Hole blocking PbI2/CH3NH3PbI3 interface

Modulated charge separation across (MO)/CH₃NH₃PbI₃ and (MO)/PbI₂/CH₃NH₃PbI₃ (MO = TiO₂, MoO₃) interfaces was investigated by surface photovoltage (SPV) spectroscopy. Perovskite layers were deposited by solution‐based one‐step preparation and two‐step preparation methods. An unreacted PbI₂ layer remained at the interface between the metal oxide and CH₃NH₃PbI₃ for two‐step preparation. For the two‐step preparation on TiO₂, the SPV signal related to absorption in CH₃NH₃PbI₃ increased in comparison to the one‐step preparation due to electron transfer from CH₃NH₃PbI₃ via PbI₂ into TiO₂ whereas the SPV signal related to defect transitions decreased. For the one‐step preparation on MoO₃, holes photogenerated in CH₃NH₃PbI₃ recombined with electrons in MoO₃. In contrast, a hole transfer from CH₃NH₃PbI₃ towards MoO₃ was blocked by the PbI₂ interlayer for the two‐step preparation on MoO₃. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Ultrasonically sprayed-on perovskite solar cells-effects of organic cation on defect formation of CH3NH3PbI3 films

Methylammonium lead iodide (CH₃NH₃PbI₃) based perovskite having low degrees of the disorder is of great interest for optoelectronic and photovoltaic applications. In this work, a layer of CH₃NH₃PbI₃ was successfully prepared using an ultrasonically sprayed-nebulous method. Changes in structural and optical properties alongside with photo-induced charge separation and transportation behavior were systematically studied. The surface photovoltage spectra reveal a significant reduction of the density of deep defect states as the organic content was increased. It was observed that the measured values of Urbach energies decrease from 33.36 to 28.24 meV as the amount of organic content was increased to an optimum value. The best perovskite solar cells obtained using the sprayed-on approach exhibited a J_sc of 16.54 mA/cm², a V_oc of 0.99 V, and a FF of 62.4, resulting in an overall PCE of 10.09%.     

钙钛矿/银电极界面降解和离子迁移的原位研究

本文对CH_3NH_3PbI_3钙钛矿层与Ag电极之间的界面降解和离子迁移过程进行了全面地研究.利用原位光电子能谱检测于段,发现了Ag电极会诱导钙钛矿层的降解,导致PbI_2和AgI物种的形成以及Pb~(2+)离子在界面处还原成金属Pb物种.I 3d谱峰强度的反常增强为碘离子从CH_3NH_3PbI_3下表面迁移到Ag电极提供了直接的实验证据.此外,Ag电极和钙钛矿层接触会在CH_3NH_3PbI_3/Ag界面处诱导0.3 eV的界面偶极,这可能进一步促进碘离子扩散迁移,导致钙钛矿层的分解和Ag电极的侵蚀.     

Sonochemical synthesis of CH3NH3PbI3 perovskite ultrafine nanocrystal sensitizers for solar energy applications

The organic–inorganic hybrid perovskite CH₃NH₃PbI₃ is becoming an interesting material in the field of energy harvesting. This material is one of the cleanest and cheapest components in solar cells which is available in ample amounts. However, most of the previous research work was done on thin film of this material. In the present work we describe the preparation of a powder containing nanoparticles of CH₃NH₃PbI₃ using a sonochemical method. Characterization of the product was done by various methods, such as HRTEM, FTIR, PL, DLS and XRD. The particles were found to be highly crystalline (tetragonal crystal structure), polygonal in shape and having diameters of 10–40 nm.     

Modulation of strain,electric field and organic cation rotation on the band gap and electronic structures of organic-inorganic hybrid perovskite CH3NH3PbI3

Band gap modulation engineering is an important step in the application of optoelectronic materials. In this paper, the first-principles calculations were carried out to study the influence of strain, external electric field, spatial orientation of organic cation on the band gaps and electronic structures of organic-inorganic hybrid halide perovskites CH₃NH₃PbI₃. The results show that both the uniform strain and the tetragonal deformation can modulate the band gap obviously. The electric field of 0.2 V/Å is the critical point of the band gap modulation. The band gap increases when an electric field is applied from 0 to 0.2 V/Å. The electric field above 0.2 V/Å will cause the band gap to decrease. The spatial orientation of the organic cation also has modulation influence on the band gap of CH₃NH₃PbI₃, but has no effect on the direct semiconductor characteristics. The above results will be helpful to study the band gap modulation of other organic-inorganic hybrid halide perovskites.     

Humidity controlled crystallization of thin CH3NH3PbI3 films for high performance perovskite solar cell

Control of crystallization of a solution‐processed perovskite layer is of prime importance for high performance solar cells. In spite of the negative effect of water on perovskite solar energy conversion in several previous works, we observed that humidity plays a critical role to develop a thin uniform, dense perovskite film with preferred crystals, in particular, in a device with architecture of ITO/PEDOT:PSS/CH₃NH₃PbI₃/ PC₇₁BM/LiF/Al fabricated by two‐step sequential spin‐coating process. Humidity controlled spin‐coating of CH₃NH₃I on the pre‐formed PbI₂ layer was the most influential process and systematic structural investigation as a function of humidity revealed that grains of CH₃NH₃PbI₃ perovskite crystals increase in size with their preferred orientation while film surface becomes roughened as the humidity increases. The performance of a device was closely related to the humidity dependent film morphology and in 40% relative humidity, the device exhibited the maximum power conversion efficiency of approximately 12% more than 10 times greater than that of a device fabricated at 20% humidity. The results suggest that our process with controlled humidity can be another efficient route for high performance and reliable perovskite solar cells. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Growth behaviors and emission properties of Co-deposited MAPbI3 ultrathin films on MoS2

Hybrid organic-inorganic perovskite thin films have attracted much attention in optoelectronic and information fields because of their intriguing properties. Due to quantum confinement effects, ultrathin films in nm scale usually show special properties. Here, we report on the growth of methylammonium lead iodide (MAPbI₃) ultrathin films via co-deposition of PbI₂ and CH₃NH₃I (MAI) on chemical-vapor-deposition-grown monolayer MoS₂ as well as the corresponding photoluminescence (PL) properties at different growing stages. Atomic force microscopy and scanning electron microscopy measurements reveal the MoS₂ tuned growth of MAPbI₃ in a Stranski-Krastanov mode. PL and Kelvin probe force microscopy results confirm that MAPbI₃/MoS₂ heterostructures have a type-II energy level alignment at the interface. Temperaturedependent PL measurements on layered MAPbI₃ (at the initial stage) and on MAPbI₃ crystals in averaged size of 500 nm (at the later stage) show rather different temperature dependence as well as the phase transitions from tetragonal to orthorhombic at 120 and 150 K, respectively. Our findings are useful in fabricating MAPbI₃/transition-metal dichalcogenide based innovative devices for wider optoelectronic applications.     

两步化学气相沉积法制备In2Se3/MoSe2范德华尔斯异质结

Two-dimensional transition metal dichalcogenides heterostructures have stimulated wide interest not only for the fundamental research,but also for the application of next generation electronic and optoelectronic devices.Herein,we report a successful two-step chemical vapor deposition strategy to construct vertically stacked van der Waals epitaxial In₂Se₃/MoSe₂ heterostructures.Transmission electron microscopy characterization reveals clearly that the In₂Se₃ has well-aligned lattice orientation with the substrate of monolayer MoSe₂.Due to the interaction between the In₂Se₃ and MoSe₂ layers,the heterostructure shows the quenching and red-shift of photoluminescence.Moreover,the current rectification behavior and photovoltaic effect can be observed from the heterostructure,which is attributed to the unique band structure alignment of the heterostructure,and is further confirmed by Kevin probe force microscopy measurement.The synthesis approach via van der Waals epitaxy in this work can expand the way to fabricate a variety of two-dimensional heterostructures for potential applications in electronic and optoelectronic devices.     

Characteristics of a type-II n-MoS2/p-Ge van der Waals heterojunction

A few-atomic-layer molybdenum disulfide (MoS₂) film on Si/SiO₂ substrates grown by metal-organic chemical vapor deposition was investigated. The few-atomic-layer MoS₂ film was subsequently transferred onto a (100) p-Ge substrate to build a van der Waals n-p heterojunction. The as-grown few-atomic-layer MoS₂ film and the MoS₂/Ge heterostructure were characterized atomic force microscopy, spectroscopic ellipsometry, high-resolution scanning transmission electron microscopy, Raman spectroscopy analyses, photoluminescence (PL) measurements at room temperature (RT, 300 K), and type-II band alignment of the heterostructure determined by ultraviolet photoelectron spectroscopy. The RT-PL measurements showed dominant peaks at 1.96 and 1.8 eV for the as-grown MoS₂ and red-shifted PL peaks for that transferred onto Ge. We examined the electrical characteristics of the few-atomic-layer MoS₂ by forming a type-II band alignment van der Waals heterojunction with a highly doped p-Ge. The heterojunction solar cell exhibited an open-circuit voltage of 0.15 V and a short-circuit current density of 45.26 μA/cm². The external quantum efficiency measurements showed a spectral response up to approximately 500 nm owing to the absorption by the few-atomic-layer MoS₂ film.     

Optical properties of CH3NH3PbI3 crystal grown using inverse temperature crystallization

Perovskite CH₃NH₃PbI₃ (MAPbI₃) single crystal was grown using inverse temperature crystallization method. Crystallinity of the perovskite was confirmed by X-ray diffraction. Photoluminescence (PL) spectra revealed abnormal behavior due to a temperature-induced orthorhombic to the tetragonal phase transition. Four PL emission peaks, A, B, C, and D, were observed in the low temperature regime. Peaks A and B were observed at 756 and 776?nm?at 12?K, and were blue-shifted and disappeared at 130 and 70?K, respectively. Peaks C and D were observed at 789 and 807?nm?at 40?K and were also blue-shifted to 780 and 794?nm?at 100?K. On the other hand, the peak C red-shifted to 799?nm from 100 to 140?K because of an orthorhombic to the tetragonal phase change and was also blue-shifted above 140?K. From the excitation intensity- and temperature-dependent PL results, peaks A and B were assigned to the free-exciton and bound-exciton of the orthorhombic phase crystal, respectively. In addition, peaks C and D were associated with the free-exciton and bound-exciton of the tetragonal phase crystal, respectively. The activation energy of peak C was calculated to be 98?meV from temperature dependence of the PL intensity.     

钙钛矿晶体的电荷复合动力学研究

本文利用紫外吸收光谱和稳态荧光光谱技术结合理论模型，研究了钙钛矿材料CH₃NH₃PbI₃晶体在光激发过程中的电荷复合动力学行为，进而获得晶体的扩散长度. 电荷载体的扩散长度是判断光电材料的重要参数. 研究通过合成两种不同缺陷态浓度的CH₃NH₃PbI₃晶体，测量这两种晶体在0.019∽4.268 μJ/cm²的激光激发下的时间分辨荧光光谱，利用动力学模型对光谱进行拟合，可以获得每个晶体的掺杂浓度，空穴浓度以及电荷复合参数. 将这些参数结合已有公式，最终可获得每个晶体的电荷载体的扩散长度.     

Why cannot all divalent cations completely substitute the Pb cations of CH3NH3PbI3 perovskite?

Organic-inorganic hybrid CH₃NH₃PbI₃ perovskite has a great potential for applications in low-cost photovoltaic devices. However, the doped and substitution of Pb sites in CH₃NH₃PbI₃ has not been widely reported. In this article, a quantum mechanical model was applied to determine why all divalent cations cannot substitute the Pb cations of CH₃NH₃PbI₃ perovskite. The evaluation was performed by comparison the model with experimental results. On this basis, we carefully examined 42 types of cations and identified only nine kinds of cations including Ca²⁺, Sr²⁺, Sc²⁺, Ti²⁺, V²⁺, Y²⁺, Zr²⁺, Nb²⁺ and Sn²⁺ for doped into Pb sites. In these cases, it is expected that the corresponding compound would be single phase. Finally, an analysis was performed based on first principle, and the results indicate that divalent cations substituting the Pb sites modify the band structure and influence the performance of perovskite-based photostatics.     

Edge assisted epitaxy of CsPbBr3 nanoplates on Bi2O2Se nanosheets for enhanced photoresponse

Bi$_{2}$O$_{2}$Se has been proved to be a promising candidate for electronic and optoelectronic devices due to their unique physical properties. However, it is still a great challenge to construct the heterostructures with direct epitaxy of hetero semiconductor materials on Bi$_{2}$O$_{2}$Se nanosheets. Here, a two-step chemical vapor deposition (CVD) route was used to directly grow the CsPbBr$_{3}$ nanoplate-Bi$_{2}$O$_{2}$Se nanosheet heterostructures. The CsPbBr$_{3}$ nanoplates were selectively grown on the Bi$_{2}$O$_{2}$Se nanosheet along the edges, where the dangling bonds provide the nucleation sites. The epitaxial relationships between CsPbBr$_{3}$ and Bi$_{2}$O$_{2}$Se were determined as ${[200]}_{\rm Bi_{2}O_{2}Se}||{[110]}_{\rm CsPbBr_{3}}$ and ${[110]}_{\rm Bi_{2}O_{2}Se}||{[200]}_{\rm CsPbBr_{3}}$ by transmission electron microscopy characterization. The photoluminescence (PL) results reveal that the formation of heterostructures results in the remarkable PL quenching due to the type-I band arrangement at CsPbBr$_{3}$/Bi$_{2}$O$_{2}$Se interface, which was confirmed by ultraviolet photoelectron spectroscopy (UPS) and Kelvin probe measurements, and makes the photogenerated carriers transfer from CsPbBr$_{3}$ to Bi$_{2}$O$_{2}$Se. Importantly, the photodetectors based on the heterostructures exhibit a 4-time increase in the responsivity compared to those based on the pristine Bi$_{2}$O$_{2}$Se sheets, and the fast rise and decay time in microsecond. These results indicate that the direct epitaxy of the CsPbBr$_{3}$ plates on the Bi$_{2}$O$_{2}$Se sheet may improve the optoelectronic performance of Bi$_{2}$O$_{2}$Se based devices.     

Multistep spin–spray deposition of large-grain-size CH3NH3PbI3 with bilayer structure for conductive-carbon-based perovskite solar cells

Large-grain-size and void-free CH₃NH₃PbI₃ films with bilayer structure are fabricated by spin-coating a PbI₂ layer onto a mesoporous TiO₂ layer and sequentially spraying CH₃NH₃I (methylammonium iodide, MAI) multilayers. The sprayer is controlled by a homemade three-axis computer numerical control machine; thus, the substrates are coated by successive parallel passes achieved by moving the nozzle. Spray deposition at the optimal spray rate and substrate temperature produces a large-grain-size and void-free methylammonium lead iodide (MAPbI₃) bilayer structure. The mesoporous TiO₂ layer plays an important role in electron transport by preventing the return of electrons to the perovskite layer and decreasing the contact resistance at the perovskite/compact TiO₂/fluorine tin oxide interface. When the films are incorporated into a solar cell device with a conductive carbon counter electrode, a maximum power conversion efficiency of 10.58% is realised.     

Low cost,high throughput and centimeter‐scale fabrication of efficient hybrid perovskite solar cells by closed space vapor transport

Hybrid perovskite solar cell is a fast‐growing photovoltaic technology. Here, we present a method based on the closed space vapor transport deposition, which has the potential for large‐scale production due to its low cost, high throughput, and large‐area uniformity. We demonstrate CH₃NH₃PbI₃ solar cells with high power conversion efficiencies of 16.2%. Furthermore, the large area devices have high efficiency of 13.8% and good uniformity in a large substrate of 3 cm × 3 cm. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Hierarchical ZnO/Bi2O3 nanostructures: synthesis, characterization, and electron-beam modification

Two types of ZnO/Bi₂O₃ nanonecklace heterostructures were fabricated using the vapor-phase transport (VPT) method for the first time. These hierarchical structures were well characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM) with energy dispersive spectroscopy (EDS) attached. The growth mechanism of the novel structures were proposed based on these characterizations. Electron-beam irradiation was found to be a powerful and controllable tool in further tailoring such ZnO/Bi₂O₃ nanonecklace heterostructures. In addition, photoluminescence (PL) emission from the hierarchical nanostructures showed enhancement comparing to the pure Bi₂O₃ powder.     

One-dimensional excitons in inorganic–organic self-organized quantum-wire crystals [NHC(I)=NH]PbI and [CHSC(=NH)NH]PbI

Optical properties of lead-iodide-based one-dimensional perovskite-type crystals [NH₂C(I)=NH₂]₃PbI₅ and [CH₃SC(=NH₂)NH₂]₃PbI₅ have been investigated theoretically and experimentally. The electronic and excitonic structures are studied based on group theoretical consideration and first-principle band calculation. Strong one-dimensional anisotropy of the optical absorption spectra, large Stokes shifts (1.0 eV) and huge exchange energies (70 meV) indicate that the excitons in these crystals are one-dimensional Frenkel excitons.     

Controllable growth and characterizations of hybrid spiral-like atomically thin molybdenum disulfide

Monolayer MoS₂ is an emerging two-dimensional semiconductor with wide-ranging potential applications in novel electronic and optoelectronic devices. Here, we reported controlled vapor phase growth of hybrid spiral-like MoS₂ crystals investigated by multiple means of X-Ray photoemission spectroscopy, scanning electron microscopy, atomic force microscopy, kelvin probe force microscopy, Raman and Photoluminescence techniques. Morphological characterizations reveal an intriguing hybrid spiral-like MoS₂ feature whose lower planes are AB Bernal stacking and upper structure is spiral. We ascribe the hybrid spiral-like structure to a screw dislocation drive growth mechanism owing to lower supersaturation and layer-by-layer growth mode. In addition, the electrostatic properties of MoS₂ microflakes with hybrid spiral structures are obvious inhomogeneous and dependent on morphology manifested by kelvin probe force microscopy. Our work deepens the understanding of growth mechanisms of CVD-grown MoS₂, which is also adoptable to other TMDC materials.     

Large grained and high charge carrier lifetime CH3NH3PbI3 thin-films: implications for perovskite solar cells

Spin coated perovskite thin films are known to have an issue of pinholes & poor morphology control which lead to poor device-to-device repeatability, that is an impediment to scale-up. In this work, Methylamine vapor annealing process is demonstrated which consistently leads to high-quality perovskite thin-films with an average grain-size of 10–15 μm. The improvement in film morphology enables improvement in effective carrier recombination lifetime, from 21 μs in as-deposited films to 54 μs in vapor-annealed films. The annealed films with large-grains are also more stable in ambient conditions. Devices made on annealed perovskite films are very consistent, with a standard deviation of only 0.7%. Methylamine vapor annealing process is a promising method of depositing large-grain CH₃NH₃PbI₃ films with high recombination lifetime and the devices with improved performance.     

Immobilization of avidin on (001) GaAs surface

To reliably immobilize different biomoieties on surfaces of III-V semiconductors is one of the most critical issues in the development of biodetector devices based on the optical/electronic properties of these materials. Herein we demonstrate the successful immobilization of avidin, a robust and well-studied protein, on a (001) GaAs surface. The immobilization was investigated via specific binding to biotin, which was connected to the GaAs surface through commercially available long- or short-chain amino group terminated alkanethiols (HS(CH₂)₁₁NH₂ or HS(CH₂)₂NH₂), or through a biotinylated thiol synthesized in our laboratory. The immobilization performance was evaluated by photoluminescence and fluorescence microscopy measurements. We found that the biotinylated thiol mixed with a diluent thiol provides the highest avidin immobilization efficiency. PACS 81.05.Ea; 82.65.+r; 87.14.Ee