聚噻吩单链量子热输运的第一性原理研究

聚噻吩块体通常被视为绝热材料,其热导率小于1W·m~(-1)·K~(-1).但近年发现对于室温下沿聚噻吩分子链方向排列的无定形聚噻吩纳米纤维,其热导率高于聚噻吩块体,可达4.4W·m~(-1)·K~(-1).为了相对准确地揭示纳米尺度聚噻吩单链热输运的微观特征,从量子力学出发,在密度泛函理论计算的基础上,应用中间插入延展方法结合非平衡格林函数方法,对长度为25.107nm、包含448个原子的聚噻吩单链的量子热输运及其同位素效应进行了研究,并与分子动力学方法模拟的结果进行了详细比较.结果表明:室温下32 nm长的纯聚噻吩单链热导率上限高达30.2 W·m~(-1)·K~(-1),与铅的热导率35 W·m~(-1).K~(-1)相近;相同掺杂比例(原子百分数)下C元素热导的同位素效应比S元素显著;室温下聚噻吩单链中~(12)C,~(13)C等比例随机掺杂时的同位素效应最为显著,此时聚噻吩单链的平均热导至少降低了30%;室温下纯聚噻吩单链的热导随C的相对原子质量增加近似呈反比例减小,随S的相对原子质量增加呈非线性单调增加.该研究对认识和调控聚噻吩这种新型功能材料的热输运特性具有积极的价值.     

Mn/C共掺杂ZnS纳米管磁性质研究（英文）

采用第一性原理密度泛函理论系统地研究Mn原子单掺杂和双掺杂ZnS纳米管的结构、电子性质和磁性质.掺杂纳米管的形成能比纯纳米管形成能更低,表明掺杂是个放热过程.掺杂纳米管的能隙远小于纯纳米管能隙.计算结果表明Mn掺杂纳米管趋于反铁磁态.为了获得室温铁磁性,用一个C原子替代一个S原子.发现铁磁态能量比反铁磁态能量低0.454 e V.如此大的能量差表明这类材料中有可能获得室温铁磁性.     

二维锑烯声子输运的第一性原理研究

二维锑烯作为具有宽带隙的新型半导体材料,在热电、光电等领域具有良好的应用前景。本文利用第一性原理方法研究了不同层数二维锑烯的电子结构、热力学稳定性与声子输运特性.二维锑烯随着层数的增加,原子层弯曲程度减小,电子带隙值下降,呈现了半导体-金属特性的转变.单层锑烯在室温下单位截面积声子热导约为0.190 GW·m~(-2)K~(-1)。由于层间相互作用力的存在以及原子层弯曲程度的改变,声子热导随层数的增加而逐渐减小,四层锑烯的声子热导已经接近块体锑的声子热导。     

导热高分子聚合物研究进展

传统高分子聚合物是良好的电绝缘体和热绝缘体.高分子聚合物具备质量轻、耐腐蚀、可加工、可穿戴、电绝缘、低成本等优异特性.高分子聚合物被广泛应用于各种器件.由于高分子材料的热导率比较低(0.1—0.5 W·m^-1·K^-1),热管理(散热)面临严峻的挑战.理论及实验工作表明,先进高分子材料可以具有比传统传热材料(金属和陶瓷)更高热导率. Fermi-Pasta-Ulam (FPU)理论结果发现低维度原子链具有非常高的热导率.广泛使用的聚乙烯热绝缘体可以被转变为热导体:拉伸聚乙烯纳米纤维的热导率大约为104 W·m^-1·K^-1,拉伸的聚乙烯薄膜热导率大约为62 W·m^-1·K^-1.首先,本文通过理论和实验结果总结导热高分子材料的传热机理研究进展,并讨论了导热高分子聚合物的制备策略;然后,讨论了在传热机制及宏量制备方面,高分子聚合物研究领域所面临的新挑战;最后,对导热高分子的热管理应用前景进行了展望.例如,导热高分子聚合物在耐腐蚀散热片、低成本太阳能热水收集器、可穿...     

嵌入线型缺陷的石墨纳米带的热输运性质

采用非平衡格林函数方法研究了嵌入有限长、半无限长、 无限长线型缺陷的锯齿型石墨纳米带 (ZGNR)的热输运性质.结果表明, 缺陷类型和缺陷长度对ZGNR的热导有重要影响. 当嵌入的线型缺陷长度相同时, 包含t5t7线型缺陷的石墨纳米带比包含Stone-Wales线型缺陷的条带热导低. 对于嵌入有限长、同种缺陷的ZGNR, 其热导随线型缺陷的长度增加而降低, 但是当线型缺陷很长时, 其热导对缺陷长度的变化不再敏感.通过比较嵌入有限长、半无限长、无限长线型缺陷的ZGNR, 我们发现嵌入无限长缺陷的条带比嵌入半无限长缺陷的条带热导高, 而后者比嵌入有限长线型缺陷的条带热导高. 这主要是因为在这几种结构中声子传输方向的散射界面数不同所导致的. 散射界面越多, 对应的热导就越低. 通过分析透射曲线和声子局域态密度图, 解释了这些热输运现象. 这些研究结果表明线型缺陷能够有效地调控石墨纳米带的热输运性质. 关键词： 石墨烯 线型缺陷 热导     

Cr掺杂ZnS纳米管结构和磁性质

采用第一性原理密度泛函理论系统研究Cr原子单掺杂和双掺杂单壁ZnS纳米管的结构和磁性质.研究发现掺杂纳米管的形成能比纯纳米管的形成能低,说明掺杂过程是放热的.单掺杂纳米管的总磁矩主要来自Cr原子3d态的贡献.结果表明Cr原子掺杂单壁ZnS纳米管趋向于铁磁态.但铁磁态和反铁磁态的能量差仅为0036eV.为获得室温铁磁性,我们用一个C原子替代掺杂体系中的一个S原子.计算发现铁磁态的能量比反铁磁态低0497eV.表明此掺杂体系可能获得室温铁磁性.     

磁控溅射结合脉冲激光制备钛掺杂硅薄膜的研究（英文）

发展了一种改进的新型超掺杂工艺,通过真空磁控溅射多层镀膜后结合532nm波长可见纳秒脉冲激光熔融处理,进行超掺杂钛的硅薄膜材料的制备,并对材料的超掺杂层的性质和红外吸收性能进行了探究.结果表明,硅膜层中掺杂的钛原子的百分比浓度超过1%左右,对应钛原子浓度约为5×10~(20) cm~(-3)左右,超过钛在硅中形成超掺杂所对应的原子浓度.钛超掺杂层的厚度超过200nm左右,相对传统工艺具有明显提升,并且钛原子的浓度变化范围不超过20%,分布比较均匀.小角度X射线衍射测试表明经过可见脉冲激光熔融处理后的硅薄膜层材料结晶度为25%左右,呈多晶结构.同时红外吸收谱测试表明,样品的钛掺杂硅膜层在大于1 100nm波长的区域具有很高的红外吸收效果,最高的红外吸收系数达到1.2×10~4 cm~(-1),远超过单晶硅材料.具有比较明显的亚能带吸收的特征,呈现出Ec-0.26eV的掺杂能级.霍尔效应测试表明硅膜层具有较高的载流子浓度,超过了8×10~(18)cm~(-3).     

L型石墨纳米结的热输运

利用非平衡格林函数方法研究了由半无限长扶手椅型和锯齿型边界石墨纳米带连接而成的L型石墨纳米结的热输运性质.结果表明,L型石墨纳米结的热导依赖于L型石墨纳米结的夹角和石墨纳米带的宽度.在L型石墨纳米结的夹角从30°增加到90°再增加到150°过程中,其热导显著增大.夹角为90°的L型石墨纳米结的热导随着扶手椅型纳米带宽度增加时,在低温区热导随着宽度的增大而降低,在高温区热导随宽度的增大而升高.对于夹角为150°的L型石墨纳米结,其热导无论是在低温区还是在高温区都随着锯齿型纳米带宽度的增加而降低.利用声子透射谱对这些热输运现象进行了合理的解释.研究结果阐明了不同L型石墨纳米结中的热输运机理,为设计基于石墨纳米结的热输运器件提供了重要的物理模型和理论依据. 关键词： 石墨纳米结 热输运 热导     

热电材料的热输运调控及其在微型器件中的应用

热电能量转换技术是一种利用材料实现热能和电能直接相互转换的清洁能源技术.热电材料的性能是决定热电转换效率的关键因素,而热电材料的性能优化涉及电输运和热输运性能的协同优化.文章介绍了近期热电材料中热输运的调控机制和方法,其中重点论述了基于原子分子层次调控热传导的宽频声子散射效应和横波阻尼效应,以及低维结构和复合材料中的基于纳米微米尺度的微结构调控.最后介绍了室温附近热传导的调控机制及其在高效微型热电器件研发中的应用和进展.     

垂直各向异性Ho3Fe5O12薄膜的外延生长与其异质结构的自旋输运

垂直磁各向异性稀土-铁-石榴石纳米薄膜在自旋电子学中具有重要应用前景.本文使用溅射方法在(111)取向掺杂钇钪的钆镓石榴石(Gd_0.63Y_2.37Sc₂Ga₃O₁₂,GYSGG)单晶衬底上外延生长了2—100 nm厚的钬铁石榴石(Ho₃Fe₅O₁₂,HoIG)薄膜,并进一步在HoIG上沉积了3 nm Pt薄膜.测量了室温下HoIG的磁各向异性和HoIG/Pt异质结构的自旋相关输运性质.结果显示,厚度薄至2 nm的HoIG薄膜(小于2个单胞层)在室温仍具有铁磁性,且由于外延应变,2—60 nm厚HoIG薄膜都具有很强的垂直磁各向异性,有效垂直各向异性场最大达350 mT;异质结构样品表现出非常可观的反常霍尔效应和“自旋霍尔/各向异性”磁电阻效应,前者在HoIG厚度小于4 nm时开始缓慢下降,而后者当HoIG厚度小于7 nm时急剧减小,说明相较于反常霍尔效应,磁电阻效应对HoIG的体磁性相对更加敏感;此外,自旋相关热电压随HoIG厚度减薄在整个厚度范围以指数方式下降,说明遵从热激化磁振子运动规律的自旋塞贝克效应是其主要贡献者.本文结果表明HoIG纳米薄膜具有可调控的垂直磁各向异性,厚度大于4 nm的HoIG/Pt异质结构具有高效的自旋界面交换作用,是自旋电子学应用发展的一个重要候选材料.     

Thermoelectric enhancement in triple-doped strontium titanate with multi-scale microstructure

Strontium titanate(SrTiO_3) is a thermoelectric material with large Seebeck coefficient that has potential applications in high-temperature power generators.To simultaneously achieve a low thermal conductivity and high electrical conductivity,polycrystalline SrTiO_3 with a multi-scale architecture was designed by the co-doping with lanthanum,cerium,and niobium.High-quality nano-powders were synthesized via a hydrothermal method.Nano-inclusions and a nano/microsized second phase precipitated during sintering to form mosaic crystal-like and epitaxial-like structures,which decreased the thermal conductivity.Substituting trivalent Ce and/or La with divalent Sr and substituting pentavalent Nb with tetravalent Ti enhanced the electrical conductivity without decreasing the Seebeck coefficient.By optimizing the dopant type and ratio,a low thermal conductivity of 2.77 W·m~(-1)·K~(-1) and high PF of 1.1 mW·m~(-1)·K~(-2) at 1000 K were obtained in the sample co-doped with 5-mol% La,5-mol% Ce,and 5-mol% Nb,which induced a large ZT of 0.38 at 1000 K.     

Ca2+掺杂对CdO多晶热电性能的影响

以CaCO₃作为Ca²⁺源, 利用传统固相烧结法制备了Cd_1-xCa_xO (x=0, 0.01, 0.03, 0.05) 多晶块体样品并研究了Ca²⁺掺杂对CdO高温热电性能的影响. CaCO₃的掺入会导致CdO多晶载流子浓度降低, 使Cd_1-xCa_xO的电阻率ρ和塞贝克系数的绝对值|S|增大、电子热导率κ_e减小. 同时, 在CdO中掺入CaCO₃会引入点缺陷和气孔并可抑制CdO晶粒长大、晶界增多, 从而增加了对声子的散射, 使样品的声子热导率κ_p减小. 由于总热导率的大幅降低, Cd_0.99Ca_0.01O多晶样品在1000 K时的热电优值ZT可达0.42, 比本征CdO提高了约27%, 为迄今n型氧化物热电材料报道的最好结果之一.     

Thermoelectric performance of XI2 (X = Ge,Sn, Pb) bilayers

We study the thermal and electronic transport properties as well as the thermoelectric (TE) performance of three two-dimensional (2D) XI₂ (X=Ge, Sn, Pb) bilayers using density functional theory and Boltzmann transport theory. We compared the lattice thermal conductivity, electrical conductivity, Seebeck coefficient, and dimensionless figure of merit (ZT) for the XI₂ monolayers and bilayers. Our results show that the lattice thermal conductivity at room temperature for the bilayers is as low as ~1.1 W·m^{-1·K-1-1.7 W}·m^{-1·K-1, which is about 1.6 times as large as the monolayers for all the three materials. Electronic structure calculations show that all the} XI₂ bilayers are indirect-gap semiconductors with the band gap values between 1.84 eV and 1.96 eV at PBE level, which is similar as the corresponding monolayers. The calculated results of ZT show that the bilayer structures display much less direction-dependent TE efficiency and have much larger n-type ZT values compared with the monolayers. The dramatic difference between the monolayer and bilayer indicates that the inter-layer interaction plays an important role in the TE performance of XI₂, which provides the tunability on their TE characteristics.     

微波低温制备Mg2Si0.4Sn0.6-yBiy热电材料的传输机理

德拜弛豫理论表明, 在频率为2.45 GHz的外加交变电磁场的作用下, 微波对极性分子的极化过程约为10^-10 s, 因此利用微波固相反应可以在短时低温条件下制备出纳米粉体材料. 本文以MgH₂代替Mg粉, 利用微波固相反应在低温下制备了Mg₂Si_0.4Sn_0.6-yBi_y (0 ≤y ≤q 0.03)固溶体, 并结合单带抛物线计算模型对其热电传输机理进行了分析. 研究结果表明: 利用该工艺可以有效抑制Mg的挥发和MgO 的生成, 在400 ℃保温15 min内即可完成MgH₂与Si粉和Sn粉的固相反应, 获得片层间距为100 nm的超细化学计量比产物; 杂质Bi的引入可以有效增加载流子浓度, 并引起晶格畸变, 在晶格畸变和样品特有的纳米片层结构的协同作用下, 声子得到有效散射, 样品具有最低的热导率1.36 W·m^-1·K^-1. 较低的有效掺杂率和复杂的能带结构具有降低能带态密度有效质量和减小载流子弛豫时间的双刃效应, 使得本征激发提前, 在600 K样品取得最大ZT值为0.66.     

Facile fabrication of highly flexible,porous PEDOT: PSS/SWCNTs films for thermoelectric applications

High-performance organic composite thermoelectric(TE)materials are considered as a promising alternative for harvesting heat energy.Herein,composite films of poly(3,4-ethyienedioxythiophene):poly(styrene sulfonate)/single-walled carbon nanotubes(PEDOT:PSS/SWCNTs)were fabricated by utilizing a convenient solution mixing method.Thereafter,the as-prepared hybrid films were treated using sulfuric acid(H₂SO₄)to further optimize the TE performance.Film morphological studies revealed that the sulfuric acid treated PEDOT:PSS/SWCNTs composite samples all possessed porous structures.Due to the successful fabrication of highly conductive networks,the porous nano-architecture also exhibited much more excellent TE properties when compared with the dense structure of the pristine samples.For the post-treated sample,a high power factor of 156.43μW·m^-1·K^-2can be achieved by adjusting the content of CNTs,which is approximately 3 orders of magnitude higher than that of the corresponding untreated samples(0.23μW·m^-1·K^-2).Besides,the obtained films also showed excellent mechanical flexibility,owing to the porous nanostructure and the strong p–p interactions between the two components.This work indicates that the H₂SO₄ treatment could be a promising strategy for fabricating highly-flexible and porous PEDOT:PSS/SWCNTs films with high TE performances.     

Enhancing the thermoelectric performance through the mutual interaction between conjugated polyelectrolytes and single-walled carbon nanotubes

We present a method of constructing composites composed of conjugated polyelectrolytes(CPEs)and singlewalled carbon nanotubes(SWCNTs)to obtain a high-performing flexible thermoelectric generator.In this approach,three kinds of polymers,namely,poly[(1,4-(2,5-didodecyloxybenzene)-alt-2,5-thiophene](P1),poly[(1,4-(2,5-bis-sodium butoxysulfonate-phenylene)-alt-2,5-thiophene](P2),and poly[(1,4-(2,5-bis-acid butoxysulfonic-phenylene)-alt-2,5-thiophene](P3)are designed,synthesized and complexed with SWCNTs as thermoelectric composites.The electrical conductivities of the CPEs/SWCNTs(P2/SWCNTs,and P3/SWCNTs)nanocomposites are much higher than those of non-CPEs/SWCNTs(P1/SWCNTs)nanocomposites.Among them,the electrical conductivity of P2/SWCNTs with a ratio of 1:4 reaches 3686 S·cm^-1,which is 12.4 times that of P1/SWCNTs at the same SWCNT mass ratio.Moreover,CPEs/SWCNTs composites(P2/SWCNTs)display remarkably improved thermoelectric properties with the highest power factor(PF)of 163μW·m^-1·K^-1.In addition,a thermoelectric generator is fabricated with P2/SWCNTs composite films,and the output power and power density of this generator reach 1.37μW and 1.4 W·m;(cross-section)at△T=70 K.This result is over three times that of the thermoelectric generator composed of non-CPEs/SWCNTs composite films(P1/SWCNTs,0.37μW).The remarkably improved electrical conductivities and thermoelectric properties of the CPEs/SWCNTs composites(P2/SWCNTs)are attributed to the enhanced interaction.This method for constructing CPEs/SWCNTs composites can be applied to produce thermoelectric materials and devices.     

Enhanced thermoelectric performance of PEDOT:PSS films via ionic liquid post-treatment

Thermoelectric(TE)energy harvesting can effectively convert waste heat into electricity,which is a crucial technology to solve energy concerns.As a promising candidate for energy conversion,poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)has gained significant attention owing to its easy doping,high transparency,and solution processability.However,the TE performance of PEDOT:PSS still needs to be further enhanced.Herein,different approaches have been applied for tuning the TE properties:(i)direct dipping PEDOT:PSS thin films in ionic liquid;(ii)post-treatment of the films with concentrated sulfuric acid(H₂SO₄),and then dipping in ionic liquid.Besides,the same bis(trifluoromethanesulfonyl)amide(TFSI)anion and different cation salts,including 1-ethyl-3-methylimidazolium(EMIM+)and lithium(Li+),are selected to study the influence of varying cation types on the TE properties of PEDOT:PSS.The Seebeck coefficient and electrical conductivity of the PEDOT:PSS film treated with H2SO4EMIM:TFSI increase simultaneously,and the resulting maximum power factor is 46.7μW·m^-1·K^-2,which may be attributed to the ionic liquid facilitating the rearrangement of the molecular chain of PEDOT.The work provides a reference for the development of organic films with high TE properties.     

Anisotropic thermoelectric transport properties in polycrystalline SnSe_2

It is reported that SnSe_2 consisting of the same elements as SnSe, is a new promising thermoelectric material with advantageous layered structure. In this work, the thermoelectric performance of polycrystalline SnSe_2 is improved through introducing SnSe phase and electron doping(Cl doped in Se sites). The anisotropic transport properties of SnSe_2 are investigated. A great reduction of the thermal conductivity is achieved in SnSe_2 through introducing SnSe phase, which mainly results from the strong SnSe_2–SnSe inter-phase scattering. Then the carrier concentration is optimized via Cl doping, leading to a great enhancement of the electrical transport properties, thus an extraordinary power factor of ～5.12 μW·cm~(-1)·K~(-2) is achieved along the direction parallel to the spark plasma sintering(SPS) pressure direction( P). Through the comprehensive consideration on the anisotropic thermoelectric transport properties, an enhanced figure of merit ZT is attained and reaches to ～ 0.6 at 773 K in SnSe_2-2% SnSe after 5% Cl doping along the P direction, which is much higher than ～ 0.13 and ～ 0.09 obtained in SnSe_2-2% SnSe and pristine SnSe_2 samples, respectively.     

Thermoelectric characteristics of flexible reduced graphene oxide/silver selenide nanowire composites prepared by a facile vacuum filtration process

The reduced graphene oxide/silver selenide nanowire (rGO/Ag₂Se NW) composite powders were fabricated via a wet chemical approach, and then flexible rGO/Ag₂Se NW composite film was prepared by a facile vacuum filtration method combined with cold-pressing treatment. A highest power factor of 228.88 μW·m^-1·K^-2 was obtained at 331 K for the cold-pressed rGO/Ag₂Se NW composite film with 0.01 wt% rGO. The rGO/Ag₂Se NW composite film revealed superior flexibility as the power factor retained 94.62% after bending for 500 times with a bending radius of 4 mm, which might be due to the interwoven network structures of Ag₂Se NWs and pliability of rGO as well as nylon membrane. These results demonstrated that the GO/Ag₂Se NW composite film has a potential for preparation of flexible thermoelectric devices.