Chen Weijie

The factors affecting the V _OC in 2D perovskite cells with different [PbI₆]⁴⁻ layer sheets (n = 2–4) are elucidated. Nonradiative recombination at the perovskite/C₆₀ interface is found to dominate except for the n = 2 system where the bulk recombination determines the properties of the cell. Substantial V _OC gains through suppression of interfacial recombination at the top interface are expected.

Abstract

2D Ruddlesden–Popper perovskite (RPP) solar cells have excellent environmental stability. However, the power conversion efficiency (PCE) of RPP cells remains inferior to 3D perovskite‐based cells. Herein, 2D (CH₃(CH₂)₃NH₃)₂(CH₃NH₃) _{n −1}Pb _n I_{3 n +1} perovskite cells with different numbers of [PbI₆]⁴⁻ sheets (n = 2–4) are analyzed. Photoluminescence quantum yield (PLQY) measurements show that nonradiative open‐circuit voltage (V _OC) losses outweigh radiative losses in materials with n > 2. The n = 3 and n = 4 films exhibit a higher PLQY than the standard 3D methylammonium lead iodide perovskite although this is accompanied by increased interfacial recombination at the top perovskite/C₆₀ interface. This tradeoff results in a similar PLQY in all devices, including the n = 2 system where the perovskite bulk dominates the recombination properties of the cell. In most cases the quasi‐Fermi level splitting matches the device V _OC within 20 meV, which indicates minimal recombination losses at the metal contacts. The results show that poor charge transport rather than exciton dissociation is the primary reason for the reduction in fill factor of the RPP devices. Optimized n = 4 RPP solar cells had PCEs of 13% with significant potential for further improvements.

Perovskite solar cells based on polarized ferroelectric polymers are fabricated by doping the ferroelectric polymer into the perovskite layer with different polarizing electric fields and different doping concentrations, different polarized ferroelectric polymers' interlayers between the perovskite and the hole‐transporting layer, and both doping and interlayer. After these treatments, the fabricated devices show a maximum power conversion efficiency of 21.38%.

Abstract

In hybrid organic–inorganic lead halide perovskite solar cells, the energy loss is strongly associated with nonradiative recombination in the perovskite layer and at the cell interfaces. Here, a simple but effective strategy is developed to improve the cell performance of perovskite solar cells via the combination of internal doping by a ferroelectric polymer and external control by an electric field. A group of polarized ferroelectric (PFE) polymers are doped into the methylammonium lead iodide (MAPbI₃) layer and/or inserted between the perovskite and the hole‐transporting layers to enhance the build‐in field (BIF), improve the crystallization of MAPbI₃, and regulate the nonradiative recombination in perovskite solar cells. The PFE polymer‐doped MAPbI₃ shows an orderly arrangement of MA⁺ cations, resulting in a preferred growth orientation of polycrystalline perovskite films with reduced trap states. In addition, the BIF is enhanced by the widened depletion region in the device. As an interfacial dipole layer, the PFE polymer plays a critical role in increasing the BIF. This combined effect leads to a substantial reduction in voltage loss of 0.14 V due to the efficient suppression of nonradiative recombination. Consequently, the resulting perovskite solar cells present a power conversion efficiency of 21.38% with a high open‐circuit voltage of 1.14 V.

This work reports a strategy that ensures the degree of nonradiative recombination can be measured accurately in low‐energetic‐offset organic photovoltaic systems and reports key observations on the relationship between the nonradiative recombination loss and properties of the donor/acceptor interface, including an observed correlation between high domain purity and high nonradiative recombination loss.

Abstract

Open‐circuit voltage (V _OC) losses in organic photovoltaics (OPVs) inhibit devices from reaching V _OC values comparable to the bandgap of the donor–acceptor blend. Specifically, nonradiative recombination losses (∆V _nr) are much greater in OPVs than in silicon or perovskite solar cells, yet the origins of this are not fully understood. To understand what makes a system have high or low loss, an investigation of the nonradiative recombination losses in a total of nine blend systems is carried out. An apparent relationship is observed between the relative domain purity of six blends and the degree of nonradiative recombination loss, where films exhibiting relatively less pure domains show lower ∆V _nr than films with higher domain purity. Additionally, it is shown that when paired with a fullerene acceptor, polymer donors which have bulky backbone units to inhibit close π–π stacking exhibit lower nonradiative recombination losses than in blends where the polymer can pack more closely. This work reports a strategy that ensures ∆V _nr can be measured accurately and reports key observations on the relationship between ∆V _nr and properties of the donor/acceptor interface.

Three enamine hole‐transporting materials (HTMs) based on Tröger's base scaffold were synthesized. These compounds are obtained in a three‐step facile synthesis from commercially available materials without the need of expensive catalysts, inert conditions or time‐consuming purification steps.

Abstract

The synthesis of three enamine hole‐transporting materials (HTMs) based on Tröger's base scaffold are reported. These compounds are obtained in a three‐step facile synthesis from commercially available materials without the need of expensive catalysts, inert conditions or time‐consuming purification steps. The best performing material, HTM3, demonstrated 18.62 % PCE in PSCs, rivaling spiro‐OMeTAD in efficiency, and showing markedly superior long‐term stability in non‐encapsulated devices. In dopant‐free PSCs, HTM3 outperformed spiro‐OMeTAD by a factror of 1.6. The high glass‐transition temperature (T _g=176 °C) of HTM3 also suggests promising perspectives in device applications.

The technological potential of emerging perovskite solar cells is determined by the stability of the power generated. Alkali salts used as interface modifiers positively affect device performance and stability and mitigate current–voltage hysteresis. Devices modified with potassium nitrate deliver a power conversion efficiency of 19.2% attributed to an improved charge carrier extraction and suppression of transient capacitive effects in device operation.

After demonstration of a 23% power conversion efficiency, a high operational stability is the next most important scientific and technological challenge in perovskite solar cells (PSCs). A potential failure mechanism is tied to a bias‐induced ion migration, which causes current–voltage hysteresis and a decay in the device performance over time. Herein, alkali salts are shown to mitigate hysteresis and stabilize device performance in n‐i‐p hybrid planar PSCs. Different alkali salts of potassium chloride, iodide, and nitrate as well as sodium chloride and iodide are deposited from aqueous solution onto the n‐type contact, based on SnO₂, prior to deposition of the perovskite absorber Cs_0.05(FA_0.83MA_0.17)_0.95Pb(I_0.83Br_0.17)₃. Introduction of potassium‐based alkali salts suppresses the current–voltage hysteresis and stabilizes the operational device stability at the maximum power point. This is attributed to the suppression of hole trapping at the n‐type selective transport layer (SnO₂)/perovskite interface observed by surface photovoltage spectroscopy, which is interpreted to reduce interfacial recombination and improve charge carrier extraction. The best and most stable performance of 19% is achieved using potassium nitrate as the interface modifier. Devices with higher and more stable performance exhibit substantially lower current transients, analyzed during maximum power point tracking.

Highly‐efficient, low‐cost, solution‐processed perovskite solar cells, exhibiting remarkable environmental stability, are reported. The fabrication strategy relies on the rational design of the molecular structure of arylamine‐substituted copper(II) phthalocyanine (CuPc) derivatives, which are used as dopant‐free hole‐transport materials. The resulting devices reach a power conversion efficiency of 19.7% and display enhanced long‐term stability with respect to standard (doped) materials.

Abstract

A power conversion efficiency (PCE) as high as 19.7% is achieved using a novel, low‐cost, dopant‐free hole transport material (HTM) in mixed‐ion solution‐processed perovskite solar cells (PSCs). Following a rational molecular design strategy, arylamine‐substituted copper(II) phthalocyanine (CuPc) derivatives are selected as HTMs, reaching the highest PCE ever reported for PSCs employing dopant‐free HTMs. The intrinsic thermal and chemical properties of dopant‐free CuPcs result in PSCs with a long‐term stability outperforming that of the benchmark doped 2,2′,7,7′‐Tetrakis‐(N,N‐di‐p‐methoxyphenylamine)‐9,9′‐Spirobifluorene (Spiro‐OMeTAD)‐based devices. The combination of molecular modeling, synthesis, and full experimental characterization sheds light on the nanostructure and molecular aggregation of arylamine‐substituted CuPc compounds, providing a link between molecular structure and device properties. These results reveal the potential of engineering CuPc derivatives as dopant‐free HTMs to fabricate cost‐effective and highly efficient PSCs with long‐term stability, and pave the way to their commercial‐scale manufacturing. More generally, this case demonstrates how an integrated approach based on rational design and computational modeling can guide and anticipate the synthesis of new classes of materials to achieve specific functions in complex device structures.

A novel strategy is reported where control over the surface‐adsorbed water on a transparent conducting oxide substrate is used to mediate the in situ nanocrystalline regrowth of a SnO₂ electron transport layer (ETL) at near room temperature. The new ETL is key to achieving a high power conversion efficiency of 20.5% and 17.5% in rigid and flexible perovskite solar cells, respectively.

Abstract

Electron transport layer (ETL) is a functional layer of great significance for boosting the power conversion efficiency (PCE) of perovskite solar cells (PSCs). To date, it is still a challenge to simultaneously reduce the surface defects and improve the crystallinity in ETLs during their low‐temperature processing. Here, a novel strategy for the mediation of in situ regrowth of SnO₂ nanocrystal ETLs is reported: introduction of controlled trace amounts of surface absorbed water on the fluorinated tin oxide (FTO) or indium–tin oxide (ITO) surfaces of the substrates using ultraviolet ozone (UVO) pretreatment. The optimum amount of adsorbed water plays a key role in balancing the hydrolysis–condensation reactions during the structural evolution of SnO₂ thin films. This new approach results in a full‐coverage SnO₂ ETL with a desirable morphology and crystallinity for superior optical and electrical properties, as compared to the control SnO₂ ETL without the UVO pretreatment. Finally, the rigid and flexible PSC devices based on the new SnO₂ ETLs yield high PCEs of up to 20.5% and 17.5%, respectively.

Nonfullerene n‐type organic semiconductors possess unique advantages over inorganic semiconductors and/or fullerene derivatives in perovskite solar cells. This research news article summarizes and discusses the recent development of the multifunctional nonfullerene n‐type organic semiconductors used in perovskite solar cells.

Abstract

Compared to inorganic semiconductors and/or fullerene derivatives, nonfullerene n‐type organic semiconductors present some advantages, such as low‐temperature processing, flexibility, and molecule structure diversity, and have been widely used in perovskite solar cells (PSCs). In this research news article, the recent advances in nonfullerene n‐type organic semiconductors which function as electron‐transporting, interface‐modifying, additive, and light‐harvesting materials in PSCs are summarized. The remaining challenges and promising future directions of nonfullerene‐based PSCs are also discussed.

Me₄NBr is introduced to passivate the Sn–Pb based perovskite interface, leading to an improved efficiency of 13.97%, mainly due to the effective reduction of defects. By adopting the poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate) (PEDOT:PSS)/poly(triarylamine) (PTAA) as the hole transport material (HTM), a Sn‐based perovskite solar cell with an efficiency of 14.56% is obtained. Furthermore, the Me₄NBr treated Sn–Pb perovskite cells also demonstrate a significant stability enhancement.

Abstract

Tin–lead (Sn–Pb) based hybrid perovskite solar cell is investigated as a potential solution to extend the light absorption spectrum range, and to reduce environmental hazard caused by lead in the perovskite materials. Nonetheless, due to the instability of tin, the Sn–Pb based perovskite solar cells suffer from more severe efficiency degradation when compared to the lead‐based perovskite solar cells, which restricts its further development. Here, a quaternary ammonium halide compound, Me₄NBr, is introduced to passivate the Sn–Pb based perovskite surface. The Me₄NBr effectively reduces the surface defects and enhances the open circuit voltage and fill factor of the Sn–Pb based perovskite solar cell. Moreover, the Me₄NBr treated Sn–Pb perovskite cells also demonstrate a significant stability enhancement when compared with the untreated Sn–Pb perovskite cells.

By soldering adjacent perovskite grains with the synergistic effects of formamidinium and chloride ions, the trap state density and non‐radiative recombination rate of perovskite films are remarkably reduced. Perovskite solar cells, using unannealed nickel oxide as the hole transport layer, could achieve a power conversion efficiency of 19.6% with open‐circuit voltages as high as 1.10 V.

Abstract

Grain boundaries (GBs) are one of the major sources of defects in a polycrystalline perovskite solar cell and can greatly increase the rate of charge carrier recombination. In the push to optimize the efficiency of perovskite solar cells, it is therefore extremely important to maximize the grain size and minimize the number of GBs. In the present work, the number of GBs is effectively reduced by introducing a suitable number of formamidinium and chloride ions into the methylammonium lead iodide (MAPbI₃) absorber layer. Inverted perovskite solar cells, using NiO _x nanocrystals as the low‐temperature‐fabricated hole transport layer, are prepared; the champion cell has an efficiency of 19.6%. This work demonstrates a simple method of minimizing the number of grain boundaries, which is critical to the future development of this technology.

Machine‐learning approaches are utilized to build models for the prediction of efficiency using important frontier molecular orbital energy levels of organic materials as features. Furthermore, a versatile Random Forest model reveals that the lowest unoccupied molecular orbital energy of donor can be considered as a critical feature in design of ternary organic solar cells.

Abstract

Ternary organic solar cells (OSCs) have progressed significantly in recent years due to the sufficient photon harvesting of the blend photoactive layer including three absorption‐complementary materials. With the rapid development of highly efficient ternary OSCs in photovoltaics, the precise energy‐level alignment of the three active components within ternary OSC devices should be taken into account. The machine‐learning technique is a computational method that can effectively learn from previous historical data to build predictive models. In this study, a dataset of 124 fullerene derivatives‐based ternary OSCs is manually constructed from a diverse range of literature along with their frontier molecular orbital theory levels, and device structures. Different machine‐learning algorithms are trained based on these electronic parameters to predict photovoltaic efficiency. Thus, the best predictive capability is provided by using the Random Forest approach beyond other machine‐learning algorithms in the dataset. Furthermore, the Random Forest algorithm yields valuable insights into the crucial role of lowest unoccupied molecular orbital energy levels of organic donors in the performance of ternary OSCs. The outcome of this study demonstrates a smart strategy for extracting underlying complex correlations in fullerene derivatives‐based ternary OSCs, thereby accelerating the development of ternary OSCs and related research fields.

A platinum(II) complexation strategy is developed to regulate the crystallinity of a newly designed s‐tetrazine‐containing wide‐bandgap copolymer donor PSFTZ, and optimize the morphology of the PSFTZ:Y6 active blend film, which boosts successfully the power conversion efficiency of the resulting nonfullerene polymer solar cells (NF‐PSCs) from 13.03% to 16.35%. 16.35% is the new record for single‐junction NA‐PSCs at present.

Abstract

A new strategy of platinum(II) complexation is developed to regulate the crystallinity and molecular packing of polynitrogen heterocyclic polymers, optimize the morphology of the active blends, and improve the efficiency of the resulting nonfullerene polymer solar cells (NF‐PSCs). The newly designed s‐tetrazine (s‐TZ)‐containing copolymer of PSFTZ (4,8‐bis(5‐((2‐butyloctyl)thio)‐4‐fluorothiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐alt‐3,6‐bis(4‐octylthiophen‐2‐yl)‐1,2,4,5‐tetrazine) has a strong aggregation property, which results in serious phase separation and large domains when blending with Y6 ((2,2′‐((2Z,2′Z)‐((12,13‐bis(2‐ethylhexyl)‐3,9‐diundecyl‐12,13‐dihydro‐[1,2,5]thiadiazolo[3,4‐e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2‐g]thieno[2′,3′:4,5]thieno[3,2‐b]indole‐2,10‐diyl)bis(methanylylidene))bis(5,6‐difluoro‐3‐oxo‐2,3‐dihydro‐1H‐indene‐2,1‐diylidene))dimalononitrile)), and produces a power‐conversion efficiency (PCE) of 13.03%. By adding small amount of Pt(Ph)₂(DMSO)₂ (Ph, phenyl and DMSO, dimethyl sulfoxide), platinum(II) complexation would occur between Pt(Ph)₂(DMSO)₂ and PSFTZ. The bulky benzene ring on the platinum(II) complex increases the steric hindrance along the polymer main chain, inhibits the polymer aggregation strength, regulates the phase separation, optimizes the morphology, and thus improves the efficiency to 16.35% in the resulting devices. 16.35% is the highest efficiency for single‐junction PSCs reported so far.

Publication date: 17 July 2019

Source: Joule, Volume 3, Issue 7

Author(s): Guitao Feng, Junyu Li, Yakun He, Wenyu Zheng, Jing Wang, Cheng Li, Zheng Tang, Andres Osvet, Ning Li, Christoph J. Brabec, Yuanping Yi, He Yan, Weiwei Li

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Graphical Abstract

The current status and recent advances in perovskite‐based tandem solar cells, including perovskite–silicon, perovskite–perovskite, and perovskite–copper indium gallium selenide (CIGS) integrations, are comprehensively reviewed. Different configurations, key issues regarding the photoelectric properties, and material design are discussed. The critical role of perovskite bandgap optimization, interface engineering, and recombination layers are analyzed to outline the roadmaps for future investigations.

Metal halide perovskite‐based solar cells have achieved rapidly increasing efficiencies of up to 23.7%. However, it is still far away from the Shockley–Quiesser limit of 33.16%. Tandem solar cells, consisting of two subcells with complementary absorption, are suggested as an alternative to beat this limit due to the fact that a maximum efficiency of 42% can be reached using two subcells with bandgaps of 1.9 eV/1.0 eV, opening up a great potential to develop perovskite‐based tandem solar cells. In this review, the current status of and recent advances in perovskite‐based tandem solar cells are highlighted, including perovskite–silicon, perovskite–perovskite, and perovskite–copper indium gallium selenide (CIGS) integrations. Different configurations, key issues regarding the photoelectric properties, present efficiency limitations, and material design are discussed. The critical role of perovskite bandgap optimization, interface engineering, and recombination layers are also analyzed to outline the roadmaps for future investigation. The current challenging issues and future perspectives are also provided. It is hoped that the findings will provide new perspectives for perovskite‐based tandem solar cells with an unprecedented performance and the opportunity for commercialization.

Hybrid organic-inorganic halide perovskites have shown remarkable optoelectronic properties, exhibiting an impressive tolerance to defects believed to originate from correlated motion of charge carriers and the polar lattice forming large polarons. Few experimental techniques are capable of directly probing these correlations, requiring simultaneous sub–millielectron volt energy and femtosecond temporal resolution after absorption of a photon. Here, we use time-resolved multi-THz spectroscopy, sensitive to the internal excitations of the polaron, to temporally and energetically resolve the coherent coupling of charges to longitudinal optical phonons in single-crystal CH₃NH₃PbI₃ (MAPI). We observe room temperature intraband quantum beats arising from the coherent displacement of charge from the coupled phonon cloud. Our measurements provide strong evidence for the existence of polarons in MAPI at room temperature, suggesting that electron/hole-phonon coupling is a defining aspect of the hybrid metal-halide perovskites contributing to the protection from scattering and enhanced carrier lifetimes that define their usefulness in devices.

Publication date: 17 July 2019

Source: Joule, Volume 3, Issue 7

Author(s): Dong Hoe Kim, Christopher P. Muzzillo, Jinhui Tong, Axel F. Palmstrom, Bryon W. Larson, Chungseok Choi, Steven P. Harvey, Stephen Glynn, James B. Whitaker, Fei Zhang, Zhen Li, Haipeng Lu, Maikel F.A.M. van Hest, Joseph J. Berry, Lorelle M. Mansfield, Yu Huang, Yanfa Yan, Kai Zhu

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Summary

Graphical Abstract