Academic literature on the topic 'Methylammonium Dipoles'

The SAM layer which formed hydrogen-bonding to the methylammonium of the perovskite induced dipole moments at the interface, resulting in energy band bending and increased built-in voltage, and consequently, improved charge transfer of the PSC.

High absorption ability and direct bandgap makes lead-based perovskite to acquire high photovoltaic performance. However, lead content in perovskite becomes a double-blade for counterbalancing photovoltaic performance and sustainability. Herein, we develop a methylammonium bismuth iodide (MBI), a perovskite-derivative, to serve as a lead-free light absorber layer. Owing to the short carrier diffusion length of MBI, its film quality is a predominant factor to photovoltaic performance. Several candidates of non-polar solvent are discussed in aspect of their dipole moment and boiling point to reveal the effects of anti-solvent assisted crystallization. Through anti-solvent engineering of toluene, the morphology, crystallinity, and element distribution of MBI films are improved compared with those without toluene treatment. The improved morphology and crystallinity of MBI films promote photovoltaic performance over 3.2 times compared with the one without toluene treatment. The photovoltaic device can achieve 0.26% with minor hysteresis effect, whose hysteresis index reduces from 0.374 to 0.169. This study guides a feasible path for developing MBI photovoltaics.

The reaction of N-methyl-N-(2,4,6-trinitrophenyl)glycinamide (Ic with methoxide in methanol produces the spiro adduct IIc(A). In methanolic acetate buffers, the equilibrium is rapidly established between the spiro adduct IIc(A) and the dipolar ion of 2-methylamino-N-(2,4,6-trinitrophenyl)acetamide (IIIc(Z)). The equilibrium constant of the reaction IIIc(Z) ⇆ IIc(A) + H+ is by eight orders of magnitude greater than that of the analogous cyclization of 2-methylamino-N-methyl-N-(2,4,6-trinitrophenyl)acetamide to the spiro adduct. In chloracetate buffers, the dipolar ion is protonated to give 2-methylammonium-N-(2,4,6-trinitrohenyl)acetamide IIIc(K). The kinetics of the reversible reaction IIIc(Z) ⇆ IIc(A) + H+ has been studied in acetate buffers, aliphatic amine – ammonium salt buffers, and methoxide solutions. In all cases, the rate-limiting step was the proton transfer with half-lives in milliseconds. In more basic methanolic buffers (pH > 10) the rate-limiting step consists in the formation of spiro adduct from the zwiterion IIIc(Z) resulting from the protonation of the anion IIIc(A). n acetate buffers, the second reaction pathway via the cation IIIc(K) is predominant.

Perovskites have stood out as excellent photoactive materials with high efficiencies and stabilities, achieved via cation mixing techniques. Overcoming challenges to the stabilization of Perovskite solar cells calls for the development of design principles of large cation incorporation in halide perovskite to accelerate the discovery of optimal stable compositions. Large fluorinated organic cations incorporation is an attractive method for enhancing the intrinsic stability of halide perovskites due to their high dipole moment and moisture-resistant nature. However, a fluorinated cation has a larger ionic size than its non-fluorinated counterpart, falling within the upper boundary of the mixed-cation incorporation. Here, we report on the intrinsic stability of mixed Methylammonium (MA) lead halides at different concentrations of large cation incorporation, namely, ehtylammonium (EA; [CH3CH2NH3]+) and 2-fluoroethylammonium (FEA; [CH2FCH2NH3]+). Density functional theory (DFT) calculations of the enthalpy of the mixing and analysis of the perovskite structural features enable us to narrow down the compositional search domain for EA and FEA cations around concentrations that preserve the perovskite structure while pointing towards the maximal stability. This work paves the way to developing design principles of a large cation mixture guided by data analysis of DFT data. Finally, we present the automated search of the minimum enthalpy of mixing by implementing Bayesian optimization over the compositional search domain. We introduce and validate an automated workflow designed to accelerate the compositional search, enabling researchers to cut down the computational expense and bias to search for optimal compositions.

Abstract Cation engineering provides a route to control the structure and properties of hybrid halide perovskites, which has resulted in the highest performance solar cells based on mixtures of Cs, methylammonium, and formamidinium. Here, we present a multi-technique experimental and theoretical study of structural phase transitions, structural phases and dipolar dynamics in the mixed methylammonium/dimethylammonium MA1-xDMAxPbBr3 hybrid perovskites (0 ≤ x ≤ 1). Our results demonstrate a significant suppression of the structural phase transitions, enhanced disorder and stabilization of the cubic phase even for a small amount of dimethylammonium cations. As the dimethylammonium concentration approaches the solubility limit in MAPbBr3, we observe the disappearance of the structural phase transitions and indications of a glassy dipolar phase. We also reveal a significant tunability of the dielectric permittivity upon mixing of the molecular cations that arises from frustrated electric dipoles.

Abstract Methylammonium lead iodide perovskite can make high-efficiency solar cells, which also show an unexplained photocurrent hysteresis dependent on the device-poling history. Here we report quasielastic neutron scattering measurements showing that dipolar CH3NH3 + ions reorientate between the faces, corners or edges of the pseudo-cubic lattice cages in CH3NH3PbI3 crystals with a room temperature residence time of ∼14 ps. Free rotation, π-flips and ionic diffusion are ruled out within a 1–200-ps time window. Monte Carlo simulations of interacting CH3NH3 + dipoles realigning within a 3D lattice suggest that the scattering measurements may be explained by the stabilization of CH3NH3 + in either antiferroelectric or ferroelectric domains. Collective realignment of CH3NH3 + to screen a device’s built-in potential could reduce photovoltaic performance. However, we estimate the timescale for a domain wall to traverse a typical device to be ∼0.1–1 ms, faster than most observed hysteresis.

AbstractA microscopic viewpoint of structure and dipolar configurations in hybrid organic–inorganic perovskites is crucial to understanding their stability and phase transitions. The necessity of incorporating dispersion interactions in the state-of-the-art density functional theory for the $$CH_3NH_3PbI_3$$ C H 3 N H 3 P b I 3 perovskite (MAPI) is demonstrated in this work. Some of the vdW methods were selected to evaluate the corresponding energetics properties of the cubic MAPI with various azimuthally rotated MA organic cation orientations. The highest energy barrier obtained from PBEsol reaches 18.6 meV/MA-ion, which is equivalent to 216 K, the temperature above which the MA cations randomly reorient. Energy profiles calculated by vdW incorporated functionals, on the other hand, exhibit various distinct patterns. The well-developed vdW-DF-cx functional was selected, thanks to its competence, to evaluate the total energies of different MA dipolar configurations in $$2\times 2\times 2$$ 2 × 2 × 2 cubic supercell of MAPI under pressures. The centrosymmetric arrangement of the MA cations that provide zero total dipole moment configuration results in the lowest energy state profiles under pressure, while the non-centrosymmetric scheme displays a unique behaviour. Despite being overall unpolarised, the latter calculated with PBEsol leads to a rigid shift of energy from the profile obtained from the dispersive vdW-DF-cx functional. It is noteworthy that the energy profile responsible for the maximum polarised configuration nevertheless takes the second place in total energy under pressure.

The interface states have significant effects on the optoelectronic properties of quantum dots-based light emitting diodes (QLEDs). Herein, we employed a dielectric interlayer, namely, phenylethylammonium bromide (PEABr): methylammonium bromine (MABr),...

AbstractHerein, an unprecedented report is presented on the incorporation of size-dependent gold nanoparticles (AuNPs) with polyvinylpyrrolidone (PVP) capping into a conventional hole transport layer, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). The hole transport layer blocks ion-diffusion/migration in methylammonium-lead-bromide (MAPbBr3)-based perovskite light-emitting diodes (PeLEDs) as a modified interlayer. The PVP-capped 90 nm AuNP device exhibited a seven-fold increase in efficiency (1.5%) as compared to the device without AuNPs (0.22%), where the device lifetime was also improved by 17-fold. This advancement is ascribed to the far-field scattering of AuNPs, modified work function and carrier trapping/detrapping. The improvement in device lifetime is attributed to PVP-capping of AuNPs which prevents indium diffusion into the perovskite layer and surface ion migration into PEDOT:PSS through the formation of induced electric dipole. The results also indicate that using large AuNPs (> 90 nm) reduces exciton recombination because of the trapping of excess charge carriers due to the large surface area.

Organic-inorganic hybrid perovskites have emerged as promising photovoltaic materials in the last few years, with the possibility of easy, solution synthesis. In this thesis, we have investigated some intrinsic material properties of the hybrid lead halide perovskites in an attempt to understand factors responsible for the excellent photovoltaic behaviour. The presence of the (CH3NH3)+ or methylammonium (MA) ion with a permanent dipole moment in CH3NH3PbI3 gives rise to the possibility of ferroelectricity. In view of the continued controversy concerning the ferroelectric/non-ferroelectric nature of CH3NH3PbI3, we have addressed the more basic question of whether it is polar or not. We have measured the Second Harmonic Generation (SHG) efficiency, which is a sensitive probe to the presence of centre of inversion in the system and show that SHG efficiency of CH3NH3PbI3, if non-zero, is below the detection limit, strongly indicative of a nonpolar structure; consistent with P-E loop and single crystal XRD measurements. This nonpolar structure is a time-averaged description of the MA dipoles, consistent with many different dynamic behaviours, such as MA units rotating freely or in a correlated manner or frozen randomly. A comparison of temperature dependent dielectric constants of MAPbX3 and CsPbBr3 (without dipolar units) suggests that the MA+ dipoles are rotating freely with time scales much faster than μs. Ab initio molecular dynamics simulations show that these dipoles are randomly oriented with no net dipole moment when averaged over even a few unit cells, with a rotational time scale of ~ 7 ps at 300 K for these dipoles. Further, using pump-probe SHG efficiency measurements in MAPbX3 we have ruled out the possibility of a transient ferroelectric state in presence of photoexcitation. Further, we have carried out detailed investigation of dielectric properties of a larger class of hybrid lead halide perovskites, specifically the formamidinium lead halides (FAPbX3). Although the behaviour of dielectric constants of FAPbCl3 and FAPbBr3 in the low temperature resemble that of the MAPbX3 system, the absence of its strong temperature dependence in contrast to MAPbX3 lead us to conclude that the formamidinium (FA) dipoles are frozen in a glassy state. This is supported by the temperature dependent single crystal XRD results, which reveal disordered FA ions in the room temperature as well as at 100 K. Exciton binding energy is an important parameter in a photovoltaic material since it determines whether the mechanism is dominated by free charge carriers or excitons at room temperature. The exciton binding energy reported for MAPbI3 in the literature varies over a wide range of values. From careful experiments to measure temperature dependent PL spectra of MAPbI3 and MAPbBr3 we have estimated the exciton binding energy. PL intensity of MAPbBr3 films is observed to be sensitive to vacuum, environmental conditions and illumination. Since the penetration depth of the excitation wavelength, 405 nm, is very small in the sample, most part of the PL intensity observed can be considered to be from the near-surface region of the sample. We propose that defects are created at the surface of MAPbBr3 by the evaporative loss of MABr due to dynamic pumping. Considering all these factors, we have obtained the binding energy of MAPbBr3 film to be 79 meV, which corresponds to the intrinsic nature of the surface of MAPbBr3 film in vacuum.

碩士<br>國立臺灣大學<br>應用物理研究所<br>107<br>Electric-field-induced dipole rotation of the intercalated organic molecules in halide perovskites has been suggested to be one controllable factor for fundamental properties and stabilities in perovskites. However, up to now, how the electric field triggers the dipole rotation of the intercalated organic molecules is still unknown. Here, we record the real-space atomic image and simultaneously probe the corresponding current-voltage (I-V) hysteresis in the methylammonium lead bromide (MAPbBr3) system using cross-sectional scanning tunneling microscopy and spectroscopy. In this work, we addressed the change of topography at specific bias intervals and anomalous I-V hysteresis with four gap-like regions as well as two unusual inflection points at forward 1.68 V and backward -0.87 V under ramp reversal scanning mode. We suppose that the dipole rotation, initiated by an electric field, concludes to two opposite surface dipole moments, creating an electronic transformation between the n-type-like and p-type-like feature. The two inflection points correspond to the critical voltage of dipole rotation. The transformation thus forms an abnormal I-V hysteresis behavior in MAPbBr3.