Synthesis and properties of two novel copolymers based on squaraine and fluorene units for solar cell materials

Two novel copolymers based on squaraine and fluorine units have been synthesized through palladium catalyzed Suzuki coupling reaction and Sonogashira coupling reaction,respectively.The structures and properties of the two copolymers were characterized by FT-IR.NMR,UV-vis absorbance（Abs）,gel permeation chromatography（GPC）,thermal gravimetric analysis （TGA）,differential scanning calorimetry（DSC） and cyclic voltammetry（CV）.The solution absorption spectrums of P_1 and P_2 show two distinct absorption bands,one locates at 300-500 nm and the other at 600-800 nm.The absorption spectrums of P_1 and P_2 in films are broadened obviously and the spectral responses are extended up to 900 nm.Thermal gravimetric analysis demonstrates that the polymers are stable.Cyclic voltammetry experiment shows that the band gaps of the copolymers are 1.65 eV and 1.67 eV. respectively,suggesting their potential for applications as solar cells materials.

Progress in hole-transporting materials for perovskite solar cells

In recent years the photovoltaic community has witnessed the unprecedented development of perovskite solar cells（PSCs） as they have taken the lead in emergent photovoltaic technologies. The power conversion efficiency of this new class of solar cells has been increased to a point where they are beginning to compete with more established technologies. Although PSCs have evolved a variety of structures, the use of hole-transporting materials（HTMs） remains indispensable. Here, an overview of the various types of available HTMs is presented. This includes organic and inorganic HTMs and is presented alongside recent progress in associated aspects of PSCs, including device architectures and fabrication techniques to produce high-quality perovskite films. The structure, electrochemistry, and physical properties of a variety of HTMs are discussed, highlighting considerations for those designing new HTMs. Finally, an outlook is presented to provide more concrete direction for the development and optimization of HTMs for highefficiency PSCs.

Truxene-based Hole-transporting Materials for Perovskite Solar Cells

Three star-shaped truxene-based small molecules（namely TXH,TXM,TXO） were synthesized,characterized and used as hole-transporting materials（HTMs） for perovskite solar cells（Pv SCs）. The device based on TXO delivered a respectable power conversion efficiency（PCE） of 7.89% and a high open-circuit voltage（Voc） of 0.97 V,which far exceeded the values of the devices based on other two small molecules. The highest PCE for the device based on TXO is mainly contributed from its lowest series resistance（Rs） value and largest short-circuit current（Jsc） value under the same circumstances. All these results indicate that TXO is a promising HTM candidate for Pv SCs.

Materials Research Advances towards High-Capacity Battery/Fuel Cell Devices(Invited paper)

The world has entered an era featured with fast transportations,instant communications,and prompt technological revolutions,the further advancement of which all relies fundamentally,yet,on the development of cost-effective energy resources allowing for durable and high-rate energy supply.Current battery and fuel cell systems are challenged by a few issues characterized either by insufficient energy capacity or by operation instability and,thus,are not ideal for such highly-demanded applications as electrical vehicles and portable electronic devices.In this mini-review,we present,from materials perspectives,a few selected important breakthroughs in energy resources employed in these applications.Prospectives are then given to look towards future research activities for seeking viable materials solutions for addressing the capacity,durability,and cost shortcomings associated with current battery/fuel cell devices.

Recent theoretical progress in the development of perovskite photovoltaic materials

Since the seminal work by Kojima et al. in 2009, solar cells based on hybrid organic-inorganic perovskites have attracted considerable attention and experienced an exponential growth, with photovoltaic efficiencies as of today reaching above 22%. Despite such an impressive development, some key scientific issues of these materials, including the presence of toxic lead, the poor long-term device stability under heat and humidity conditions, and the anomalous hysteresis of the current-voltage curves shown by various solar cell devices, still remain unsolved and constitute an important focus of experimental and theoretical researchers throughout the world. Density functional theory calculations have been successfully applied to exploring structural and electronic properties of semiconductors, complementing the experimental results in search and discovery of novel functional materials. In this review, we summarize the current progress in perovskite photovoltaic materials from a theoretical perspective. We discuss design of lead-free perovskite materials, humidity-induced degradation mechanisms and possible origins for the observed solar cell hysteresis, and assess future research directions for advanced perovskite solar cells based on computational materials design and theoretical understanding of intrinsic properties.

3D printing of osteocytic Dll4 integrated with PCL for cell fate determination towards osteoblasts in vitro

Since 3D printed hard materials could match the shape of bone,cell survival and fate determination towards osteoblasts in such materials have become a popular research target.In this study,a scaffold of hardmaterial for 3D fabrication was designed to regulate developmental signal(Notch)transduction guiding osteoblast differentiation.We established a polycaprolactone(PCL)and cell-integrated 3D printing system(PCI3D)to reciprocally print the beams of PCL and cell-laden hydrogel for a module.This PCI3D module holds good cell viability of over 87%,whereas cells show about sixfold proliferation in a 7-day culture.The osteocytic MLO-Y4 was engineered to overexpress Notch ligand Dll4,making up 25%after mixing with 75%stromal cells in the PCI3D module.Osteocytic Dll4,unlike other delta-like family members such as Dll1 or Dll3,promotes osteoblast differentiation and themineralization of primary mouse and a cell line of bone marrow stromal cells when cultured in a PCI3D module for up to 28 days.Mechanistically,osteocytic Dll4 could not promote osteogenic differentiation of the primary bone marrow stromal cells(BMSCs)after conditional deletion of the Notch transcription factor RBPjκby Cre recombinase.These data indicate that osteocytic Dll4 activates RBPjκ-dependent canonical Notch signaling in BMSCs for their oriented differentiation towards osteoblasts.Additionally,osteocytic Dll4 holds a great potential for angiogenesis in human umbilical vein endothelial cells within modules.Our study reveals that osteocytic Dll4 could be the osteogenic niche determining cell fate towards osteoblasts.This will open a new avenue to overcome the current limitation of poor cell viability and low bioactivity of traditional orthopedic implants.

A novel phenoxazine-based hole transport material for efficient perovskite solar cell

Based on the previous research work in our laboratory, we have designed and synthesized a small-molecule, hole transport material （HTM） POZ6-2 using phenoxazine （POZ） as central unit and dicyanovinyl units as electron-withdrawing terminal groups. Through the introduction ofa 2-ethyl-hexyl bulky chain into the POZ core unit, POZ6-2 exhibits good solubility in organic solvents. In addition, POZ6-2 possesses appropriate energy levels in combination with a high hole mobility and conductivity in its pristine form. Therefore, it can readily be used as a dopant-flee HTM in perovskite solar cells （PSCs） and a conversion efficiency of 10.3% was obtained. The conductivity of the POZ6-2 layer can be markedly enhanced via doping in combination with typical additives, such as 4-tert-butylpyridine （TBP） and lithium bis（trifluoromethanesulfonyl） imide （LiTFS1）. Correspondingly, the efficiency of the PSCs was further improved to 12.3% using doping strategies. Under the same conditions, reference devices based on the well-known HTM Spiro-OMeTAD show an efficiency of 12.8%.

Titanylphthalocyanine as hole transporting material for perovskite solar cells

Titanylphthalocyanine （TiOPc） as hole transporting material （HTM） was successfully synthesized by a simple process with low cost. Perovskite solar cells using the TiOPc as HTM were fabricated and characterized. TiOPc as HTM plays an important role in increasing the power conversion efficiency （PCE） by minimizing recombi- nation losses at the perovskite/Au interface because TiOPc as HTM can extract photogenerated holes from the perovskite and then transport quickly these charges to the back metal electrode. In the research, the β-TiOPc gives a higher PCE than α-TiOPc for the devices due to sufficient transfer dynamics, The β-TiOPc was applied in perovskite solar cells without clopping to afford an impressive PCE of 5.05% under AM 1.5G illumination at the thickness of 40 nm which is competitive with spiro-OMeTAD at the same condition. The present work suggests a guideline for optimizing the photovoltaic properties ofperovskite solar cells using the TiOPc as the HTM.

High efficiency ETM-free perovskite cell composed of CuSCN and increasing gradient CH_(3)NH_(3)PbI_(3)

To enhance device performance and reduce fabrication cost,a series of electron transporting material(ETM)-free perovskite solar cells(PSCs)is developed by TCAD Atlas.The accuracy of the physical mode of PSCs is verified,due to the simulations of PEDOT:PSS-CH_(3)NH_(3)PbI_(3)-PCBM and CuSCN-CH_(3)NH_(3)PbI_(3)-PCBM p-i-n PSCs showing a good agreement with experimental results.Different hole transporting materials(HTMs)are selected and directly combined with n-CH_(3)NH_(3)PbI_(3),and the CuSCN-CH_(3)NH_(3)PbI_(3) is the best in these ETM-free PSCs.To further study the CuSCN-CH_(3)NH_(3)PbI_(3) PSC,the influences of back electrode material,gradient band gap,thickness,doping concentration,and bulk defect density on the performance are investigated.Energy band and distribution of electric field are utilized to optimize the design.As a result,the efficiency of CuSCN-CH_(3)NH_(3)PbI_(3) PSC is achieved to be 26.64%.This study provides the guideline for designing and improving the performances of ETM-free PSCs.

Piperazine-Assisted Construction of 2D/3D Wide-Bandgap Perovskite for Realizing High-Efficiency Perovskite/Organic Tandem Solar Cells

Monolithic perovskite/organic tandem solar cells(TsCs)have gained significant attention due to their easy device integration and the potential to surpass the Shockley-Queisser limit of single-junction solar cells.However,the surfaces of wide-bandgap perovskite films are densely populated with defects,leading to severe non-radiative recombination and energy loss.As a consequence,the power conversion efficiency(PCE)of perovskite/organic TSCs lags behind that of other TSC counterparts.To address these issues,we designed a functional ammonium salt,4-(2-hydroxyethyl)piperazin-1-ium iodide(Pzol),comprising a piperazine iodide and a terminated hydroxyl group,which was applied for post-treating the perovskite surface.Our findings reveal that Pzol reacts with and consumes residual PbX_(2)(X:I or Br)to form a 2D perovskite component,thereby eliminating Pb^(0)defects,while the terminated hydroxyl group in PZOI can also passivate uncoordinated Pb^(2+).Consequently,the shallow/deep-level defect densities of the 2D/3D perovskite film were significantly reduced,leading to an enhanced PCE of single-junction 2D/3D wide-bandgap perovskite solar cells to 18.18% with a reduced energy loss of 40 mev.Importantly,the corresponding perovskite/organic TSCs achieved a remarkable PCE of 24.05% with enhanced operational stability(T_(90)~500h).

Study on Improving the Internal Quality of Tobacco Stems by Using Pectinase

[Objective] This study aimed to reduce the content of cell wall materials in tobacco stems and improve their internal quality. [Method] Pectinase was used to decompose cell wall materials in tobacco stems, followed by determination of the contents of four cell wall materials, six routine chemical components, as well as aroma constituents. [Result] Pectinase could effectively reduce the contents of cell wall materials in tobacco stems, with the largest decrease of 6.84%; after pectinase treatment,the content of reducing sugar in tobacco stems increased obviously, and the contents of total sugar, potassium ion, chloride ion and total nitrogen increased to varying degrees, of which the contents of potassium ion and reducing sugar displayed upward trends with the increase of pectinase concentration. Pectinase treatment significantly increased the contents of Maillard reaction products, with the most increase of 67.2%;the contents of carotenoid degradation products, phenylalanine degradation products and neophytadiene all increased to varying extents, and the contents of both Maillard reaction products and phenylalanine degradation products revealed ascending trends with the increase of pectinase concentration. [Conclusion] Pectinase treatment can effectively decompose cell wall materials in tobacco stems, improve routine chemical constituents, and increase the contents of aroma constituents.

Recent progress on advanced transmission electron microscopy characterization for halide perovskite semiconductors

Halide perovskites are strategically important in the field of energy materials. Along with the rapid development of the materials and related devices, there is an urgent need to understand the structure–property relationship from nanoscale to atomic scale. Much effort has been made in the past few years to overcome the difficulty of imaging limited by electron dose,and to further extend the investigation towards operando conditions. This review is dedicated to recent studies of advanced transmission electron microscopy(TEM) characterizations for halide perovskites. The irradiation damage caused by the interaction of electron beams and perovskites under conventional imaging conditions are first summarized and discussed. Low-dose TEM is then discussed, including electron diffraction and emerging techniques for high-resolution TEM(HRTEM) imaging. Atomic-resolution imaging, defects identification and chemical mapping on halide perovskites are reviewed. Cryo-TEM for halide perovskites is discussed, since it can readily suppress irradiation damage and has been rapidly developed in the past few years. Finally, the applications of in-situ TEM in the degradation study of perovskites under environmental conditions such as heating,biasing, light illumination and humidity are reviewed. More applications of emerging TEM characterizations are foreseen in the coming future, unveiling the structural origin of halide perovskite’s unique properties and degradation mechanism under operando conditions, so to assist the design of a more efficient and robust energy material.

Effects of Nitric Oxide on the Quality and Pectin Metabolism of Yali Pears During Cold Storage

The effect of fumigation with 10, 20, and 30 μL L-1 nitric oxide （NO） was investigated to study the effects of NO on the quality of Yali pears during cold storage. The ethylene production, composition of cell walls, and cell-wall-modifying enzyme activities were measured on fruits which were fumigated with NO （20 μL L-1）. The results showed that NO not only reduced the peak value of ethylene production rate, the soluble sugar, soluble solid content, maintained higher firmness, starch, and NO content, but also retarded the degradation of covalent soluble pectin, accumulation of ionic soluble pectin and water soluble pectin. Moreover, NO fumigation decreased the activities of polygalacturonase （PG） and b-galactosidase（b-Gal） and delayed the peak of PG activity of fruits. Therefore, it indicated that NO fumigation could delay the softening and ripening of Yali pears.

Synthesis and properties of novel low band-gap polymers bearing squaraine units

Novel main-chain-conjugated poly(carbazol-alt-squaraine) and poly(dipyridyl-alt-squaraine) were successfully synthesized through direct polycondensation of 9-(2-ethylhexyl)carbazole-bridged or dipyridyl-bridged bispyrrole and squaric acid.The structures and properties of the polymers were characterized using ~1H NMR,FT-IR,UV-vis and cyclic voltammetry.Both polymers exhibit excellent solubility in common organic solvents and good thermal stability.Their UV-vis absorption spectra indicated the polymers have b...

Photoelectrochemical properties of MWCNT-TiO_2 hybrid materials as a counter electrode for dye-sensitized solar cells

The MWCNT-Ti02 hybrid materials were prepared by a simply mixing method and used as a counter electrode （CE） for dye-sensitized solar cells. Compared with the platinum CE, MWCNT-TiO2 CE has the similar redox voltage and current response in the cyclic voltammetry. The electrochemical catalytic activity was characterized by the electrochemical impedance spectroscopy and Tafel curve, including the equivalent circuit, the exchange current density, the limiting diffusion current density, and the diffusion coefficient of triiodide/iodide redox species. The results indicate that the reduction process from triiodide to iodide is determined by the kinetic-controlled and diffusion-limited processes. The device performance is optimal based on the MWCNT-TiO2 （mass ratio of 2：1） CE, such as the open-circuit voltage of 0.72 V, the short-circuit photocurrent density of 15.71 mA/cm2, the fill factor of 0.68, and the photon-to-electron conversion efficiency of 7.69%.

Organic thin-film solar cells:Devices and materials

In recent years, the performance of organic thinfilm solar cells has gained rapid progress, of which the power conversion efficiencies （r/p） of 3%-5% are commonly achieved, which were difficult to obtain years ago and are improving steadily now. The r/p of 7.4% was achieved in the year 2010, and r/p of 9.2% was disclosed and confirmed at website of Mitsubishi Chemical in April, 2011. The promising future is that the r/p of 10% is achievable according to simulation results. Apparently, these are attributed to material innovations, new device structures, and also the better understanding of device physics. This article summarizes recent progress in organic thinfilm solar cells related to materials, device structures and working principles. In the device functioning part, after each brief summary of the working principle, the methods for improvements, such as absorption increment, organic/electrode interface engineering, morphological issues, are addressed and summarized accordingly. In addition, for the purpose of increasing exciton diffusion efficiency, the benefit from triplet exciton, which has been proposed in recent years, is highlighted. In the active material parts, the chemical nature of materials and its impact on device performance are discussed. Particularly, emphasis is given toward the insight for better understanding device physics as well as improvements in device performance either by development of new materials or by new device architecture.

Recent advances in the design of dopant-free hole transporting materials for highly efficient perovskite solar cells

Continuous success has been achieved for solution-processed inorganic-organic hybrid perovskite solar cells（PVSCs） in the past several years, in which organic charge transporting materials play an important role. At present, most of the commonly used hole-transporting materials（HTMs） such as spiro-OMeTAD derivatives for PVSCs require additional chemical doping process to ensure sufficient conductivity and shift the Fermi level towards the HOMO level for efficient hole transport and collection. However, this doping process not only increases the complexity and cost of device fabrication, but also decreases the device stability. Thus development of efficient dopant-free HTMs for PVSCs is highly desirable and remains as a major challenge in this field. In this review, we will summarize the recent advances in the molecular design of dopant-free HTMs for PVSCs.

Rapid development in two-dimensional layered perovskite materials and their application in solar cells

Two-dimensional （2D） layered organic-inorganic hybrid perovskite （2D PVK） materials have beenrecently developed as a novel candidate for photovoltaic application with high stability and a maximumpower conversion efficiency of 12.5%. This article summarized these newly emerging 2D PVK materialsand their uses in solar cells. The structural, physical, and chemical properties as well as the classificationof 2D PVK materials are discussed. The photovoltaic performance parameters of various 2D perovsldtesolar cells （2D PSCs） are summarized and their device stability is compared with conventional 3Dperovskite solar cells （3D PSCs）. It has been concluded that 2D PVKs show greater stability upon humidity,heat stress, and light intensity as compared to 3D analogues and act as a class of promising materials forapplication in solar cells.

Development of electron and hole selective contact materials for perovskite solar cells

Nowadays,both n-i-p and p-i-n perovskite solar cells（PSCs） device structures are reported to give high performance with photo conversion efficiencies（PCEs） above 20%.The efficiency of the PSCs is fundementally determined by the charge selective contact materials.Hence,by introducing proper contact materials with good charge selectivity,one could potentially reduce interfacial charge recombination as well as increase device performance.In the past few years,copious charge selective contact materials have been proposed.Significant improvements in the corresponding devices were observed and the reported PCEs were close to that of classic Spiro-OMeTAD.This mini-review summarizes the state-of-the-art progress of typical electron/hole selective contact materials for efficient perovskite solar cells and an outlook to their development is made.

D-A structural protean small molecule donor materials for solution-processed organic solar cells

Under the synergistic effect of molecular design and devices engineering, small molecular organic solar cells have presented an unstoppable tendency for rapid development with putting forward donor- acceptor （D-A） structures. Up to now, the highest power conversion efficiency of small molecules has exceeded 11%, comparable to that of polymers. In this review, we summarize the high performance small molecule donors in various classes of typical donor-acceptor （D-A） structures and discuss their relationships briefly.