玻璃基质中ZnS纳米晶Mn2+的EPR谱

用融熔法制备分散有ZnS:Mn²⁺纳米晶的纳硼硅(Na₂O-B₂O₃-SiO₂)玻璃在不同温度、时间对样品进行退火处理,得到不同尺寸的纳米晶.研究了玻璃基质中ZnS:Mn²⁺纳米晶的EPR谱、微波功率饱和EPR谱及发射光谱,发现Mn²⁺有二种组态,即替位组态和间隙位组态.分析结果表明替位组态Mn²⁺及周围立方晶场的畸变程度直接影响光学发光特性.     

Classical simulations of magnetic structures for chromium clusters: Size effects

Classical (Heisenberg) simulations show that the total magnetization of the lowest-energy states of clusters made of antiferromagnetically coupled chromium atoms is planar, rather than collinear, depending on the arrangement of the atoms. Although the model Hamiltonian is not restrictive, many cluster configurations of various numbers of atoms do not use all three directions for the spins. This result confirms the conclusion drawn from the local-spin DFT calculation by Kohl and Bertsch that clusters of N≤13 have non-collinear magnetic moments. The present simulations show non-collinear spin ordering also for bigger clusters, designed to be as spherical as possible following the bcc arrangement, when atoms interact both with the nearest and next-nearest neighbours. Depending on the signs of the coupling constants frustration appears. The advantage of the discrete model, despite the simplicity, is that very large clusters and magnetization at finite temperatures can be studied. This model predicts that clusters with specific numbers of atoms interacting only with the nearest neighbours have collinear spins as in the bulk. We also apply the model to simulate the destruction of the anti-ferromagnetic ordering by thermal fluctuations. This model shows no unique magnetization of mixed Fe _0.33 Cr _0.67, which is consistent with experimental observations.     

Gd基非晶与Gd纳米晶复合结构的磁制冷效应

通过调控冷却速率和成分配比, 制备出了Gd基非晶与Gd纳米晶的复合材料. 采用X射线衍射、热分析、原子力和磁力显微镜对其微结构进行表征, 从多个角度证实了非晶/纳米晶的复合结构. 磁性测试结果表明: 内生的纳米晶颗粒能有效改善非晶基体的磁熵效应, 相对于Gd基块体纯非晶和Gd单质, 复合体系的磁制冷效率大幅提高达到了10³ J. kg^-1; 磁熵变化峰Δ S _m的半高宽超过纯Gd的5倍; 最大磁熵变区出现平台区,但Δ S _m峰值有待于进一步提高. 理论分析表明, 复合结构中超顺磁纳米团簇的形成有效提高了磁制冷温区和效率. 结合磁滞小和电阻大等优点, Gd基非晶/Gd纳米晶复合材料具有一定的发展潜力.     

Essential Amino Acid–Enabled Lead Bromide Perovskite Nanocrystals with High Stability

This work reports the first synthesis of MAPbBr₃ perovskite nanocrystals (PNCs) using amino acids as the ligand with excellent optical properties. A variety of amino acids are used to optimize the luminescence properties. A mechanochemical approach has taken lead over conventional colloidal chemistry during synthesis. All morphological and optical studies are performed to characterize the synthesized perovskite nanoparticles. Later, stability studies are investigated through thermogravimetric analysis, temperature‐dependent photoluminescence, time‐dependent X‐ray diffraction, as well as X‐ray photoelectron spectroscopy. In an application, interestingly, these perovskites show high luminescence upon scratching on flexible conducting plates and on plain paper surface. These results suggest that the amino acid–ligated perovskite nanocrystals can be potential materials for optoelectronic application including light‐emitting diodes and imaging.     

Mn掺杂Zn-In-S量子点的制备及发光性质研究

制备了Mn掺杂Zn-In-S量子点并研究了Zn/In的量比和反应温度对其发光性质的影响。在Mn掺杂的Zn-In-S量子点的发光谱中观测到一个600 nm发光带。通过改变Zn/In的量比,掺杂量子点的吸收带隙可从3.76 e V(330 nm)调谐到2.82 e V(440 nm),但600 nm发光峰的波长只有略微移动。这些掺杂量子点的最长荧光寿命为2.14 ms。当反应温度从200℃增加到230℃时,掺杂量子点的发光强度增加并达到最大值;而继续升高温度至260℃时,发光强度迅速减弱。此外,测量了Mn掺杂Zn-In-S量子点的变温发光光谱。发现随着温度的升高,发光峰位发生蓝移,发光强度明显下降。分析认为,Mn掺杂Zn-In-S量子点的600 nm发光来自于Mn2+离子的4T1和6A1之间的辐射复合。     

Fluctuation-theory constraint for extensive entropy in Monte-Carlo simulations

The entropy per particle in most Monte-Carlo simulations is size dependent due to correlated energy fluctuations. Guided by nanothermodynamics, we find a constraint for the Ising model that enhances the fluctuations and lowers the free energy, while making the entropy homogeneous, additive, and extensive. Although the average interaction energy becomes size dependent, the resulting distribution of energies provides a mechanism for the heterogeneity found in the dynamics of many materials.     

On the fragmentation of multiply charged sodium clusters

The fragmentation of multiply charged atomic sodium clusters of mass 200 is investigated using the Micro-canonical Metropolis Monte Carlo (MMMC) statistical technique for excitation energies up to 200 eV and for cluster charges up to +9e. In this work we present caloric curves and charged and uncharged fragment mass distributions for clusters with charges 0, 2, and 4. The caloric curves show a dip at the critical point implying a negative specific heat, as expected for finite systems, while the fragment mass distributions corroborate the picture of a phase transition from one dominant liquid-like cluster to complete vaporization. Received 7 November 2001 / Received in final form 4 April 2002 Published online 28 June 2002     

玻璃中CdSeS纳米晶体的室温光致发光谱

对掺有过饱和的镉、硒和少量硫的玻璃在500～800℃分别退火4h,生长了不同尺寸的CdSe_1-xS_x纳米晶体。测量了纳米晶体的室温吸收光谱和光致发光(PL)光谱,550℃生长的样品在300～800nm的范围没有观察到吸收和发光峰,表明温度低于550℃玻璃中不能形成纳米晶体。生长温度在600～650℃,纳米晶体的PL光谱主要为两个宽的发光带,即带边激子发光带和通过表面态复合的发光带。随着生长温度的升高,带边复合发光的蓝移减小,通过表面态的发光逐渐消失,并出现了叠加于宽发光带上的一系列明显的弱发射峰。不同温度生长的样品中,叠加峰的能量相同。同一样品中叠加峰的能量不随激发光波长的变化而变化。     

Tm3+/Yb3+ ∶LaF3纳米体系中掺杂Yb3+ 离子对Tm3+ 离子荧光发射的影响

为研究Yb³⁺离子浓度变化对Tm³⁺离子在蓝色波段荧光强度的影响,以NaF和La(NO₃)₃为原料,采用水热法制备了Tm³⁺和Yb³⁺共掺的Tm³⁺/ Yb³⁺∶LaF₃纳米颗粒.用X射线衍射对LaF₃纳米颗粒进行表征的结果显示,纳米晶体结构呈六方相.透射电镜的观测结果显示,纳米颗粒样品大小均匀、分散性良好.在波长为800 nm的激光激发下,观测到了上转换蓝光发射,其中包括波长为474 nm和479 nm的较强的荧光辐射(相应的跃迁为1G4→3H6)和波长位于450 nm的强度较弱的荧光发射(相应的跃迁为1D2→3F4).通过观测不同Yb³⁺离子浓度条件下共掺Tm³⁺/Yb³⁺∶LaF₃样品的荧光光谱,研究了Yb³⁺离子掺杂浓度对于Tm³⁺离子的荧光发射的影响,并探讨了产生这种现象的原因.研究结果显示,对于1G4→3H6跃迁产生的荧光发射(474 nm),当Yb³⁺离子浓度增大时,反向能量传递速率的增加导致了荧光强度的增大.然而,当Yb³⁺离子浓度增大到一定程度时,Yb³⁺离子激发态能级寿命的减少将引发荧光强度的下降.相比较而言,Yb³⁺离子的浓度的变化对于1D2→3F4跃迁产生的位于450 nm处荧光强度的影响较弱.     

Observation of large low‐field magnetoresistance in spinel cobaltite: A new half‐metal

Low‐field magnetoresistance is an effective and energy‐saving way to use half‐metallic materials in magnetic reading heads and magnetic random access memory. Common spin‐polarized materials with low field magnetoresistance effect are perovskite‐type manganese, cobalt, and molybdenum oxides. In this study, we report a new type of spinel cobaltite materials, self‐assembled nanocrystalline NiCo₂O₄, which shows large low field magnetoresistance as large as –19.1% at 0.5 T and –50% at 9 T (2 K). The large low field magnetoresistance is attributed to the fast magnetization rotation of the core nanocrystals. The surface spin‐glass is responsible for the observed weak saturation of magnetoresistance under high fields. Our calculation demonstrates that the half‐metallicity of NiCo₂O₄ comes from the hopping e_g electrons within the tetrahedral Co‐atoms and the octahedral Ni‐atoms. The discovery of large low‐field magnetoresistance in simple spinel oxide NiCo₂O₄, a non‐perovskite oxide, leads to an extended family of low‐field magnetoresistance materials. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)