自组装半导体碳纳米管薄膜的光电特性

采用自组装的方法制备99%高纯度半导体碳纳米管平行阵列条带,以金属钯和钪为非对称接触电极制备碳纳米管(CNT)薄膜晶体管(TFTs)器件.主要研究不同沟道长度碳纳米管薄膜晶体管器件的电输运特性和红外光电响应特性,分析了其中的载流子输运和光生载流子分离的物理机制.我们发现薄膜晶体管器件的电学性能和光电性能依赖于器件沟道长度(L)和碳纳米管的平均长度(LCNT).当沟道长度小于碳纳米管的平均长度时,器件开关比最低;当沟道长度超过碳纳米管平均长度时,随着沟道长度的增加,器件开关比增加,光电流减小.相关研究结果为高纯碳纳米管薄膜晶体管器件在红外光探测器方面的进一步应用提供参考依据.     

印刷半导体碳纳米管薄膜晶体管光电性能研究

本文研究了聚[(2,7-9,9-二辛基芴基)-4,7-双(噻吩-2-基)苯并-2,1,3-噻二唑]（PFO-DBT）分离的半导体碳纳米管薄膜晶体管的光电性能。在超声和高速离心辅助下,PFO-DBT能够从商业化单壁碳纳米管中选择性分离出高纯的半导体碳纳米管。用得到的半导体碳纳米管溶液通过气溶胶喷墨印刷方法构建出高性能印刷薄膜晶体管器件。印刷碳纳米管薄膜晶体管表现出高的开关比（10⁷）和高迁移率（15.6 cm²·V^-1·s^-1）。并且所有制备的印刷薄膜晶体管具有很好的光敏感特性和很好的稳定性。     

全印刷碳纳米管薄膜晶体管构建及电性能研究

利用纳米压印和电刷镀技术在PET基体上制作出大面积金源、漏电极阵列。分别采用钛酸钡复合材料为介电层,印刷银电极为顶电极,聚芴-二噻吩基吡咯并吡咯二酮(PF8DPP)分离的半导体碳纳米管为有源层,在柔性基体上构建出全印刷碳纳米管薄膜晶体管器件和反相器。全印刷碳纳米管薄膜晶体管的开关比和迁移率分别达到4×10⁴和6 cm²·V^-1·s^-1,且器件表现出零回滞特性。构建的反相器在V_dd =8 V时,其增益可以达到12。     

双极性碳纳米管薄膜晶体管构建及电性能研究

本文用聚 (PFO-BT)分离的半导体碳纳米管作为有源层,通过气溶胶喷墨打印技术在刚性基体上构建出底栅结构的碳纳米管薄膜晶体管器件。用钛酸钡复合材料封装后,碳纳米管薄膜晶体管表现出很好的双极性、较高的开关比和零回滞特性,同时阈值电压能够控制在0 V附近。通过两个双极性薄膜晶体管连接而成的反相器表现出零回滞、高电压增益(V_dd=1.5 V时,其增益可达到35)和大噪声容限(V_dd=1 V时,最大噪声容限为0.44 V)。     

溶胶凝胶法制备TiO2@Cf柔性忆阻器交叉开关

以碳纤维作为柔性衬底和电极材料,通过溶胶凝胶法在其表面镀覆TiO₂阻变活性层,进而通过“十”字搭接制备成柔性纤维忆阻器（TiO₂@C_f）。采用X射线衍射、扫描电子显微镜、X射线光电子能谱等测试手段对TiO₂@C_f结构进行表征并对其忆阻特性及阻变机理进行研究。结果表明：碳纤维上的TiO₂涂层为锐钛矿型晶体结构,其氧空位的浓度约为19.5%;制备的TiO 2@C_f柔性忆阻器为突变型忆阻器,其高低阻态阻值开关比可达10⁴;经过疲劳耐受性测试,忆阻器件的高低阻态开关比稳定在2个数量级左右。TiO₂@C_f忆阻器的机理表现为：在高阻态和低阻态时是以欧姆导电为主导的载流子输运机制,其阻态转变机制与氧空位导电细丝的形成和断裂有关。制备的TiO₂@C_f柔性忆阻器在一定程度上具有柔性弯曲变形,同时满足可编织、穿戴等功能。     

PEDOT的电化学合成及其在固态染料敏化太阳能电池中的应用研究

本工作主要围绕PEDOT的合成及其在固态染料敏化太阳能电池对电极中的应用开展研究,重点研究了循环伏安法电化学沉积过程中循环次数（10~50次）对PEDOT薄膜的形貌、厚度及光学性质的影响.通过红外光谱、SEM、紫外-可见吸收光谱表征了PEDOT的结构、形貌及光性质;通过J-V、动态调制光电流谱（IMPS）/光电压谱（IMVS）以及Tafel测试表征了基于PEDOT透明对电极染料敏化太阳能电池的光电化学性能.结果表明：采用循环伏安法电沉积合成PEDOT制备固态染料敏化太阳能电池对电极时,CV循环30~40次之间时可以获得最佳的光电性能,固态器件的光电转换效率为5.34%,这是因为在该条件下所制备的PEDOT具有均匀致密的表面、较好的光学性质以及较高的光电催化性能（J₀=2.51×10^-3 A·cm^-2）,使得器件可以获得较大的扩散系数（D_n=28.80 μm²·ms^-1）和载流子扩散长度（L=21.41 μm）,有利于电荷的传输.当CV循环次数大于40次时,PEDOT薄膜会在掺氟的SnO₂透明导电玻璃（FTO）表面发生溶解、脱附,从而使得其光电催化性能下降.在双面光照条件下,以电沉积PEDOT作为透明对电极的器件光电性能提升了20%左右.     

贫PbI2基体的胶体量子点固体用于高效红外太阳能电池(英文)

胶体量子点(CQD)具有优异的红外光吸收能力和光谱可调特性,是用于制备高效太阳能电池最有前途的红外光电材料之一。然而,以醋酸铵(AA)为添加剂的液相配体交换会导致CQD固体中产生宽带隙PbI₂基质,其将作为电荷传输势垒,在很大程度上影响了CQD太阳能电池(CQDSC)中载流子的提取,从而影响了光伏性能。本文报道利用二甲基碘化铵(DMAI)调节CQD配体交换过程,使载流子在CQD固体中的传输势垒大幅降低。通过对CQD固体进行全面的表征和理论计算,充分揭示了DMAI和CQD之间的相互作用。结果表明,通过DMAI调节CQD配体交换过程,使CQD固体均匀堆积,提高了载流子输运性能,并且陷阱辅助复合受到显著抑制。因此,CQDSC器件中的载流子提取得到了大幅提高,能量转换效率(PCE)比用AA制备的CQDSC器件提高了17.8%。此工作为调控CQD表面化学特性提供了新的研究思路,并为降低CQD固体中载流子输运的势垒提供了可行的方法。     

输运层厚度对双层有机器件复合发光的影响

采用ITO/PVK/Alq/Al双层电致发光(EL)结构,制备了三种载流子输运层厚度分别为30、 60、 120 nm,发光层厚度均为300 nm的有机薄膜EL器件,测试其EL谱及J-V特性曲线.根据有机EL器件中载流子的产生和输运过程导出了载流子复合几率及电子和空穴密度分布表示式,用以解释其发光强度随输运层厚度的变化关系,用一维无序结构载流子随机跃迁模型讨论输运层厚度对器件电流密度及启动电压的影响,探讨了载流子在薄膜中的输运过程,其理论与实验符合得很好.     

二氧化硅栅绝缘层的制备与表面修饰

研究了有机薄膜晶体管的二氧化硅栅绝缘层的性质。二氧化硅绝缘层的制备采用热生长法，氧化气氛是O₂(g)+H₂O(g)，工艺为干氧-湿氧-干氧的氧化过程。制得的绝缘层漏电流在10^-9 A左右。以该二氧化硅作为有机薄膜晶体管的栅绝缘层，并五苯作为有源层制作了有机薄膜晶体管器件。实验表明采用十八烷基三氯硅烷(OTS)进行表面修饰的器件具有OTS/SiO₂双绝缘层结构，可以有效地降低SiO₂栅绝缘层的表面能并改善表面的平整度。修饰后器件的场效应迁移率提高了1.5倍、漏电流从10^-9 A降到10^-10 A、阈值电压降低了5 V、开关电流比从10⁴增加到10⁵。结果显示具有OTS/SiO₂双绝缘层的器件结构能有效改进有机薄膜晶体管的性能。     

CuInS2量子点阻变效应

采用改进的热分解法制备了具有半导体效应的CuInS₂量子点,量子点尺寸均匀、大小为4.2 nm。组装的Au/CuInS₂/FTO阻变存储器件表现出典型的双极性阻变特点,其开态电压为-3.8 V,关态电压为4 V,ON/OFF开关比约为10³。对器件的I-V特性曲线线性拟合发现,器件的阻变机制在高阻态时表现为空间限制电荷（SCLC）传导机制,在低阻态时表现为欧姆传导机制。器件的阻变特性主要是由于电荷被CuInS₂薄膜中的缺陷产生的势阱捕获导致。通过调节陷阱势垒高度引起电荷在陷阱中移动,导致导电通路的产生和断裂,使器件处于高阻态和低阻态。     

Finite-length models of carbon nanotubes based on Clar sextet theory

Finite-length models of metallic and semiconducting carbon nanotubes (CNTs) based on Clar sextet theory of aromatic systems are proposed. For metallic CNTs, the electronic properties of finite-length models converge monotonically to the values expected for quasi-monodimensional metallic systems. For semiconducting CNTs, the use of finite-length models as proposed in this work leads to a fast convergence of the electronic properties to the values expected for the corresponding infinite-length nanotube.     

Electronic properties of single-walled carbon nanotubes inside cyclic supermolecules

Possible ways for manipulating carbon nanotubes (CNTs) with cyclic supermolecules are studied using density functional theory. Electronic structure calculations with structure optimizations have been performed for the (4,4) and (8,0) single-walled carbon nanotubes (SWNTs) complexed with crown ethers as well as for the (4,0) SWNT with beta-cyclodextrin. A slight polarization of charge in both the nanotube and the supermolecule is observed upon rotaxane complexation, but the interaction is mainly repulsive, and the systems stay 2.8-3.5 A apart. The supermolecule does not affect the electronic band structure of the nanotube significantly within such a configuration. The situation differs noticeably for chemically cross-linked SWNTs and crown ethers, where a peak arises at the Fermi energy in the density of states. As a result, the band gap of semiconducting CNT(8,0) (0.5 eV) vanishes, and a new conduction channel opens for the metallic CNT(4,4).     

Ab initio simulations of doped single-walled carbon nanotube sensors

The interactions between oxygen and nitrogen atoms with single-walled carbon nanotubes were investigated for nanotubes with two different geometrical configurations using first-principle calculations within the framework of the density functional theory. We introduced a new type of toxic gas sensor that can detect the presence of H₂, Cl₂, CO, and NO molecules. We also demonstrated that the sensitivity of this device can be controlled by the concentration of the dopants on the surface of the nanotube. In addition, the transport properties of the doped nanotube were studied for different concentrations of oxygen or nitrogen atoms that were randomly distributed on the surface of the single-walled carbon nanotube. We observed that small amounts of dopants can modify the electronic and transport properties of the nanotube and can lend metallic properties to the nanotube. Band-gap narrowing occurs when the nanotube is doped with either oxygen or nitrogen atoms.     

Carbon nanotube-carbon black hybrid counter electrodes for dye-sensitized solar cells and the effect on charge transfer kinetics

In this work, the catalytic activity of carbon nanotubes (CNTs), carbon black (CB), and CNT-CB counter electrodes in the I⁻/I₃⁻ reduction reaction is reported and compared with the Pt counter electrode. The fabricated counter electrodes were evaluated in dye-sensitized solar cells (DSSCs). The results indicate that the best cathodes were made from CNT₁₀ (240 μm) and CB with a charge transfer resistance (R_CT) of 2.70 Ω, and when the complete device shows 19.83 Ω of internal series resistance (R_S), the photovoltaic parameters of these cells were J_SC = 10.47 mA cm⁻²; V_OC = 0.70 V; and FF = 57.90, with an efficiency of 4.29%, indicating a better interaction between the CNT₁₀ in the 3D network of the counter electrode, generating a good charge transfer kinetics, in comparison with only CNT₁₀ or CB.

     

Multilayer films composed of conductive poly(3‐hydroxybutyrate)/carbon nanotubes bionanocomposites and a photoresponsive conducting polymer

In order to develop new electronic devices, it is necessary to find innovative solutions to the eco‐sustainability problem of materials as substrates for circuits. We realized a photoresponsive device consisting of a semiconducting polymer film deposited onto optically semitransparent and conductive biodegradable poly(3‐hydroxybutyrate) (PHB)/carbon nanotube (CNT) substrates. The experiments indicated that the PHB‐CNT bionanocomposite substrate behaves as an optical window trapping electric charges produced by the photoexcitation of the semiconducting polymer. Such PHB‐CNT functional substrates are expected to be attractive for eco‐friendly electronics. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 596–602     

Carbon nanotube capsules self-assembled by w/o emulsion technique

Carbon nanotube capsules (CNCs) with the diameter of 5-10 microm were fabricated from acid-modified multiwalled carbon nanotubes (CNTs) using water-in-oil (W/O) emulsion technique. The effects of the content of CNTs in water, the extent of acid treatment, and the length of CNTs used on the formation and morphology of CNCs were investigated. It was found that the amount of CNTs in water and the length of CNTs are the crucial factors for the formation of carbon nanotube capsules.     

Carbon nanotube enhanced membrane distillation for online preconcentration of trace pharmaceuticals in polar solvents

Carbon nanotube enhanced membrane distillation (MD) is presented as a novel, online analytical preconcentration method for removing polar solvents thereby concentrating the analytes, making this technique an alternate to conventional thermal evaporation. In a carbon nanotube immobilized membrane (CNIM), the CNTs serve as sorbent sites and provide additional pathways for enhanced solvent vapor transport, thus enhancing preconcentration. Enrichment using CNIM doubled compared to membranes without CNTs, while the methanol flux and mass transfer coefficients increased by 61% and 519% respectively. The carbon nanotube enhanced MD process showed excellent precision (RSD of 3-5%), linearity, and the detection limits were in the range of 0.001 to 0.009 mg L(-1) by HPLC analysis.     

Effect of nanotube-length on the transport properties of single-file water molecules: transition from bidirectional to unidirectional

We use molecular dynamics (MD) simulations to study the transport of single-file water molecules through carbon nanotubes (CNTs) with various lengths in an electric field. Most importantly, we find that even the water dipoles inside the CNT are maintained along the field direction, a large amount of water molecules can still transport against the field direction for short CNTs, leading to a low unidirectional transport efficiency (η). As the CNT length increases, the efficiency η will increase remarkably, and achieves the maximum value of 1.0 at or exceeding a critical CNT length. Consequently, the transition from bidirectional to unidirectional transport is observed and is found to be relevant to thermal fluctuations of the two reservoirs, which is explored by the interaction between water molecules inside and outside the CNT. We also find that the water flow vs CNT length follows an exponential decay of f ～ exp?(- L/L(0)), and the average translocation time of individual water molecules yields to a power law of τ(trans) ～ L(υ), where L(0) and ν are constant and slightly depend on the field strength. We further compare our results with the continuous-time random-walk (CTRW) model and find that the water flow can also be described by a power law of f ～ L(-μ) modified from CTRW. Our results provide some new physical insights into the biased transport of single-file water molecules, which show the feasibility of using CNTs with any length to pump water in an electric field. The mechanism is important for designing efficient nanofluidic apparatuses.     

Theoretical study of current-voltage characteristics of carbon nanotube wire functionalized with hydrogen atoms

A functionalized single-walled carbon nanotube (SWCNT) of a finite length with a ring-like hydrogenation around its surface is designed toward fabrication of a molecular field-effect transistor (FET) device. The molecular wire thus designed is equipped with a quantum dot inside, which is confirmed by theoretical analysis for electronic transport. In particular, the current-voltage (I-V) characteristics under influence of the gate voltage are discussed in detail.