Journal of Crystal Growth最新文献_第7页

Numerical simulation of flow and mass transport in KDP crystal growth using solution alternate jetting method 利用溶液交替喷射法对 KDP 晶体生长过程中的流动和质量传输进行数值模拟

IF 1.7 4区材料科学 Q3 CRYSTALLOGRAPHY

Journal of Crystal Growth

Pub Date : 2024-11-16 DOI: 10.1016/j.jcrysgro.2024.127994

Hailin Li , Chuan Zhou , Mingwei Li

In response to the limitations of some previous crystal growth method, which cannot generate ‘back-and-forth shear flow’ in rotating-crystal method and the partial realization of ‘back-and-forth shear flow’ in the crystal two-dimensional and three-dimensional motion methods, a novel KDP crystal growth method, named solution alternate jetting method, was proposed. This method can achieve complete coverage of crystal faces with ‘back-and-forth shear flow’. Numerical simulation results indicate that solution alternate jetting method outperforms rotating-crystal growth method and crystal two-dimensional and three-dimensional motion methods in terms of time-averaged supersaturation and its standard deviation on crystal faces. The jet velocity has a significant impact on the magnitude and distribution of time-averaged supersaturation on crystal faces. Other operating conditions, including the vertical distances from the nozzle outlet to the crystal surface, alternate jetting cycle, nozzle spray angle, and special motion velocity, have a relatively minor impact. Crystals grown with less than 50% ‘back-and-forth shear flow’ in the crystal two-dimensional and three-dimensional motion methods had significantly improved quality compared to rotating-crystal growth method. Therefore, the solution alternate jetting method, capable of achieving the ideal ‘back-and-forth shear flow’, undoubtedly holds promising application prospects.

针对以往一些晶体生长方法在旋转晶体法中无法产生 "前后剪切流 "以及晶体二维和三维运动法中部分实现 "前后剪切流 "的局限性，提出了一种新型 KDP 晶体生长方法，即溶液交替喷射法。这种方法可以实现 "前后剪切流 "对晶体面的完全覆盖。数值模拟结果表明，就晶体面上的时间平均过饱和度及其标准偏差而言，溶液交替喷射法优于旋转晶体生长法以及晶体二维和三维运动法。喷射速度对晶体表面的时间平均过饱和度的大小和分布有显著影响。其他操作条件，包括喷嘴出口到晶体表面的垂直距离、交替喷射周期、喷嘴喷射角度和特殊运动速度，影响相对较小。与旋转晶体生长法相比，晶体二维和三维运动法中 "前后剪切流 "少于 50%的晶体生长质量明显提高。因此，能够实现理想 "前后剪切流 "的溶液交替喷射法无疑具有广阔的应用前景。

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引用次数: 0

Role of synthesis temperature in the formation of ZnO nanoparticles via the Sol-Gel process 合成温度在通过溶胶-凝胶工艺形成氧化锌纳米粒子中的作用

IF 1.7 4区材料科学 Q3 CRYSTALLOGRAPHY

Journal of Crystal Growth

Pub Date : 2024-11-15 DOI: 10.1016/j.jcrysgro.2024.128003

A. Modrić-Šahbazović , A. Smajlagić , Z. Sakić , M. Novaković , N. Latas , M. Popović , M. Đekić , S. Isaković , A. Salčinović Fetić

This study examines the synthesis of ZnO powder via the sol–gel method at temperatures of 25 °C and 60 °C. Characterization was conducted using standard techniques to investigate how these temperature conditions influence the physicochemical properties of the resulting material. XRD analysis confirmed high crystallinity with a pure hexagonal wurtzite structure, with average crystallite sizes of approximately 20 nm at 25 °C and 38 nm at 60 °C. Both SEM and TEM techniques established needle-like nanorods at 25 °C and nanoflower-like structures at 60 °C. Analyzing the high-resolution XPS spectra of the Zn2p and O1s photoelectron lines revealed a predominant Zn(II) state, with the contribution of ZnO increasing from 14.6 at.% to 41.6 at.% at higher temperatures. This change was accompanied by a decrease in defective oxygen and water content. Furthermore, DSC analysis revealed significant differences in thermal properties of ZnO powders synthesized at 25 °C and 60 °C, with distinct endothermic peaks around 120 °C corresponding to the evaporation of the solvent used in the synthesis process. The energy required for phase transitions was notably higher for the 25 °C synthesis, indicating greater thermal stability and energy demands compared to the 60 °C synthesis.

本研究探讨了在 25 °C 和 60 °C 温度条件下通过溶胶-凝胶法合成氧化锌粉末的过程。采用标准技术进行了表征，以研究这些温度条件如何影响所得材料的物理化学特性。XRD 分析证实，该材料具有高结晶度和纯正的六方菱镁矿结构，25 ℃ 和 60 ℃ 时的平均结晶尺寸分别约为 20 nm 和 38 nm。扫描电子显微镜（SEM）和透射电子显微镜（TEM）技术分别在 25 °C 和 60 °C 时确定了针状纳米棒和纳米花状结构。对 Zn2p 和 O1s 光电子线的高分辨率 XPS 光谱进行分析后发现，Zn(II) 状态占主导地位，在温度较高时，ZnO 的贡献率从 14.6% 增加到 41.6%。伴随这一变化的是缺陷氧和水分含量的减少。此外，DSC 分析表明，在 25 ℃ 和 60 ℃ 下合成的氧化锌粉末的热特性存在显著差异，在 120 ℃ 左右出现明显的内热峰，与合成过程中所用溶剂的蒸发相对应。与 60°C 合成相比，25°C 合成所需的相变能量明显更高，表明热稳定性和能量需求更高。

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引用次数: 0

An electronic energy model for multi-stacking faults in reducing carrier lifetime in 4H-SiC epitaxial layers 降低 4H-SiC 外延层中载流子寿命的多堆叠疵点电子能量模型

IF 1.7 4区材料科学 Q3 CRYSTALLOGRAPHY

Journal of Crystal Growth

Pub Date : 2024-11-14 DOI: 10.1016/j.jcrysgro.2024.128005

Pengxiang Hou , Pin Wang , Yifei Li , Weiliang Zhong , Yuebin Han , Jing Wang , Le Yu , Zheyang Li , Rui Jin

The effect of stacking faults (SFs) on carrier lifetime in 110 μm 4H-SiC epilayers has been studied using photoluminescence and microwave photoconductance decay. The carrier lifetimes are associated with different types of SFs. The SFs are distinguished as multi-SFs and mono-SFs in terms of their characteristic luminescence peaks. The average lifetime at multi-SFs is about 60 % of that at mono-SFs. Contrary to the quantum well models reported previously, multi-SFs decrease the minority carrier lifetime than mono-stacking faults even with shallower energy levels. A “step-structure” quantum well model is proposed to discuss the carrier dynamics for the enhanced recombination at the multi-stacking faults.

利用光致发光和微波光电导衰减研究了堆叠断层（SF）对 110 μm 4H-SiC 外延层中载流子寿命的影响。载流子寿命与不同类型的 SF 有关。根据发光峰的特征，可将 SFs 区分为多 SFs 和单 SFs。多SFs的平均寿命约为单SFs的60%。与之前报道的量子阱模型相反，即使能级较浅，多叠层阱也比单叠层阱减少了少数载流子寿命。本文提出了一种 "阶梯结构 "量子阱模型，用于讨论多堆叠断层处载流子动态重组增强的问题。

引用次数: 0

Annealing, design and long-term operation of graphite crucibles for the growth of epitaxial graphene on SiC 用于在碳化硅上生长外延石墨烯的石墨坩埚的退火、设计和长期运行

IF 1.7 4区材料科学 Q3 CRYSTALLOGRAPHY

Journal of Crystal Growth

Pub Date : 2024-11-14 DOI: 10.1016/j.jcrysgro.2024.127988

Mykhailo Shestopalov , Veronika Stará , Martin Rejhon , Jan Kunc

We describe the annealing, geometry, storage, and lifespan of graphite crucibles for the growth of epitaxial graphene on SiC. We monitor residual gas content during the annealing of the as-manufactured graphite crucible before the growth of the first graphene samples. The high-temperature evolution of carbon monoxide points towards the reaction of solid carbon and residual water. Therefore, we propose a procedure consisting of four annealing cycles to eliminate this reaction. The residual gas evolution after long-term storage of well-baked crucibles in the air shows a similar increase in water and carbon monoxide as that in unbaked crucibles. Hence, we propose the crucible storage in argon ambient. Further, we discuss the role of the crucible shape on graphene quality. Namely, we compare the cylindrical semi-closed crucible to the flat opened crucibles. The flow-aided gas exchange in the opened crucible is more beneficial for graphene growth than the diffusion-driven gas exchange in the semi-closed cylindrical crucibles. The flow-aided gas exchange leads to more efficient removal of outgassed residual contaminants, thus outperforming the advantage of increased silicon vapor pressure in the semi-closed cylindrical crucible. We also study the graphite crucible lifespan, showing that the aged crucible leads to the enhanced inhomogeneous strain in graphene.

我们介绍了用于在碳化硅上生长外延石墨烯的石墨坩埚的退火、几何形状、存储和寿命。在第一批石墨烯样品生长之前，我们对制造完成的石墨坩埚的退火过程中的残余气体含量进行了监测。一氧化碳的高温演变表明固体碳与残留水发生了反应。因此，我们提出了一个由四个退火循环组成的程序来消除这种反应。焙烧好的坩埚在空气中长期存放后，残留气体的演变表明水和一氧化碳的增加与未焙烧的坩埚相似。因此，我们建议将坩埚存放在氩气环境中。此外，我们还讨论了坩埚形状对石墨烯质量的影响。也就是说，我们将圆柱形半封闭坩埚与扁平开口坩埚进行了比较。与半封闭圆柱形坩埚中的扩散驱动型气体交换相比，开放式坩埚中的流动辅助型气体交换更有利于石墨烯的生长。流动辅助气体交换能更有效地清除排出的残留杂质，因此优于半封闭圆柱形坩埚中硅蒸汽压增加的优势。我们还对石墨坩埚的寿命进行了研究，结果表明，老化的坩埚会导致石墨烯的不均匀应变增强。

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引用次数: 0

Low-cost preparation and characterization of new CuO/ZnO and Cu3N/ZnO nanocomposites 低成本制备和表征新型 CuO/ZnO 和 Cu3N/ZnO 纳米复合材料

IF 1.7 4区材料科学 Q3 CRYSTALLOGRAPHY

Journal of Crystal Growth

Pub Date : 2024-11-14 DOI: 10.1016/j.jcrysgro.2024.128004

R. Szczęsny , P. Sędzicki , M. Trzcinski , M. Wiśniewski , A. Ścigała , B. Derkowska-Zielinska , D.H. Gregory

CuO/ZnO and Cu₃N/ZnO nanocomposites were prepared in a three-step synthesis consisting of the co-precipitation of Cu²⁺ and Zn²⁺ hydroxide carbonates (Cu/Zn-Carb) followed by their thermal treatment first in air and second in gaseous ammonia. The morphology and phase composition of the hydroxide carbonates were determined by the Cu:Zn molar ratio and the presence of polyvinylpyrrolidone (PVP) acting as a capping agent, respectively. The Cu/Zn-carbonates could be annealed in the air at 550 °C either as powders or as thin films. The latter were deposited on a silicon substrate using a choice of spin- or dip-coating techniques. The resulting CuO/ZnO samples were heated under gaseous ammonia at 300 °C in the final step of the process to form Cu₃N/ZnO nanocomposites. The fabricated samples were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) with energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), thermogravimetric − differential thermal analysis (TG-DTA) and infrared spectroscopy (IR). SEM and XRD analysis indicates that the average diameter of spherical particles was about 130 nm (CuO/ZnO) and 100 nm (Cu₃N/ZnO), composed of crystallites with 10–20 nm sizes. The thermal treatment under air and NH₃ did not affect the morphology of the composites. The implication is, therefore, that the shape and size of CuO/ZnO oxide and Cu₃N/ZnO nitride/oxide composite nanostructures are determined at the point of hydroxide carbonate coprecipitation and can be controlled during precursor synthesis. This has significant ramifications for the reproducible fabrication of nanocomposite films of precise stoichiometry and bespoke morphology.

通过三步合成法制备了 CuO/ZnO 和 Cu3N/ZnO 纳米复合材料，包括共沉淀 Cu2+ 和 Zn2+ 氢氧化碳酸盐（Cu/Zn-Carb），然后先在空气中进行热处理，再在气态氨中进行热处理。氢氧化碳酸盐的形态和相组成分别由 Cu:Zn 摩尔比和作为封端剂的聚乙烯吡咯烷酮（PVP）的存在决定。铜/锌碳酸盐可以粉末或薄膜形式在 550 °C 的空气中退火。后者可通过旋涂或浸涂技术沉积在硅基底上。在工艺的最后一步，在 300 ℃ 的气态氨下加热所得到的 CuO/ZnO 样品，以形成 Cu3N/ZnO 纳米复合材料。粉末 X 射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、能量色散 X 射线分析（EDX）、X 射线光电子能谱（XPS）、热重-差热分析（TG-DTA）和红外光谱（IR）对制备的样品进行了表征。SEM 和 XRD 分析表明，球形颗粒的平均直径约为 130 nm（CuO/ZnO）和 100 nm（Cu3N/ZnO），由 10-20 nm 大小的晶粒组成。在空气和 NH3 中进行热处理不会影响复合材料的形态。因此，这意味着 CuO/ZnO 氧化物和 Cu3N/ZnO 氮化物/氧化物复合纳米结构的形状和尺寸在碳酸氢盐共沉淀时就已确定，并可在前驱体合成过程中加以控制。这对可重复制造具有精确化学计量和定制形态的纳米复合薄膜具有重要意义。

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引用次数: 0

Thermal atomic layer deposition of Ga2O3 films using trimethylgallium and H2O 使用三甲基镓和 H2O 的热原子层沉积 Ga2O3 薄膜

IF 1.7 4区材料科学 Q3 CRYSTALLOGRAPHY

Journal of Crystal Growth

Pub Date : 2024-11-12 DOI: 10.1016/j.jcrysgro.2024.127974

Chufeng Hou , Kai Liang , Ziyu Yang , Qiang Wang , Yuefei Zhang , Fei Chen

The Atomic Layer Deposition (ALD) technique is regarded as an effective method for fabricating high-quality Ga₂O₃ thin films. Trimethyl gallium (TMG), with its high vapor pressure at room temperature (227 Torr), is widely utilized as a gallium precursor in this technique. For oxygen precursors, common choices include O₃ and O₂ plasma. However, the impact of H₂O as an oxygen precursor on Ga₂O₃ thin films during Thermal Atomic Layer Deposition (TALD) remains insufficiently explored. This study investigates the temperature window and growth characteristics of Ga₂O₃ thin films, deposited using TMG and H₂O as precursors, on sapphire substrates within the temperature range of 250–500 °C. At 250 °C, deposited Ga₂O₃ films exhibit an amorphous structure, whereas within the 300–500 °C substrate temperature range, they transition to the α-phase. The half-peak width (FWHM) narrows as the temperature increases, with characteristic peaks of the (0006) facets shifting to higher angles at 500 °C. STEM analysis reveals complete coherence between α-Ga₂O₃ films and the sapphire substrate, indicating a pseudo-crystalline structure formation. The growth rate of the films at 450 °C is 0.083 Å/cycle. Ga₂O₃ films prepared with H₂O as the oxygen precursor exhibit Ga-rich properties, with (Ga + Al)/O atomic ratios between 0.88 and 0.91 across the 250–500 °C temperature range. The films’ roughness (Ra) ranges from 0.453 to 0.646 nm. Island-like particles form on the film surface within the 400–500 °C range, smoothing out as the temperature rises. The film’s band gap peaks at 5.50 eV at 450 °C. The reaction of TMG with H₂O on sapphire substrates yields Ga₂O₃ films and CH₄ by-products, akin to the trimethylaluminum process.

原子层沉积（ALD）技术被认为是制造高质量 Ga2O3 薄膜的有效方法。三甲基镓（TMG）在室温下具有很高的蒸气压（227 托），被广泛用作该技术中的镓前驱体。对于氧前驱体，常见的选择包括 O3 和 O2 等离子体。然而，在热原子层沉积（TALD）过程中，H2O 作为氧前驱体对 Ga2O3 薄膜的影响仍未得到充分探讨。本研究调查了以 TMG 和 H2O 为前驱体在蓝宝石基底上沉积的 Ga2O3 薄膜在 250-500 °C 温度范围内的温度窗口和生长特性。在 250 ℃ 时，沉积的 Ga2O3 薄膜呈现无定形结构，而在 300 ℃ 至 500 ℃ 的基底温度范围内，它们过渡到 α 相。半峰宽（FWHM）随着温度的升高而变窄，在 500 ℃ 时，(0006) 面的特征峰向更高的角度移动。STEM 分析表明，α-Ga2O3 薄膜与蓝宝石基底之间具有完全的一致性，表明形成了假晶结构。450 °C 时薄膜的生长速率为 0.083 Å/周期。用 H2O 作为氧前驱体制备的 Ga2O3 薄膜具有富镓特性，在 250 ℃ 至 500 ℃ 的温度范围内，（Ga + Al）/O 原子比介于 0.88 和 0.91 之间。薄膜的粗糙度（Ra）在 0.453 至 0.646 nm 之间。在 400-500 °C 温度范围内，薄膜表面形成岛状颗粒，随着温度的升高，颗粒变得平滑。薄膜的带隙在 450 °C 时达到峰值 5.50 eV。TMG 与蓝宝石衬底上的 H2O 反应会产生 Ga2O3 薄膜和 CH4 副产品，这与三甲基铝过程类似。

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引用次数: 0

Doping behavior and occurrence state of Na impurity in α-calcium sulfate hemihydrate prepared in Na2SO4 solution 在 Na2SO4 溶液中制备的α-半水硫酸钙中 Na 杂质的掺杂行为和发生状态

IF 1.7 4区材料科学 Q3 CRYSTALLOGRAPHY

Journal of Crystal Growth

Pub Date : 2024-11-10 DOI: 10.1016/j.jcrysgro.2024.127993

Lusong Wang , Xianbo Li , Yuqi He , Hu Huang , Yawen Du

α-calcium sulfate hemihydrate (α-CSH) is a green building material. The synthesis of α-CSH from industrial phosphogypsum (PG) in Na₂SO₄ solution is a promising technique, but Na impurity may be introduced into α-CSH crystal. In this study, the doping behavior of Na into α-CSH was investigated, and the occurrence state of Na in α-CSH was clarified. The results show that Na impurity was doped into α-CSH in the form of Na₂Ca₅(SO₄)₂·3H₂O, and the doping content of Na₂O in α-CSH increases with the Na₂SO₄ concentration and reaction time. Density functional theory (DFT) calculation shows Na impurity is likely to be doped into α-CSH crystal through interstitial filling. Unfortunately, the doping of Na into α-CSH could cause a visible frost phenomenon for the hardened plaster, which has a negative impact on the practical utilization of α-CSH.

半水硫酸钙（α-CSH）是一种绿色建材。以工业磷石膏（PG）为原料在 Na2SO4 溶液中合成 α-CSH 是一种很有前景的技术，但 Na 杂质可能会引入 α-CSH 晶体中。本研究考察了 Na 在 α-CSH 中的掺杂行为，并阐明了 Na 在 α-CSH 中的出现状态。结果表明，Na杂质以Na2Ca5(SO4)2-3H2O的形式掺入α-CSH中，且α-CSH中Na2O的掺入量随Na2SO4浓度和反应时间的增加而增加。密度泛函理论（DFT）计算表明，Na 杂质很可能是通过间隙填充掺杂到 α-CSH 晶体中的。遗憾的是，Na 在 α-CSH 中的掺杂会导致硬化石膏出现明显的结霜现象，这对α-CSH 的实际应用产生了负面影响。

引用次数: 0

Correlation of interface structure and optical properties of Ga(N,As) and Ga(As,Bi) based type-II hetero structures 基于 Ga(N,As)和 Ga(As,Bi)的 II 型异质结构的界面结构与光学特性的相关性

IF 1.7 4区材料科学 Q3 CRYSTALLOGRAPHY

Journal of Crystal Growth

Pub Date : 2024-11-09 DOI: 10.1016/j.jcrysgro.2024.127976

Thilo Hepp, Saleh Firoozabadi, Robin Günkel, Varun Chejarla, Oliver Maßmeyer, Andreas Beyer, Kerstin Volz

The type-II band alignment of particular III/V heterostructures is a promising route towards achieving certain wavelengths on specific substrates, which would not be possible with type-I structures. One example is telecommunication lasers on GaAs substrates. This study reports on the progress in combining dilute nitrides and dilute bismides in W-type hetero structures to improve the luminescence intensity, which is a fundamental prerequisite for future incorporation in a laser structure. Increasing the emission wavelength of these structures is challenging and the interface formation is critical, especially as two metastable materials are combined. Here, we investigate the impact of different interface configurations by growing Ga(N,As)/Ga(As,Bi) and Ga(As,Bi)/Ga(N,As) type-II structures. We employ metal–organic vapor phase epitaxy (MOVPE) to grow Ga(N,As) and Ga(As,Bi) layers and investigate the effects of interlayer thicknesses on the structural and optical properties of the hetero structures. The results indicate that − while the introduction of a GaAs interlayer can affect the direct and indirect transitions intensities − it does not significantly improve the interface quality. However, this is strongly influenced by the order in which the materials are grown. The growth of Ga(N,As) on Ga(As,Bi) shows no peculiarities, while the type II transition energy is shifted to lower energies when Ga(As,Bi) is grown on Ga(N,As). High-resolution X-ray diffraction (HR-XRD), photoluminescence (PL) spectroscopy, atomic force microscopy (AFM), and scanning transmission electron microscopy (STEM) were used to characterize the samples.

特定 III/V 异质结构的 II 型波段排列是在特定衬底上实现特定波长的一条大有可为的途径，而 I 型结构则无法实现这一点。其中一个例子就是砷化镓衬底上的电信激光器。本研究报告介绍了在 W 型异质结构中结合稀氮化物和稀双质化物以提高发光强度方面的进展，这是未来将其纳入激光结构的基本前提。提高这些结构的发射波长具有挑战性，而界面的形成至关重要，尤其是当两种瞬变材料结合在一起时。在此，我们通过生长 Ga（N，As）/Ga（As，Bi）和 Ga（As，Bi）/Ga（N，As）II 型结构来研究不同界面配置的影响。我们采用金属有机气相外延 (MOVPE) 技术生长 Ga(N,As) 和 Ga(As,Bi) 层，并研究了层间厚度对异质结构的结构和光学特性的影响。结果表明，虽然引入砷化镓中间层会影响直接和间接跃迁强度，但并不会显著改善界面质量。然而，这在很大程度上受到材料生长顺序的影响。在 Ga（As,Bi）上生长 Ga（N,As）没有显示出特殊性，而在 Ga（N,As）上生长 Ga（As,Bi）时，II 型跃迁能量会向低能量方向移动。高分辨率 X 射线衍射 (HR-XRD)、光致发光 (PL) 光谱、原子力显微镜 (AFM) 和扫描透射电子显微镜 (STEM) 被用来表征样品。

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引用次数: 0

Quantum chemical study of trimethylindium and trimethylgallium gas-phase reaction pathways in InGaN MOCVD growth 对 InGaN MOCVD 生长过程中三甲基铟和三甲基镓气相反应途径的量子化学研究

IF 1.7 4区材料科学 Q3 CRYSTALLOGRAPHY

Journal of Crystal Growth

Pub Date : 2024-11-07 DOI: 10.1016/j.jcrysgro.2024.127992

Zhigang Lu , Jianfeng Pan , Hong Zhang , Chao Jiang , Wenming Yang

Density functional theory was used to analyze the formation of InGaN from trimethylindium (TMIn) and trimethylgallium (TMGa) by metalorganic chemical vapor deposition in ammonia in terms of the reaction between trimethyl compounds and NH₃, as well as the subsequent reactions of the key amino species DMInNH₂. The calculation model is established in GAUSSIAN 09, and the results obtained by the calculation model are proved to be reliable by comparing with the previous research results. Reaction pathways were assumed and the Gibbs free energy and activation free energy calculation were conducted at different temperatures. TMIn and TMGa can undergo adduct reactions with the first NH₃ molecule at reaction temperatures below 596 K and 465 K, respectively, but they cannot further react with the second NH₃ molecule to form additional products. The temperature range for adduct reactions between TMIn and NH₃ is wider compared to TMGa and NH₃. In the absence of H radicals in the reaction chamber, DMInNH₂ does not undergo spontaneous CH₃ radical elimination reactions or CH₄ elimination reactions. Instead, DMInNH₂ is more inclined to undergo dimerization reactions and CH₄ elimination reactions with NH₃, leading to the formation of subsequent products, In(NH₂)₃ and dimers. However, in the presence of H radicals in the reaction chamber, H radicals can facilitate the CH₃ radical elimination reaction of DMInNH₂ and also promote the NH₂ radical elimination reaction of In(NH₂)_3, In(NH₂)₂ and InNH₂, enabling these reactions to occur spontaneously within the studied temperature range. Consequently, the subsequent products of DMInNH₂ become indium atoms and dimers.

采用密度泛函理论分析了三甲基铟（TMIn）和三甲基镓（TMGa）在氨中通过金属有机化学气相沉积形成 InGaN 的过程中，三甲基化合物与 NH3 的反应以及关键氨基 DMInNH2 的后续反应。计算模型是在 GAUSSIAN 09 中建立的，通过与前人的研究成果进行比较，证明了计算模型得到的结果是可靠的。假设了反应路径，并在不同温度下进行了吉布斯自由能和活化自由能计算。在低于 596 K 和 465 K 的反应温度下，TMIn 和 TMGa 可分别与第一个 NH3 分子发生加成反应，但它们不能与第二个 NH3 分子进一步反应生成额外的产物。与 TMGa 和 NH3 相比，TMIn 和 NH3 之间发生加成反应的温度范围更广。在反应室中没有 H 自由基的情况下，DMInNH2 不会发生自发的 CH3 自由基消除反应或 CH4 消除反应。相反，DMInNH2 更倾向于与 NH3 发生二聚化反应和 CH4 消去反应，从而形成后续产物 In(NH2)3 和二聚物。然而，如果反应室中存在 H 自由基，H 自由基会促进 DMINH2 的 CH3 自由基消除反应，也会促进 In(NH2)3、In(NH2)2 和 InNH2 的 NH2 自由基消除反应，从而使这些反应在研究的温度范围内自发发生。因此，DMInNH2 的后续产物变成了铟原子和二聚体。

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引用次数: 0

Characterization and mid-infrared laser operation in Er:CaF2 single crystal fiber grown by the laser heated pedestal growth method 用激光加热基座生长法生长的 Er:CaF2 单晶光纤的特性和中红外激光器工作原理

IF 1.7 4区材料科学 Q3 CRYSTALLOGRAPHY

Journal of Crystal Growth

Pub Date : 2024-11-06 DOI: 10.1016/j.jcrysgro.2024.127991

Xu Wu, Zhen Zhang, Yunfei Wang, Shaochen Liu, Zhonghan Zhang, Liangbi Su, Anhua Wu

Er:CaF₂ crystal, characterized by low doping and high efficiency, is a suitable material for single-crystal fiber (SCF). 3 at.% Er:CaF₂ SCFs were grown using the laser heated pedestal growth (LHPG) method. Significant oxidation-induced whitening phenomena were observed during growth. Increasing the growth rate helped mitigate further deterioration due to oxidation. This is likely because higher growth speeds allow the SCF to quickly move away from temperature ranges conducive to oxidation. As oxidation progressed, the phonon energy of 3 at.% Er:CaF₂ SCF increased, causing the emission intensity at ∼ 1 μm to decrease from 77 % in the initial source rod to 6 % in the fully whitened state. Additionally, the lifetime of the ⁴I_11/2 level decreased by approximately 10 times, from 8.988 ms to 0.822 ms. Continuous laser output at ∼ 2.8 μm was achieved using the transparent portion of 3 at.% Er:CaF₂ SCF. With an output mirror transmission of 2 %, a maximum output power of 251 mW and a slope efficiency of 15.9 % were obtained. The laser experiment demonstrated the potential application of LHPG-grown Er:CaF₂ SCF in ∼ 2.8 μm lasers, but further performance enhancement requires additional strategies to address oxidation issues. This work provides valuable insights into the growth of Er:CaF₂ SCF using the LHPG method.

Er:CaF2 晶体具有低掺杂和高效率的特点，是一种适用于单晶光纤（SCF）的材料。利用激光加热基座生长（LHPG）法生长出了 3 at.% 的 Er:CaF2 SCF。在生长过程中观察到了明显的氧化引起的白化现象。提高生长速度有助于缓解氧化引起的进一步恶化。这可能是因为较高的生长速度能使 SCF 快速脱离有利于氧化的温度范围。随着氧化的进行，3 at.% Er:CaF2 SCF 的声子能量增加，导致 1 μm 处的发射强度从初始源棒的 77% 下降到完全白化状态的 6%。此外，4I11/2 水平的寿命降低了约 10 倍，从 8.988 毫秒降至 0.822 毫秒。利用 3 at.% Er:CaF2 SCF 的透明部分实现了 ∼ 2.8 μm 的连续激光输出。输出镜透射率为 2%，最大输出功率为 251 mW，斜率效率为 15.9%。该激光实验证明了 LHPG 生长的 Er:CaF2 SCF 在 2.8 μm ∼ 激光器中的潜在应用，但要进一步提高性能，还需要采取其他策略来解决氧化问题。这项工作为使用 LHPG 方法生长 Er:CaF2 SCF 提供了宝贵的见解。

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