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Pd Nanoparticles Immobilized on Pyridinic N-Rich Carbon Nanosheets for Promoting Suzuki Cross-Coupling Reactions. 固定在富含吡啶 N 的碳纳米片上的钯纳米颗粒用于促进铃木交叉偶联反应。
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-22 DOI: 10.3390/nano14211690
Shihao Cui, Dejian Xu, Zhiyuan Wang, Libo Wang, Yikun Zhao, Wei Deng, Qingshan Zhao, Mingbo Wu

Palladium (Pd) catalysts play a crucial role in facilitating Suzuki cross-coupling reactions for the synthesis of valuable organic compounds. However, conventional heterogeneous Pd catalysts often encounter challenges such as leaching and deactivation during reactions, leading to reduced catalytic efficiency. In this study, we employed an innovative intercalation templating strategy to prepare two-dimensional carbon nanosheets with high nitrogen doping derived from petroleum asphalt, which were utilized as a versatile support for immobilizing Pd nanoparticles (Pd/N-CNS) in efficient Suzuki cross-coupling reactions. The results indicate that the anchoring effect of high-pyridinic N species on the two-dimensional carbon nanosheets enhances interactions between Pd and the support, effectively improving both the dispersibility and stability of the Pd nanoparticles. Notably, the Pd/N-CNS catalyst achieved an overall turnover frequency (TOF) of 2390 h-1 for the Suzuki cross-coupling reaction under mild conditions, representing approximately a nine-fold increase in activity compared to commercial Pd/C catalysts. Furthermore, this catalyst maintained an overall TOF of 2294 h-1 even after five reaction cycles, demonstrating excellent stability. Theoretical calculations corroborate these observed enhancements in catalytic performance by attributing them to improved electron transfer from Pd to the support facilitated by abundant pyridinic N species. This work provides valuable insights into feasible strategies for developing efficient catalysts aimed at sustainable production of biaromatic compounds.

钯(Pd)催化剂在促进合成有价值有机化合物的铃木交叉偶联反应中发挥着至关重要的作用。然而,传统的异质钯催化剂经常会在反应过程中遇到浸出和失活等难题,导致催化效率降低。在本研究中,我们采用了一种创新的插层模板策略,从石油沥青中制备出高氮掺杂的二维碳纳米片,并将其作为固定钯纳米颗粒(Pd/N-CNS)的多功能载体,用于高效的铃木交叉偶联反应。研究结果表明,二维碳纳米片上的高吡啶基 N 物种的锚定效应增强了 Pd 与支撑物之间的相互作用,从而有效提高了 Pd 纳米粒子的分散性和稳定性。值得注意的是,在温和条件下,Pd/N-CNS 催化剂进行铃木交叉偶联反应的总周转频率 (TOF) 达到 2390 h-1,与商用 Pd/C 催化剂相比,活性提高了约九倍。此外,这种催化剂在经过五个反应循环后仍能保持 2294 h-1 的总体 TOF,显示出极佳的稳定性。理论计算证实了所观察到的催化性能的提高,并将其归因于丰富的吡啶 N 物种促进了电子从钯到载体的转移。这项工作为开发高效催化剂的可行策略提供了宝贵的见解,从而实现生物芳香化合物的可持续生产。
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引用次数: 0
Effects of Hydrogen Dissociation During Gas Flooding on Formation of Metal Hydride Cluster Ions in Secondary Ion Mass Spectrometry. 充气过程中氢气解离对二次离子质谱法中金属氢化物簇离子形成的影响。
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-22 DOI: 10.3390/nano14211687
Jernej Ekar, Sabina Markelj, Miran Mozetič, Rok Zaplotnik, Janez Kovač

The application of hydrogen flooding was recently shown to be a simple and effective approach for improved layer differentiation and interface determination during secondary ion mass spectrometry (SIMS) depth profiling of thin films, as well as an approach with potential in the field of quantitative SIMS analyses. To study the effects of hydrogen further, flooding of H2 molecules was compared to reactions with atomic H on samples of pure metals and their alloys. H2 was introduced into the analytical chamber via a capillary, which was heated to approximately 2200 K to achieve dissociation. Dissociation of H2 up to 30% resulted in a significant increase in the intensity of the metal hydride cluster secondary ions originating from the metallic samples. Comparison of the time scales of possible processes provided insight into the mechanism of hydride cluster secondary ion formation. Cluster ions presumably form during the recombination of the atoms and molecules from the sample and atoms and molecules adsorbed from the gas. This process occurs on the surface or just above it during the sputtering process. These findings coincide with those of previous mechanistic and computational studies.

最近的研究表明,氢气淹没是一种简单有效的方法,可在二次离子质谱(SIMS)薄膜深度剖析过程中改进层区分和界面测定,同时也是一种在定量 SIMS 分析领域具有潜力的方法。为了进一步研究氢气的影响,将 H2 分子的淹没与纯金属及其合金样品上的原子 H 反应进行了比较。通过毛细管将 H2 引入分析室,加热至约 2200 K 以实现解离。H2 的解离度高达 30%,导致金属样品中金属氢化物簇二级离子的强度显著增加。对可能过程的时间尺度进行比较,有助于深入了解氢化物簇二级离子的形成机制。簇离子可能是在样品中的原子和分子与气体中吸附的原子和分子重新结合的过程中形成的。这一过程发生在溅射过程中的表面或其上方。这些发现与之前的机理和计算研究不谋而合。
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引用次数: 0
A Novel Method for Rapid and High-Performance SERS Substrate Fabrication by Combination of Cold Plasma and Laser Treatment. 冷等离子体和激光处理相结合的快速、高性能 SERS 基底制造新方法。
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-22 DOI: 10.3390/nano14211689
Thi Quynh Xuan Le, Thanh Binh Pham, Van Chuc Nguyen, Minh Thu Nguyen, Thu Loan Nguyen, Nguyen Thuan Dao

In this paper, we report a simple yet efficient method for rapid and high-performance SERS substrate fabrication by a combination of cold plasma and laser treatment. Our analysis reveals that cold plasma pre-treatment significantly reduced surface roughness, transforming 200 nm spikes into an almost perfectly uniform surface, while enhancing the substrate's surface energy by lowering the water contact angle from 59° to 0°, all achieved within just 30 s of 0.9-mW plasma treatment, while 15-min green-laser treatment facilitated more uniform deposition of AuNPs across the entire treated area, effectively creating the SERS substrates. The combined treatments result in enhancement of the Raman intensity (11 times) and consistency over the whole area of the SERS substrates, and their reusability (up to 10 times). The fabricated SERS substrates exhibit a significant enhancement factor of approximately 3 × 10⁸ with R6G, allowing detection down to a concentration of 10-12 M. We demonstrate the application of these SERS substrates by detecting amoxicillin-an antibiotic used worldwide to treat a diversity of bacterial infections-in a dynamic expanded linear range of seven orders (from 10-3 to 10-9 M) with high reliability (R2 = 0.98), and a detection limit of 9 × 10-10 M. Our approach to high-performance SERS substrate fabrication holds potential for further expansion to other metallic NPs like Ag, or magnetic NPs (Fe3O4).

在本文中,我们报告了一种简单而高效的方法,即通过冷等离子体和激光处理相结合的方法来快速、高性能地制造 SERS 基底。我们的分析表明,冷等离子体预处理大大降低了表面粗糙度,将 200 nm 的尖峰转变为几乎完全均匀的表面,同时通过将水接触角从 59° 降低到 0° 来增强基底的表面能,所有这一切都在 0.9 mW 等离子体处理的短短 30 秒内实现;而 15 分钟的绿色激光处理则促进了 AuNPs 在整个处理区域的更均匀沉积,从而有效地制造出 SERS 基底。综合处理的结果是,SERS 基底整个区域的拉曼强度(11 倍)和一致性都得到了增强,其可重复使用性(高达 10 倍)也得到了提高。我们通过检测阿莫西林--一种在全球范围内用于治疗多种细菌感染的抗生素--展示了这些 SERS 基底的应用,其动态线性范围扩大了 7 个等级(从 10-3 到 10-9 M),可靠性高(R2 = 0.98),检测限为 9 × 10-10 M。我们的高性能 SERS 基底制造方法具有进一步扩展到其他金属 NPs(如 Ag)或磁性 NPs(Fe3O4)的潜力。
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引用次数: 0
Targeted Polariton Flow Through Tailored Photonic Defects. 通过定制光子缺陷的定向极化子流
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-22 DOI: 10.3390/nano14211691
Elena Rozas, Yannik Brune, Ken West, Kirk W Baldwin, Loren N Pfeiffer, Jonathan Beaumariage, Hassan Alnatah, David W Snoke, Marc Aßmann

In non-Hermitian open quantum systems, such as polariton condensates, the local tailoring of gains and losses opens up an interesting possibility to realize functional optical elements. Here, we demonstrate that deliberately introducing losses via a photonic defect, realized by reducing the quality factor of a DBR mirror locally within an ultrahigh-quality microcavity, may be utilized to create directed polariton currents towards the defect. We discuss the role of polariton-polariton interactions in the process and how to tailor the effective decay time of a polariton condensate by coupling it to the defect. Our results highlight the far-reaching potential of non-Hermitian physics in polaritonics.

在极化子凝聚体等非赫米提开放量子系统中,增益和损耗的局部定制为实现功能性光学元件提供了有趣的可能性。在这里,我们展示了通过光子缺陷故意引入损耗,在超高质量微腔中局部降低 DBR 镜面的品质因数来实现,可用于产生指向缺陷的定向极化子电流。我们讨论了极化子-极化子相互作用在这一过程中的作用,以及如何通过与缺陷耦合来调整极化子凝聚态的有效衰减时间。我们的研究结果凸显了非赫米提物理学在极化中的深远潜力。
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引用次数: 0
Machine Learning as a "Catalyst" for Advancements in Carbon Nanotube Research. 机器学习是推动碳纳米管研究的 "催化剂"。
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-22 DOI: 10.3390/nano14211688
Guohai Chen, Dai-Ming Tang

The synthesis, characterization, and application of carbon nanotubes (CNTs) have long posed significant challenges due to the inherent multiple complexity nature involved in their production, processing, and analysis. Recent advancements in machine learning (ML) have provided researchers with novel and powerful tools to address these challenges. This review explores the role of ML in the field of CNT research, focusing on how ML has enhanced CNT research by (1) revolutionizing CNT synthesis through the optimization of complex multivariable systems, enabling autonomous synthesis systems, and reducing reliance on conventional trial-and-error approaches; (2) improving the accuracy and efficiency of CNT characterizations; and (3) accelerating the development of CNT applications across several fields such as electronics, composites, and biomedical fields. This review concludes by offering perspectives on the future potential of integrating ML further into CNT research, highlighting its role in driving the field forward.

由于碳纳米管(CNTs)的生产、加工和分析本身具有多重复杂性,因此其合成、表征和应用长期以来一直面临着巨大挑战。机器学习(ML)的最新进展为研究人员应对这些挑战提供了新颖而强大的工具。本综述探讨了机器学习在碳纳米管研究领域的作用,重点关注机器学习如何通过以下方式促进碳纳米管研究:(1) 通过优化复杂的多变量系统彻底改变碳纳米管合成,实现自主合成系统,减少对传统试错方法的依赖;(2) 提高碳纳米管表征的准确性和效率;(3) 加快碳纳米管在电子、复合材料和生物医学等多个领域的应用开发。本综述最后展望了将 ML 进一步融入 CNT 研究的未来潜力,强调了 ML 在推动该领域发展方面的作用。
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引用次数: 0
Flexible All-Carbon Nanoarchitecture Built from In Situ Formation of Nanoporous Graphene Within "Skeletal-Capillary" Carbon Nanotube Networks for Supercapacitors. 通过在 "骨架-毛细管 "碳纳米管网络中原位形成纳米多孔石墨烯构建柔性全碳纳米体系结构,用于超级电容器。
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-21 DOI: 10.3390/nano14201683
Tao Chen, Hongyan Li, Jiaziyi Wang, Xilai Jia

It is difficult for carbonaceous materials to combine a large specific surface area with flexibility. Here, a flexible all-carbon nanoarchitecture based on the in situ growth of nanoporous graphene within "skeletal-capillary" carbon nanotube (CNT) networks has been achieved by a chemical vapor deposition (CVD) process. Multi-path long-range conductivity is established, and the porous graphene provides a large specific surface area for charge storage. The flexibility of the films allows them to be directly used as binder-free electrodes for supercapacitors. Since the polymeric binders are saved, the supercapacitors exhibit a higher overall storage density.

碳质材料很难将大比表面积与柔性结合起来。在这里,我们通过化学气相沉积(CVD)工艺,在 "骨架-毛细管 "碳纳米管(CNT)网络中原位生长出了纳米多孔石墨烯,并在此基础上实现了柔性全碳纳米结构。多孔石墨烯为电荷存储提供了较大的比表面积。薄膜的柔韧性使其可以直接用作超级电容器的无粘结剂电极。由于省去了聚合物粘合剂,超级电容器显示出更高的整体存储密度。
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引用次数: 0
Ligands of Nanoparticles and Their Influence on the Morphologies of Nanoparticle-Based Films. 纳米粒子配体及其对纳米粒子薄膜形态的影响。
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-21 DOI: 10.3390/nano14201685
Jungwook Choi, Byung Hyo Kim

Nanoparticle-based thin films are increasingly being used in various applications. One of the key factors that determines the properties and performances of these films is the type of ligands attached to the nanoparticle surfaces. While long-chain surfactants, such as oleic acid, are commonly employed to stabilize nanoparticles and ensure high monodispersity, these ligands often hinder charge transport due to their insulating nature. Although thermal annealing can remove the long-chain ligands, the removal process often introduces defects such as cracks and voids. In contrast, the use of short-chain organic or inorganic ligands can minimize interparticle distance, improving film conductivity, though challenges such as incomplete ligand exchange and residual barriers remain. Polymeric ligands, especially block copolymers, can also be employed to create films with tailored porosity. This review discusses the effects of various ligand types on the morphology and performance of nanoparticle-based films, highlighting the trade-offs between conductivity, structural integrity, and functionality.

基于纳米粒子的薄膜正越来越多地应用于各种领域。决定这些薄膜特性和性能的关键因素之一是附着在纳米粒子表面的配体类型。虽然长链表面活性剂(如油酸)通常用于稳定纳米粒子并确保高单分散性,但由于其绝缘性,这些配体通常会阻碍电荷传输。虽然热退火可以去除长链配体,但去除过程往往会产生裂缝和空隙等缺陷。相比之下,使用短链有机或无机配体可以最大限度地减少粒子间的距离,从而提高薄膜的导电性,但配体交换不完全和残余障碍等难题依然存在。聚合物配体,尤其是嵌段共聚物,也可用于制造具有定制孔隙率的薄膜。本综述讨论了各种配体类型对基于纳米粒子的薄膜的形态和性能的影响,重点介绍了导电性、结构完整性和功能性之间的权衡。
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引用次数: 0
Phonon Drag Contribution to Thermopower for a Heated Metal Nanoisland on a Semiconductor Substrate. 半导体衬底上的受热金属纳米岛对热功率的声子拖曳贡献。
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-21 DOI: 10.3390/nano14201684
Alexander Arkhipov, Karina Trofimovich, Nikolay Arkhipov, Pavel Gabdullin

The possible contribution of phonon drag effect to the thermoelectrically sustained potential of a heated nanoisland on a semiconductor surface was estimated in a first principal consideration. We regarded electrons and phonons as interacting particles, and the interaction cross-section was derived from the basic theory of semiconductors. The solution of the equation of motion for average electrons under the simultaneous action of phonon drag and electric field gave the distributions of phonon flux, density of charge carriers and electric potential. Dimensional suppression of thermal conductance and electron-phonon interaction were accounted for but found to be less effective than expected. The developed model predicts the formation of a layer with a high density of charge carriers that is practically independent of the concentration of dopant ions. This layer can effectively intercept the phonon flow propagating from the heated nanoisland. The resulting thermoEMF can have sufficient magnitudes to explain the low-voltage electron emission capability of nanoisland films of metals and sp2-bonded carbon, previously studied by our group. The phenomenon predicted by the model can be used in thermoelectric converters with untypical parameters or in systems for local cooling.

通过第一主要考虑,估算了声子拖曳效应对半导体表面受热纳米岛的热电持续电势的可能贡献。我们将电子和声子视为相互作用的粒子,并根据半导体的基本理论推导出相互作用截面。在声子阻力和电场的同时作用下,平均电子运动方程的解给出了声子通量、载流子密度和电动势的分布。模型考虑了热导和电子-声子相互作用的尺寸抑制,但发现其效果不如预期。所建立的模型预测会形成一个电荷载流子密度很高的层,它实际上与掺杂离子的浓度无关。该层可有效拦截从加热纳米岛传播的声子流。由此产生的热电磁场足以解释我们小组之前研究的金属和 sp2 键碳纳米岛薄膜的低压电子发射能力。该模型预测的现象可用于具有非典型参数的热电转换器或局部冷却系统。
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引用次数: 0
Enhancing Charge Trapping Performance of Hafnia Thin Films Using Sequential Plasma Atomic Layer Deposition. 利用序贯等离子体原子层沉积提高哈夫纳薄膜的电荷捕获性能。
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-21 DOI: 10.3390/nano14201686
So-Won Kim, Jae-Hoon Yoo, Won-Ji Park, Chan-Hee Lee, Joung-Ho Lee, Jong-Hwan Kim, Sae-Hoon Uhm, Hee-Chul Lee

We aimed to fabricate reliable memory devices using HfO2, which is gaining attention as a charge-trapping layer material for next-generation NAND flash memory. To this end, a new atomic layer deposition process using sequential remote plasma (RP) and direct plasma (DP) was designed to create charge-trapping memory devices. Subsequently, the operational characteristics of the devices were analyzed based on the thickness ratio of thin films deposited using the sequential RP and DP processes. As the thickness of the initially RP-deposited thin film increased, the memory window and retention also increased, while the interface defect density and leakage current decreased. When the thickness of the RP-deposited thin film was 7 nm, a maximum memory window of 10.1 V was achieved at an operating voltage of ±10 V, and the interface trap density (Dit) reached a minimum value of 1.0 × 1012 eV-1cm-2. Once the RP-deposited thin film reaches a certain thickness, the ion bombardment effect from DP on the substrate is expected to decrease, improving the Si/SiO2/HfO2 interface and thereby enhancing device endurance and reliability. This study confirmed that the proposed sequential RP and DP deposition processes could resolve issues related to unstable interface layers, improve device performance, and enhance process throughput.

作为下一代 NAND 闪存的电荷捕获层材料,二氧化铪正受到越来越多的关注。为此,我们设计了一种新的原子层沉积工艺,使用顺序遥控等离子体(RP)和直接等离子体(DP)来制造电荷捕获存储器件。随后,根据使用顺序遥控等离子体和直接等离子体沉积工艺沉积的薄膜厚度比分析了器件的运行特性。随着最初 RP 沉积薄膜厚度的增加,存储器窗口和保持率也随之增加,而界面缺陷密度和漏电流则有所下降。当 RP 沉积薄膜的厚度为 7 nm 时,在 ±10 V 的工作电压下可达到 10.1 V 的最大存储窗口,界面陷阱密度 (Dit) 达到 1.0 × 1012 eV-1cm-2 的最小值。一旦 RP 沉积薄膜达到一定厚度,DP 对基底的离子轰击效应就会减弱,从而改善 Si/SiO2/HfO2 界面,进而提高器件的耐久性和可靠性。这项研究证实,建议的 RP 和 DP 顺序沉积工艺可以解决与不稳定界面层有关的问题,改善器件性能,并提高工艺吞吐量。
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引用次数: 0
On the Synthesis of Graphene Oxide/Titanium Dioxide (GO/TiO2) Nanorods and Their Application as Saturable Absorbers for Passive Q-Switched Fiber Lasers. 氧化石墨烯/二氧化钛(GO/TiO2)纳米棒的合成及其作为无源 Q 开关光纤激光器饱和吸收体的应用。
IF 4.4 3区 材料科学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-10-20 DOI: 10.3390/nano14201682
Zain Ul Abedin, Ajaz Ul Haq, Rizwan Ahmed, Tahani A Alrebdi, Ali M Alshehri, Muhammad Irfan, Haroon Asghar

We report passively Q-switched pulse operation through an erbium-doped fiber laser (EDFL) utilizing graphene oxide/titania (GO/TiO2) nanorods as a saturable absorber. The GO/TiO2 nanorods were fabricated using a Sol-gel-assisted hydrothermal method. The optical and physical characterization of the GO/TiO2 was then characterized using a field-emission-scanning electron microscope (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), and diffuses reflectance spectroscopy (DRS). To investigate the performance of the Q-switched EDFL based on the GO/TiO2 SA, the prepared nanorods were mechanically deposited on the fiber ferrule employing adhesion effects of in-dex-matching gel. This integration of the nanorod SA resulted in a self-starting Q-switching opera-tion initiated at a pump power of 17.5 mW and sustained up to 306.9 mW. When the pump range was tuned from 17.5 to 306.9 mW, the emission wavelength varied from 1564.2 to 1562.9 nm, pulse repetition rates increased from 13.87 kHz to 83.33 kHz, and pulse width decreased from 30.27 µs to 3.75 µs. Moreover, at the maximum pump power of 306.9 mW, the laser exhibited an average output power of 0.74 mW, a peak power of 1.54 mW, and a pulse energy of 8.88 nJ. Furthermore, this study investigates the GO/TiO2 damage threshold and prolonged stability of the proposed EDFL system.

我们报告了利用氧化石墨烯/二氧化钛(GO/TiO2)纳米棒作为可饱和吸收体,通过掺铒光纤激光器(EDFL)实现无源 Q 开关脉冲操作的情况。氧化石墨烯/二氧化钛纳米棒采用溶胶-凝胶辅助水热法制造。然后使用场发射扫描电子显微镜(FE-SEM)、能量色散 X 射线光谱(EDS)和漫反射光谱(DRS)对 GO/TiO2 纳米棒的光学和物理特性进行了表征。为了研究基于 GO/TiO2 SA 的 Q 开关 EDFL 的性能,利用内德克斯匹配凝胶的粘附效应,将制备的纳米棒机械沉积在光纤套圈上。纳米棒 SA 的这种集成方式可在泵功率为 17.5 mW 时启动自启动 Q 开关操作,并可持续到 306.9 mW。当泵功率范围从 17.5 mW 调整到 306.9 mW 时,发射波长从 1564.2 nm 变为 1562.9 nm,脉冲重复率从 13.87 kHz 增加到 83.33 kHz,脉冲宽度从 30.27 µs 减小到 3.75 µs。此外,在最大泵浦功率为 306.9 mW 时,激光器的平均输出功率为 0.74 mW,峰值功率为 1.54 mW,脉冲能量为 8.88 nJ。此外,本研究还探讨了 GO/TiO2 损坏阈值以及所提议的 EDFL 系统的长期稳定性。
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引用次数: 0
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