Strain effects on halide perovskite solar cells.

Halide perovskite solar cells (PSCs) have achieved power conversion efficiencies (PCEs) approaching 26%, however, the stability issue hinders their commercialization. Due to the soft ionic nature of perovskite materials, the strain effect on perovskite films has been recently recognized as one of the key factors that affects their opto-electronic properties and the device stability. Herein, we summarized the origins of strain, characterization techniques, and implications of strain on both perovskite film and solar cells as well as various strategies to control the strain. Finally, we proposed effective strategies for future strain engineering. We believe this comprehensive review could further facilitate researchers with a deeper understanding of strain effect and enhance the research activity in engineering the strain to further improve performance and especially the device stability toward commercialization.

Asymmetrically Substituted 10H,10'H-9,9'-Spirobi[acridine] Derivatives as Hole-Transporting Materials for Perovskite Solar Cells.

Hole-transporting materials (HTMs) based on the 10H, 10'H-9,9'-spirobi [acridine] core (BSA50 and BSA51) were synthesized, and their electronic properties were explored. Experimental and theoretical studies show that the presence of rigid 3,6-dimethoxy-9H-carbazole moieties in BSA 50 brings about improved hole mobility and higher work function compared to bis(4-methoxyphenyl)amine units in BSA51, which increase interfacial hole transportation from perovskite to HTM. As a result, perovskite solar cells (PSCs) based on BSA50 boost power conversion efficiency (PCE) to 22.65 %, and a PSC module using BSA50 HTM exhibits a PCE of 21.35 % (6.5×7 cm) with a Voc of 8.761 V and FF of 79.1 %. The unencapsulated PSCs exhibit superior stability to devices employing spiro-OMeTAD, retaining nearly 90 % of their initial efficiency after 1000 h operation output. This work demonstrates the high potential of molecularly engineered spirobi[acridine] derivatives as HTMs as replacements for spiro-OMeTAD.

Doped but Stable: Spirobisacridine Hole Transporting Materials for Hysteresis-Free and Stable Perovskite Solar Cells.

Four spirobisacridine (SBA) hole-transporting materials were synthesized and employed in perovskite solar cells (PSCs). The molecules bear electronically inert alkyl chains of different length and bulkiness, attached to in-plane N atoms of nearly orthogonal spiro-connected acridines. Di-p-methoxyphenylamine (DMPA) substituents tailored to the central SBA-platform define electronic properties of the materials mimicking the structure of the benchmark 2,2',7,7'-tetrakis(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene (spiro-MeOTAD), while the alkyl pending groups affect molecular packing in thin films and affect the long-term performance of PSCs. Devices with SBA-based hole transporting layers (HTL) attain efficiencies on par with spiro-MeOTAD. More importantly, solar cells with the new HTMs are hysteresis-free and demonstrate good operational stability, despite being doped as spiro-MeOTAD. The best performing MeSBA-DMPA retained 88% of the initial efficiency after a 1000 h aging test under constant illumination. The results clearly demonstrate that SBA-based compounds are potent candidates for a design of new HTMs for PSCs with improved longevity.

Organic solar cells using CVD-grown graphene electrodes.

We report on the development of flexible organic solar cells (OSCs) incorporating graphene sheets synthesized by chemical vapor deposition (CVD) as transparent conducting electrodes on polyethylene terephthalate (PET) substrates. A key barrier that must be overcome for the successful fabrication of OSCs with graphene electrodes is the poor-film properties of water-based poly(3,4-ethylenedioxythiphene):poly(styrenesulfonate) (PEDOT:PSS) when coated onto hydrophobic graphene surfaces. To form a uniform PEDOT:PSS film on a graphene surface, we added perfluorinated ionomers (PFI) to pristine PEDOT:PSS to create 'GraHEL', which we then successfully spin coated onto the graphene surface. We systematically investigated the effect of number of layers in layer-by-layer stacked graphene anode of an OSC on the performance parameters including the open-circuit voltage (Voc), short-circuit current (Jsc), and fill factor (FF). As the number of graphene layers increased, the FF tended to increase owing to lower sheet resistance, while Jsc tended to decrease owing to the lower light absorption. In light of this trade-off between sheet resistance and transmittance, we determined that three-layer graphene (3LG) represents the best configuration for obtaining the optimal power conversion efficiency (PCE) in OSC anodes, even at suboptimal sheet resistances. We finally developed efficient, flexible OSCs with a PCE of 4.33%, which is the highest efficiency attained so far by an OSC with CVD-grown graphene electrodes to the best of our knowledge.

Shallow-level defect passivation by 6H perovskite polytype for highly efficient and stable perovskite solar cells.

The power conversion efficiency of perovskite solar cells continues to increase. However, defects in perovskite materials are detrimental to their carrier dynamics and structural stability, ultimately limiting the photovoltaic characteristics and stability of perovskite solar cells. Herein, we report that 6H polytype perovskite effectively engineers defects at the interface with cubic polytype FAPbI3, which facilitates radiative recombination and improves the stability of the polycrystalline film. We particularly show the detrimental effects of shallow-level defect that originates from the formation of the most dominant iodide vacancy (VI+) in FAPbI3. Furthermore, additional surface passivation on top of the hetero-polytypic perovskite film results in an ultra-long carrier lifetime exceeding 18 µs, affords power conversion efficiencies of 24.13% for perovskite solar cells, 21.92% (certified power conversion efficiency: 21.44%) for a module, and long-term stability. The hetero-polytypic perovskite configuration may be considered as close to the ideal polycrystalline structure in terms of charge carrier dynamics and stability.

Phase-Pure Quasi-2D Perovskite by Protonation of Neutral Amine.

Phase control of low-dimensional metal-halide perovskites (LDPs) greatly affects their optoelectronic properties, and phase-pure LDPs are desirable to achieve efficient perovskite optoelectronic devices such as solar cells and light-emitting diodes. Herein, we introduce a method to obtain phase-pure LDP by using a neutral amine, cyclohexylmethyl amine (CHMA). The incorporation of CHMA into a formamidinium lead bromide (FAPbBr3) precursor solution leads to the protonation of the amine that allows the phase transition of 3D FAPbBr3 to phase-pure quasi-2D perovskite (n = 2). For comparison, cyclohexylmethylammonium bromide (CHMABr), which is a conventional form of ammonium halide salt with the same organic moiety to the amine, is used, which resulted in a 2D perovskite (n = 1). The perovskite films fabricated by the two different methodologies are characterized. This study paves the way for further research on the realization of phase-pure perovskites and their relevant optoelectronic devices.

Molecular Design and Operational Stability: Toward Stable 3D/2D Perovskite Interlayers.

Despite organic/inorganic lead halide perovskite solar cells becoming one of the most promising next-generation photovoltaic materials, instability under heat and light soaking remains unsolved. In this work, a highly hydrophobic cation, perfluorobenzylammonium iodide (5FBzAI), is designed and a 2D perovskite with reinforced intermolecular interactions is engineered, providing improved passivation at the interface that reduces charge recombination and enhances cell stability compared with benchmark 2D systems. Motivated by the strong halogen bond interaction, (5FBzAI)2PbI4 used as a capping layer aligns in in-plane crystal orientation, inducing a reproducible increase of ≈60 mV in the V oc, a twofold improvement compared with its analogous monofluorinated phenylethylammonium iodide (PEAI) recently reported. This endows the system with high power conversion efficiency of 21.65% and extended operational stability after 1100 h of continuous illumination, outlining directions for future work.

Proton-transfer-induced 3D/2D hybrid perovskites suppress ion migration and reduce luminance overshoot.

Perovskite light-emitting diodes (PeLEDs) based on three-dimensional (3D) polycrystalline perovskites suffer from ion migration, which causes overshoot of luminance over time during operation and reduces its operational lifetime. Here, we demonstrate 3D/2D hybrid PeLEDs with extremely reduced luminance overshoot and 21 times longer operational lifetime than 3D PeLEDs. The luminance overshoot ratio of 3D/2D hybrid PeLED is only 7.4% which is greatly lower than that of 3D PeLED (150.4%). The 3D/2D hybrid perovskite is obtained by adding a small amount of neutral benzylamine to methylammonium lead bromide, which induces a proton transfer from methylammonium to benzylamine and enables crystallization of 2D perovskite without destroying the 3D phase. Benzylammonium in the perovskite lattice suppresses formation of deep-trap states and ion migration, thereby enhances both operating stability and luminous efficiency based on its retardation effect in reorientation.

Solution-Processed n-Type Graphene Doping for Cathode in Inverted Polymer Light-Emitting Diodes.

n-Type doping with (4-(1,3-dimethyl-2,3-dihydro-1H-benzoimidazol-2-yl)phenyl) dimethylamine (N-DMBI) reduces a work function (WF) of graphene by ∼0.45 eV without significant reduction of optical transmittance. Solution process of N-DMBI on graphene provides effective n-type doping effect and air-stability at the same time. Although neutral N-DMBI act as an electron receptor leaving the graphene p-doped, radical N-DMBI acts as an electron donator leaving the graphene n-doped, which is demonstrated by density functional theory. We also verify the suitability of N-DMBI-doped n-type graphene for use as a cathode in inverted polymer light-emitting diodes (PLEDs) by using various analytical methods. Inverted PLEDs using a graphene cathode doped with N-DMBI radical showed dramatically improved device efficiency (∼13.8 cd/A) than did inverted PLEDs with pristine graphene (∼2.74 cd/A). N-DMBI-doped graphene can provide a practical way to produce graphene cathodes with low WF in various organic optoelectronics.

Efficient Flexible Organic/Inorganic Hybrid Perovskite Light-Emitting Diodes Based on Graphene Anode.

Highly efficient organic/inorganic hybrid perovskite light-emitting diodes (PeLEDs) based on graphene anode are developed for the first time. Chemically inert graphene avoids quenching of excitons by diffused metal atom species from indium tin oxide. The flexible PeLEDs with graphene anode on plastic substrate show good bending stability; they provide an alternative and reliable flexible electrode for highly efficient flexible PeLEDs.

High-Efficiency Solution-Processed Inorganic Metal Halide Perovskite Light-Emitting Diodes.

This paper reports highly bright and efficient CsPbBr3 perovskite light-emitting diodes (PeLEDs) fabricated by simple one-step spin-coating of uniform CsPbBr3 polycrystalline layers on a self-organized buffer hole injection layer and stoichiometry-controlled CsPbBr3 precursor solutions with an optimized concentration. The PeLEDs have maximum current efficiency of 5.39 cd A-1 and maximum luminance of 13752 cd m-2 . This paper also investigates the origin of current hysteresis, which can be ascribed to migration of Br- anions. Temperature dependence of the electroluminescence (EL) spectrum is measured and the origins of decreased spectrum area, spectral blue-shift, and linewidth broadening are analyzed systematically with the activation energies, and are related with Br- anion migration, thermal dissociation of excitons, thermal expansion, and electron-phonon interaction. This work provides simple ways to improve the efficiency and brightness of all-inorganic polycrystalline PeLEDs and improves understanding of temperature-dependent ion migration and EL properties in inorganic PeLEDs.

Versatile Metal Nanowiring Platform for Large-Scale Nano- and Opto-Electronic Devices.

A versatile metal nanowiring platform enables the fabrication of Ag nanowires (AgNW) at a desired position and orientation in an individually controlled manner. A printed, flexible AgNW has a diameter of 695 nm, a resistivity of 5.7 µΩ cm, and good thermal stability in air. Based on an Ag nanowiring platform, an all-NW transistors array, as well as various optoelectronic applications, are successfully demonstrated.

Flexible Lamination Encapsulation.

A novel flexible encapsulation method (Flex Lami-capsulation) is reported, which can be applied in the roll-to-roll process for mass production of organic electronic devices. Flex Lami-capsulation is very simple, fast, and getter-free, and is as effective as glass encapsulation. Use of this method is feasible in large-area flexible displays and does not have the drawbacks of conventional encapsulation methods.

Boosting the power conversion efficiency of perovskite solar cells using self-organized polymeric hole extraction layers with high work function.

A self-organized hole extraction layer (SOHEL) with high work function (WF) is designed for energy level alignment with the ionization potential level of CH3 NH3 PbI3 . The SOHEL increases the built-in potential, photocurrent, and power conversion efficiency (PCE) of CH3 NH3 PbI3 perovskite solar cells. Thus, interface engineering of the positive electrode of solution-processed planar heterojunction solar cells using a high-WF SOHEL is a very effective way to achieve high device efficiency (PCE = 11.7% on glass).

Ultrathin organic solar cells with graphene doped by ferroelectric polarization.

Graphene has been employed as transparent electrodes in organic solar cells (OSCs) because of its good physical and optical properties. However, the electrical conductivity of graphene films synthesized by chemical vapor deposition (CVD) is still inferior to that of conventional indium tin oxide (ITO) electrodes of comparable transparency, resulting in a lower performance of OSCs. Here, we report an effective method to improve the performance and long-term stability of graphene-based OSCs using electrostatically doped graphene films via a ferroelectric polymer. The sheet resistance of electrostatically doped few layer graphene films was reduced to ∼70 Ω/sq at 87% optical transmittance. Such graphene-based OSCs exhibit an efficiency of 2.07% with a superior stability when compared to chemically doped graphene-based OSCs. Furthermore, OSCs constructed on ultrathin ferroelectric film as a substrate of only a few micrometers show extremely good mechanical flexibility and durability and can be rolled up into a cylinder with 7 mm diameter.