Structural Transformation of 2,7-Dibromopyrene on Au(111) Mediated by Halogen-Bonding Motifs.

Fundamental understanding of the bonding motifs that elaborately mediate the formation of supramolecular nanostructures is essential for the rational design of stable artificial organic architectures. Herein, the structural transformation of the adsorption complex of 2, 7-dibromopyrene (Br2 Py) on the Au(111) surface has been investigated by scanning tunnelling microscopy combined with X-ray photoemission spectroscopy and density function theory calculations. In the initial stage of self-assembly, well ordered patterns are formed in the manner of extended supramolecular structures balanced by intermolecular halogen bonding motifs, whilst the Au(111) reconstruction is still fairly visible. Subsequent thermal annealing promotes the dehalogenation and on-surface Ullmann coupling, and polymerized oligomers are consequently constructed. Interestingly, such polymerized chains are still stably mediated by the halogen bonding motif via dissociated Br atoms which are revealed to be absorbed on the bridge site of Au(111), while the number of halogen bonds increases significantly from self-assembly to Ullmann coupling polymerization, indicating that the halogen bonding motif contributes significantly to the extended one-dimensional polymers.

Interfacial electronic structures revealed at the rubrene/CH3NH3PbI3 interface.

The electronic structures of rubrene films deposited on CH3NH3PbI3 perovskite have been investigated using in situ ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS). It was found that rubrene molecules interacted weakly with the perovskite substrate. Due to charge redistribution at their interface, a downward 'band bending'-like energy shift of ∼0.3 eV and an upward band bending of ∼0.1 eV were identified at the upper rubrene side and the CH3NH3PbI3 substrate side, respectively. After the energy level alignment was established at the rubrene/CH3NH3PbI3 interface, its highest occupied molecular orbital (HOMO)-valence band maximum (VBM) offset was found to be as low as ∼0.1 eV favoring the hole extraction with its lowest unoccupied molecular orbital (LUMO)-conduction band minimum (CBM) offset as large as ∼1.4 eV effectively blocking the undesired electron transfer from perovskite to rubrene. As a demonstration, simple inverted planar solar cell devices incorporating rubrene and rubrene/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole transport layers (HTLs) were fabricated in this work and yielded a champion power conversion efficiency of 8.76% and 13.52%, respectively. Thus, the present work suggests that a rubrene thin film could serve as a promising hole transport layer for efficient perovskite-based solar cells.

Unveiling the degraded electron durability in reduced-dimensional perovskites.

The operational stability of reduced-dimensional metal halide perovskites (RD-MHPs) lags far behind the practical requirements for future high-definition displays. Thereinto, the electron durability of RD-MHPs plays a critical role in stable LEDs during continuous operation, however, it still lacks adequate research and a deep understanding. Herein, the electron durability and deterioration mechanism of phenethylammonium (PEA+)-modified RD-MHPs are systematically conducted through an in situ photoelectron spectroscopy technique by implementing tunable electron-beam radiation to simulate device operation. The formation of detrimental metallic lead (Pb0) caused by the reduction of lead ions (Pb2+) is observed along with the decomposition of PEA+ under electron-beam radiation, thereby changing the photophysical properties of PEA+-doped RD-MHPs. These results provide deep insight into the process of how injected electrons affect the performance of PEA+-doped perovskite LEDs, which may also provide potential guidance for designing robust and effective organic spacers for RD-MHPs.

Unraveling the Hole-Transport-Layer-Manipulated Carrier Transfer Dynamics in Perovskite Light-Emitting Diodes.

Charge transfer dynamics is decisive for the performance of perovskite light emitting diodes (PeLEDs), and deep insight into the charge transfer process inside the working device is indispensable. Here, the influence of the hole transport layer on charge transport and recombination processes in PeLEDs is investigated via impedance spectroscopy. The results demonstrate that the rational interfacial energy level alignment can improve the radiative recombination by reducing the leakage current and carrier transport resistance. Shockley-Read-Hall recombination and Auger recombination enlarge the lifetime of carrier transfer in the working devices as determined from the electroluminescence spectrum. Our work provides a distinctive and reliable method to explore the charge transfer property and highlights the importance of interfaces to boost the performance of PeLEDs.

Initiating Ullmann-like coupling of Br2Py by a semimetal surface.

Intensive efforts have been devoted to surface Ullmann-like coupling in recent years, due to its appealing success towards on-surface synthesis of tailor-made nanostructures. While attentions were mostly drawn on metallic substrates, however, Ullmann dehalogenation and coupling reaction on semimetal surfaces has been seldom addressed. Herein, we demonstrate the self-assembly of 2, 7-dibromopyrene (Br2Py) and the well controllable dehalogenation reaction of Br2Py on the Bi(111)-Ag substrate with a combination of scanning tunnelling microscopy (STM) and density functional theory calculations (DFT). By elaborately investigating the reaction path and formed organic nanostructures, it is revealed that the pristinely inert bismuth layer supported on the silver substrate can initiate Ullmann-like coupling in a desired manner by getting alloyed with Ag atoms underneath, while side products have not been discovered. By clarifying the pristine nature of Bi-Ag(111) and Ullmann-like reaction mechanisms, our report proposes an ideal template for thoroughly exploring dehalogenative coupling reaction mechanisms with atomic insights and on-surface synthesis of carbon-based architectures.

Surface-induced phase engineering and defect passivation of perovskite nanograins for efficient red light-emitting diodes.

Organic-inorganic hybrid lead halide perovskites are potential candidates for next-generation light-emitting diodes (LEDs) in terms of tunable emission wavelengths, high electroluminescence efficiency, and excellent color purity. However, the device performance is still limited by severe non-radiative recombination losses and operational instability due to a high degree of defect states on the perovskite surface. Here, an effective surface engineering method is developed via the assistance of guanidinium iodide (GAI), which allows the formation of surface-2D heterophased perovskite nanograins and surface defect passivation due to the bonding with undercoordinated halide ions. Efficient and stable red-emission LEDs are realized with the improved optoelectronic properties of GAI-modified perovskite nanograins by suppressing the trap-mediated non-radiative recombination loss. The champion device with a high color purity at 692 nm achieves an external quantum efficiency of 17.1%, which is 2.3 times that of the control device. Furthermore, the operational stability is highly improved, showing a half-lifetime of 563 min at an initial luminance of 1000 cd m-2. The proposed GAI-assisted surface engineering is a promising approach for defect passivation and phase engineering in perovskite films to achieve high-performance perovskite LEDs.

High-Light-Tolerance PbI2 Boosting the Stability and Efficiency of Perovskite Solar Cells.

Excess lead iodide (PbI2) plays a crucial role in passivating the defects of perovskite films and boosting the power conversion efficiency (PCE) of perovskite solar cells (PSCs). However, the photolysis of PbI2 is easily triggered by light illumination, which accelerates the decomposition of perovskite materials and weakens the long-term stability of PSCs. Herein, the high light tolerance of lead iodide (PbI2) is reported by introducing an electron-donor molecule, namely, 2-thiophenecarboxamide (2-TCAm), to strengthen the [PbX6]4- frame. Characterization reveals that the retarded decomposition of PbI2 is attributed to the interactions between Pb2+ and the organic functional groups in 2-TCAm as well as the optimized distribution of PbI2. The crystallization and morphology of 2-TCAm-doped perovskite films are improved simultaneously. The 2-TCAm-based PSCs achieve a 16.8% increase in PCE and nearly 12 times increase in the lifetime as compared to the reference device. The demonstrated method provides insight into the stability of PbI2 and its influence on PSCs.

Interfacial "Anchoring Effect" Enables Efficient Large-Area Sky-Blue Perovskite Light-Emitting Diodes.

While tremendous progress has recently been made in perovskite light-emitting diodes (PeLEDs), large-area blue devices feature inferior performance due to uneven morphologies and vast defects in the solution-processed perovskite films. To alleviate these issues, a facile and reliable interface engineering scheme is reported for manipulating the crystallization of perovskite films enabled by a multifunctional molecule 2-amino-1,3-propanediol (APDO)-triggered "anchoring effect" at the grain-growth interface. Sky-blue perovskite films with large-area uniformity and low trap states are obtained, showing the distinctly improved radiative recombination and hole-transport capability. Based on the APDO-induced interface engineering, synergistical boost in device performance is achieved for large-area sky-blue PeLED (measuring at 100 mm2 ) with a peak external quantum efficiency (EQE) of 9.2% and a highly prolonged operational lifetime. A decent EQE up to 6.1% is demonstrated for the largest sky-blue device emitting at 400 mm2 .

Interaction of the Cation and Vacancy in Hybrid Perovskites Induced by Light Illumination.

Mixed A-site engineering is an emerging strategy to overcome the difficulties in realizing high-quality perovskite films together with high ambient stability. Particularly, the α-FACsPbI3-based hybrid perovskites have been considered as a promising candidate for solar cell applications. However, the degradation mechanism of α-FACsPbI3 hybrid perovskites induced by light illumination remains unclear. Here, the illumination-caused instability of α-FACsPbI3 hybrid perovskites is investigated using various surface detection technologies, including photoelectron spectroscopy, scanning electron microscopy, and grazing incidence X-ray diffraction. The experimental findings reveal that the A-site vacancies arise from the migration of Cs+ cations from the perovskite surface into the bulk under light illumination, while their content is dependent on the light energy. The visible light enlarges the crystal lattice on the perovskite surface, leading to the Cs+ cation migration along with the lattice distortion of the PbI64- octahedron and phase separation. However, the ultraviolet light further causes a stronger interaction between FA+ and [PbI6]4-, leading to the partial decomposition of [PbI6]4- into Pb0 and I-. These results enrich the photodegradation mechanism, guiding the design of efficient and stable perovskite solar cells through surface passivation to suppress the Cs+ cation migration and to increase the octahedron dissociation energy.

Hierarchically Manipulated Charge Recombination for Mitigating Energy Loss in CsPbI2Br Solar Cells.

All-inorganic perovskite cesium lead iodide/bromide (CsPbI2Br) is considered as a robust absorber for perovskite solar cells (PSCs) because of its excellent thermal stability that guarantees its long-term operation stability. Efficient CsPbI2Br PSCs are available when obtaining low energy loss, which needs efficient charge generation, less charge recombination, and balanced charge extraction. However, numerous traps in perovskites hinder the photon-electron conversion process. Herein, hierarchical manipulation of charge recombination is proposed for CsPbI2Br PSCs featuring low energy loss. Nonselective trap reduction and selective halogen vacancy passivation are performed using 2,2'-(ethylenedioxy)diethylamine and phenylbutylammonium iodide for the bottom and top contacts, respectively. Because of all-around suppressed charge recombination, balanced charge extraction and suppressed hysteresis are realized. The champion PSC achieves an open-circuit voltage of 1.30 eV, a fill factor of 80.2%, and a power conversion efficiency of 16.6% that is 28.6% higher than that of the reference device. Moreover, the thermostability of PSCs is simultaneously enhanced because of the limited defect-assisted degradation.

Long-range ordered and atomic-scale control of graphene hybridization by photocycloaddition.

Chemical reactions that convert sp2 to sp3 hybridization have been demonstrated to be a fascinating yet challenging route to functionalize graphene. So far it has not been possible to precisely control the reaction sites nor their lateral order at the atomic/molecular scale. The application prospects have been limited for reactions that require long soaking, heating, electric pulses or probe-tip press. Here we demonstrate a spatially selective photocycloaddition reaction of a two-dimensional molecular network with defect-free basal plane of single-layer graphene. Directly visualized at the submolecular level, the cycloaddition is triggered by ultraviolet irradiation in ultrahigh vacuum, requiring no aid of the graphene Moiré pattern. The reaction involves both [2+2] and [2+4] cycloadditions, with the reaction sites aligned into a two-dimensional extended and well-ordered array, inducing a bandgap for the reacted graphene layer. This work provides a solid base for designing and engineering graphene-based optoelectronic and microelectronic devices.

Recent Progress with In Situ Characterization of Interfacial Structures under a Solid-Gas Atmosphere by HP-STM and AP-XPS.

: Surface science is an interdisciplinary field involving various subjects such as physics, chemistry, materials, biology and so on, and it plays an increasingly momentous role in both fundamental research and industrial applications. Despite the encouraging progress in characterizing surface/interface nanostructures with atomic and orbital precision under ultra-high-vacuum (UHV) conditions, investigating in situ reactions/processes occurring at the surface/interface under operando conditions becomes a crucial challenge in the field of surface catalysis and surface electrochemistry. Promoted by such pressing demands, high-pressure scanning tunneling microscopy (HP-STM) and ambient pressure X-ray photoelectron spectroscopy (AP-XPS), for example, have been designed to conduct measurements under operando conditions on the basis of conventional scanning tunneling microscopy (STM) and photoemission spectroscopy, which are proving to become powerful techniques to study various heterogeneous catalytic reactions on the surface. This report reviews the development of HP-STM and AP-XPS facilities and the application of HP-STM and AP-XPS on fine investigations of heterogeneous catalytic reactions via evolutions of both surface morphology and electronic structures, including dehydrogenation, CO oxidation on metal-based substrates, and so on. In the end, a perspective is also given regarding the combination of in situ X-ray photoelectron spectroscopy (XPS) and STM towards the identification of the structure-performance relationship.

Revealing the Adsorption and Decomposition of EP-PTCDI on a Cerium Oxide Surface.

Cerium oxide has constantly attracted intense attention during the past decade both in research and industry as an appealing catalyst or a noninert support for catalysts, for instance, in the water-gas shift reaction and hydrogenation of the ketone group. Herein, the cerium oxide surface has been chosen to investigate the adsorption and decomposition behaviors of the N,N'-bis(1-ethylpropyl)-perylene-3,4,9,10-tetracarboxdiimide (EP-PTCDI) molecule by photoelectron spectroscopy. As expected, EP-PTCDI molecules self-assemble on the cerium oxide surface comprising both trivalent and tetravalent cerium at room temperature. Interestingly, the EP-PTCDI molecule exhibits selective adsorption on cerium oxide after the heating treatment. It was found that the ketone group of EP-PTCDI first undergoes hydrogenation after annealing to 400 °C, which is probably related to the fact that high temperature annealing provides sufficient thermal energy to trigger the reaction between the ketone group and trivalent cerium. Furthermore, EP-PTCDI molecules are discovered to start to decompose hierarchically on the ceria substrate from annealing at 400 °C due to the strong molecule-substrate interaction and the effective catalysis by the trivalent cerium, whereas the decomposition sequence of functional groups is revealed to be, first, the ethyl propyl group (-C5H9), followed by the hydrogenated ketone (alcohols) group. Finally, our study may provide a new platform for the fundamental understanding of complex organic reactions on the cerium oxide surface.

Graphene oxide as an additive to improve perovskite film crystallization and morphology for high-efficiency solar cells.

The quality of a perovskite film has a great impact on its light absorption and carrier transport, which is vital to improve high-efficiency perovskite solar cells (PSCs). Herein, it is demonstrated that graphene oxide (GO) can be used as an effective additive in the precursor solution for the preparation of high-quality solution-processed CH3NH3PbI3 (MAIPbI3) films. It is evidenced by scanning electron microscopy that the size of the grains inside these films not only increases but also becomes more uniform after the introduction of an optimized amount of 1 vol% GO. Moreover, 1 vol% GO also enhances the crystallization of perovskite film with intact preferential out-of-plane orientation as proven by 2-dimensional grazing-incidence X-ray diffraction. As a consequence of the improved film quality, enhanced charge extraction efficiency and optical absorption are demonstrated by photoluminescence (PL) spectroscopy and UV-visible absorption spectroscopy, respectively. Using 1 vol% GO, the fabricated champion heterojunction PSC with a structure of ITO/SnO2/perovskite/spiro-OMeTAD/Au shows a significant power conversion efficiency increase to 17.59% with reduced hysteresis from 16.10% for the champion device based on pristine perovskite. The present study thus proposes a simple approach to make use of GO as an effective and cheap addictive for high-performance PSCs with large-scale production capability.