Strategy of Enhancing Built-in Field to Promote the Application of C-TiO2 /SnO2 Bilayer Electron Transport Layer in High-Efficiency Perovskite Solar Cells (24.3%).

Combining two kinds of electron transport layer (ETL) which have complementary advantages into a bilayer structure to form a bilayer ETL is an effective way to transcend inherent limitations of single-layer ETL, which is very helpful in the development of perovskite solar cells (PSCs). In this work, a strategy is proposed to break constraints on the application of the staggered bilayer ETL in high-efficiency PSC, namely utilizing a built-in field to overcome the dilemma in ECBM making it possible to improve VOC and FF simultaneously by tuning the Fermi level of ETLs properly. According to the strategy, a bilayer ETL structure comprised of C-TiO2 and SnO2 layer and corresponding Li-doping process are developed, and the characterization results confirm the effectiveness of the strategy, making the potentials of the C-TiO2 (Li)/SnO2 bilayer ETL fully released for its application in high-efficiency PSCs: a VOC of 1.201 V for an ordinary triple-cation-perovskite-based PSC and a photoelectric conversion efficiency of 24.3% for a low-bandgap-perovskite-based PSC with high haze FTO superstrate are successfully achieved, indicating that the C-TiO2 (Li)/SnO2 bilayer ETL is a successful application paradigm of the proposed strategy and very promising in the application of high-efficiency PSCs.

Li-Doped ZnO Electron Transport Layer for Improved Performance and Photostability of Organic Solar Cells.

Organic solar cells (OSCs) based on an inverted architecture generally have better stability compared to those based on a standard architecture. However, the photoactive area of the inverted solar cells increases under ultraviolet (UV) or solar illuminatiom because of the too-high conductivity of the UV-illuminated zinc oxide (ZnO) interlayer. This limits the potential of the inverted solar cells for industrial applications. Herein, lithium-doped ZnO (Li-ZnO) films are employed as the cathode interlayer to construct inverted OSCs. The incorporation of Li ions is found to reduce the lateral conductivity of the UV-treated ZnO films because of the presence of Li ions, preventing the high-quality-growth of ZnO nanocrystals. This addresses the problem of having too-high conductivity in the UV-treated ZnO layer, causing the increased photoactive area of inverted solar cells. The overall performance of the solar cell is shown to be higher after the incorporation of Li ions in the ZnO layer, mainly due to the increased fill factor (FF), originating from the reduced trap-assisted recombination losses. Finally, the inverted solar cells based on the Li-ZnO interlayer are demonstrated to have a much better long-term stability, as compared to those based on ZnO. This allows the ZnO-based interlayers to be used for the mass production of organic solar cell modules.

Uncommon Behavior of Li Doping Suppresses Oxygen Redox in P2-Type Manganese-Rich Sodium Cathodes.

Utilizing both cationic and anionic oxygen redox reactions is regarded as an important approach to exploit high-capacity layered cathode materials with earth abundant elements. It has been popular strategies to effectively elevate the oxygen redox activities by Li-doping to introduce unhybridized O 2p orbitals in Nax MnO2 -based chemistries or enabling high covalency transition metals in P2-Na0.66 Mnx TM1- x O2 (TM = Fe, Cu, Ni) materials. Here, the effect of Li doping on regulating the oxygen redox activities P2-structured Na0.66 Ni0.25 Mn0.75 O2 materials is investigated. Systematic X-ray characterizations and ab initio simulations have shown that the doped Li has uncommon behavior in modulating the density of states of the neighboring Ni, Mn, and O, leading to the suppression of the existing oxygen and Mn redox reactivities and the promotion of the Ni redox. The findings provide a complementary scenario to current oxygen redox mechanisms and shed lights on developing new routes for high-performance cathodes.

Bioactivity and Antibacterial Behaviors of Nanostructured Lithium-Doped Hydroxyapatite for Bone Scaffold Application.

The material for bone scaffold replacement should be biocompatible and antibacterial to prevent scaffold-associated infection. We biofunctionalized the hydroxyapatite (HA) properties by doping it with lithium (Li). The HA and 4 Li-doped HA (0.5, 1.0, 2.0, 4.0 wt.%) samples were investigated to find the most suitable Li content for both aspects. The synthesized nanoparticles, by the mechanical alloying method, were cold-pressed uniaxially and then sintered for 2 h at 1250 °C. Characterization using field-emission scanning electron microscopy (FE-SEM) revealed particle sizes in the range of 60 to 120 nm. The XRD analysis proved the formation of HA and Li-doped HA nanoparticles with crystal sizes ranging from 59 to 89 nm. The bioactivity of samples was investigated in simulated body fluid (SBF), and the growth of apatite formed on surfaces was evaluated using SEM and EDS. Cellular behavior was estimated by MG63 osteoblast-like cells. The results of apatite growth and cell analysis showed that 1.0 wt.% Li doping was optimal to maximize the bioactivity of HA. Antibacterial characteristics against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were performed by colony-forming unit (CFU) tests. The results showed that Li in the structure of HA increases its antibacterial properties. HA biofunctionalized by Li doping can be considered a suitable option for the fabrication of bone scaffolds due to its antibacterial and unique bioactivity properties.

First-principles study of pristine and Li-doped borophene as a candidate to detect and scavenge SO2gas.

In this research, the potential application of borophene as gas sensor device is explored. The first-principles theory is employed to investigate the sensing performance of pristine and Li-doped borophene for SO2and five main atmospheric gases (including CH4, CO2, N2, CO and H2). All gases are found to be adsorbed weakly on pristine borophene, which shows weak physical interaction between the pristine borophene and gases. The gas adsorption performance of borophene is improved by the doping of Li atom. The results of adsorption energy suggest that Li-borophene exhibits high selectivity to SO2molecule. Moreover, analyses of the charge transfer, density of states and work function also confirm the introduction of Li adatom on borophene significantly enhances the selectivity and sensitivity to SO2. In addition, desorption time of gas from pristine and Li doped borophene indicates the Li-borophene has good desorption characteristics for SO2molecule at high temperatures. This research would be helpful for understanding the influence of Li doping on borophene and presents the potential application of Li-borophene as a SO2gas sensor or scavenger.

(Li,Na)SbS2 as a promising solar absorber material: A theoretical investigation.

NaSbS2 has been proposed as a novel photovoltaic material, but its band gap is not suitable for single-junction solar cells. In the present study, the systematic first-principles calculations were carried out to investigate the structural, mechanical, electronic and optical properties of ASbS2 (A = Li, Na, K) and Na1-xLixSbS2 solid solutions. These structures show good structural stability compared to CH3NH3PbI3. The results indicate that all the structures are indirect band gap semiconductors. The band gap of ASbS2 increases gradually when the alkali metal changes from Li to K. The band gap of NaSbS2 can be tuned by manipulating the amount of Li doping. The Na1-xLixSbS2 solid solutions have suitable band gaps for light-absorber semiconductors in solar cells. Moreover, the suitable band gap of NaSbS2 can be also obtained under moderate pressure. The mechanical properties of these materials are also analyzed, and the results indicate that they are brittle materials except for KSbS2. The optical absorption coefficients of these compounds are large over 10-5 cm-1 in the visible light region. We find that alloying can provide a feasible and effective approach for improving the photovoltaic performance of NaSbS2-based solar cells.

Li-Doping Effect on Characteristics of ZnO Thin Films Resistive Random Access Memory.

In this study, a Pt/Ag/LZO/Pt resistive random access memory (RRAM), doped by different Li-doping concentrations was designed and fabricated by using a magnetron sputtering method. To determine how the Li-doping concentration affects the crystal lattice structure in the composite ZnO thin films, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) tests were carried out. The resistive switching behaviors of the resulting Pt/Ag/LZO/Pt devices, with different Li-doping contents, were studied under direct current (DC) and pulse voltages. The experimental results showed that compared with the devices doped with Li-8% and -10%, the ZnO based RRAM device doped by 5% Li-doping presented stable bipolar resistive switching behaviors with DC voltage, including a low switching voltage (<1.0 V), a high endurance (>103 cycles), long retention time (>104 s), and a large resistive switching window. In addition, quick switching between a high-resistance state (HRS) and a low-resistance state (LRS) was achieved at a pulse voltage. To investigate the resistive switching mechanism of the device, a conduction model was installed based on Ag conducting filament transmission. The study of the resulting Pt/Ag/LZO/Pt devices makes it possible to further improve the performance of RRAM devices.

Highly efficient green upconversion luminescence of ZnMoO4:Yb3+/Er3+/Li+ for accurate temperature sensing.

Upconversion luminescence and optical temperature sensing properties of Yb3+/Er3+/Li+ tri-doped ZnMoO4 phosphors were investigated. It has been demonstrated that Li+ doping affected not only the local symmetry of Yb3+ and Er3+ but also the distribution of them in the host lattice. As a result, the significantly improved green upconversion luminescence was obtained when excited at 980 nm. The pumping power dependent photo-thermal behavior was used to evaluate the reliability of upconversion temperature sensing. An accurate temperature scale was established by eliminating the impact of thermal effect, and the sensing ability was evaluated via a comparison with the results reported in literatures.

Enhanced Charge Extraction of Li-Doped TiO2 for Efficient Thermal-Evaporated Sb2S3 Thin Film Solar Cells.

We provided a new method to improve the efficiency of Sb2S3 thin film solar cells. The TiO2 electron transport layers were doped by lithium to improve their charge extraction properties for the thermal-evaporated Sb2S3 solar cells. The Mott-Schottky curves suggested a change of energy band and faster charge transport in the Li-doped TiO2 films. Compared with the undoped TiO2, Li-doped mesoporous TiO2 dramatically improved the photo-voltaic performance of the thermal-evaporated Sb2S3 thin film solar cells, with the average power conversion efficiency (PCE) increasing from 1.79% to 4.03%, as well as the improved open-voltage (Voc), short-circuit current (Jsc) and fill factors. The best device based on Li-doped TiO2 achieved a power conversion efficiency up to 4.42% as well as a Voc of 0.645 V, which are the highest values among the reported thermal-evaporated Sb2S3 solar cells. This study showed that Li-doping on TiO2 can effectively enhance the charge extraction properties of electron transport layers, offering a new strategy to improve the efficiency of Sb2S3-based solar cells.

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.

Porous Carbon Materials Based on Graphdiyne Basis Units by the Incorporation of the Functional Groups and Li Atoms for Superior CO2 Capture and Sequestration.

The graphdiyne family has attracted a high degree of concern because of its intriguing and promising properties. However, graphdiyne materials reported to date represent only a tiny fraction of the possible combinations. In this work, we demonstrate a computational approach to generate a series of conceivable graphdiyne-based frameworks (GDY-Rs and Li@GDY-Rs) by introducing a variety of functional groups (R = -NH2, -OH, -COOH, and -F) and doping metal (Li) in the molecular building blocks of graphdiyne without restriction of experimental conditions and rapidly screen the best candidates for the application of CO2 capture and sequestration (CCS). The pore topology and morphology and CO2 adsorption and separation properties of these frameworks are systematically investigated by combining density functional theory (DFT) and grand canonical Monte Carlo (GCMC) simulations. On the basis of our computer simulations, combining Li-doping and hydroxyl groups strategies offer an unexpected synergistic effect for efficient CO2 capture with an extremely CO2 uptake of 4.83 mmol/g at 298 K and 1 bar. Combined with its superior selectivity (13 at 298 K and 1 bar) for CO2 over CH4, Li@GDY-OH is verified to be one of the most promising materials for CO2 capture and separation.

New Insight of Li-Doped Cu2ZnSn(S,Se)4 Thin Films: Li-Induced Na Diffusion from Soda Lime Glass by a Cation-Exchange Reaction.

In our recent report (ACS Appl. Mater. Interfaces 2016, 8, 5308), Li+ ions had been successfully incorporated into the lattice of the selenized Cu2ZnSn(S,Se)4 thin film on a quartz substrate by substituting equivalent Cu+ ions, and Li+ ions was also found to have the little effect on the crystal growth and defect passivation. To further improve the cell performance of Li-doped CZTSSe devices, we conducted the same experiments on the sodium-rich soda-lime glass (SLG) substrate in this study, instead of sodium-free quartz substrate. Surprisingly, only trace amounts of Li (Li/Cu molar ratio ∼1 × 10-4) were detected in the final CZTSSe thin films; meanwhile, a large amount of sodium was present on the surface and at the grain boundaries of the selenized thin films. A Li/Na exchange mechanism is used to explain this phenomenon. Only on the sodium-free substrate can Li+ ions enter the CZTSSe host lattice, and doping Li+ ions on the SLG substrate are nearly identical to doping Na+ ions.

The effect of Li doping on the nonlinear optical properties of [2.2]paracyclophane.

The similar molecules [2.2]paracyclophane (22PCP) and 1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane (8F22PCP) have both generated considerable synthetic interest since they were first prepared. In this work, the nonlinear optical properties of 22PCP, 8F22PCP, and the related Li-doped systems 22PCP-Li and 8F22PCP-Li (which have a Li atom above 22PCP and 8F22PCP, respectively) were investigated. An analysis of natural bond orbital charges showed that there is greater charge transfer from the Li atom to the benzene rings in 8F22PCP-Li than in 22PCP-Li. The variation in the calculated nucleus independent chemical shift (NICS) value as a function of the distance from the lower benzene ring towards the upper benzene ring was found to be W-shaped for both 22PCP and 22PCP-Li. Moreover, whereas all of the NICS values of 22PCP and 22PCP-Li were markedly negative, all of the NICS values of 8F22PCP and 8F22PCP-Li were either positive or only moderately negative. Calculations of the electro-optical properties of these systems showed that the first hyperpolarizability of 22PCP-Li was noticeably larger than that of 8F22PCP-Li. According to the two-level model, the larger first hyperpolarizability of 22PCP-Li is due to its smaller transition energy.

Atomic disorder of Li0.5Ni0.5O thin films caused by Li doping: estimation from X-ray Debye-Waller factors.

Cubic type room-temperature (RT) epitaxial Li0.5Ni0.5O and NiO thin films with [111] orientation grown on ultra-smooth sapphire (0001) substrates were examined using synchrotron-based thin-film X-ray diffraction. The 1[Formula: see text]1 and 2[Formula: see text]2 rocking curves including six respective equivalent reflections of the Li0.5Ni0.5O and NiO thin films were recorded. The RT B1 factor, which appears in the Debye-Waller factor, of a cubic Li0.5Ni0.5O thin film was estimated to be 1.8 (4) Å2 from its 1[Formula: see text]1 and 2[Formula: see text]2 reflections, even though the Debye model was originally derived on the basis of one cubic element. The corresponding Debye temperature is 281 (39) K. Furthermore, the B2 factor in the pseudo-Debye-Waller factor is proposed. This parameter, which is evaluated using one reflection, was also determined for the Li0.5Ni0.5O thin film by treating Li0.5Ni0.5O and NiO as ideal NaCl crystal structures. A structural parameter for the atomic disorder is introduced and evaluated. This parameter includes the combined effects of thermal vibration, interstitial atoms and defects caused by Li doping using the two Debye-Waller factors.