Recent progress in layered metal halide perovskites for solar cells, photodetectors, and field-effect transistors.

Metal halide perovskite materials demonstrate immense potential for photovoltaic and electronic applications. In particular, two-dimensional (2D) layered metal halide perovskites have advantages over their 3D counterparts in optoelectronic applications due to their outstanding stability, structural flexibility with a tunable bandgap, and electronic confinement effect. This review article first analyzes the crystallography of different 2D perovskite phases [the Ruddlesden-Popper (RP) phase, the Dion-Jacobson (DJ) phase, and the alternating cations in the interlayer space (ACI) phase] at the molecular level and compares their common electronic properties, such as out-of-plane conductivity, crucial to vertical devices. This paper then critically reviews the recent development of optoelectronic devices, namely solar cells, photodetectors and field effect transistors, based on layered 2D perovskite materials and points out their limitations and potential compared to their 3D counterparts. It also identifies the important application-specific future research directions for different optoelectronic devices providing a comprehensive view guiding new research directions in this field.

Nanoscale localized contacts for high fill factors in polymer-passivated perovskite solar cells.

Polymer passivation layers can improve the open-circuit voltage of perovskite solar cells when inserted at the perovskite-charge transport layer interfaces. Unfortunately, many such layers are poor conductors, leading to a trade-off between passivation quality (voltage) and series resistance (fill factor, FF). Here, we introduce a nanopatterned electron transport layer that overcomes this trade-off by modifying the spatial distribution of the passivation layer to form nanoscale localized charge transport pathways through an otherwise passivated interface, thereby providing both effective passivation and excellent charge extraction. By combining the nanopatterned electron transport layer with a dopant-free hole transport layer, we achieved a certified power conversion efficiency of 21.6% for a 1-square-centimeter cell with FF of 0.839, and demonstrate an encapsulated cell that retains ~91.7% of its initial efficiency after 1000 hours of damp heat exposure.

In Situ Formation of Mixed-Dimensional Surface Passivation Layers in Perovskite Solar Cells with Dual-Isomer Alkylammonium Cations.

Dimensional engineering of perovskite solar cells has attracted significant research attention recently because of the potential to improve both device performance and stability. Here, a novel 2D passivation scheme for 3D perovskite solar cells is demonstrated using a mixed cation composition of 2D perovskite based on two different isomers of butylammonium iodide. The dual-cation 2D perovskite outperforms its single cation 2D counterparts in surface passivation quality, resulting in devices with an impressive open-circuit voltage of 1.21 V for a perovskite composition with an optical bandgap of ≈1.6 eV, and a champion efficiency of 23.27%. Using a combination of surface elemental analysis and valence electron spectra decomposition, it is shown that an in situ interaction between the 2D perovskite precursor and the 3D active layer results in surface intermixing of 3D and 2D perovskite phases, providing an effective combination of defect passivation and enhanced charge transfer, despite the semi-insulating nature of the 2D perovskite phase. The demonstration of the synergistic interaction of multiple organic spacer cations in a 2D passivation layer offers new opportunities for further enhancement of device performance with mixed dimensional perovskite solar cells.

Effects of Hydroiodic Acid Concentration on the Properties of CsPbI3 Perovskite Solar Cells.

Inorganic cesium lead triiodide (CsPbI3) perovskite materials are becoming increasingly attractive for use in perovskite/silicon tandem solar cells, due to their almost ideal band gap energy (E g) of about 1.7 eV. To be useful as photovoltaic absorbers, the CsPbI3 must form the cubic or black phase (α-CsPbI3). To do so at relatively low temperatures, hydroiodic acid (HI) is required as a solution additive. This paper demonstrates CsPbI3 perovskite solar cells with an efficiency of 6.44%, formed using a HI concentration of 36 µL/mL. This value is higher than the previous most commonly used HI additive concentration. Herein, by undertaking a systematic study of the HI concentration, we demonstrate that the structural, morphological, optical, and electrical properties of CsPbI3 solar cells, processed with this HI additive concentration, are superior.

Adsorbed carbon nanomaterials for surface and interface-engineered stable rubidium multi-cation perovskite solar cells.

The current work reports the simultaneous enhancement in efficiency and stability of low-temperature, solution-processed triple cation based MA0.57FA0.38Rb0.05PbI3 (MA: methyl ammonium, FA: formamidinium, Rb: rubidium) perovskite solar cells (PSCs) by means of adsorbed carbon nanomaterials at the perovskite/electron transporting layer interface. The quantity and quality of the adsorbents are precisely controlled to electronically modify the ETL surface and lower the energy barrier across the interface. Carbon derivatives namely fullerene (C60) and PC71BM ([6,6]-phenyl C71 butyric acid methyl ester) are employed as adsorbents in conjunction with ZnO and together serve as a bilayer electron transporting layer (ETL). The adsorbed fullerene (C60-ZnO, abbreviated as C-ZnO) passivates the interstitial trap-sites of ZnO with interstitial intercalation of oxygen atoms in the ZnO lattice structure. C-ZnO ETL based PSCs demonstrate about a 19% higher average PCE compared to conventional ZnO ETL based devices and a nearly 9% higher average PCE than PC71BM adsorbed-ZnO (P-ZnO) ETL based PSCs. In addition, the interstitial trap-state passivation with a C-ZnO film upshifts the Fermi-level position of the C-ZnO ETL by 130 meV, with reference to the ZnO ETL, which contributes to an enhanced n-type conductivity. The photocurrent hysteresis phenomenon in C-ZnO PSCs is also substantially reduced due to mitigated charge trapping phenomena and concomitant reduction in an electrode polarization process. Another major highlight of this work is that, C-ZnO PSCs demonstrate a superior device stability retaining about 94% of its initial PCE in the course of a month-long, systematic degradation study conducted in our work. The enhanced device stability with C-ZnO PSCs is attributed to their high resistance to aging-induced recombination phenomena and a water-induced perovskite degradation process, due to a lower content of oxygen-related chemisorbed species on the C-ZnO ETL. The intricate mechanisms behind the efficiency and stability enhancement are investigated in detail and explained in the context of enhanced surface and interfacial electronic properties.

Photo-degradation of high efficiency fullerene-free polymer solar cells.

Polymer solar cells are a promising technology for the commercialization of low cost, large scale organic solar cells. With the evolution of high efficiency (>13%) non-fullerene polymer solar cells, the stability of the cells has become a crucial parameter to be considered. Among the several degradation mechanisms of polymer solar cells, burn-in photo-degradation is relatively less studied. Herein, we present the first systematic study of photo-degradation of novel PBDB-T:ITIC fullerene-free polymer solar cells. The thermally treated and as-prepared PBDB-T:ITIC solar cells were exposed to continuous 1 sun illumination for 5 hours. The aged devices exhibited rapid losses in the short-circuit current density and fill factor. The severe short-circuit current and fill factor burn in losses were attributed to trap mediated charge recombination, as evidenced by an increase in Urbach energy for aged devices.

Interfacial engineering of hole transport layers with metal and dielectric nanoparticles for efficient perovskite solar cells.

In this work, we have demonstrated the incorporation of metal (Ag NPs) and dielectric nanoparticles (SiO2 NPs) into the hole transporting layers of inverted PSCs using facile deposition methods. Interfacial engineering in PSCs is accomplished by incorporating 50 nm Ag NPs or SiO2 NPs within the PEDOT:PSS interlayer. Dielectric SiO2 NPs were used for comparison purposes as a control sample to isolate morphological impacts without plasmonic effects. The photovoltaic performance of the devices significantly improved due to increased charge selectivity and enhanced charge collection properties across the interface (HTL). The recombination resistance of the SiO2 NP incorporated HTL based PSCs was 193% higher than that of the conventional devices. In-depth analysis using impedance measurements revealed that devices containing Ag or SiO2 NPs have low electrode polarization and consequently lower charge accumulation at the interface. Lower electrode polarization in the modified devices was also found to improve the charge carrier selectivity, which eventually led to enhanced fill factor and lower parasitic resistances. Interfacial engineering via NPs yielded improvements in the electrical characteristics of non-optical origin, which not only enhanced device performance, but also reduced the hysteresis effects to much lower than in the conventional inverted PSCs based on a pristine PEDOT:PSS interlayer.

Solution-Processed Lithium-Doped ZnO Electron Transport Layer for Efficient Triple Cation (Rb, MA, FA) Perovskite Solar Cells.

The current work reports the lithium (Li) doping of a low-temperature processed zinc oxide (ZnO) electron transport layer (ETL) for highly efficient, triple-cation-based MA0.57FA0.38Rb0.05PbI3 (MA: methylammonium, FA: formamidinium, Rb: rubidium) perovskite solar cells (PSCs). Lithium intercalation in the host ZnO lattice structure is dominated by interstitial doping phenomena, which passivates the intrinsic defects in ZnO film. In addition, interstitial Li doping also downshifts the Fermi energy position of Li-doped ETL by 30 meV, which contributes to the reduction of the electron injection barrier from the photoactive perovskite layer. Compared to the pristine ZnO, the power conversion efficiency (PCE) of the PSCs incorporating lithium-doped ZnO (Li-doped) is raised from 14.07 to 16.14%. The superior performance is attributed to the reduced current leakage, enhanced charge extraction characteristics, and mitigated trap-assisted recombination phenomena in Li-doped devices, thoroughly investigated by means of electrochemical impedance spectroscopy (EIS) analysis. Li-doped PSCs also exhibit lower photocurrent hysteresis than ZnO devices, which is investigated with regard to the electrode polarization phenomena of the fabricated devices.

A high performance and low-cost hole transporting layer for efficient and stable perovskite solar cells.

Here we report a small molecule oxidant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-quinodimethane (F4TCNQ) doped, low cost 2',7'-bis(bis(4-methoxyphenyl)amino)spiro[cyclopenta[2,1-b:3,4-b']dithiophene-4,9'-fluorene] (FDT) hole transporting layer (HTL) for efficient mixed organic cation based MA0.6FA0.4PbI3 (MA = methyl ammonium, FA = formamidinium) perovskite solar cells (PSCs), fabricated via a highly reproducible controlled nucleation assisted restricted volume solvent annealing method, having full temperature compatibility with flexible substrates. The optimized (1 wt%) F4TCNQ doped FDT HTL based devices (F-FDT devices) demonstrate simultaneous enhancement of photovoltaic performance and device stability as well as significant reduction in photo-current hysteresis, as compared to conventional bis(trifluoromethylsulfonyl)amine lithium (Li-TFSI) additive based FDT HTL devices (L-FDT devices). Adding to the merits, F-FDT PSCs exhibit about 75% higher device stability compared to conventional L-FDT devices during the course of three weeks. Mott-Schottky analysis and in-depth charge transport characterization were carried out using electrochemical impedance spectroscopy (EIS) of the fabricated devices to understand the superior performance of the F-FDT devices. In addition, detailed polaronic intensity characterization of the doped HTL films was performed via ultraviolet-visible near-infrared (UV-vis-NIR) spectroscopy to investigate the underlying mechanism. Mitigated photocurrent hysteresis in the F-FDT devices has also been examined in terms of the inherent electrode polarization phenomenon. Furthermore, the superior device stability of the F-FDT PSCs has been probed in terms of variation in electronic properties, surface wettability, crystallinity, and microstrain dislocation density, and a detailed picture of the underlying mechanism behind stability enhancement is presented.