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1.
2D perovskites have recently been shown to exhibit significantly improved environmental stability. Derived from their 3D analogues, 2D perovskites are formed by inserting bulky alkylammonium cations in‐between the anionic layers. However, these insulating organic spacer cations also hinder charge transport. Herein, such a 2D perovskite, (iso‐BA)2(MA)3Pb4I13, that contains short branched‐chain spacer cations (iso‐BA+) and shows a remarkable increase of optical absorption and crystallinity in comparison to the conventional linear one, n‐BA+, is designed. After applying the hot‐casting (HC) technique, all these properties are further improved. The HC (iso‐BA)2(MA)3Pb4I13 sample exhibits the best ambient stability by maintaining its initial optical absorption after storage of 840 h in an environmental chamber at 20 °C with a relative humidity of 60% without encapsulation. More importantly, the out‐of‐plane crystal orientation of (iso‐BA)2(MA)3Pb4I13 film is notably enhanced, which increases cross‐plane charge mobility. As a result, the highest power conversion efficiencies (PCEs) measured from for current density versus voltage curves afford 8.82% and 10.63% for room‐temperature and HC‐processed 2D perovskites based planar solar cells, respectively. However, the corresponding steady‐state PCEs are remarkably lower, which is presumably due to the significant hysteresis phenomena caused by low charge extraction efficiency at interfaces of C60/2D perovskites.  相似文献   

2.
Organic spacer cations in layered 2D (A1)2(A2)n?1BnX3n+1 (where A1 is an organic cation acting as a spacer between the perovskite layers, A2 is a monovalent cation, e.g., Cs+,CH3NH3+, CH(NH2)2+) perovskite materials improve the long‐term stability of the resulting solar cells, but hamper their power conversion efficiency due to poor carrier generation/transportation. Rational guidelines are thus required to enable the design of organic spacer cations. Herein, mixed A1 cations are employed in layered 2D perovskites to investigate the interplay between alkylamine cations and unsaturated alkylamine cations. It is revealed that alkylamine spacer cations are able to facilitate precursor assembly, which results in the orientated growth of perovskite crystals. Unsaturated alkylamine cations further lead to reduced exciton binding energy, which improves carrier pathway in the 2D perovskites. By mixing both cations, substantially improved open circuit voltage is observed in the resultant photovoltaic cells with the efficiency of 15.46%, one of the highest one based on (A1)2(A2)3Pb4I13 layered 2D perovskites. The generality of the design principle is further extended to other cation combinations.  相似文献   

3.
Formamidinium (FA)‐based 3D perovskite solar cells (PSCs) have been widely studied and they show reduced bandgap, enhanced stability, and improved efficiency compared to MAPbI3‐based devices. Nevertheless, the FA‐based spacers have rarely been studied for 2D Ruddlesden–Popper (RP) perovskites, which have drawn wide attention due to their enormous potential for fabricating efficient and stable photovoltaic devices. Here, for the first time, FA‐based derivative, 2‐thiopheneformamidinium (ThFA), is successfully synthesized and employed as an organic spacer for 2D RP PSCs. A precursor organic salts‐assisted crystal growth technique is further developed to prepare high quality 2D (ThFA)2(MA)n?1PbnI3n+1 (nominal n = 3) perovskite films, which shows preferential vertical growth orientations, high charge carrier mobilities, and reduced trap density. As a result, the 2D RP PSCs with an inverted planar p‐i‐n structure exhibit a dramatically improved power conversion efficiency (PCE) from 7.23% to 16.72% with negligible hysteresis, which is among the highest PCE in 2D RP PSCs with low nominal n‐value of 3. Importantly, the optimized 2D PSCs exhibit a dramatically improved stability with less than 1% degradation after storage in N2 for 3000 h without encapsulation. These findings provide an effective strategy for developing FA‐based organic spacers toward highly efficient and stable 2D PSCs.  相似文献   

4.
Perovskite solar cells are one of the most promising photovoltaic technologies, although their molecular level design and stability toward environmental factors remain a challenge. Layered 2D Ruddlesden–Popper perovskite phases feature an organic spacer bilayer that enhances their environmental stability. Here, the concept of supramolecular engineering of 2D perovskite materials is demonstrated in the case of formamidinium (FA) containing A2FAn?1PbnI3n+1 formulations by employing (adamantan‐1‐yl)methanammonium (A) spacers exhibiting propensity for strong Van der Waals interactions complemented by structural adaptability. The molecular design translates into desirable structural features and phases with different compositions and dimensionalities, identified uniquely at the atomic level by solid‐state NMR spectroscopy. For A2FA2Pb3I10, efficiencies exceeding 7% in mesoscopic device architectures without any additional treatment or use of antisolvents for ambient temperature film deposition are achieved. This performance improvement over the state‐of‐the‐art FA‐based 2D perovskites is accompanied by high operational stability under humid ambient conditions, which illustrates the utility of the approach in perovskite solar cells and sets the basis for advanced supramolecular design in the future.  相似文献   

5.
Hybrid halide 2D perovskites deserve special attention because they exhibit superior environmental stability compared with their 3D analogs. The closer interlayer distance discovered in 2D Dion–Jacobson (DJ) type of halide perovskites relative to 2D Ruddlesden–Popper (RP) perovskites implies better carrier charge transport and superior performance in solar cells. Here, the structure and properties of 2D DJ perovskites employing 3‐(aminomethyl)piperidinium (3AMP2+) as the spacing cation and a mixture of methylammonium (MA+) and formamidinium (FA+) cations in the perovskite cages are presented. Using single‐crystal X‐ray crystallography, it is found that the mixed‐cation (3AMP)(MA0.75FA0.25)3Pb4I13 perovskite has a narrower bandgap, less distorted inorganic framework, and larger Pb? I? Pb angles than the single‐cation (3AMP)(MA)3Pb4I13. Furthermore, the (3AMP)(MA0.75FA0.25)3Pb4I13 films made by a solvent‐engineering method with a small amount of hydriodic acid have a much better film morphology and crystalline quality and more preferred perpendicular orientation. As a result, the (3AMP)(MA0.75FA0.25)3Pb4I13‐based solar cells exhibit a champion power conversion efficiency of 12.04% with a high fill factor of 81.04% and a 50% average efficiency improvement compared to the pristine (3AMP)(MA)3Pb4I13 cells. Most importantly, the 2D DJ 3AMP‐based perovskite films and devices show better air and light stability than the 2D RP butylammonium‐based perovskites and their 3D analogs.  相似文献   

6.
Increasing the power conversion efficiency (PCE) of the two‐dimensional (2D) perovskite‐based solar cells (PVSCs) is really a challenge. Vertical orientation of the 2D perovskite film is an efficient strategy to elevate the PCE. In this work, vertically orientated highly crystalline 2D (PEA)2(MA)n–1PbnI3n+1 (PEA= phenylethylammonium, MA = methylammonium, n = 3, 4, 5) films are fabricated with the assistance of an ammonium thiocyanate (NH4SCN) additive by a one‐step spin‐coating method. Planar‐structured PVSCs with the device structure of indium tin oxide (ITO)/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)/(PEA)2(MA)n–1PbnI3n+1/[6,6]‐phenyl‐C61‐butyric acid methyl ester/bahocuproine/Ag are fabricated. The PCE of the PVSCs is boosted from the original 0.56% (without NH4SCN) to 11.01% with the optimized NH4SCN addition at n = 5, which is among the highest PCE values for the low‐n (n < 10) 2D perovskite‐based PVSCs. The improved performance is attributed to the vertically orientated highly crystalline 2D perovskite thin films as well as the balanced electron/hole transportation. The humidity stability of this oriented 2D perovskite thin film is also confirmed by the almost unchanged X‐ray diffraction patterns after 28 d exposed to the moisture in a humidity‐controlled cabinet (Hr = 55 ± 5%). The unsealed device retains 78.5% of its original PCE after 160 h storage in air atmosphere with humidity of 55 ± 5%. The results provide an effective approach toward a highly efficient and stable PVSC for future commercialization.  相似文献   

7.
2D Ruddlesden–Popper perovskites (RPPs) have emerged as a promising solar cell material. A group of novel RPPs with cyclohexane methylamine (CMA) as a spacer cation is presented. Unlike previously reported RPPs, the deposited films of (CMA)2(MA)n?1PbnI3n+1 (MA is CH3NH3+, n = 1, 2, 3, …) exhibit multiple phases with reverse‐graded quantum well (QW) distribution; small n (n = 2) RPPs are located at the surface and large n (n ≥ 10) RPPs at the bottom. This has three advantages: (a) The outer, more moisture resistant, small n RPPs create a stable barrier that protects the vulnerable large n RPP lattice from being attacked by water molecules. (b) It forms a type‐II band alignment between different phases, which favors self‐driven charge transport. (c) The natural structure of graded QWs expands the range of photon collection. Attributed to these properties, the best efficiency of 15.05%, with high open‐circuit voltage (Voc) of 1.10 V for a first‐generation solar cell containing (CMA)2(MA)8Pb9I28, is achieved. A notable enhancement in short wavelength is observed in the Incident photon‐to‐current conversion efficiency spectra. This device shows significantly improved long‐term stability, retaining ≈95% of the initial efficiency after 4600 h exposure in ambient conditions with 40–70% relative humidity.  相似文献   

8.
As the race toward higher efficiency for inorganic/organic hybrid perovskite solar cells (PSCs) is becoming highly competitive, a design scheme to maximize carrier transport toward higher power efficiency has been urgently demanded. In this study, a hidden role of A‐site cations of PSCs in carrier transport, which has been largely neglected is unraveled, i.e., tuning the Fröhlich electron–phonon (e–ph) coupling of longitudinal optical (LO) phonon by A‐site cations. The key for steering Fröhlich polaron is to control the interaction strength and the number of proton (or lithium) coordination to halide ions. The coordination to I? alleviates electron–phonon scattering by either decreasing the Born effective charge or absorbing the LO motion of I. This novel principle discloses low electron–phonon coupling in several promising organic cations including hydroxyl–ammonium cation (NH3OH+), hydrazinium cation (NH3NH2+) and possibly Li+ solvating methylamine (Li+???NH2CH3), on a par with methyl–ammonium cations. A new perspective on the role of A‐site cations could help in improving power efficiency and accelerating the application of PSCs.  相似文献   

9.
In the past years, hybrid perovskite materials have attracted great attention due to their superior optoelectronic properties. In this study, the authors report the utilization of cobalt (Co2+) to partially substitute lead (Pb2+) for developing novel hybrid perovskite materials, CH3NH3Pb1‐xCoxI3 (where x is nominal ratio, x = 0, 0.1, 0.2 and 0.4). It is found that the novel perovskite thin films possess a cubic crystal structure with superior thin film morphology and larger grain size, which is significantly different from pristine thin film, which possesses the tetragonal crystal structure, with smaller grain size. Moreover, it is found that the 3d orbital of Co2+ ensures higher electron mobilities and electrical conductivities of the CH3NH3Pb1‐xCoxI3 thin films than those of pristine CH3NH3Pb4 thin film. As a result, a power conversion efficiency of 21.43% is observed from perovskite solar cells fabricated by the CH3NH3Pb0.9Co0.1I3 thin film. Thus, the utilization of Co, partially substituting for Pb to tune physical properties of hybrid perovskite materials provides a facile way to boost device performance of perovskite solar cells.  相似文献   

10.
Adding cesium (Cs) and rubidium (Rb) cations to FA0.83MA0.17Pb(I0.83Br0.17)3 hybrid lead halide perovskites results in a remarkable improvement in solar cell performance, but the origin of the enhancement has not been fully understood yet. In this work, time‐of‐flight, time‐resolved microwave conductivity, and thermally stimulated current measurements are performed to elucidate the impact of the inorganic cation additives on the trap landscape and charge transport properties within perovskite solar cells. These complementary techniques allow for the assessment of both local features within the perovskite crystals and macroscopic properties of films and full devices. Strikingly, Cs‐incorporation is shown to reduce the trap density and charge recombination rates in the perovskite layer. This is consistent with the significant improvements in the open‐circuit voltage and fill factor of Cs‐containing devices. By comparison, Rb‐addition results in an increased charge carrier mobility, which is accompanied by a minor increase in device efficiency and reduced current–voltage hysteresis. By mixing Cs and Rb in quadruple cation (Cs‐Rb‐FA‐MA) perovskites, the advantages of both inorganic cations can be combined. This study provides valuable insights into the role of these additives in multiple‐cation perovskite solar cells, which are essential for the design of high‐performance devices.  相似文献   

11.
Efficient perovskite solar cells (PSCs) are mainly fabricated by a solution coating processes. However, the efficiency of such devices varies significantly with the aging time of the precursor solution used to fabricate them, which includes a mixture of perovskite components, especially methylammonium (MA), and formamidinium (FA) cations. Herein, how the inorganic–organic hybrid perovskite precursor solution of (FAPbI3)0.95(MAPbBr3)0.05 degrades over time and how such degradation can be effectively inhibited is reported on, and the associated mechanism of degradation is discussed. Such degradation of the precursor solution is closely related to the loss of MA cations dissolved in the FA solution through the deprotonation of MA to volatile methylamine (CH3NH2). Addition of elemental sulfur (S8) drastically stabilizes the precursor solution owing to amine–sulfur coordination, without compromising the power conversion efficiency (PCE) of the derived PSCs. Furthermore, sulfur introduced to stabilize the precursor solution results in improved PSC stability.  相似文献   

12.
With the potential of achieving high efficiency and low production costs, perovskite solar cells (PSCs) have attracted great attention. However, their unstableness under moist condition has retarded the commercial development. Recently, 2D perovskites have received a lot of attention due to their high moisture resistance. In this work, four quasi 2D quasi perovskites are prepared, then their stability under moist condition is investigated. The surface morphology, crystal structure, optical properties, and photovoltaic performance are measured. Among the four quasi‐2D perovskites, (C6H5CH2NH3)2(FA)8Pb9I28 has the best performance: uniform and dense film, extremely well‐oriented crystal structure, strong absorption, and a high power conversion efficiency (PCE) of 17.40%. The aging tests show that quasi‐2D perovskites are more stable under moist conditions than FAPbI3 is. The (C6H5CH2NH3)2(FA)8Pb9I28 quasi‐2D perovskite devices exhibit high humidity stability, maintaining 80% of the starting PCE after 500 h under 80% relative humidity. Compared with other quasi‐2D perovskites, (C6H5CH2NH3)2(FA)8Pb9I28 has the highest humidity stability, due to their strongest hydrophobicity from C6H5CH2NH3+. This work demonstrates that the properties of perovskite materials can be modified by adding different ammonium salts into FAPbI3. Thus, by introducing ammonium salts with high hydrophobic properties the fabrication of highly efficient and stable 2D PSCs may be possible.  相似文献   

13.
The influence of monovalent cation halide additives on the optical, excitonic, and electrical properties of CH3NH3PbI3 perovskite is reported. Monovalent cation halide with similar ionic radii to Pb2+, including Cu+, Na+, and Ag+, have been added to explore the possibility of doping. Significant reduction of sub‐bandgap optical absorption and lower energetic disorder along with a shift in the Fermi level of the perovskite in the presence of these cations has been observed. The bulk hole mobility of the additive‐based perovskites as estimated using the space charge limited current method exhibits an increase of up to an order of magnitude compared to the pristine perovskites with a significant decrease in the activation energy. Consequentially, enhancement in the photovoltaic parameters of additive‐based solar cells is achieved. An increase in open circuit voltage for AgI (≈1.02 vs 0.95 V for the pristine) and photocurrent density for NaI‐ and CuBr‐based solar cells (≈23 vs 21 mA cm?2 for the pristine) has been observed. This enhanced photovoltaic performance can be attributed to the formation of uniform and continuous perovskite film, better conversion, and loading of perovskite, as well as the enhancement in the bulk charge transport along with a minimization of disorder, pointing towards possible surface passivation.  相似文献   

14.
2D Ruddlesden–Popper perovskites (RPPs) are emerging as potential challengers to their 3D counterpart due to superior stability and competitive efficiency. However, the fundamental questions on energetics of the 2D RPPs are not well understood. Here, the energetics at (PEA)2(MA)n?1PbnI3n+1/[6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) interfaces with varying n values of 1, 3, 5, 40, and ∞ are systematically investigated. It is found that n–n junctions form at the 2D RPP interfaces (n = 3, 5, and 40), instead of p–n junctions in the pure 2D and 3D scenarios (n = 1 and ∞). The potential gradient across phenethylammonium iodide ligands that significantly decreases surface work function, promotes separation of the photogenerated charge carriers with electron transferring from perovskite crystal to ligand at the interface, reducing charge recombination, which contributes to the smallest energy loss and the highest open‐circuit voltage (Voc) in the perovskite solar cells (PSCs) based on the 2D RPP (n = 5)/PCBM. The mechanism is further verified by inserting a thin 2D RPP capping layer between pure 3D perovskite and PCBM in PSCs, causing the Voc to evidently increase by 94 mV. Capacitance–voltage measurements with Mott–Schottky analysis demonstrate that such Voc improvement is attributed to the enhanced potential at the interface.  相似文献   

15.
An efficient perovskite photovoltaic‐thermoelectric hybrid device is demonstrated by integrating the hole‐conductor‐free perovskite solar cell based on TiO2/ZrO2/carbon structure and the thermoelectric generator. The whole solar spectrum of AM 1.5 G is fully utilized with the ≈1.55 eV band gap perovskite (5‐AVA)x(MA)1?xPbI3 absorbing the visible light and the carbon back contact absorbing the infrared light. The added thermoelectric generator improves the device performance by converting the thermal energy into electricity via the Seebeck effect. An optimized hybrid device is obtained with a maximum point power output of 20.3% and open‐circuit voltage of 1.29 V under the irradiation of 100 mW cm?2.  相似文献   

16.
A comprehensive investigation of the electronic energy levels of an n = 2 Ruddlesden–Popper phase perovskite is presented. Ultraviolet and inverse photoemission spectroscopies are used to probe the density of states in the valence and conduction bands, respectively, of the quasi‐2D perovskite, butylammonium cesium lead iodide (BA2CsPb2I7). By comparing experimental spectra with calculated projected density of states, the contributions from Cs, Pb, and I to the quantum well states are identified, and distinguished from those of the organic ligand barrier layer. The ionization energy, electron affinity, and exciton binding energy of this material are derived. The energetics of the quantum well structure are discussed in terms of the number of Pb‐halide layers. The resulting energy diagram suggests that a type‐I heterojunction would be formed with the n = 1 BA2PbI4. Finally, surface photovoltage performed via Kelvin probe force microscopy is used to evaluate band bending at the surface of the BA2CsPb2I7 thin films.  相似文献   

17.
Remarkable power conversion efficiencies (PCE) of metal–halide perovskite solar cells (PSCs) are overshadowed by concerns about their ultimate stability, which is arguably the prime obstacle to commercialization of this promising technology. Herein, the problem is addressed by introducing ethane‐1,2‐diammonium (+NH3(CH2)2NH3+, EDA2+) cations into the methyl ammonium (CH3NH3+, MA+) lead iodide perovskite, which enables, inter alia, systematic tuning of the morphology, electronic structure, light absorption, and photoluminescence properties of the perovskite films. Incorporation of <5 mol% EDA2+ induces strain in the perovskite crystal structure with no new phase formed. With 0.8 mol% EDA2+, PCE of the MAPbI3‐based PSCs (aperture of 0.16 cm2) improves from 16.7% ± 0.6% to 17.9% ± 0.4% under 1 sun irradiation, and fabrication of larger area devices (aperture 1.04 cm2) with a certified PCE of 15.2% ± 0.5% is demonstrated. Most importantly, EDA2+/MA+‐based solar cells retain 75% of the initial performance after 72 h of continuous operation at 50% relative humidity and 50 °C under 1 sun illumination, whereas the MAPbI3 devices degrade by approximately 90% within only 15 h. This substantial improvement in stability is attributed to the steric and coulombic interactions of embedded EDA2+ in the perovskite structure.  相似文献   

18.
Objective: To compare erythrocyte aggregation (EA) in patients with severe obesity without other cardiovascular risk factors with a control group, using the Myrenne and the Sefam aggregometers, and to evaluate the effect of weight loss on this parameter. Research Methods and Procedures: This was a longitudinal, clinical intervention study of a very low‐calorie diet for 4 weeks followed by a low‐calorie diet for 2 months. In 67 severely obese patients, an anthropometric and analytical evaluation [plasmatic lipids, fibrinogen (Fbg), and EA] was performed at baseline and 3 months after diet. The same determinations were performed in 67 normal‐weight volunteers. EA was measured with the Myrenne MA1, which determines EA at stasis (EA0) and at a low shear of 3 seconds?1 (EA1), and the Sefam aggregometer, which determines aggregation index at 10 seconds?1 (IA10), aggregation time (Ta), and disaggregation threshold (γD). Insulin resistance (IR) was calculated by homeostasis model assessment. Results: Obese patients showed higher Fbg levels, EA0, EA1, IA10, and γD values, and lower Ta values. Differences between obese patients and control group for EA0, EA1, Ta, IA10, and γD disappeared after adjusting for BMI or for homeostasis model assessment but were maintained after adjusting for Fbg or low‐density lipoprotein‐cholesterol. Obese patients with IR showed higher EA0 and EA1 values. After weight loss, EA1 showed a significant improvement. Discussion: Obese patients show increased EA. Erythrocyte hyperaggregation does not seem to be related to a high Fbg level or to an abnormal lipid profile but to IR. Hyperagreggation improves after weight loss.  相似文献   

19.
Photosynthetic organisms live in a dynamic environment where light typically fluctuates around a mean level that is slowly drifting during the solar day. We show that the far-from-equilibrium photosynthesis occurring in a rapidly fluctuating light differs vastly from the stationary-flux photosynthesis attained in a constant or slowly drifting light. Photosynthetic organisms in a static or slowly drifting light can be characterized by a steady-state quantum yield of chlorophyll fluorescence emission F′ that is changing linearly with small and slow variations of the incident irradiance II(t): F′(II(t))≈ Fmean(dF)/(dI)·ΔI(t). In Synechocystis sp. PCC 6803, the linear approximation holds for an extended interval covering largely the static irradiance range experienced by the cyanobacteria in nature. The photosynthetic dynamism and, consequently, the dynamism of the chlorophyll fluorescence emission change dramatically when exposing the organism to a fluctuating irradiance. Harmonically-modulated irradiance II · sin(2πt/T), T ≈ 1–25 s induces perpetual, far-from-equilibrium forced oscillations that are strongly non-linear, exhibiting significant hysteresis with multiple fluorescence levels corresponding to a single instantaneous level of the incident irradiance. We propose that, in nature, the far-from-equilibrium dynamic phenomena represent a significant correction to the steady-state photosynthetic activity that is typically investigated in laboratory. Analysis of the forced oscillations by the tools of systems biology suggests that the dynamism of photosynthesis observed in fluctuating light can be explained by a delayed action of regulatory agents.  相似文献   

20.
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