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.     

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.     

聚乙烯单链量子热输运的同位素效应

高分子导热材料的有效调控受到了日益广泛的关注.应用密度泛函理论(DFT)、中央插入延展(central insertion scheme,CIS)方法及非平衡格林函数(NEGF)理论,对包含432个原子、长18.533 nm的聚乙烯单链量子热输运的同位素效应进行了研究.计算结果表明,室温下长100 nm的纯12C聚乙烯单链的热导率理论上限高达314.1 W·m~(-1)·K~(-1);对于~(12)C聚乙烯单链,其他条件一定时,~(14)C掺杂引起的热导同位素效应比~(13)C更为显著;室温下纯~(12)C聚乙烯单链中~(14)C掺杂原子百分数为50%时同位素效应最显著,此时平均热导比未掺杂时下降了51%.这对探索聚乙烯材料热输运的同位素影响机理具有十分积极的意义.     

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.     

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.     

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.     

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.     

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.     

势能模型对石墨烯导热性质分子动力学模拟的影响

针对常用的Tersoff势、Rebo势和Airebo势,系统性地分析势能模型对分子动力学模拟计算石墨烯色散关系、声子态密度、群速度和热导率的影响. 结果表明：Rebo势和Airebo势描述的声子色散关系接近实验值,Airebo势对应的声子态密度与第一性原理计算的结果较为符合,Rebo势和Airebo势计算的Γ点处声子群速度高于Tersoff势. 采用Airebo势得到石墨烯热导率约为1 150 W·（m·K）^-1,与实验值相近. 综合各种影响,相比于Tersoff势和Rebo势,Airebo势能模型更适合计算石墨烯的导热性质.     

退火温度对电子束蒸发沉积Cu_2O薄膜性能的影响

近年来,钙钛矿太阳电池(PSCs)得到了迅猛发展,而无机空穴传输材料(IHTMs)的使用可进一步降低电池的成本,提高电池的稳定性.本文通过电子束蒸发制备了Cu_2O薄膜,研究了空气中退火温度及时间对薄膜组成、结构及光电性能的影响,并构筑了p-i-n反型平面异质结钙钛矿太阳电池.研究发现:由于热解作用,直接通过电子束蒸发制备的薄膜为Cu_2O和Cu的混合物;而在空气中经过退火后,由于氧化作用,随着退火温度的升高,薄膜的组分由混合物转变为纯的Cu_2O,再转变成纯的CuO.通过控制退火温度制备的Cu_2O薄膜的光学带隙约为2.5 eV,载流子迁移率约为30 cm~2·V~(-1)·s~(-1).应用于PSCs,薄膜的最佳厚度为40 nm,但电池性能低于PEDOT:PSS基的PSCs.这主要是由于钙钛矿前驱液在Cu_2O薄膜的润湿性较差,吸收层中有大量微孔洞存在,致使漏电流增强,电池的性能降低.然而,当采用Cu_2O/PEDOT:PSS双HTMs设计时,由于PEDOT:PSS对Cu_2O具有较强的腐蚀作用,使电池性能恶化.     

利用Ag_2O/PEDOT:PSS复合缓冲层提高P3HT:PCBM聚合物太阳能电池器件性能的研究

利用Ag2O/PEDOT:PSS(聚(3,4-乙撑二氧噻吩):聚苯乙烯磺酸盐)作为复合阳极缓冲层,制备了P3HT:PCBM(聚(3-已基噻吩):富勒烯衍生物)聚合物太阳能电池器件,并通过改变氧化银插入层的厚度来分析复合缓冲层对器件性能的影响.实验发现,具有阳极缓冲层修饰的器件在退火处理后,光伏性能得到了改善.相比于单一PEDOT:PSS缓冲层的器件,Ag2O/PEDOT:PSS复合缓冲层可以增大器件的短路电流密度和外量子效率,使器件效率得到提高.分析表明,退火处理可以有效改善活性层的薄膜形貌,增加光的吸收和激子的解离,而较薄氧化银的引入,可以有效降低阳极处空穴的输运势垒,提高器件空穴收集效率,并能充当化学间隔层,提高器件光伏性能和稳定性.     

旋涂法酸处理PEDOT∶PSS薄膜对OLED性能的影响

采用旋涂法对PEDOT∶PSS薄膜进行了酸处理,研究了不同方法处理PEDOT∶PSS薄膜对器件ITO/酸处理PEDOT∶PSS/NPB/Alq3/Li F/Al性能的影响。实验结果表明:用盐酸(草酸)处理PEDOT∶PSS薄膜时,以0.75 mol/L的盐酸(草酸)在120℃下退火15 min时性能更好,最大电流效率达到4.28 cd/A。并且盐酸、草酸处理PEDOT∶PSS薄膜制备器件比未处理PEDOT∶PSS薄膜制备器件的电流效率明显提高了34%。     

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.     

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.     

Conducting polymer based hybrid structure as transparent and flexible field electron emitter

An efficient cathode material with high transparency (93%) based on conducting polymer poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and single wall carbon nanotubes (SWCNTs) has been developed for the fabrication of highly transparent and flexible field electron emitters (FEE). This kind of material showed superior field emission (FE) performance with very high current density (10^–3A/cm²) at very low electric field. The FE performance of the hybrid materials was dramatically improved compared to either SWCNTs and PEDOT:PSS. Thus the hybrid structures of conducting polymer and SWCNTs might be a good choice for use as a cathode material to enhance the FE performance and for potential application in future portable displays. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Enhanced thermoelectric properties of PEDOT/PSS/Te composite films treated with H<Subscript>2</Subscript>SO<Subscript>4</Subscript>

Firstly, tellurium (Te) nanorods with a high Seebeck coefficient have been integrated into a conducting polymer PEDOT/PSS to form PEDOT/PSS/Te composite films. The Seebeck coefficient of the PEDOT/PSS/Te (90 wt.%) composite films is ~191 μV/K, which is about 13 times greater than that of pristine PEDOT/PSS. Then, H₂SO₄ treatment has been used to further tune the thermoelectric properties of the composite films by adjusting the doping level and increasing the carrier concentration. After the acid treatment, the electrical conductivity of the composite films has increased from 0.22 to 1613 S/cm due to the removal of insulating PSS and the structural rearrangement of PEDOT. An optimized power factor of 42.1 μW/mK² has been obtained at room temperature for a PEDOT/PSS/Te (80 wt.%) sample, which is about ten times larger than that of the untreated PEDOT/PSS/Te composite film.     

Crystal growth,spectral properties and Judd–Ofelt analysis of Pr: CaF_2-YF_3

The 0.6 at.% Pr~(3+)-doped CaF_2-YF_3 crystal was successfully grown by the temperature gradient technique(TGT).X-ray diffraction analysis showed that the grown crystal still had cubic structure. The absorption spectrum, emission spectrum, Judd–Ofelt analysis and fluorescence decay curve at room temperature were discussed. The fluorescence lifetime of Pr: CaF_2-YF_3 crystal was 45.46 μs, and the σem ·τ of ~3P_0→~3H_6 and ~3P_0→~3F_2 transitions were calculated to be 80.92 × 10~(-20) cm~2·μs and 388.7 × 10~(-20) cm~2·μs, respectively. The FWHMs are 20.1 nm and 6.8 nm, which are higher than those of Pr: LiYF_4, Pr:LiLuF_4, Pr: LiGdF_4 and Pr: BaY_2F_8 crystals. The results show that the Pr: CaF_2-YF_3 crystal is expected to achieve 605 nm orange light and 642 nm red light laser operation.     

哈斯勒合金Ni-Fe-Mn-In的马氏体相变与磁特性研究

利用电弧炉制备了Ni_50-xFe_xMn₃₇In₁₃(x=1, 3, 5) 多晶样品, 通过结构和磁性测量, 系统分析了Ni_50-xFe_xMn₃₇In₁₃(x=1, 3, 5)样品的晶体结构和马氏体相变. 结果表明, 三样品在室温下呈现出了不同的晶体结构. 同时, 随着Fe含量的增加, 样品的马氏体相变温度急剧下降, 而铁磁性却逐渐增强. 研究了Fe3和Fe5样品在反马氏体相变过程中的磁电阻和磁卡效应. 在外加3 T的磁场下, 两样品在反马氏体相变区域所表现出的磁电阻效应分别约为-46%和-15%, 而等温熵变则约为6 J·kg^{-1·K-1和9.5 J}·kg^{-1·K-1. 然而, 伴随非常宽的相变温跨和较小的磁滞损失, Fe3样品在反马氏体相变区域的净制冷量达到96 J}·kg^-1.     

双沟4H-SiC MESFET优化结构的解析模型及性能

优化双沟4H-SiC MESFET结构,通过求解一维和二维泊松方程,建立优化结构的解析模型,分析这种结构的直流和交流特性.结果表明,饱和电流密度的计算结果与实验一致,结构优化后4H-SiC MESFET的饱和电流密度和击穿电压分别为420μA·μm^-1和155 V,明显高于优化前的275μA·μm^-1和141 V;最高输出功率密度为7.4 W·mm^-1,比优化前提高约64%;截止频率和最高振荡频率比优化前略微提高.双沟结构经优化后其交流小信号特性未退化而功率特性获得明显改善.     

Modulating the Electrochromic Performances of Transmissive and Reflective Devices Using N,N-Dimethyl Formamide Modified Poly(3,4-Ethylenedioxythiophene)/Poly(Styrene Sulfonate) Blend as Active Layers

As one of the important factors which affect the properties and applications of conducting polymers, the electrical conductivity of a poly(3,4-ethylenedoxy-thiophene)/ poly(styrene sulfonate) (PEDOT: PSS) blend was adjusted by using various amount of an organic solvent (N,N-dimethyl formamide, DMF) as an additive. The conductivities of PEDOT: PSS thin films can be increased dramatically, from 1.0 S to 32.1 S cm^?1, with a 2/1 volume ratio of PEDOT: PSS/DMF loading after totally removing the organic solvent by annealing the film at 80° for 48 h in a vacuum oven. The optical contrasts of transmissive and reflective devices assembled using DMF-modified PEDOT: PSS as active layers exhibited a close relationship with the conductivity of PEDOT: PSS. Interestingly, high conductivity of PEDOT: PSS enhanced the contrast of a transmissive device, while high conductivity of PEDOT: PSS decreased the contrasts of a reflective device. The underlying reason is related to the different electrochromic mechanisms of these two types of device configurations.