Journal of Non-crystalline Solids最新文献_第4页

Incorporation mechanisms of niobium into lithium borate glasses: Insights from solid state nuclear magnetic resonance and Raman spectroscopy 铌在硼酸锂玻璃中的掺入机制：来自固态核磁共振和拉曼光谱的见解

IF 3.5 3区材料科学 Q1 MATERIALS SCIENCE, CERAMICS

Journal of Non-crystalline Solids

Pub Date : 2025-12-30 DOI: 10.1016/j.jnoncrysol.2025.123912

Rafaella Bartz Pena , Henrik Bradtmüller , Laureano Ensuncho , Marcos De Oliveira Jr. , Hellmut Eckert

The scientific and technological interest in niobium-bearing materials has significantly increased in recent years. Still, reports on the structural details about the short- and medium-range order of the intermediate oxide Nb₂O₅ in glasses are quite scarce. In this work, the structural mechanisms underlying the incorporation of niobium oxide into lithium metaborate glass spanning concentrations up to ∼25 mol % are investigated through standard and advanced solid-state nuclear magnetic resonance and Raman spectroscopies. The commonly encountered NbO₆ distorted octahedral coordination occurs across the entire range of concentrations. With increasing niobia content, systematic changes in the speciation of the three-coordinated boron units are observed, revealing a progressive increase in the concentration of

B O_{3 / 2}

trigonal sites at the expense of anionic

B O_{2 / 2} O^{-}

groups. Furthermore, heteronuclear dipolar ⁷Li–⁹³Nb, and unprecedented ¹¹B^(III)–⁹³Nb and ¹¹B^(IV)–⁹³Nb recoupling experiments reveal an increase in all of the dipolar interaction strengths, reflecting the formation of B-O-Nb connectivities with increasing Nb₂O₅ content.. Above 10 mol % Nb₂O₅, the Raman spectra suggest the onset of niobium-oxide clustering. Altogether, these results suggest that niobium acts as a network former in alkali borate glasses, which is in consonance with the structural role reported for Nb₂O₅ in alkali silicate and phosphate glasses.

近年来，人们对含铌材料的科技兴趣显著增加。然而，关于玻璃中中间体氧化物Nb2O5的中短程序结构细节的报道却很少。在这项工作中，通过标准和先进的固态核磁共振和拉曼光谱研究了氧化铌掺入浓度高达25 mol %的偏酸锂玻璃中的结构机制。常见的NbO6畸变八面体配位发生在整个浓度范围内。随着铌含量的增加，观察到三配位硼单元形态的系统性变化，揭示了BO3/2三角位的浓度逐渐增加，而阴离子bo2 / 20 -基团的浓度则逐渐增加。此外，异核偶极7Li-93Nb，以及前所未有的11B(III) -93Nb和11B(IV) -93Nb偶极耦合实验表明，随着Nb2O5含量的增加，所有的偶极相互作用强度都增加了，这反映了B-O-Nb连接的形成。当Nb2O5浓度超过10 mol %时，拉曼光谱表明氧化铌团簇的开始。综上所述，这些结果表明铌在碱硼酸盐玻璃中作为网络形成物，这与Nb2O5在碱硅酸盐和磷酸盐玻璃中的结构作用一致。

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引用次数: 0

Glass transition temperatures and mass densities of binary vanadate glasses in the context of the structural characteristics 玻璃化转变温度和质量密度对二元钒酸盐玻璃结构特性的影响

IF 3.5 3区材料科学 Q1 MATERIALS SCIENCE, CERAMICS

Journal of Non-crystalline Solids

Pub Date : 2025-12-30 DOI: 10.1016/j.jnoncrysol.2025.123933

Uwe Hoppe , Wyatt Urbanek , Joshua Yi , Öykü Barlin , Doruk Doğular , Steve A. Feller

Glass transition temperatures (T_g) and mass densities (ρ) for binary alkali and alkaline earth vanadate glasses—determined in this study or reported in a previous paper—are discussed to clarify the structural reasons for the property changes. A notable difference exists between the continuous increase in T_g for alkaline earth modifiers (MO) and the T_g minima observed for alkali modifiers (A₂O). Densities are analyzed based on the packing fraction, ρ_P. A uniform trend in ρ_P is characteristic of glasses containing A₂O. In contrast, the ρ_P values for each MO addition show specific behavior. Starting from vitreous V₂O₅, which contains about 50 % VO₅ pyramids, the modifier cations A⁺ and M²⁺ are proposed to coordinate terminal and bridging oxygen atoms differently. At glasses approaching 50 mol% V₂O₅, the need for charge balance and spatial accommodation of the modifier cations results in solely VO₄ chain units, regardless of whether the modifiers are alkali or alkaline earth oxides.

本文讨论了二元碱土和碱土钒酸盐玻璃的玻璃化转变温度（Tg）和质量密度（ρ），以澄清性质变化的结构原因。碱土改性剂（MO） Tg的持续升高与碱土改性剂（A2O） Tg的最小值存在显著差异。密度根据填料分数ρP进行分析。含A2O玻璃的ρP呈均匀趋势。相反，各MO加入的ρP值表现出特定的行为。从含有约50% VO5金字塔的玻璃体V2O5出发，提出了A+和M2+改性剂对末端氧原子和桥接氧原子进行不同的配位。在接近50 mol% V2O5的玻璃中，无论改性剂是碱氧化物还是碱土氧化物，都需要电荷平衡和改性剂阳离子的空间调节，从而只得到VO4链单元。

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引用次数: 0

Increasing Tc retention during nuclear waste vitrification: Structural and phase change analysis of Al-source behavior by 27Al MAS NMR 在核废料玻璃化过程中增加Tc保留：用27Al MAS NMR分析al源行为的结构和相变化

IF 3.5 3区材料科学 Q1 MATERIALS SCIENCE, CERAMICS

Journal of Non-crystalline Solids

Pub Date : 2025-12-29 DOI: 10.1016/j.jnoncrysol.2025.123926

Laura Löwy , Martina Urbanová , Matouš Eret , Jaroslav Kloužek , Petra Cincibusová , Miroslava Vernerová , Pavel Hrma , Albert A. Kruger , Ivana Sedenkova , Jiri Brus , Richard Pokorný

Efficient immobilization of volatile technetium (Tc) remains a key challenge during vitrification of low-activity nuclear waste (LAW). This study explores how different aluminum sources—kyanite, gibbsite, and boehmite—affect structural transformations in heated LAW melter feeds and influence the retention of rhenium (Re), a non-radioactive chemical surrogate for Tc. To investigate the decomposition of Al precursors and to track the formation of transient aluminum phases upon heating, we applied temperature-resolved ²⁷Al MAS NMR spectroscopy combined with principal component-based factor analysis (FA), complemented by X-ray diffraction. This FA approach, previously unexplored in nuclear waste vitrification studies, enabled precise identification and tracking of transient nanocrystalline alumina intermediates and their coordination environments formed between 400 and 900 °C. Boehmite-containing feed produced the highest proportion of ordered nanocrystalline alumina phases, followed by gibbsite, while kyanite remained undissolved to high temperature. The higher abundance of reactive Al-sites in the boehmite- and gibbsite-containing feeds correlates with improved Re retention in the glass, likely through enhanced adsorption of Re-bearing salts and/or their incorporation into transient sodalite-like aluminosilicates. Our findings not only highlight the crucial impact of Al-source selection to control intermediate phase formation and to facilitate early-stage incorporation and immobilization of volatile radionuclides, but also establish factor analysis of NMR spectra as a powerful methodology for understanding of structural and chemical transformations during vitrification.

在低活度核废料（LAW）的玻璃化过程中，挥发性锝（Tc）的有效固定化仍然是一个关键挑战。本研究探讨了不同的铝源——蓝晶石、三水铝石和薄铝石——如何影响加热法熔体进料中的结构转变，并影响铼（Re）的保留，铼是Tc的非放射性化学替代品。为了研究Al前驱体的分解并跟踪加热后瞬态铝相的形成，我们应用了温度分辨27Al MAS NMR结合主成分因子分析（FA），并辅以x射线衍射。这种FA方法以前未在核废料玻璃化研究中探索过，能够精确识别和跟踪瞬态纳米晶氧化铝中间体及其在400至900°C之间形成的配位环境。含勃水铝石的饲料产生的有序纳米晶氧化铝相比例最高，其次是三水铝石，而蓝晶石在高温下仍不溶解。在含薄水铝石和三水铝石的原料中，活性铝位点的丰度较高，这与玻璃中稀土的保留率提高有关，可能是通过增强含稀土盐的吸附和/或它们与瞬态钠石样铝硅酸盐的结合。我们的研究结果不仅强调了al源选择对控制中间相形成和促进挥发性放射性核素早期合并和固定化的重要影响，而且还建立了核磁共振波谱因子分析作为了解玻璃化过程中结构和化学转变的有力方法。

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引用次数: 0

Trace Ag addition promotes exceptional soft magnetic properties in Fe-based nanocrystalline alloys under low heating rates annealing 微量银的加入促进了铁基纳米晶合金在低加热速率退火下优异的软磁性能

IF 3.5 3区材料科学 Q1 MATERIALS SCIENCE, CERAMICS

Journal of Non-crystalline Solids

Pub Date : 2025-12-29 DOI: 10.1016/j.jnoncrysol.2025.123934

Yaocen Wang , Yan Zhang

This article reports a unique discovery that trace addition of Ag can significantly promote nano-crystallization in Fe-based amorphous alloys during annealing, which enables excellent soft magnetic properties to be achieved under low heating rates, a condition typically challenging for such materials. The designed Fe₈₂.₆B₁₅P₁Cu₁.₃Ag₀.₁ nanocrystalline alloy exhibits outstanding soft magnetic performance of 6.5 A/m in H_c and 1.85 T in B_s at a heating rate of 10 K/min. Notably, it maintains a low H_c of 8.0 A/m and a high B_s of 1.80 T even at an exceptionally slow heating rate of 0.5 K/min, highlighting its exceptional industrial manufacturability. This effect can be attributed mainly to two factors: the large positive H_mix of Fe-Ag causes segregation and local enrichment of Fe that further promots α-Fe nucleation in addition to the effect of 1.3 at.% Cu addition, and the bonding preference of Ag-metalloid along with reduction of necessary annealing temperature suppress rapid grain growth by retard the diffusion of certain metalloid atoms. Based on this understanding, by optimizing the Fe-B-P-Cu-Ag alloy system and searching for other Fe-repelling elements including those insoluble with Fe, our finding reveals a new compositional design strategy for developing high-performance Fe-based nanocrystalline alloys that combine low H_c, high B_s, and excellent industrial processability.

本文报道了一个独特的发现，微量添加Ag可以显著促进铁基非晶合金在退火过程中的纳米结晶，这使得在低加热速率下获得优异的软磁性能，这是这类材料通常具有挑战性的条件。设计的Fe₈₂.₆B₁₅P₁Cu₁.₃Ag₀。当升温速率为10 K/min时，1₁纳米晶合金表现出优异的软磁性能，Hc为6.5 A/m， Bs为1.85 T。值得注意的是，即使在异常缓慢的0.5 K/min加热速率下，它也保持了8.0 a /m的低Hc和1.80 T的高Bs，突出了其卓越的工业可制造性。这种影响主要归因于两个因素：Fe- ag的大量正Hmix导致Fe的偏析和局部富集，进一步促进α-Fe成核。% Cu的加入和ag -类金属的键合偏好以及所需退火温度的降低通过延缓某些类金属原子的扩散来抑制晶粒的快速生长。在此基础上，通过对Fe-b -p - cu - ag合金体系的优化，以及寻找不溶于铁的其他拒铁元素，我们的发现揭示了一种新的成分设计策略，可以开发出具有低Hc、高Bs和优异工业加工性能的高性能铁基纳米晶合金。

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引用次数: 0

Phase fluctuation in non-crystalline polymer 非结晶聚合物的相波动

IF 3.5 3区材料科学 Q1 MATERIALS SCIENCE, CERAMICS

Journal of Non-crystalline Solids

Pub Date : 2025-12-29 DOI: 10.1016/j.jnoncrysol.2025.123901

Thomas Juska

Non-crystalline polymer is described as a heterogenous network of cells that fluctuate between the bonded and unbonded condition. Energy fluctuations occur in all substances, but have no effect on crystalline solids due to their large-scale homogeneity. In contrast, they have a profound effect on non-crystalline substances because the regions of homogeneity, termed “cells” in this paper, are nanoscale. Due to the small size of the cells, the variation between the mean and fluctuating values of energy is comparable to their van der Waals bond energy. As a result, each cell fluctuates between the glassy and elastomeric state. The period of phase fluctuation, designated τ, varies from cell to cell. The values of τ increase with a decrease in temperature, causing the glass transition. Einstein developed the physics of thermodynamic fluctuations to explain the density fluctuations that cause critical opalescence. We use Einstein’s theoretical framework to determine the probability (W) of a phase fluctuation in non-crystalline solid. The energy fluctuations are modeled as mechanical strains imposed on individual cells due to motion of neighboring cells. The probability that a strain is large enough to cause a phase fluctuation is expressed W = 1/τ

\propto

exp(-ΔN^1c/kT), where ΔN^1c is the critical fluctuation in cell energy.

非结晶聚合物被描述为在键合和非键合状态之间波动的异质细胞网络。能量波动发生在所有物质中，但由于晶体固体的大规模均匀性，对其没有影响。相比之下，它们对非晶体物质有深远的影响，因为均匀的区域，在本文中被称为“细胞”，是纳米级的。由于细胞的尺寸小，能量的平均值和波动值之间的变化与它们的范德华键能相当。因此，每个细胞在玻璃态和弹性体态之间波动。相位波动的周期，称为τ，因细胞而异。τ值随温度的降低而增大，引起玻璃化转变。爱因斯坦发展了热力学涨落物理学来解释引起临界乳光的密度涨落。我们使用爱因斯坦的理论框架来确定非结晶固体中相位波动的概率(W)。能量波动被建模为由于相邻细胞的运动而施加在单个细胞上的机械应变。应变大到足以引起相位涨落的概率表示为W = 1/τ∝exp(-ΔN1c/kT)，其中ΔN1c为细胞能量的临界涨落。

{"title":"Phase fluctuation in non-crystalline polymer","authors":"Thomas Juska","doi":"10.1016/j.jnoncrysol.2025.123901","DOIUrl":"10.1016/j.jnoncrysol.2025.123901","url":null,"abstract":"<div><div>Non-crystalline polymer is described as a heterogenous network of cells that fluctuate between the bonded and unbonded condition. Energy fluctuations occur in all substances, but have no effect on crystalline solids due to their large-scale homogeneity. In contrast, they have a profound effect on non-crystalline substances because the regions of homogeneity, termed “cells” in this paper, are nanoscale. Due to the small size of the cells, the variation between the mean and fluctuating values of energy is comparable to their van der Waals bond energy. As a result, each cell fluctuates between the glassy and elastomeric state. The period of phase fluctuation, designated τ, varies from cell to cell. The values of τ increase with a decrease in temperature, causing the glass transition. Einstein developed the physics of thermodynamic fluctuations to explain the density fluctuations that cause critical opalescence. We use Einstein’s theoretical framework to determine the probability (W) of a phase fluctuation in non-crystalline solid. The energy fluctuations are modeled as mechanical strains imposed on individual cells due to motion of neighboring cells. The probability that a strain is large enough to cause a phase fluctuation is expressed <em>W</em> = 1/τ <span><math><mo>∝</mo></math></span> exp(-ΔN<sup>1c</sup>/kT), where ΔN<sup>1c</sup> is the critical fluctuation in cell energy.</div></div>","PeriodicalId":16461,"journal":{"name":"Journal of Non-crystalline Solids","volume":"674 ","pages":"Article 123901"},"PeriodicalIF":3.5,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880771","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Broadband ∼2 μm emissions of Tm3+/Ho3+ co-doped fluorozirconate glasses Tm3+/Ho3+共掺杂氟锆酸盐玻璃的宽带~ 2 μm发射

IF 3.5 3区材料科学 Q1 MATERIALS SCIENCE, CERAMICS

Journal of Non-crystalline Solids

Pub Date : 2025-12-27 DOI: 10.1016/j.jnoncrysol.2025.123927

Zeming Tan , Longfei Zhang , Zihua Guo , Hongxing Dong , Yiguang Jiang , Long Zhang

Herein, 50ZrF₄–33BaF₂–6YF₃–4LaF₃–7AlF₃ (ZBYLA) glass, demonstrating remarkable thermal and chemical stability, is successfully designed and fabricated by modifying 50ZrF₄–33BaF₂–10YF₃–7AlF₃ (ZBYA) glass composition through La³⁺ doping. Differential thermal analyses and immersion tests reveal that the ZBYLA glass possesses a crystallization resistance superior to that of the ZBYA glass (ΔT = 79 °C). Moreover, following 18 h of immersion, the ZBYLA glass exhibits significantly lower mass loss and reduced mid-infrared transmission loss; these results collectively confirm its enhanced stability. Furthermore, when co-doped with 4 mol% Tm³⁺ and 0.2 mol% Ho³⁺, the ZBYLA glass yields a ∼2 μm emission peak with the highest fluorescence intensity and broadest full width at half maximum of 421 nm, along with the longest Tm³⁺ fluorescence lifetime (τ_Tm = 5.18 ms) observed for this system. Finally, the mechanism of energy transfer (ET) between Tm³⁺ and Ho³⁺ is investigated, and a forward ET parameter significantly larger than the reverse parameter is revealed, which confirms the high efficiency of ET from Tm³⁺ to Ho³⁺. Overall, these findings indicate that the considerably high Tm³⁺/Ho³⁺ ratio in ZBYLA glass is advantageous for broadening the ∼2 μm emission and simultaneously enhancing its intensity. This positions Tm³⁺/Ho³⁺ co-doped ZBYLA glass as a highly promising candidate for application in tunable lasers and broadband amplifiers in the ∼2 μm band.

本文通过La³+掺杂对50ZrF₄-33BaF₂-10YF₃-7AlF3 （ZBYA）玻璃成分进行修饰，成功设计并制备了具有良好热稳定性和化学稳定性的50ZrF₄-33BaF₂-6YF₃-7AlF3 （ZBYA）玻璃。差热分析和浸渍试验表明，ZBYLA玻璃具有优于ZBYA玻璃的抗结晶性（ΔT = 79°C）。此外，浸泡18 h后，ZBYLA玻璃的质量损失和中红外透射损失显著降低；这些结果共同证实了其增强的稳定性。此外，当共掺杂4 mol% Tm³+和0.2 mol% Ho³+时，ZBYLA玻璃产生了约2 μm的发射峰，荧光强度最高，半峰宽度最宽，为421 nm，并且该体系中观察到最长的Tm³+荧光寿命（τTm = 5.18 ms）。最后，对Tm +和Ho +之间的能量传递（ET）机理进行了研究，发现正向ET参数明显大于反向ET参数，证实了Tm +向Ho +的高效ET。总的来说，这些发现表明ZBYLA玻璃中相当高的Tm³+ /Ho³+比有利于拓宽~ 2 μm发射，同时增强其强度。这使得Tm³+ /Ho³+共掺杂ZBYLA玻璃成为一种非常有前途的候选材料，可用于~ 2 μm波段的可调谐激光器和宽带放大器。

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引用次数: 0

Tunable amorphous Ge quantum dot networks in SiC & Si₃N₄ for broad-spectrum photoelectric devices 用于广谱光电器件的SiC & Si₃N₄可调谐无定形Ge量子点网络

IF 3.5 3区材料科学 Q1 MATERIALS SCIENCE, CERAMICS

Journal of Non-crystalline Solids

Pub Date : 2025-12-27 DOI: 10.1016/j.jnoncrysol.2025.123930

Gabrijela Svalina , Martina Mumelaš Petričević , Ivana Periša , Marija Tkalčević , Krešimir Salamon , Peter Nadazdy , Peter Siffalovic , Maja Mičetić

Highly efficient broadband photo-electric devices require materials with tunable photoelectric properties and scalable, low complexity fabrication routes. In this work, we demonstrate thin films comprising three-dimensional, self-assembled networks of amorphous germanium quantum dots (Ge QDs) embedded in amorphous silicon carbide (SiC) and silicon nitride (Si₃N₄) matrices on p-type Si substrates. All materials are produced by single-step magnetron sputtering process without any substrate pre-treatment, lithography, or post-growth modification. By systematically varying QD size and matrix composition, we reveal how quantum confinement and host material jointly determine photoresponse. Both matrices exhibit size-dependent confinement effects in the embedded QDs, with smaller QDs providing higher responsivity and broader spectral coverage. The matrix type strongly influences current–voltage characteristics, while dark current decreases with reducing QD size. Despite their fully amorphous structure and simple fabrication, the devices achieve external quantum efficiencies up to∼60 %, detectivities of 3 × 10¹¹ Jones, and sensitivities near 9 × 10³ at room temperature across 315–1100 nm. These findings establish tunable amorphous Ge QD networks in oxygen-free matrices as cost-effective, high-performance platforms for broadband photosensitive devices.

高效的宽带光电器件要求材料具有可调谐的光电特性和可扩展的、低复杂性的制造路线。在这项工作中，我们展示了在p型Si衬底上嵌入非晶碳化硅（SiC）和氮化硅（Si₃N₄）矩阵的非晶锗量子点（Ge QDs）的三维自组装网络薄膜。所有材料均采用单步磁控溅射工艺生产，无需衬底预处理、光刻或生长后修饰。通过系统地改变量子点大小和矩阵组成，我们揭示了量子约束和宿主材料如何共同决定光响应。这两种矩阵在嵌入的量子点中都表现出尺寸依赖的约束效应，较小的量子点提供更高的响应率和更宽的光谱覆盖。矩阵类型强烈影响电流-电压特性，暗电流随量子点尺寸的减小而减小。尽管其完全无定形结构和简单的制造，器件实现外部量子效率高达~ 60%，探测3 × 10¹¹琼斯，和灵敏度接近9 × 10³在室温下315-1100 nm。这些发现在无氧基质中建立了可调谐无定形Ge量子点网络，作为宽带光敏器件的经济高效的高性能平台。

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引用次数: 0

Correlation between magnetic analyses and optical properties of divalent Co ion in boro-tellurite glass with erbium lanthanide 镧系铒硼碲玻璃中二价钴离子的磁性分析与光学性质的相关性

IF 3.5 3区材料科学 Q1 MATERIALS SCIENCE, CERAMICS

Journal of Non-crystalline Solids

Pub Date : 2025-12-26 DOI: 10.1016/j.jnoncrysol.2025.123925

Nur Liyana Amiar Rodin , S.N. Syed Yaacob , N.A.M. Jan , Faiz Hashim , Siti Maisarah Aziz , R. Zainal , M.R. Sahar

This study investigates the optical and magnetic properties of Er³⁺-doped boro-tellurite glasses containing varying amounts of cobalt oxide nanoparticles (Co₃O₄ NPs). Glass samples with different Co₃O₄ concentrations (0.0–0.8 mol %) were prepared using the melt-quenching method. X-ray diffraction and HRTEM confirmed their amorphous structure, with lattice spacing matching the (422) plane of pure Co₃O₄. Magnetic analysis from VSM showed mainly paramagnetic behavior with slight ferromagnetic traces due to Co²⁺/³⁺ ions. EPR analysis indicated Co²⁺ ions in octahedral sites, showing strong superexchange interactions and high spin-orbit coupling. Adding Co₃O₄ NPs altered the electron distribution, increasing the optical bandgap and suggesting more tetrahedral Co²⁺ integration into the glass network. Up-conversion spectra revealed only two emission peaks (653 nm and 822 nm), with reduced luminescence at 538 nm and 554 nm. This quenching is attributed to intersystem crossing (ISC) of Co²⁺ ions in octahedral coordination, affecting the Er³⁺ emission behavior.

该研究研究了Er³+掺杂硼碲酸盐玻璃的光学和磁性能，该玻璃含有不同量的氧化钴纳米颗粒（Co₃O₄NPs）。采用熔淬法制备了不同Co₃O₄浓度（0.0 ~ 0.8 mol %）的玻璃样品。x射线衍射和HRTEM证实了它们的非晶结构，晶格间距与纯Co₃O₄的（422）平面相匹配。VSM的磁性分析主要显示出顺磁性行为，由于Co 2 + /³+离子的存在，有轻微的铁磁性痕迹。EPR分析表明，Co 2 +在八面体位点上，表现出强的超交换作用和高的自旋轨道耦合。Co₃O₄NPs改变了电子分布，增加了光学带隙，表明Co 2⁺更多地融入了玻璃网络。上转换光谱只有653 nm和822 nm两个发射峰，在538 nm和554 nm处发光减弱。这种猝灭归因于Co 2 +离子在八面体配位中的系统间交叉（ISC），影响了Er 3 +的发射行为。

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引用次数: 0

Influence of introducing yttrium on crystallization behavior and structural characteristic of sputter-deposited Sb2Te3 thin film 引入钇对溅射沉积Sb2Te3薄膜结晶行为和结构特性的影响

IF 3.5 3区材料科学 Q1 MATERIALS SCIENCE, CERAMICS

Journal of Non-crystalline Solids

Pub Date : 2025-12-24 DOI: 10.1016/j.jnoncrysol.2025.123928

Zhengquan Zhou , Weihua Wu , Yu Li , Zhichao Qi , Kangle Yong

The existing challenge of power consumption and the inherent trade-off between crystallization speed and thermal stability of traditional phase change materials have hindered their application in storage class memory. In this study, the physical properties and structural characterization of Y-doped and pure Sb₂Te₃ thin films were analyzed, including phase-change performance, electrical properties, optical properties, crystal structure, and crystallization mechanisms. Y doping can increase the crystallization temperature and widen the bandgap of Sb₂Te₃, significantly improving thermal stability and crystalline resistance. Also, Y incorporation can refine grain size and reduce surface roughness, which is of great significance for reducing power consumption and improving the reliability of Sb₂Te₃ material. Theoretical calculations revealed that Y doping can mitigate structural defects in Sb₂Te₃ by reducing Te-Te wrong-bonding configurations and forming robust Y-Te covalent bonds. Electrical measurements show that phase change cells based on Y-doped Sb₂Te₃ exhibit lower power consumption and faster switching speeds than those of Ge₂Sb₂Te₃. These findings prove that yttrium doping can effectively improve the thermal stability, resistance drift, and power consumption of Sb₂Te₃ material, providing an important insight to enhance the comprehensive performance of phase-change memory.

传统相变材料存在的功耗挑战和结晶速度与热稳定性之间的内在权衡阻碍了其在存储级存储器中的应用。本研究分析了y掺杂和纯Sb2Te3薄膜的物理性能和结构表征，包括相变性能、电学性能、光学性能、晶体结构和结晶机理。Y掺杂可以提高Sb2Te3的结晶温度，拓宽其带隙，显著提高其热稳定性和晶阻。此外，Y的加入可以细化晶粒尺寸，降低表面粗糙度，这对降低Sb2Te3材料的功耗和提高材料的可靠性具有重要意义。理论计算表明，Y掺杂可以通过减少Te-Te错误键构型和形成稳健的Y- te共价键来减轻Sb2Te3的结构缺陷。电学测量表明，基于y掺杂Sb2Te3的相变电池比基于Ge2Sb2Te3的相变电池具有更低的功耗和更快的开关速度。这些发现证明了钇掺杂可以有效改善Sb2Te3材料的热稳定性、电阻漂移和功耗，为提高相变存储器的综合性能提供了重要的见解。

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引用次数: 0

Towards stable metal organic-inorganic complex glasses 迈向稳定的金属有机-无机复合玻璃

IF 3.5 3区材料科学 Q1 MATERIALS SCIENCE, CERAMICS

Journal of Non-crystalline Solids

Pub Date : 2025-12-22 DOI: 10.1016/j.jnoncrysol.2025.123923

Tianzhao Xu , Zhencai Li , Kai Zheng , Hanmeng Zhang , Kenji Shinozaki , Huotian Zhang , Lars R. Jensen , Feng Gao , Jinjun Ren , Yanfei Zhang , Yuanzheng Yue

Metal organic-inorganic complex (MOIC) glasses have emerged as a new family of hybrid glasses. However, the low thermal stability of MOIC glasses fabricated via crystallization suppression constrains their practical applicability under ambient conditions. Here, we report a novel approach for preparing the MOIC glasses that combines slow-solvent removal with subsequent quenching to avoid gel thermal decomposition and enhance the thermal stability of the obtained glass. Specifically, the new approach utilizes an aprotic solvent (acetone) to kinetically prevent the ordering of the metal-ligand complex molecules in solution, thereby suppressing crystallization and forming a gel. The subsequent gradual drying process leads to the removal of the solvent to enhance the connections between molecules through hydrogen bonds, thus causing the formation of a hydrogen-bonded network. The increased network connectivity lowers the mobility of the molecules, thereby enhancing the thermal stability of the system. A disordered network of dried gel is frozen-in via cooling from 130 °C to room temperature, and hence, MOIC glass forms. Structural analyses reveal that hydrogen bonds are responsible for connecting the tetrahedral units. The as-prepared MOIC glass exhibits an increase in glass transition temperature (T_g) during rapid room-temperature relaxation, enhanced CO₂ uptake, and a red shift in photoluminescence. This work not only presents a novel strategy for fabricating large-sized, stable, functional MOIC glasses but also uncovers the critical role of hydrogen bonds in MOIC glass formation.

金属有机无机配合物（MOIC）玻璃是一种新型的杂化玻璃。然而，抑制结晶法制得MOIC玻璃的热稳定性较低，限制了其在环境条件下的实际应用。在这里，我们报告了一种制备MOIC玻璃的新方法，该方法结合了缓慢溶剂去除和随后的淬火，以避免凝胶热分解并提高所获得玻璃的热稳定性。具体来说，新方法利用非质子溶剂（丙酮）在动力学上阻止溶液中金属配体复合物分子的有序，从而抑制结晶和形成凝胶。随后的逐渐干燥过程导致溶剂的去除，通过氢键加强分子之间的连接，从而形成氢键网络。增加的网络连通性降低了分子的迁移率，从而增强了系统的热稳定性。通过从130°C冷却到室温，干燥凝胶的无序网络被冻结，从而形成MOIC玻璃。结构分析表明，氢键负责连接四面体单元。制备的MOIC玻璃在室温快速弛豫过程中玻璃化转变温度（Tg）升高，CO2吸收增强，光致发光红移。这项工作不仅提出了一种制造大尺寸、稳定、功能MOIC玻璃的新策略，而且揭示了氢键在MOIC玻璃形成中的关键作用。

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