelerated crystallization rate and the shortened exposure time to moisture reduce the devastation by water during film fabrication process further. Moreover, the greatly passivated defects and optimized energy level matching between perovskite and PCBM suppress the nonradiative recombination. Resultantly, the optimized device shows enhanced efficiency from 11.39% to 15.45%, and long-term stability is improved, with 97.6% efficiency remaining after storage for 1600 h. Therefore, we believe that this work can provide a promising guideline for fabricating all-inorganic inverted PSCs in a low-cost manufacturing scheme.

Exploring A‐Site Cation Variations in Dion–Jacobson Two‐Dimensional Halide Perovskites for Enhanced Solar Cell Applications: A Density Functional Theory Study

The exceptional photophysical and electronic properties of 2D hybrid perovskites possess potential applications in the field of solar energy harvesting. The present work focuses on the two systems, exhibiting the Dion–Jacobson phase of 2D perovskite consisting of methylammonium (MA) and formamidinium (FA) cations at A‐site and 3‐(aminomethyl)pyridinium (3AMPY) as ring‐shaped organic spacer. Altering A‐site cations creates a distortion of inorganic layers and hydrogen bond interactions. It has been noted that the angles of Pb–I–Pb and I–Pb–I are more symmetric (close to 180°) for (3AMPY)(MA)Pb2I7 compared to (3AMPY)(FA)Pb2I7 and result in increase of bandgap from 1.51 to 1.58 eV. This further leads to a significant difference in Rashba splitting energy under the influence of spin‐orbit coupling effects, where the highest splitting (36 meV) is calculated for conduction band edge of the (3AMPY)(FA)Pb2I7, suggesting the promising applications toward spintronics. The calculated absorption spectra cover the range from 300 to 450 nm, indicating significant optical activity of 2D (3AMPY)(MA)Pb2I7 and (3AMPY)(FA)Pb2I7 in the visible and ultraviolet regions, which bodes well for their application in advanced optoelectronic devices. The bandgap and high absorption coefficients present more than 30% of theoretical power conversion efficiency for both systems, as calculated from the spectroscopic‐limited maximum efficiency.

Nanoplatelet Superlattices by Tin-Induced Transformation of FAPbI3 Nanocrystals.

The transition from 3D to 2D lead halide perovskites is traditionally led by the lattice incorporation of bulky organic cations. However, the transformation into a coveted 2D superlattice-like structure by cationic substitution at the Pb2+ site of 3D perovskite is unfamiliar. It is demonstrated that the gradual increment of [Sn2+ ] alters the FASnx Pb1- x I3 nanocrystals into the Ruddlesden-Popper-like nanoplatelets (NPLs), with surface-absorbed oleic acid (OA) and oleylamine (OAm) spacer ligand at 80°C (FA+ : formamidinium cation). These NPLs are stacked either by a perfect alignment to form the superlattice or by offsetting the NPL edges because of their lateral displacements. The phase transition occurs from the Sn/Pb ratio ≥0.011, with 0.64 wt% of Sn2+ species. At and above Sn/Pb = 0.022, the NPL superlattice stacks start to grow along [00l] with a repeating length of 4.37(3) nm, comprising the organic bilayer and the inorganic block having two octahedral layers (n = 2). Besides, a photoluminescence quantum yield of 98.4% is obtained with Sn/Pb = 0.011 (n ≥ 4), after surface passivation by trioctylphosphine (TOP).

Composition-Property Relations for GAx FAy MA1- x - y PbI3 Perovskites.

Halide perovskites are materials for diverse optoelectronic applications owing to a combination of factors, including their compositional flexibility. A major source of this diversity of compositions comes from the use of mixed organic cations in the A-site of such compounds to form solid solutions. Many organic cations are possible for this purpose. Although significant progress is made over years of intensive research, the determination of systematic relationships between the compositions and properties of halide perovskites is not exploited accordingly. Using the MAPbI3 prototype, a wide range of compositions substituted by formamidinium (FA+ ) and guanidinium (GA+ ) cations are studied. From a detailed collection of experimental data and results reported in the literature, heat maps correlating the composition of GAx FAy MA1- x - y PbI3 solid solutions with phase transition temperatures, dielectric permittivity, and activation energies are constructed. Considering the characteristics of organic cations, namely their sizes, dipole moments, and the number of N─H bonds, it is possible to interpret the heat maps as consequences of these characteristics. This work brings a systematization of how obtaining specific properties of halide perovskites might be possible by customizing the characteristics of the A-site organic cations.