非醇醚类助焊剂及其焊膏的研究

研究了多元醇类溶剂及其复配物对Sn0.3Ag0.7Cu焊膏性能的影响。结果表明:四氢糠醇和聚丙二醇对冰白和水白松香都具有较强的溶解性。当四氢糠醇和聚丙二醇以质量比9:1复配时,获得的焊膏平均铺展率可达87%以上,焊点完整、饱满、无焊球和桥连等缺陷,储存时间较长,是一种综合性能良好的焊膏。     

Ultrafast Electrochemical Growth of Lithiophilic Nano-Flake Arrays for Stable Lithium Metal Anode

Lithium dendrites caused by nonuniform Li⁺ flux leads to the capacity fade and short-circuit hazard of lithium metal batteries. The solid electrolyte interface (SEI) is critical to the uniformity of Li⁺ flux. Here, an ultrafast preparation of uniform and vertical Cu₇S₄ nano-flake arrays (Cu₇S₄ NFAs) on the Cu substrate is reported. These arrays can largely improve the lithiophilicity of the anode and form Li₂S-enriched SEI due to the electrochemical reduction of Cu₇S₄ NFAs with lithium. A further statistical analysis suggests that the SEI, with a higher content of Li₂S, is more effective to inhibit the formation of lithium dendrites and yields less dead lithium. A quite stable coulombic efficiency of 98.6% can be maintained for 400 cycles at 1 mA cm^–2. Furthermore, at negative to positive electrode capacity ratio of 1.5 (N/P = 1.5), the full battery of Li@Cu₇S₄ NFAs||S shows 83% capacity retention after 100 cycles at 1 C, much higher than that of Li@Cu||S (33%). The findings demonstrate that high Li₂S content in the SEI is crucial for the dendrite inhibition to achieve better electrochemical performance.     

Triphenylamine-based trinuclear Pt(II) complexes for solution-processed OLEDs displaying efficient pure yellow and red emissions

Highly efficient phosphors are critical in solution-processed organic light-emitting devices (OLEDs). Multinuclear Ir(III) complexes containing more than one metal center have showed great potential in fabricating high performance OLEDs, yet the electroluminescent (EL) properties of multinuclear Pt(II) complexes are rarely studied. In this work, two neutral trinuclear Pt(II) complexes are synthesized based on the triphenylamine core bearing three bidentate ligand arms. Both the yellow emitter (PyTPt) and deep-red emitter (IqTPt) exhibit improved photoluminescent quantum yields (PLQYs) compared with their corresponding mononuclear Pt(II) complexes. Furthermore, the PLQYs of PyTPt and IqTPt doped films are increased to 0.63 and 0.47, respectively. The solution-processed pure yellow-emitting device based on PyTPt achieves impressively high external quantum efficiency (EQE), current efficiency (CE), and power efficiency (PE) of 16.92%, 56.74 cd/A and 29.09 lm W⁻¹, respectively, which are among the best performance reported for the OLEDs employing multinuclear Pt(II) complexes. The solution-processed device based on IqTPt shows pure red emission with the peak EQE approaching 9.0%. Both PyTPt and IqTPt display much higher EL efficiencies than their corresponding mononuclear Pt(II) complexes. This work demonstrates that it is an attritive strategy to develop multinuclear Pt(II) complexes for high-performance OLEDs.     

Theoretical design study on the origin of the improved phosphorescent efficiency of DPEphos quinoline-substituted derivatives for OLEDs

Various tetrahedral heteroleptic Cu(I) complexes, as red organic light-emitting diodes (OLEDs), show a concern of maximizing the quantum yield (QY) in order to improve the optoelectronic performance. Herein, three experimental [Cu(N^N) (bis [2-(diphenylphosphino)phenyl]ether)]⁺ (named 1, 2 and 3) were selected as the jumping-off point, following two complexes (named 4 and 5) were successfully designed by introducing bulky electron-donating substituents into N^N ligands continuously. As expected, the QY of designed complexes 4 (0.26) and 5 (0.13) exhibit over twice higher than that of 3 (5.4 × 10⁻²). This can be attributed to the enhanced electron-donating property of N^N ligand, which accelerated the radiative transition rate (k_r) through the apparently elevated energy level of the lowest triplet excited state (T₁) and strengthened transition dipole moments, even though the spin-orbit coupling (SOC) effect is weakened. Simultaneously, the tetrahedral geometric distortion could be effectively restrained by the bulky N^N ligands, but the high vibrational freedom of the terminal substituents could also bring in some unfavorable intra-ligand deformation, resulting in an upward of the nonradiative transition rate (k_nr) at 5 (k_nr: 0.30 × 10⁵ s⁻¹ for 4; 0.95 × 10⁵ s⁻¹ for 5). Therefore, it's worth noting that the balance of excited state energy level, SOC effect as well as the reorganization energy ought to be elaborately regulated to achieve the optimal QY. This detailed investigation on the microscopic mechanism of these Cu(I) complexes can provide instructive inspiration for experimentalists.     

Luminescent cationic/neutral Cu(I) complexes for use in light-emitting diodes: Synthesis,structural characterization,DFT studies and properties

Cationic and neutral mononuclear Cu(I) complexes, [Cu(PPh₃)₂(PmH)]BF₄ (1a), [Cu(DPEphos) (PmH)]BF₄ (2a), [Cu(Xantphos) (PmH)]BF₄ (3a), [Cu(PPh₃)₂(Pm)] (1b), [Cu(DPEphos) (Pm)] (2b) and [Cu(Xantphos) (Pm)] (3b) (PPh₃ = triphenylphosphine, DPEphos = bis(2-diphenylphosphinophenyl)ether, Xantphos = 9, 9-dimethyl-bis(diphenylphosphino)xanthenes, PmH = 2-(pyridin-2-yl)benzimidazole, Pm=(2-(Pyridin-2-yl)benzimidazolate), have been prepared and characterized by IR, ¹H NMR, ¹³C NMR, ³¹P NMR, XRD, elemental analysis and X-ray crystal structure analysis. The structural analysis shows that each of Cu(I) complexes includes a tetrahedral [Cu(NN) (PP)]⁺ moiety, and temperature variation from 99 K to 298 K leads to the change of bonds lengths, angles and weak interactions. Meanwhile, theoretical calculations indicate that the differences between cationic and neutral Cu(I) complexes affect the composition of HOMO and LUMO orbitals, and the effect of temperature on Mülliken atomic charges is limited. Furthermore, neutral Cu(I) complexes 1b–3b show better luminescence in comparison to cationic Cu(I) complexes 1a-3a at room temperature, and temperature variations from 99 K to 298 K result in changing photoluminescence to some extent, which partly agrees with the related calculation results. In these cationic and neutral Cu(I) complexes, the maximum phosphorescent lifetime and quantum yield reach respectively 137 μs and 42% at room temperature. Moreover, cationic and neutral Cu(I) complexes are utilized to fabricate the monochromatic LEDs, showing favorable electroluminescence with the maximum EQE of 7.10%.     

Boosting H2O2‐Guided Chemodynamic Therapy of Cancer by Enhancing Reaction Kinetics through Versatile Biomimetic Fenton Nanocatalysts and the Second Near‐Infrared Light Irradiation

Fenton reaction–based chemodynamic therapy (CDT) has attracted considerable attention for tumor treatment, because the Fenton reaction can degrade endogenous H₂O₂ within the tumor to form reactive oxygen species (ROS) to kill cancer cells. The kinetics of the Fenton reaction has significantly influenced its treatment efficacy. It is crucial to enhance the reaction kinetics at the maximum H₂O₂ concentration to quickly produce vast amounts of ROS to achieve treatment efficacy, which to date, has not been realized. Herein, reported is an efficacious CDT treatment of breast cancer using biomimetic CS‐GOD@CM nanocatalysts, which are rationally designed to significantly boost the Fenton reaction through improvement of H₂O₂ concentration within tumors, and application of the second near‐infrared (NIR‐II) light irradiation at the maximum concentration, which is monitored by photoacoustic imaging. The biomimetic nanocatalysts are composed of ultra‐small Cu_2?xSe (CS) nanoparticles, glucose oxidase (GOD), and tumor cell membrane (CM). The nanocatalysts can be retained in tumor for more than two days to oxidize glucose and produce an approximately 2.6‐fold increase in H₂O₂ to enhance the Fenton reaction under the NIR‐II irradiation. This work demonstrates for the first time the CDT treatment of cancer enhanced by the NIR‐II light.     

Ultrasmall Pd‐Cu‐Pt Trimetallic Twin Icosahedrons Boost the Electrocatalytic Performance of Glycerol Oxidation at the Operating Temperature of Fuel Cells

Recently, in order to improve the energy conversion efficiency of direct polyol fuel cells, the engineering of effective Pd‐ and/or Pt‐based electrocatalysts to rupture C? C bonds has received increasing attention. Here, an example is shown to synthesize highly uniform sub‐10 nm Pd‐Cu‐Pt twin icosahedrons by controlling the nucleation phase. Because of the synergies of the electronic effect, synergistic effect, geometric effect, and abundant surface active sites originating from the formation of near surface alloy and special icosahedral shape, the Pd‐Cu‐Pt twin icosahedrons exhibit excellent electrocatalytic performance in glycerol electrocatalysis at the operating temperature of direct alcohol fuel cells (70 °C) in KOH electrolyte. The Pd_50.2Cu_38.4Pt_11.4 icosahedrons show mass activities of 9.7 A mg^?1_Pd+Pt and 13.7 A mg^?1_Pd. Furthermore, the Pd_50.2Cu_38.4Pt_11.4 icosahedrons demonstrate long‐term durability in current–time test for 36 000 s and high in situ anti‐CO poisoning performance. In addition, the introduction of CO can enhance electro‐oxidation endurance on Pd_50.2Cu_38.4Pt_11.4 icosahedrons, and the peak mass activity can reach to 14.4 A mg^?1_Pd+Pt. The in situ Fourier transform infrared spectroscopy spectra indicate that the Pd_50.2Cu_38.4Pt_11.4 icosahedrons possess a high capacity to break C? C bonds and may efficiently convert glycerol into CO₂, thus improving the utilization efficiency of energy‐containing molecule glycerol.     

Impact of Transition-Metal Contamination on Oxygen Precipitation in Czochralski Silicon Under Rapid Thermal Processing

研究了快速热处理工艺下直拉单晶硅中过渡族金属铜、镍对内吸杂工艺中氧沉淀形成规律的影响.实验结果表明:在快速热处理工艺下,间隙铜对氧沉淀几乎没有影响,铜沉淀却能显著地促进氧沉淀的形成;而间隙镍或镍沉淀对氧沉淀的形成都没有影响.基于实验结果并结合氧沉淀的形核理论,对金属铜、镍对氧沉淀的影响机理进行了解释.     

Near‐Infrared Light‐Emitting Diodes (LEDs) Based on Poly(phenylene)/Yb‐tris(β‐Diketonate) Complexes

Near‐infrared‐emitting electroluminescent (EL) devices using blue‐light‐emitting polymers blended with the Yb complexes Yb(DBM)₃phen (DBM = dibenzoylmethane), Yb(DNM)₃phen (DNM = dinaphthoylmethane), and Yb(TPP)L(OEt) (L(OEt) = [(C₅H₅)Co{P(O)Et₂}₃]^–) have been studied. EL devices composed of Yb(DNM)₃phen blended with PPP‐OR11 showed enhanced near‐IR output at 977 nm when compared to those fabricated with Yb(DBM)₃phen/PPP‐OR11 blends. The maximum near‐IR external efficiencies of the devices with Yb(DBM)₃phen and Yb(DNM)₃phen are, respectively, 7 × 10^–5 (at 6 V and at 0.81 mA mm^–2) and 4 × 10^–4 (at 7 V, and 0.74 mA mm^–2). The optimal blend composition for EL device performance consisted of PPP‐OR11 blended with 10–20 mol‐% Yb(DNM)₃phen. A device fabricated using Yb‐(TPP)L(OEt)/PPP‐OR11 showed significantly enhanced near‐IR output efficiency, and future efforts will focus on devices fabricated using porphyrin‐based materials.     

铜锡合金纳米粒子的制备和性能研究

通过化学还原方法制备了铜锡合金纳米粒子,并研究分析了其的尺寸和热学性能。铜锡纳米粒子的X射线衍射分析结果显示,合成产物主要是锡纳米颗粒和铜锡合金(Cu6Sn5)纳米颗粒组成,且这些纳米粒子并未被氧化。其示差扫描量热法测得结果表明,本次合成的纳米颗粒的熔点为202.98 ℃,适合现代电子封装技术对低熔点封装材料的要求。