单层Cu2X的热电性质

具有低晶格热导率和高热电优值的二维(2D)材料可用于热电器件的制备.本文通过第一性原理和玻尔兹曼输运理论,系统地预测了单层Cu₂X (X=S, Se)的热电性质.研究发现单层Cu₂Se较Cu₂S在室温下具有更低的晶格热导率(1.93 W/(m·K)和3.25 W/(m·K)),这源于其更低的德拜温度和更强的非谐性.单层Cu₂X(X=S, Se)价带顶处的能带简并效应显著增大了其载流子有效质量,导致p型掺杂下具有高的塞贝克系数和低的电导率.在最优掺杂浓度下,单层Cu₂S (Cu₂Se) n型的功率因数16.5 mW/(m·K²)(25.9 mW/(m·K²))远高于其p型的功率因数1.1 mW/(m·K²)(6.6 mW/(m·K²)),且随着温度的提升这一优势将更加明显.温度为700 K时,单层Cu₂S和Cu₂Se在n型最优掺...     

应变增强Nb掺杂SrTiO3薄膜热电性能

高性能热电材料的发展有望帮助解决未来能源危机,且随着可穿戴器件的发展与应用,热电材料和器件除了要具备更高的热-电转化性能以外,还必须具有良好的柔性.将热电材料制成薄膜既可以为微型器件供电,也有潜力应用于柔性器件.本文使用脉冲激光沉积方法,在商用SrTiO₃ (STO)和La_0.3Sr_0.7Al_0.65Ta_0.35O₃ (LSAT)衬底上制备得到了不同厚度的高质量铌掺杂钛酸锶薄膜(Nb:STO),并对薄膜的表面形貌、结构以及热电性能进行表征与测试.结果显示,使用LSAT作为衬底可以对薄膜施加面内压应变,随着薄膜厚度的增大,应变逐渐释放并接近于块体Nb:STO.随着厚度的增大,薄膜的热电性能逐渐提升,在STO衬底上生长的208 nm厚样品的室温功率因子相比于52 nm样品提升了187%.此外, 144 nm厚度的Nb:STO/LSAT薄膜室温塞贝克系数达到了265.95 μV/K,这是由于衬底应变导致薄膜样品的能带变化.本工作表明通过应变工程调控铌掺杂钛酸锶薄...     

铜锌锡硫薄膜材料及其器件应用研究进展

铜锌锡硫薄膜材料组成元素储量丰富, 环境友好, 成本低廉, 成为最具前景的薄膜材料之一. 目前, Cu₂ZnSn(S, Se)₄ (CZTSSe)薄膜太阳电池的最高转换效率已经达到12.6%. 本文总结了Cu₂ZnSnS₄ (CZTS)的发展历史, 依次介绍了CZTS薄膜材料的结构特性、光学特性、电学特性、界面特性和Na对CZTS 薄膜的影响, 详细介绍了CZTS薄膜的制备方法及器件应用的最新研究进展, 总结了目前CZTS薄膜太阳电池发展中存在的问题, 展望了今后的研究方向.     

金属有机物化学气相沉积生长GaN薄膜的室温热电特性研究

采用金属有机物化学气相沉积技术生长了不同掺杂浓度的GaN薄膜, 并且通过霍尔效应测试和塞贝克效应测试, 表征了室温下GaN薄膜的载流子浓度、迁移率和塞贝克系数. 在实验测试的基础上, 计算了GaN薄膜的热电功率因子, 并且结合理论热导率确定了室温条件下GaN薄膜的热电优值(ZT). 研究结果表明: GaN薄膜的迁移率随着载流子浓度的增加而减小, 电导率随着载流子浓度的增加而增加; GaN 薄膜材料的塞贝克系数随载流子浓度的增加而降低, 其数量级在100–500 μV/K范围内; GaN薄膜材料在载流子浓度为1.60×10¹⁸ cm^-3时, 热电功率因子出现极大值4.72×10^-4 W/mK²; 由于Si杂质浓度的增加, 增强了GaN薄膜中的声子散射, 使得GaN薄膜的热导率随着载流子浓度的增加而降低. GaN薄膜的载流子浓度为1.60×10¹⁸ cm^-3时, 室温ZT达到极大值0.0025.     

Bi2O2Se纳米线的生长及其超导量子干涉器件

Bi₂O₂Se是一种新型半导体材料,具有载流子迁移率高、空气中稳定和自旋轨道耦合强等优点,并且其合成方法多种多样,应用范围十分广泛.但已有研究大多集中在其二维薄膜,本文介绍一种使用三温区管式炉通过化学气相沉积生长Bi₂O₂Se一维纳米线的方法,研究了云母衬底处于水平方向不同位置以及竖直方向不同高度对Bi₂O₂Se纳米线生长的影响,并归纳出适于其生长的优化条件.之后,基于生长的Bi₂O₂Se纳米线构建了超导量子干涉器件,并观测到随磁场的超导量子干涉,为拓宽Bi₂O₂Se纳米线的应用提供了思路.     

Pb(Zr0.3Ti0.7)O3铁电薄膜激光感生电压效应

采用脉冲激光沉积(PLD)技术在LaSrAlTaO₃(LSATO),LaAlO₃(LAO)和SrTiO₃(STO)的单晶倾斜衬底上成功制备了Pb(Zr_0.3Ti_0.7)O₃(PZT)薄膜,在三种倾斜衬底上生长的PZT薄膜中都首次发现了LIV效应.对PZT/LSATO薄膜在a,c轴两种不同取向择优生长下的LIV效应做了研究,发现在薄膜c轴取向择优生长 关键词： 激光感生电压效应 铁电薄膜 薄膜生长取向 原子层热电堆     

Bi-Sb-Te基热电薄膜温差电池离子束溅射制备与表征

本文采用离子束溅射Bi/Te和Sb/Te二元复合靶,直接制备n型Bi₂Te₃热电薄膜和p型Sb₂Te₃热电薄膜.在退火时间同为1 h的条件下,对所制备的Bi₂Te₃薄膜和Sb₂Te₃薄膜进行不同温度的退火处理,并对其热电性能进行表征.结果表明,在退火温度为150 ℃时,制备的n型Bi₂Te₃关键词： 薄膜温差电池 2Te₃薄膜')" href="#">Sb₂Te₃薄膜 2Te₃薄膜')" href="#">Bi₂Te₃薄膜 离子束溅射     

Stage2沉积速率对低温生长CIGS薄膜特性及器件的影响

研究了三步法第二步沉积速率对低温生长Cu(In,Ga)Se₂薄膜结构、 电学特性和器件特性的影响. 通过改变第二步沉积速率发现, 提高沉积速率可以显著促进薄膜晶粒生长, 提高晶粒紧凑程度降低晶界复合, 同时有效改善两相分离现象, 提高电池的开路电压和短路电流, 有助于Cu(In,Ga)Se₂电池光电转换效率的提高. 但同时研究表明, 随着第二步沉积速率的增加, 会促进暂态Cu_2-xSe晶粒的生长, 引起Cu(In,Ga)Se₂薄膜表面粗糙度增大, 并阻碍Na向Cu(In,Ga)Se₂薄膜表面的扩散, 造成施主缺陷钝化效应降低, 薄膜载流子浓度下降和电阻率升高, 且过高的沉积速率会引起电池内部复合增加并产生分流路径, 造成开路电压下降进而引起电池效率恶化. 最终, 通过最佳化第二步沉积速率, 在衬底温度为420℃时, 得到最高转换效率为11.24%的Cu(In,Ga)Se₂薄膜太阳电池.     

Mn掺杂后三元黄铜矿结构半导体CuInTe2的缺陷特征与热电性能

三元黄铜矿结构(也称类金刚石结构)半导体是一类具有热电转换潜力的新型热电材料. 本次工作中采用电负性更小的Mn元素替换CuInTe₂黄铜矿结构半导体中的Cu元素, 设计制备贫Cu化合物Cu_1-xInMn_xTe₂. 研究表明, 当Mn含量较低时, Mn优先占位在In 位置产生受主缺陷Mn_In^-. 因此随着Mn含量的增大, 载流子浓度和电导率均得到改善. 但当Mn含量进一步增大后, Mn可同时占位在In位置和Cu位置, 除产生受主缺陷Mn_In^-外, 还能产生施主缺陷Mn_Cu⁺. 由于两类极性相反的缺陷之间的湮灭现象, 使得缺陷浓度及载流子浓度开始降低, 晶格结构畸变有变小趋势, 因此在高温下晶格热导率仅略有提高. 研究结果表明, 在某一特定的Mn含量(x=0.05)时, 材料具有最优的热电性能(ZT=0.84@810.0 K), 这一性能约是未掺杂CuInTe₂的2倍.     

Er∶YbF3转光薄膜的制备及衬底温度对其光学性能的影响

采用脉冲激光沉积(PLD)方法在Si(100)衬底上成功制备了具有上下转换的Er∶YbF₃转光薄膜。研究发现,所制备的Er∶YbF₃转光薄膜实现了上下转换两种机制的结合,能有效地把紫外光和红外光转换到非晶硅太阳能电池最佳响应范围内的656 nm处。进一步分析了衬底温度对薄膜相结构及光学性能影响的物理机制。当衬底温度高于500 ℃时,薄膜会随着温度的升高而结晶性变强,但有杂相生成。研究结果表明,Er∶YbF₃转光薄膜的光学性能在衬底温度为500 ℃时最佳,有望应用到非晶硅太阳能电池上使其光电效率提高。     

Synthesis and thermoelectric properties of Bi-doped SnSe thin films

Bi doped n-type SnSe thin films were prepared by chemical vapor deposition (CVD) and their structure and thermoelectric properties were studied. The x-ray diffraction patterns, x-ray photoelectron spectroscopy, and microscopic images show that the prepared SnSe thin films were composed of pure SnSe crystals. The Seebeck coefficients of the Bi-doped SnSe were greatly improved compared to that of undoped SnSe thin films. Specifically, Sn_0.99Bi_0.01Se thin film exhibited a Seebeck coefficient of -905.8μV·K^-1 at 600 K, much higher than 285.5 μV·K^-1 of undoped SnSe thin film. Further first-principles calculations reveal that the enhancement of the thermoelectric properties can be explained mainly by the Fermi level lifting and the carrier pockets increasing near the Fermi level due to Bi doping in the SnSe samples. Our results suggest the potentials of the Bi-doped SnSe thin films in thermoelectric applications.     

Probing thermal properties of vanadium dioxide thin films by time-domain thermoreflectance without metal film

Vanadium dioxide(VO_2) is a strongly correlated material, and it has become known due to its sharp metal–insulator transition(MIT) near room temperature. Understanding the thermal properties and their change across MIT of VO_2 thin film is important for the applications of this material in various devices. Here, the changes in thermal conductivity of epitaxial and polycrystalline VO_2 thin film across MIT are probed by the time-domain thermoreflectance(TDTR) method.The measurements are performed in a direct way devoid of deposition of any metal thermoreflectance layer on the VO_2 film to attenuate the impact from extra thermal interfaces. It is demonstrated that the method is feasible for the VO_2 films with thickness values larger than 100 nm and beyond the phase transition region. The observed reasonable thermal conductivity change rates across MIT of VO_2 thin films with different crystal qualities are found to be correlated with the electrical conductivity change rate, which is different from the reported behavior of single crystal VO_2 nanowires. The recovery of the relationship between thermal conductivity and electrical conductivity in VO_2 film may be attributed to the increasing elastic electron scattering weight, caused by the defects in the film. This work demonstrates the possibility and limitation of investigating the thermal properties of VO_2 thin films by the TDTR method without depositing any metal thermoreflectance layer.     

碲化铋薄膜载能粒子相互作用的超快研究

碲化铋禁带宽度非常窄而具有高电导率和塞贝克系数,同时具有低热导率,成为已知室温下优值系数最高的热电材料。已有研究表明,纳米薄膜和超晶格是进一步提高材料热电性能的可行途径。因此超快研究碲化铋纳米薄膜中载能子间的相互作用过程对开发高性能热电材料有重要意义。本文采用飞秒激光泵浦-探测技术,实验研究了沉积在硅基底上厚度为100 nm碲化铋薄膜中各载能粒子的相互作用过程。通过改变延迟时间步长,分别观察到价带电子被光子激发跃迁至导带,激发电子在导带内与声子的能量弛豫及导带电子与空穴复合跃迁至价带,并将能量传递给声子导致声子温度升高的过程。此外,还观察到热应力产生的声波,并据此得到了碲化铋薄膜中纵波声速为2649 m s^-1。     

环境友好半导体Mg2Si薄膜的研究进展

介绍了近年来Mg2Si薄膜的研究进展。从Mg2Si材料的晶体结构出发,重点对Mg2Si薄膜的基本性质、制备方法和应用前景进行了论述。研究表明,Mg2Si是一种窄带隙间接半导体材料,在光电和热电领域都具有较好的应用价值,因其兼具了组成元素地层含量丰富、无毒、无污染等优点,被视为是一种新型的环境友好半导体材料。在Mg2Si薄膜的外延生长技术方面,目前比较成熟的方法有分子束外延、脉冲激光沉积、反应扩散等多种,但普遍存在制备条件较苛刻,成膜质量不高等缺点。最后,对目前存在的问题及未来的研究动向做了简要讨论。     

PbSe-MnSe纳米复合热电材料的微结构和电热输运性能

相比于常见的热电材料PbTe, 另一种硫族铅化合物PbSe具有熔点高、Se储量更丰富等优势, 从而越来越受到科学界的关注. 本文采用熔融淬火结合快速热压烧结工艺制备了Pb_0.98-xMn_xNa_0.02Se(0 ≤x ≤ 0.12)纳米复合热电材料, 系统地研究了不同Mn含量对材料微纳结构、机械性能和热电性能的影响规律. 发现纳米复合样品中有面心立方结构的MnSe球状和薄层状析出物, 显微硬度得到显著增强. 少量固溶的Mn增加了能带简并度, 使功率因子提高, 球状析出物使声子散射增强、热导率降低, 体系的热电优值ZT得到优化; 但是当Mn含量更高时, 赛贝克系数趋于饱和, 连续析出物使晶格热导率反常增大, ZT 没有得到进一步改善. 通过进一步调节Na含量优化了载流子浓度, 获得了ZT=0.65的PbSe-MnSe纳米复合热电材料.     

Scalable fabrication of Bi_2O_2Se polycrystalline thin film for near-infrared optoelectronic devices applications

We present a controlled, stepwise formation of layered semiconductor Bi_2O_2 Se thin films prepared via the vapour process by annealing topological insulator Bi_2Se_3 thin films in low oxygen atmosphere for different reactions. Photodetectors based on Bi_2O_2 Se thin film show a responsivity of 1.7×10~4 A/W at a wavelength of 980 nm. Field-effect transistors based on Bi_2O_2 Se thin film exhibit n-type behavior and present a high electron mobility of 17 cm~2/V·s. In addition, the electrical properties of the devices after 4 months keeping in the air shows little change, implying outstanding air-stability of our Bi_2O_2 Se thin films. From the obtained results, it is evident that low oxygen annealing is a surprisingly effective method to fabricate Bi_2O_2 Se thin films for integrated optoelectronic applications.     

退火处理对磁控溅射制备LaCoO_3薄膜性能的影响

采用磁控溅射法在硅衬底上制备了LaCoO_3(LCO)薄膜,研究了退火温度对LCO薄膜组织结构、表面形貌及热电特性的影响,并利用X射线衍射仪、原子力显微镜(AFM)、激光导热仪等对LCO薄膜的晶体结构、表面形貌、热扩散系数等进行测量与表征.结果表明:退火温度对LCO薄膜的结晶度、晶粒尺寸和薄膜表面形貌都有较大影响;退火前后LCO薄膜的热扩散系数都随温度的升高而减小,且变化速率逐渐减缓; LCO薄膜的热扩散系数随退化温度的升高先增大后减小.LCO薄膜经过700℃退火后得到最佳的综合性能,其薄膜表面致密、平整,结晶质量最好,热扩散系数最小,热电性能最好.     

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.     

Realization of semiconducting Cu2Se by direct selenization of Cu(111)

Bulk group IB transition-metal chalcogenides have been widely explored due to their applications in thermoelectrics. However, a layered two-dimensional form of these materials has been rarely reported. Here, we realize semiconducting Cu₂Se by direct selenization of Cu(111). Scanning tunneling microcopy measurements combined with first-principles calculations allow us to determine the structural and electronic properties of the obtained structure. X-ray photoelectron spectroscopy data reveal chemical composition of the sample, which is Cu₂Se. The observed moiré pattern indicates a lattice mismatch between Cu₂Se and the underlying Cu(111)-$\sqrt{3}$×$\sqrt{3}$ surface. Differential conductivity obtained by scanning tunneling spectroscopy demonstrates that the synthesized Cu₂Se exhibits a band gap of 0.78 eV. Furthermore, the calculated density of states and band structure demonstrate that the isolated Cu₂Se is a semiconductor with an indirect band gap of ～ 0.8 eV, which agrees quite well with the experimental results. Our study provides a simple pathway varying toward the synthesis of novel layered 2D transition chalcogenides materials.