Mechanically Robust and Flexible Films of Ionic Liquid-Modulated Polymer Thermoelectric Composites

In the recent decade, polymer thermoelectric (TE) composite has witnessed explosive achievements to address energy generation and utilization. Besides the significant progress in enhancement of TE performance, the high mechanical property has received increasing attention, being important for practical applications in complex environments. However, the mechanical performance has always been improved at the sacrifice of TE performance, and vice versa, which poses a great challenge. Here, ionic liquid (IL)-assisted fabrication of flexible films of polymer TE composites with simultaneously high TE and mechanical performances based on poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), polyvinyl alcohol (PVA), and single-walled carbon nanotubes (SWCNTs) are reported. The resultant composite shows a high TE performance with a power factor of 106.1 ± 8.2 µW m⁻¹ K⁻² at room temperature, and strong mechanical robustness with a tensile modulus of 4.2 ± 0.5 GPa and fracture strength of 136.5 ± 10.6 MPa. It is the most mechanically robust TE composite known with such a high power factor in the available literature. The present study provides a promising way to help address the longstanding and intractable issue of inferior mechanical performance of TE composites without compromising TE performance.     

Anisotropic Change of Liquid‐Crystal Domains by Polarized Infrared Pulse Laser Irradiation for a Columnar Mesophase

The infrared photoinduced alignment change of liquid‐crystal domains was investigated for a hexagonal columnar mesophase of a liquid‐crystalline triphenylene derivative. A uniform and anisotropic alignment change of domains was observed when a polarized infrared (IR) light corresponding to the wavelength of the aromatic C–C stretching absorption band of the triphenylene core was used to irradiate the sample. The relationship between the aligned azimuthal angle of the columnar axis and the polarization of the IR incident irradiation was investigated. IR absorption dichroism is induced as a result of the reorientation of triphenylene core. Texture observation and polarizing microscope FTIR spectra show that a change of the molecular alignment occurred and that the direction of columns depends on the polarization angle of the IR light used for irradiation. The mechanism of the alignment change in a columnar liquid crystal film by IR irradiation is also discussed. The technique could provide a novel technology to control the columnar alignment of highly viscous liquid crystals.     

Self‐Healable and Stretchable Organic Thermoelectric Materials: Electrically Percolated Polymer Nanowires Embedded in Thermoplastic Elastomer Matrix

Self‐healable and stretchable energy‐harvesting materials can provide a new avenue for the realization of self‐powered wearable electronics, including electronic skins, whose main materials are required to be robust to and stable under external damage and severe mechanical stresses. However, thermoelectric (TE) materials showing both self‐healing properties and stretchability have not yet been demonstrated despite their great potential to harvest thermal energy in the human body. As most existing TE materials are either mechanically brittle or unrecoverable after being subjected to damage, a novel approach is necessary for designing such materials. Herein, self‐healable and stretchable TE materials based on all‐organic composite system wherein polymer semiconductor nanowires are p‐doped with a molecular dopant and embedded in a thermoplastic elastomer matrix are reported. The polymer nanowires are electrically percolated in the matrix, and the resulting composite materials exhibit good TE performance. The composites also exhibit both excellent self‐healing properties under mild heat and pressure conditions and good stretchability. It is believed that this work can be a cornerstone for the design of self‐healable and stretchable energy‐harvesting materials as it provides useful guidelines for imparting electrical conductivity to insulating thermoplastic elastomers, which typically possess versatile and useful mechanical properties.     

正交实验法优化六方氮化硼薄膜的制备工艺

采用射频磁控溅射法,在Si(100)衬底上制备了适用于声表面波(SAW)器件的氮化硼(BN)薄膜。通过正交实验法,以薄膜中六方相的纯度和取向为指标,优化了磁控溅射方法制备六方BN(h-BN)薄膜的工艺条件。利用傅里叶变换红外光(FTIR)谱和X射线衍射(XRD)谱对薄膜进行了表征,实验结果表明,溅射功率为300W、无衬底负偏压、温度为400℃和N2∶Ar=7∶8vol.%时可以制备出高纯度且高c-轴择优取向的h-BN。     

Thermal Cycling, Mechanical Degradation, and the Effective Figure of Merit of a Thermoelectric Module

Thermoelectric modules experience performance reduction and mechanical failure due to thermomechanical stresses induced by thermal cycling. The present study subjects a thermoelectric module to thermal cycling and evaluates the evolution of its thermoelectric performance through measurements of the thermoelectric figure of merit, ZT, and its individual components. The Seebeck coefficient and thermal conductivity are measured using steady-state infrared microscopy, and the electrical conductivity and ZT are evaluated using the Harman technique. These properties are tracked over many cycles until device failure after 45,000 thermal cycles. The mechanical failure of the TE module is analyzed using high-resolution infrared microscopy and scanning electron microscopy. A reduction in electrical conductivity is the primary mechanism of performance reduction and is likely associated with defects observed during cycling. The effective figure of merit is reduced by 20% through 40,000 cycles and drops by 97% at 45,000 cycles. These results quantify the effect of thermal cycling on a commercial TE module and provide insight into the packaging of a complete TE module for reliable operation.     

低LUMO/HOMO共轭聚合物的制备及其电子传输性能

为了探究聚合物结构与性能的关系,获得电子传输型半导体材料。采用Stille交叉偶联反应,制备了基于噻吩-氰基乙烯-噻吩(TCNT)和2-氧吲哚-3-亚基-二氢吡咯吲哚-二酮(BDID)结构的一种新型的低能带隙给体-受体共轭聚合物PBDID-TCNT。采用热重分析仪、示差扫描量热仪、紫外-可见-近红外分光光度计、电化学工作站与原子力显微镜等测试手段对聚合物的热性能、光学性能、电化学性能以及微观结构进行了表征。结果表明:聚合物PBDID-TCNT具有优异的热稳定性,宽的吸收光谱,低的最低未占轨道/最高占有轨道能级(LUMO/HOMO)。首次制得了PBDID-TCNT型的聚合物,以聚合物为半导体层的有机薄膜晶体管器件展现出电子传输特性,电子迁移率达到0.11cm~2/(V·s),同时开关比超过10~5。     

A Facile Method for the Growth of Organic Semiconductor Single Crystal Arrays on Polymer Dielectric toward Flexible Field‐Effect Transistors

Polymer dielectrics with intrinsic mechanical flexibility are considered as a key component for flexible organic field‐effect transistors (OFETs). However, it remains a challenge to fabricate highly aligned organic semiconductor single crystal (OSSC) arrays on the polymer dielectrics. Herein, for the first time, a facile and universal strategy, polar surface‐confined crystallization (PSCC), is proposed to grow highly aligned OSSC arrays on poly(4‐vinylphenol) (PVP) dielectric layer. The surface polarity of PVP is altered periodically with oxygen‐plasma treatment, enabling the preferential nucleation of organic crystals on the strong‐polarity regions. Moreover, a geometrical confinement effect of the patterned regions can also prevent multiple nucleation and misaligned molecular packing, enabling the highly aligned growth of OSSC arrays with uniform morphology and unitary crystallographic orientation. Using 2,7‐dioctyl[1]benzothieno[3,2‐b]benzothiophene (C8‐BTBT) as an example, highly aligned C8‐BTBT single crystal arrays with uniform molecular packing and crystal orientation are successfully fabricated on the PVP layer, which can guarantee their uniform electrical properties. OFETs made from the C8‐BTBT single crystal arrays on flexible substrates exhibit a mobility as high as 2.25 cm² V^?1 s^?1, which has surpassed the C8‐BTBT polycrystalline film‐based flexible devices. This work paves the way toward the fabrication of highly aligned OSSCs on polymer dielectrics for high‐performance, flexible organic devices.     

The Influence of UV Irradiation on Ketonic Defect Emission in Fluorene‐Based Copolymers

The influence of UV irradiation in inert atmosphere on the emission spectrum of fluorenone containing poly[9,9‐bis(2‐ethyl)hexylfluorene] (PF2/6) has been investigated by means of optical absorption, photoluminescence (PL) and Fourier transform infrared (FTIR) spectroscopy. It is shown that a substantial reduction of green emission arising from ketonic defect sites can be achieved by irradiation of thin films with UV light. This is found to be accompanied by partial cross‐linking of the films. FTIR measurements show no reduction of the C=O stretching mode upon irradiation, and, moreover, the degree of cross‐linking does not scale with the relative fluorenone content (0.1, 0.5, and 5%). Therefore, the reduced emission intensity in the green spectral region is rather associated with the occurrence of interruptions in the polymer backbone, which reduce the effective conjugation length and subsequently inhibit the energy transfer onto the ketonic defect sites. The found results enabled us to build organic light emitting devices (OLEDs) that can be structured by selective illumination of the emitting layer with an intense UV light source. This method allows for the fabrication of rather efficient (2000 cd m⁻² at 7 V) two‐color OLEDs.     

掺N类金刚石薄膜的制备及微观结构分析

采用直流磁控溅射法,在光学玻璃衬底上沉积类金刚石(DLC)和掺N类金刚石薄膜(DLC:N)。用喇曼光谱、X射线光电子能谱(XPS)、傅里叶红外光谱(FTIR)等研究分析了所制备薄膜的微观结构。喇曼光谱的结果表明,掺N类金刚石膜仍具有典型的类金刚石膜结构,在类金刚石薄膜中掺N不仅有助于提高膜中sp3/sp2的比例,而且还能阻止sp2键向石墨相的转化,稳定并优化薄膜的类金刚石属性。FTIR表明,薄膜中N与C原子形成了C—N、CN及C≡N等键合方式。XPS谱表明,掺N类金刚石膜中除了C和N元素外,还出现了少量的O元素,而C1s和N1s的解谱显示,掺N后的类金刚石膜中的C、N结合能发生了明显的移动,由计算得出薄膜中N的含量为13.5%。薄膜的表面形貌图(AFM)表明,在类金刚石薄膜中掺N能够改善其表面形貌。     

Significant Enhancement of Thermoelectric Figure of Merit in BiSbTe-Based Composites by Incorporating Carbon Microfiber

Bismuth telluride-based materials are already being commercially developed for thermoelectric (TE) cooling devices and power generators. However, the relatively low efficiency, which is characterized by a TE figure of merit, zT, is the main obstacle to more widespread application. Significant advances in the TE performance have been made through boundary engineering via embedding nanoinclusions or nanoscale grains. Herein, an effective approach to greatly enhance the TE performance of p-type BiSbTe material by incorporating carbon microfibers is reported. A high zT of 1.4 at 375 K and high average zT of 1.25 for temperatures in the range of 300 to 500 K is achieved in the BiSbTe/carbon microfiber (BST/CF) composite materials. Their superior TE performance originates from the low thermal conductivity and the relatively high power factor. A TE unicouple device based on the p-type BST/CF composite material and the commercially available n-type bismuth telluride-based material shows a huge cooling temperature drop in the operating temperature range of 299–375 K, and is greatly superior to the unicouple device made of both commercial p-type and n-type bismuth telluride-based material. The materials demonstrate a high average zT and excellent mechanical properties and are strong candidates for practical applications.     

硅基中长波红外减反微结构研究

采用微加工工艺在Si衬底上制备了微柱和微锥阵列,结合光学建模分析,研究了结构参数对中长波（2.5~9 m）红外光反射率的影响规律。使用严格耦合波分析方法（RCWA）计算的微结构反射光衍射效率与傅里叶红外变换光谱仪（FTIR）测试的反射率结果吻合较好。研究结果表明,Si基微结构对TM及TE偏振光均有良好的红外光减反特性,微锥结构具有更好的减反效果,2.5~6.5 m中红外偏振光的反射率低至2%,同时表现出良好的宽谱与广角度减反特性。     

Stretchable Mesh-Patterned Organic Semiconducting Thin Films on Creased Elastomeric Substrates

Recently, many researchers have tried to develop stretchable semiconducting thin films that can maintain their electrical performance under stretching. However, the fabrication processes have not been sufficiently practical and feasible to be used for soft electronics. Here, a stretchable high-performance organic semiconducting thin film is fabricated by exploiting simultaneous patterning and pinning of a polymer semiconductor solution on an elastomeric substrate in which creasing-instability has occurred. As a result, a mesh-like polymer semiconducting thin film having vacant regions in the crease centers and surrounding crystalline regions near them can be fabricated. Due to the mesh-like morphology and the percolated crystalline regions, the polymer semiconducting thin film shows superior stretchability and charge-transport performance compared to the reference flat polymer thin film. When incorporated into organic thin-film transistors, the DPP-DTT polymer semiconducting thin film maintains its high field-effect carrier mobility (0.53 ± 0.03 cm² (V s)⁻¹) under a strain ε of 80% and is highly stable under repeated stretching cycles at an ε of 50%.     

AlGaAs/GaAs quantum well infrared photodetector focal plane array based on MOCVD technology

128 × 128, 128 × 160 and 256 × 256 AlGaAs/ GaAs quantum well infrared photodetector (QWIP) focal plane arrays (FPA) as well as a large area test device are designed and fabricated. The device with n-doped back-illuminated AIGaAs/GaAs quantum structure is achieved by metal organic chemical vapor deposition (MOCVD) epitaxial growth and GaAs integrated circuit processing technology. The test device is valued by its dark current performance and Fourier transform infrared spectroscopy (FTIR) spectra at 77 K. Cut off wavelengths of 9 and 10.9 μm are realized by using different epitaxial structures. The blackbody detectivity DB* is as high as 2.6 × 109 cm· Hz1/2·W-1. The 128 × 128 FPA is flip-chip bonded on a CMOS readout integrated circuit with indium (In) bumps. The infrared thermal images of some targets under room temperature background have been successfully demonstrated at 80 K operating temperature. In addition, the methods to further improve the image quality are discussed.     

Synthesis and characterization of TiO2-doped Polyaniline nanocomposites by chemical oxidation method

Polyaniline (PANI)/TiO₂ nanocomposite samples with various dopant percentages of TiO₂ were synthesized at room temperature using a chemical oxidative method. The samples were characterized by ultraviolet-visible spectrometer, Fourier transform infrared (FTIR) spectrometer, X-ray diffraction (XRD), scanning electron microscopy (SEM), EDAX and conductivity measurements. Incorporation of TiO₂ nanoparticles caused a slight red shift at 310 nm in the absorption spectra due to the interactions between the conjugated polymer chains and TiO₂ nanoparticles with π–π^? transition. FTIR confirmed the presence of TiO₂ in the molecular structure. In PANI/TiO₂ composites, two additional bands at 1623 cm^?1 and 1105 cm^?1 assigned to Ti–O and Ti–O^–C stretching modes were present. It can be concluded that Ti organic compounds are formed with an alignment structure of TiO₂ particles. XRD patterns revealed that, as the TiO₂ percentage was increased, the amorphous nature disappeared and the composites became more strongly oriented along the (1 1 0) direction, which showed the tetragonal structure of nanocrystalline TiO₂. SEM studies revealed the formation of uniform granular morphology with average grain size of 200 nm for (50%) PANI/TiO₂ nanocomposite samples.     

Hierarchical Calcite Crystals with Occlusions of a Simple Polyelectrolyte Mimic Complex Biomineral Structures

Biominerals are complex inorganic‐organic structures that often show excellent mechanical properties. Here a bio‐inspired study of a remarkably simple synthetic system is presented in which only one charged polymer additive (poly(sodium 4‐styrenesulfonate)) is able to induce hierarchical structuring of calcite similar to biominerals. The interaction of the negatively charged polymer with the nucleation and growth of the mineral, in particular via selective adsorption to internal and external (001) facets of the calcite lattice, implies structural features from the micrometer down to the nanometer level. The crystals exhibit a distinct rounded morphology and a controlled orientation. Moreover, the polymer molecules are occluded within the crystals with different concentrations in well‐defined regions. This leads to the induction of a mesoscale structure based on 100 nm sized mineral building blocks with granular substructure and rough surface, as well as small modifications of the crystallographic structure. Such a combination of hierarchically organized structural features has previously only been reported for biogenic calcite, which is typically grown in a complex process involving multiple organic additives. It is also shown that the organic occlusions in the calcite‐PSS hybrid crystals strongly affect the mechanical performance, as known for some biominerals.     

靶基距对反应溅射AlN薄膜微结构和性能的影响

采用射频(RF)磁控反应溅射法在Si基底上制备了氮化铝(AlN)薄膜,利用X射线衍射(XRD)、傅立叶红外光谱(FTIR)、扫描电子显微镜(SEM)和纳米力学测试系统研究靶基距对AlN薄膜取向性、微结构、形貌和力学性能的影响。结果表明,靶基距较大时,形成的AlN薄膜为非晶态,薄膜表面较疏松;随着靶基距的减少,AlN薄膜变为多晶态,且具有(100)择优取向;随着靶基距的进一步减少,薄膜结晶质量变好,晶粒变大,薄膜变得更致密,择优取向也由(100)逐渐向(002)转变;靶基距较小时,AlN压电薄膜与基底结合得更牢固,而压电薄膜与基底结合的紧密程度对多层膜声表面波(SAW)器件性能优劣的影响至关重要。     

（英）离子束溅射法制备碳化锗薄膜的红外光学特性和力学特性

采用离子束溅射法通过在CH4和Ar 的混合气体中溅射Ge靶材制备碳化锗(Ge1-xCx)薄膜.分别通过原子力显微镜、拉曼光谱和X射线光电子能谱、傅里叶变换红外光谱以及纳米压痕测试研究了薄膜的表面形貌、化学结构、光学特性和力学特性.同时分析了制备薄膜时的离子源束压和薄膜性质之间的关系.结果表明,薄膜的粗糙度随束压的增大而减小.在较高束压下制备的薄膜含有较少的C元素和较多的Ge-C键.薄膜具有非常好的红外光学特性和力学特性.薄膜在较大波长范围内具有良好的透光性能.C元素含量随着束压的升高而降低,进而导致薄膜的折射率在束压从300 V增大到800 V的过程中逐渐升高.薄膜的硬度大于8 GPa.由于薄膜中的Ge-C键代替了C-C 键和C-Hn键,薄膜的硬度随束压的增加逐渐增加.     

Observing the Stimulated Raman Gain Spectra of Solutions Using an Infrared Pump Pulse with Narrow Linewidth and a Low-Noise CW Probe Laser

Stimulated Raman gain (SRG) spectroscopy using infrared pump pulses with narrow linewidth and a low-noise cw probe infrared laser was proposed. High-resolution Raman spectra of solutions were obtained. The SRG spectra of crystal GaP, benzene, and toluene were measured to confirm the spectral resolution and sensitivity over the terahertz (THz) region. We discuss the polarization dependence of the spectral measurement of carbon tetrachloride. Our system can detect organic molecules in aqueous solutions.     

Molecular order,charge injection efficiency and the role of intramolecular polar bonds at organic/organic heterointerfaces

The effect of orientational changes in thin films of the non-crystalline hole transport material α-N-N′-diphenyl N-N″-bis(1 naphthayl)-1,1′-biphenyl-4,4′-diamine (α-NPD) on the energy level alignment and the film electronic structure has been investigated by angle-resolved ultraviolet photoelectron spectroscopy and related to the transport characteristics of hole-only devices. Changes in the anisotropic α-sexithiophene (α-6T) substrate from a “standing” to a “flat” molecular orientation induced by mechanical rubbing lead to molecular order and a preferential orientation in subsequently deposited thin α-NPD films and cause a reduction of the charge injection barrier at the organic/organic interface. The results show that the height of this barrier is determined by the surface dipoles of the individual organic films that relate to the orientation of intramolecular polar bonds at the interface.     

An Intrinsically Stretchable High‐Performance Polymer Semiconductor with Low Crystallinity

For wearable and implantable electronics applications, developing intrinsically stretchable polymer semiconductor is advantageous, especially in the manufacturing of large‐area and high‐density devices. A major challenge is to simultaneously achieve good electrical and mechanical properties for these semiconductor devices. While crystalline domains are generally needed to achieve high mobility, amorphous domains are necessary to impart stretchability. Recent progresses in the design of high‐performance donor–acceptor polymers that exhibit low degrees of energetic disorder, while having a high fraction of amorphous domains, appear promising for polymer semiconductors. Here, a low crystalline, i.e., near‐amorphous, indacenodithiophene‐co‐benzothiadiazole (IDTBT) polymer and a semicrystalline thieno[3,2‐b]thiophene‐diketopyrrolopyrrole (DPPTT) are compared, for mechanical properties and electrical performance under strain. It is observed that IDTBT is able to achieve both a high modulus and high fracture strain, and to preserve electrical functionality under high strain. Next, fully stretchable transistors are fabricated using the IDTBT polymer and observed mobility ≈0.6 cm² V^?1 s^?1 at 100% strain along stretching direction. In addition, the morphological evolution of the stretched IDTBT films is investigated by polarized UV–vis and grazing‐incidence X‐ray diffraction to elucidate the molecular origins of high ductility. In summary, the near‐amorphous IDTBT polymer signifies a promising direction regarding molecular design principles toward intrinsically stretchable high‐performance polymer semiconductor.