Dual Functional Titanium Hydride Particles for Anti-Ultraviolet and Anti-Oxidant Applications

TiO₂ is a typical anti-ultraviolet agent in sunscreen cream, but it suffers from a lack of anti-oxidant activity for scavenging reactive oxygen species. Other traditional sunscreen ingredients, such as C₆₀ and ferulic acid, have moderate antioxidant and UV protection capabilities, and the products do not provide further UV protection. Herein, titanium hydride (TiH_1.97) particles with dual functions of anti-oxidant and anti-ultraviolet are presented as an active material to remove the highly oxidizing and harmful hydroxide free radicals from the skin surface. Owing to the active hydrogen in TiH₂, it shows great potential to eliminate hydroxyl radicals, and the rate is roughly proportional to the exposed surface area (50% /20 min). Together with the biocompatibility of the in situ formed TiO₂, which has a strong ability to absorb ultraviolet light during OH radical scavenging. At the same time, adding titanium hydride to sunscreen also enhances sun protection. The SPF value of sunscreen containing 1% titanium hydride and 20% titanium dioxide can reach 31.8, which exceeds the 20% titanium dioxide (15) by more than twofold. Therefore, titanium hydride with anti-ultraviolet and antioxidant functions can be regarded as a promising and safe ingredient for sunscreen cream.     

Dopant‐Free Spiro‐Triphenylamine/Fluorene as Hole‐Transporting Material for Perovskite Solar Cells with Enhanced Efficiency and Stability

Chemical doping is often used to enhance electric conductivity of the conjugated molecule as hole‐transporting material (HTM) for the application in optoelectronics. However, chemical dopants can promote ion migration at the electrical field, which deteriorates the device efficiency as well as increases the fabrication cost. Here, two star HTMs, namely 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenyl‐amine) 9,9′‐spirobifluorene (Spiro‐OMeTAD) and poly(triarylamine) are subjeted to chemical combination to yield dopant‐free N2,N2,N2′,N2′,N7,N7,N7′,N7′‐octakis(4‐methoxyphenyl)‐10‐phenyl‐10H‐spiro[acridine‐9,9′‐fluorene]‐2,2′,7,7′‐tetraamine (SAF‐OMe). The power conversion efficiencies (PCEs) of 12.39% achieved by solar cells based on pristine, dopant‐free SAF‐OMe are among the highest reported for perovskite solar cells and are even comparable to devices based on chemically doped Spiro‐OMeTAD (14.84%). Moreover, using a HTM comprised of SAF‐OMe with an additional dopant results in a record PCE of 16.73%. Compared to Spiro‐OMeTAD‐based devices, SAF‐OMe significantly improves stability.     

Multifunctional Electrode Design Consisting of 3D Porous Separator Modulated with Patterned Anode for High‐Performance Dual‐Ion Batteries

Searching for low‐cost and high‐capacity electrode materials such as metal anodes is of important significance for the development of new generation rechargeable batteries. However, metal anodes always suffer from severe volume expansion/contraction during a repeated electrochemical alloying/dealloying process. In this study, a novel concept about modifying metal‐anodes‐based battery construction with a multifunctional electrode (ME) design is provided. The ME consists of a 3D porous separator that is modulated with a patterned aluminum anode, which simultaneously works as a current collector, anode material, and separator in a dual‐ion battery (DIB). The 3D porous separator not only enables the ME to possess significantly improved electrolyte uptake and retention capabilities, but also acts as a protecting layer to restrict the surface pulverization of the Al anode. The ME‐DIB displays remarkably enhanced cell performances, including excellent cycling stability with 92.4% capacity retention after 1000 cycles at a current density of 2 C, and superior rate performance with 80.7% capacity retention at 10 C.     

Study and formation of 2D microstructures of sapphire by focused ion beam milling

Dry etching of C-plane sapphire wafer has been studied using Ga⁺ focused ion beam milling (FIBM). Due to a much lower milling rate of sapphire compared to GaN, it has been proven that gas-assisted FIBM (GAFIBM) is a necessity. Furthermore, it needs to be determined whether XeF₂- or I₂-GAFIBM can improve the technique. We found that XeF₂-GAFIBM gave the highest milling rate. The obtained enhancement factor of the XeF₂-GAFIBM milling rate compared to FIBM rate varied from 2.3 to 1.2 for the ion beam current in the range 20 pA-1 nA. A favorable milling rate selectivity of sapphire to nickel film of about 1.5 was obtained by XeF₂-GAFIBM at 350 pA. We have successfully fabricated a variety of 2D sapphire-based submicron pillar or hole arrays in regular crystals, quasicrystals and aperiodic symmetries. The nearest neighbor distance was down to 230 nm. The depth achieved was deeper than 400 nm. The air filling factor ranged from 12% to 60%. These sapphire-based 2D microstructures were applied on flip-chip GaN-based light emitting diodes (LEDs) and more than 40% improvement in light extraction was obtained.     

Sodium distribution in thermal oxide on silicon by radiochemical and MOS analysis

Direct comparison has been made between Na distribution determined radiochemically and electrically in 6000 Å thermal oxide on 10Ω-cm n-type Si. Na withinsiml 1000Å of Si/SiO2interface correlates in most cases with MOS flat band voltage shift, i.e. NNa(siml 1000Å) ≈ +ΔQMOS. Appreciable Na, which does not appear to affect Si surface potential, is found through the bulk of the oxide. Neutron activation of "clean" oxide (grown in wet or dry oxygen) showed ∼1 ppm Na throughout, ∼10 ppm at free surface. Gold was also identified at ppm concentrations but did not correlate with ΔQMOS. The U-shaped profile seen after diffusion (300 to 1000°C in dry N2) or in-drift (∼200°C, 5 × 10⁵V/cm) is believed due to rate limitation at the free surface; electrostatic binding plus enhanced solubility at the Si/SiO2interface. Time dependence was observed in diffusion at 500 and 800°C, which is not expected from the fast diffusion of Na. This is also attributed to the surface rate limitation. The anion significantly affects Na diffusion kinetics and distribution in contamination experiments with radiotracer Na²⁴OH, Na²⁴Cl, and Na²⁴Br⁸². Br is found to accompany Na diffusion, suggesting anion neutralization of Na within the bulk oxide. P2O5. SiO2is seen to "getter" Na from the oxide. These results support the suggestion of Snow et al. that Na is responsible for uncontrolled drift of surface potential in oxidized Si devices.     

Stepwise Hollow Prussian Blue Nanoframes/Carbon Nanotubes Composite Film as Ultrahigh Rate Sodium Ion Cathode

Prussian blue and its analogues (PBAs) have been proposed as promising cathode materials for sodium‐ion batteries (SIBs) due to high theoretical capacity and low cost, but they often suffer from poor electronic conductivity and structural instability. Herein, a stepwise hollow cubic framework structure is first designed and a hybridized hierarchical film synthesized from single‐crystal PBA nanoframes/carbon nanotubes (CNTs) composite is demonstrated as a binder‐free ultrahigh rate sodium ion cathode. This hierarchical configuration offers improved tolerance for lattice expansion, reduced sodium ion diffusion path, enhanced electronic conductivity, and optimized redox reactions, thereby achieving the excellent rate capability, high specific capacity, and long cycle life. As expected, the developed FeHCFe nanoframes/CNTs electrode film exhibits a super high rate capacity of 149.2 mAh g^?1 at 0.1C and 35.0 mAh g^?1 at 100C. Moreover, it displays an excellent cycling stability with about 92% capacity retention at 5C after 500 cycles. This work will pave a new way to engineer advanced electrode materials for ultrahigh rate SIBs.     

Ultrafast Discharge/Charge Rate and Robust Cycle Life for High‐Performance Energy Storage Using Ultrafine Nanocrystals on the Binder‐Free Porous Graphene Foam

A hierarchical architecture fabricated by integrating ultrafine titanium dioxide (TiO₂) nanocrystals with the binder‐free macroporous graphene (PG) network foam for high‐performance energy storage is demonstrated, where mesoporous open channels connected to the PG facilitate rapid ionic transfer during the Li‐ion insertion/extraction process. Moreover, the binder‐free conductive PG network in direct contact with a current collector provides ultrafast electronic transfer. This structure leads to unprecedented cycle stability, with the capacity preserved with nearly 100% Coulombic efficiency over 10 000 Li‐ion insertion/extraction cycles. Moreover, it is proven to be very stable while cycling 10 to 100‐fold longer compared to typical electrode structures for batteries. This facilitates ultrafast charge/discharge rate capability even at a high current rate giving a very short charge/discharge time of 40 s. Density functional theory calculations also clarify that Li ions migrate into the TiO₂–PG interface then stabilizing its binder‐free interface and that the Li ion diffusion occurs via a concerted mechanism, thus resulting in the ultrafast discharge/charge rate capability of the Li ions into ultrafine nanocrystals.     

Influence of iron concentration on its structural position in KNbO3 lattice

In this paper variations of structural positions of Fe³⁺ ions in KNbO₃ crystals depending on iron content in growth components have been studied by the ESR method. Crystals of KNbO₃ have been grown by the Czochralski method. In addition to finding two EPR spectra published by Siegel we have found two novel types of paramagnetic centers (I, IV) caused by incorporation of iron impurity. One of them is observed at the low concentration of iron impurity. This center (I) has C_3V symmetry, S=5/2 and is due to incorporation of Fe³⁺ ions into the potassium positions of regular lattice. Increasing iron content in growth mixture up to 200 ppm resulted in disappearance of this center and two ESR spectra (II, III) described by Siegel arose. Limited content of (II) and (III) iron-containing defects is due to a restricted solubility of iron in KNbO₃ crystal. An increase of iron content in growth mixture over 400 ppm produces new a type of defect—(IV). This center has C_3V symmetry, electronic spin S=1/2 and is due to 3d⁵ electronic state of Fe³⁺ ion in strong crystalline field. The structural models of observed centers are discussed.     

In‐Plane Assembled Orthorhombic Nb2O5 Nanorod Films with High‐Rate Li+ Intercalation for High‐Performance Flexible Li‐Ion Capacitors

Organic hybrid supercapacitors that consist of a battery electrode and a capacitive electrode show greatly improved energy density, but their power density is generally limited by the poor rate capability of battery‐type electrodes. In addition, flexible organic hybrid supercapacitors are rarely reported. To address the above issues, herein an in‐plane assembled orthorhombic Nb₂O₅ nanorod film anode with high‐rate Li⁺ intercalation to develop a flexible Li‐ion hybrid capacitor (LIC) is reported. The binder‐/additive‐free film exhibits excellent rate capability (≈73% capacity retention with the rate increased from 0.5 to 20 C) and good cycling stability (>2500 times). Kinetic analyses reveal that the high rate performance is mainly attributed to the excellent in‐plane assembly of interconnected single‐crystalline Nb₂O₅ nanorods on the current collector, ensuring fast electron transport, facile Li‐ion migration in the porous film, and greatly reduced ion‐diffusion length. Using such a Nb₂O₅ film as anode and commercial activated carbon as cathode, a flexible LIC is designed. It delivers both high gravimetric and high volumetric energy/power densities (≈95.55 Wh kg^?1/5350.9 W kg^?1; 6.7 mW h cm^?3/374.63 mW cm^?3), surpassing previous typical Li‐intercalation electrode‐based LICs. Furthermore, this LIC device still keeps good electrochemical attributes even under serious bending states (30°–180°).     

The role of oxygen in electron cyclotron resonance etching of silicon carbide

The electron cyclotron resonance (ECR) etching of silicon carbide (SiC) was studied using SF₆ + O₂ based plasma. The role of O₂ was studied by varying the O₂ flow rate while keeping the total gas flow constant. It was found that oxygen enhances the etch rate at low O₂ fraction through releasing more fluorine atoms, while lowers the etch rate at high O₂ fraction by diluting fluorine atoms and forming an oxide-like layer. The etched surface roughness was found to be affected by the surface oxidation and oxygen ion related physical ion bombardment. The role of oxygen in chemical etching of carbon was found to be insignificant. In general, the etched surface is smooth and free of micromasking effect that can arise from Al contamination and C rich layer.     

Molybdenum Oxide Nanosheets with Tunable Plasmonic Resonance: Aqueous Exfoliation Synthesis and Charge Storage Applications

Herein, a simple aqueous‐exfoliation strategy is introduced for the fabrication of a series of MoO_3?x nanosheets (where x stands for oxygen vacancies) using two commercial molybdenum oxide precursors, MoO₂ and MoO₃. The nanosheets offer a localized surface plasmon resonance (LSPR) effect which is dependent on the structure and local environment of the nanosheets. The LSPR can be efficiently tuned by changing the weight ratio between the molybdenum oxide precursor(s) and/or by solar light irradiation using a low‐energy UV lamp (36 W). For the pristine MoO_3?x nanosheets, the highest LSPR signal is obtained for nanosheets prepared using 80% MoO₂. On the contrary, after solar light irradiation, the nanosheets prepared using pure MoO₃ offer the highest LSPR response. The nanosheets also show an outstanding rate capability when used as binder‐free supercapacitor electrodes in an acidified Na₂SO₄ electrolyte. The electrodes exhibit discharge capacities of 110 and 75 C g^?1 at a scan rate of 20 and 1000 mV s^?1, respectively. The MoO_3?x nanosheets can likewise be used as a negative electrode material for lithium‐ion batteries. The efficient eco‐friendly synthesis and the ability to tune the photochemical and electrochemical properties of the nanosheets make this approach interesting to many energy‐related research fields.     

Interface Functionalization of Photoelectrodes with Graphene for High Performance Dye‐Sensitized Solar Cells

The microstructures of photo‐ and counter‐electrodes play critical roles in the performance of dye‐sensitized solar cells (DSSCs). In particular, various interfaces, such as fluorinated‐tin oxide (FTO)/TiO₂, TiO₂/TiO₂, and TiO₂/electrolyte, in DSSCs significantly affect the final power conversion efficiency (PCE). However, research has generally focused more on the design of various nanostructured semiconducting materials with emphasis on optimizing chemical or/and physical properties, and less on these interface functionalizations for performance improvement. This work explores a new application of graphene to modify the interface of FTO/TiO₂ to suppress charge recombination. In combination with interfaces functionalization of TiO₂/TiO₂ for low charge‐transport resistance and high charge‐transfer rate, the final PCE of DSSC is remarkably improved from 5.80% to 8.13%, achieving the highest efficiency in comparison to reported graphene/TiO₂‐based DSSCs. The method of using graphene to functionalize the surface of FTO substrate provides a better alternative method to the conventional pre‐treatment through hydrolyzing TiCl₄ and an approach to reduce the adverse effect of microstructural defect of conducting glass substrate for electronic devices.     

电子墨水用SiO2白色电泳颗粒的表面包裹及荷电

采用控制正硅酸乙酯在氨水-无水乙醇中水解的方法,制备出适合电子墨水使用的白色SiO2颗粒。将经H2O2浸泡,由甲基丙烯酰氧基丙基三甲氧基硅烷(MPS)表面改性的SiO2颗粒,与苯乙烯单体分散在异丙醇中,采用自由基共聚法在SiO2颗粒表面包裹不同厚度的聚苯乙烯包4裹层。采用场发射扫描电镜(Field Emission Scanning Electron Micro-scopes)、高分辨率透射电镜(High Resolution Transmission Electron Microscopes)、傅立叶变换红外光谱(Fourier Transform Infrared Ray)、纳米粒度及Zeta电位分析(Zetasizer)等分析方法,研究了包裹前后SiO2颗粒的表面形貌、颗粒尺寸及包裹层厚,包裹后颗粒的表面化学键合情况,颗粒在四氯乙烯中的表面Zeta电位以及在四氯乙烯中的分散性。结果表明:自制SiO2颗粒呈球形,粒径约300 nm,SiO2颗粒表面包裹了聚苯乙烯,包裹层较为均匀完整,层厚约为10～25 nm,并随包裹颗粒时所加苯乙烯单体量增大而变厚,颗粒在四氯乙烯中的表面Zeta电位由-4.26 mV提高到-49.47 mV,包裹后颗粒在电势为9 V的电场下,响应时间理论计算值到达40 ms,颗粒在四氯乙烯中的分散性良好,分散后静置48 h,分散率可达到87%。     

不同离子束参数诱导单晶硅纳米微结构与光学性能

使用微波回旋共振离子源,研究了低能Ar+离子束正入射时不同离子束能量和束流密度对单晶硅（100）表面的刻蚀效果及光学性能。结果表明,当离子束能量为1 000 eV,束流密度为88~310 A/cm2时,样品表面出现自组装纳米点状结构,且随着离子束流密度增加排列紧密而有序;粗糙度呈现先减小后迅速增大的趋势,在160 A/cm2附近达到极小值;刻蚀后,近红外波段内平均透过率由53%提高到57%以上,且随着纳米自组装结构有序性的提高而增大。当束流密度为270 A/cm2,能量为500~1 500 eV时,样品表面出现纳米点状结构,且随着离子束能量的增加趋于密集有序;粗糙度呈现先缓慢增加,在1 100 eV附近达到极大值,之后粗糙度迅速下降;刻蚀后样品透过率明显提高,且平均透过率随着点状结构有序性的提高而增大;刻蚀速率与离子束能量的平方成正比。自组织纳米结构的转变是溅射粗糙化和表面驰豫机制相互作用的结果。     

Self‐Standing Porous LiCoO2 Nanosheet Arrays as 3D Cathodes for Flexible Li‐Ion Batteries

Self‐standing electrodes are the key to realize flexible Li‐ion batteries. However, fabrication of self‐standing cathodes is still a major challenge. In this work, porous LiCoO₂ nanosheet arrays are grown on Au‐coated stainless steel (Au/SS) substrates via a facile “hydrothermal lithiation” method using Co₃O₄ nanosheet arrays as the template followed by quick annealing in air. The binder‐free and self‐standing LiCoO₂ nanosheet arrays represent the 3D cathode and exhibit superior rate capability and cycling stability. In specific, the LiCoO₂ nanosheet array electrode can deliver a high reversible capacity of 104.6 mA h g^?1 at 10 C rate and achieve a capacity retention of 81.8% at 0.1 C rate after 1000 cycles. By coupling with Li₄Ti₅O₁₂ nanosheet arrays as anode, an all‐nanosheet array based LiCoO₂//Li₄Ti₅O₁₂ flexible Li‐ion battery is constructed. Benefiting from the 3D nanoarchitectures for both cathode and anode, the flexible LiCoO₂//Li₄Ti₅O₁₂ battery can deliver large specific reversible capacities of 130.7 mA h g^?1 at 0.1 C rate and 85.3 mA h g^?1 at 10 C rate (based on the weight of cathode material). The full cell device also exhibits good cycling stability with 80.5% capacity retention after 1000 cycles at 0.1 C rate, making it promising for the application in flexible Li‐ion batteries.     

High Reversible Pseudocapacity in Mesoporous Yolk–Shell Anatase TiO2/TiO2(B) Microspheres Used as Anodes for Li‐Ion Batteries

As an anode material for lithium‐ion batteries, titanium dioxide (TiO₂) shows good gravimetric performance (336 mAh g^?1 for LiTiO₂) and excellent cyclability. To address the poor rate behavior, slow lithium‐ion (Li⁺) diffusion, and high irreversible capacity decay, TiO₂ nanomaterials with tuned phase compositions and morphologies are being investigated. Here, a promising material is prepared that comprises a mesoporous “yolk–shell” spherical morphology in which the core is anatase TiO₂ and the shell is TiO₂(B). The preparation employs a NaCl‐assisted solvothermal process and the electrochemical results indicate that the mesoporous yolk–shell microspheres have high specific reversible capacity at moderate current (330.0 mAh g^?1 at C/5), excellent rate performance (181.8 mAh g^?1 at 40C), and impressive cyclability (98% capacity retention after 500 cycles). The superior properties are attributed to the TiO₂(B) nanosheet shell, which provides additional active area to stabilize the pseudocapacity. In addition, the open mesoporous morphology improves diffusion of electrolyte throughout the electrode, thereby contributing directly to greatly improved rate capacity.     

Facile chemical method of etching polyimide films for failure analysis (FA) applications and its etching mechanism studies

A new strategy has been developed for discovering a novel/facile way of etching polyimide film for FA application. The aromatic polyimide synthesized from pyromellitic dianhydride and 2,2′-dimethyl-4,4′-diaminobiphenyl in the presence of an acid catalyst. This polyimide film was used to study its physical attributes and the chemical etching rate which can be evaluated in microelectronic package application as dielectric film. Chemical etching rates of polyimide film by an alkaline etching solution with the presence of different kinds of etchants were studied by film-thickness measurement and UV absorption spectroscopy of dispersible etching residue. The etching rate of polyimide film in alkaline ethylenediamine solution is highest among the etching solution studied in the present experiment. If an external bias voltage was applied during etching, the etching rate was increased. The effect of temperature, solubility of the etchant was also discussed. The presence of a radical in the process of etching reveals that the etching reaction is a type of radical chain reaction. It was found that the deprocessing technique (drenched alkaline aqueous solution of ethylenediamine and then instantaneously combined with mix acid (2:1 Nitric 90% fuming to Sulfuric mix at 40 °C)) could be extended to remove polyimide in different package geometry and different thickness of film.     

印刷带状偶极子天线与经典三维柱状偶极子天线的等效理论研究

相对于传统的柱状偶极子,印制偶极子天线更适合应用于现代通讯系统.本文通过引入边缘场效应,对传统的基于感应电动势法的柱状电偶极子辐射阻抗公式进行修正,并在此基础上将其推广至印制偶极子天线中.此外,本文还采用合成渐进法,基于物理概念,推导出平面偶极子天线的谐振频率及谐振频率处辐射电阻的两个计算机辅助计算公式.数值计算及验证表明,两个公式的精度均在2%以内,可以用于指导工程设计.     

Chemically assisted ion beam etching of gallium nitride

Chemically assisted ion beam etching of gallium nitride (GaN) grown by metalorganic chemical vapor deposition has been characterized using an Ar ion beam and Cl₂gas. The etch rate of GaN was found to increase linearly with Ar ion beam current density, increase linearly then saturate with Ar ion beam energy, vary slightly with Cl₂ flow rate, and lastly, increase moderately with substrate temperature. Etch rates as high as 330 nm/min were obtained at high beam energies and 210 nm/min at a more nominal level of 500 eV. The anisotropy of etched profiles improved in the presence of Cl₂ in comparison to those etched by Ar ion milling only. Elevated substrate temperatures further enhanced the anisotropy to obtain near-vertical profiles for fairly deep-etched structures. Auger electron spectroscopy was used to investigate etch-induced surface changes. Oxygen contamination was observed on the as-etched surface but a dilute HC1 treatment restored the stoichiometry of the material to its unetched state.     

适合计算方法课程的考查课实验评估探索

针对考查课实验效率低、报告质量不高的问题，采取的措施主要有：1） 形式上，课前做实验，课内汇报，汇报后一天内提交报告。2） 成绩组成上，由实验报告和互评两部分加权求和。采取上述措施后，提高了实验效率和报告质量。以计算方法课程为例，对比2021年春季和秋季两个教学班，优良率明显提升（由48.9%提升至64%），不及格率明显降低（由21.3%降低至0%），平均成绩提高（74.6分提高83.5分）。