Mechanism of Crystallization and Implications for Charge Transport in Poly(3‐ethylhexylthiophene) Thin Films

In this work, crystallization kinetics and aggregate growth of poly(3‐ethylhexylthiophene) (P3EHT) thin films are studied as a function of film thickness. X‐ray diffraction and optical absorption show that individual aggregates and crystallites grow anisotropically and mostly along only two packing directions: the alkyl stacking and the polymer chain backbone direction. Further, it is also determined that crystallization kinetics is limited by the reorganization of polymer chains and depends strongly on the film thickness and average molecular weight. Time‐dependent, field‐effect hole mobilities in thin films reveal a percolation threshold for both low and high molecular weight P3EHT. Structural analysis reveals that charge percolation requires bridged aggregates separated by a distance of ≈2–3 nm, which is on the order of the polymer persistence length. These results thus highlight the importance of tie molecules and inter‐aggregate distance in supporting charge percolation in semiconducting polymer thin films. The study as a whole also demonstrates that P3EHT is an ideal model system for polythiophenes and should prove to be useful for future investigations into crystallization kinetics.     

Growth of Transparent and Conductive Polycrystalline (0001)‐ZnO Films on Glass Substrates Under Low‐Temperature Hydrothermal Conditions

Flat panel display technology seems to be an ever‐expanding field developing into a multibillion dollar market. A set of technical solutions involve a transparent conducting film (TCF) that is today still dominated by indium‐tin‐oxide (ITO). In a race to find alternatives that would avoid the indium pitfalls, mainly due to its increasing price and limited natural availablity, replacement materials have been extensively investigated. This work demonstrates that by exploiting basic principles of crystal growth in geometrically constrained conditions, zinc oxide (ZnO) could easily be utilized for this purpose. ZnO layers were grown on inexpensive glass substrates via low‐temperature citrate‐assisted hydrothermal (HT) method. It was shown that in the nucleation stage the crystal growth can be efficiently controlled by spatially confined oriented growth (SCOG) mechanism to produce smooth and dense (0001) oriented polycrystalline ZnO films with superb optical properties. Our products show optical transparency of 82% and surprisingly low sheet resistance for undoped ZnO, only in the order of few 100 Ω sq^?1. We believe that a very high degree of self‐organization between the ZnO crystals in our polycrystalline films grown under controlled SCOG conditions is main reason for the highest so far reported transparency to conductivity ratio for undoped ZnO thin film ceramics.     

Band-Like Charge Transport in Phytic Acid-Doped Polyaniline Thin Films

We explore the charge transport properties of phytic acid (PA) doped polyaniline thin films prepared by the surfactant monolayer-assisted interfacial synthesis (SMAIS). Structural and elemental analysis confirms the inclusion of PA in the thin films and reveals a progressive loss of crystallinity with the increase of PA doping content. Charge transport properties are interrogated by time-resolved terahertz (THz) spectroscopy. Notably, independently of doping content and hence crystallinity, the frequency-resolved complex conductivity spectra in the THz region can be properly described by the Drude model, demonstrating band-like charge transport in the samples and state-of-the-art charge carrier mobilities of ≈1 cm²V⁻¹s⁻¹. A temperature-dependent analysis for the conductivity further supports band-like charge transport and suggest that charge carrier mobility is primarily limited by impurity scattering. This work highlights the potential of PA doped polyaniline for organic electronics.     

Following Chemical Charge Trapping in Pentacene Thin Films by Selective Impurity Doping and Wavelength‐Resolved Electric Force Microscopy

Charge trapping is one of several factors that limit the performance of organic electronic materials, yet even in pentacene, a prototypical small‐molecule semiconductor, the precise chemical nature of charge trapping remains poorly understood. Here the effects of three chemical trap‐precursor candidates are examined by layering thin‐film pentacene transistors with different pentacene defect species. The resulting charge trapping is studied in each device via scanning‐probe electric force microscopy coupled with variable‐wavelength sample illumination. Firstly, it is found that layering with pentacen‐6(13H)‐one (PHO) readily produces uniform charge trapping everywhere in the transistor channel, as expected for an active blanket‐deposited trap‐precursor. However, layering with 6,13‐dihydropentacene (DHP) produces fewer, more‐isolated traps, closely resembling the surface potential distribution in pristine pentacene thin films. Secondly, the rates of trap‐clearing versus illuminating wavelength (trap‐clearing spectra) are measured, revealing enhanced trap‐clearing rates at wavelengths assigned to the absorption of either pentacene or the charged trap species. The trap‐clearing spectrum for the PHO‐layered sample closely resembles the spectrum obtained from pentacene aged in a working transistor, while the trap‐clearing spectrum for the DHP‐layered sample resembles the spectrum observed in pristine pentacene. We conclude that PHO competently creates traps in pentacene that match the expected trap‐clearing spectrum for degraded pentacene, while DHP does not, and that the chemical trap species in aged pentacene is very likely PHO⁺.     

Lithium Titanate Anode Thin Films for Li‐Ion Solid State Battery Based on Garnets

Solid state electrolytes, such as Li‐Garnets, are fastest Li‐ionic conductor materials that have attracted attention for safe hybrid and full solid state battery architectures. Turning to oxide‐based low voltage anodes gives opportunities to avoid Li‐dendrite formation and also to reach full thin film microbattery architectures based on garnets as high energy density replacement for supercapacitors. Herein, it is demonstrated that Li₄Ti₅O₁₂ thin films deposited by pulsed laser deposition can show stable structures and cycling kinetics reaching almost close to theoretical capacity of 175 mAh g^?1 when combined to Li_6.25Al_0.25La₃Zr₂O₁₂ pellets. Stable operation at room temperature with 90% of theoretical capacity retention at 2.5 mA g^?1 over 22 cycles is achieved on bilayer half cell batteries. Rate capability studies show promising charge and discharge capacities and act as a case study for the well‐known Li₄Ti₅O₁₂ thin film anode, demonstrating its good compatibility with the investigated solid garnet electrolyte. This gives new perspective on the use of oxide‐based low voltage anodes for future strategies avoiding Li‐dendrite formation or safe solid state microbattery thin film assemblies based on Li‐garnets.     

Proton Conduction in Dense and Porous Nanocrystalline Ceria Thin Films

The electrical conductivity of ceria thin films (epitaxial as well as dense and porous nanocrystalline) is investigated in dry and wet atmosphere at temperatures below 500 °C. For the epitaxial and the fully dense nanocrystalline samples, no significant differences can be observed between dry and wet conditions. In marked contrast, the nanocrystalline porous films obtained via spin coating exhibit a considerable enhancement of the protonic conductivity below 300 °C in wet atmosphere. This outcome reveals that the residual open mesoporosity plays the key role for the enhancement of the proton transport at low temperatures and not the high density of grain boundaries. The quantitative analysis of the various pathways, along which the proton transport can take place, indicates that the observed proton conduction can arise not only from bulk water adsorbed in the open pores but also from the space charge zones on the water side of the water/oxide interface.     

溅射法生长高度取向ZnO的实验研究

采用直流磁控反应溅射法，在3种衬底上获得c轴(002)定向生长的ZnO薄膜，并利用X射线衍射、PL谱对上述薄膜进行了实验研究。结果表明N型(100)Si衬底上，ZnO(002)取向度最高，分析认为是由于N型(100)Si与ZnO(002)晶格匹配度高所致。     

Space‐Charge‐Stabilized Ferroelectric Polarization in Self‐Oriented Croconic Acid Films

Great progress has been made recently in molecular ferroelectrics with properties even comparable to those of inorganic ferroelectrics. However, it is difficult to develop basic thin films and devices for practical applications since most molecular ferroelectrics are uniaxial. The single polar axes of crystallites inside their films, if available, are usually oriented randomly. These can induce the components without contribution to ferroelectric polarization and a large depolarization electric field to suppress polarization. In this work, it is demonstrated that uniaxial croconic acid films in two‐terminal devices, deposited by thermal evaporation, can show effective ferroelectric polarization and nonvolatile memory switching behavior with small coercive fields of 11–30 kV cm^?1. The polar c‐axes in thick crystalline films (>500 nm) are found to be self‐oriented nearly at a desired direction. With the assistance of trapped charges, stable ferroelectric polarization can be achieved, in spite of the existence of nonferroelectric components. These may pave a way to utilize uniaxial molecular ferroelectrics for various applications, such as gate dielectrics, electrets, and memory devices.     

Thickness‐Dependent Structure–Property Relationships in Strained (110) SrRuO3 Thin Films

Thickness‐dependent structure–property relationships in strained SrRuO₃ thin films on GdScO₃ (GSO) substrates are reported. The film is found to have epitaxially stabilized crystal structures that vary with the film thickness. Below 16 nm, the √2a_pc × √2a_pc × 2a_pc monoclinic structure is stabilized while above 16 nm the film has the a_pc × 2a_pc × a_pc tetragonal structure. The thickness‐dependent structural changes are ascribed to the substrate‐induced modification in the RuO₆ octahedral rotation pattern, which highlights the significance of the octahedral rotations for the epitaxial strain accommodation in the coherently‐grown films. Close relationships between the structural and physical properties of the films are also found. The monoclinic film has the uniaxial magnetic easy axis 45° away from the [110]_GSO direction while the tetragonal film has the one that lies along the in‐plane [1–10]_GSO direction. The results demonstrate that the octahedral rotations in the strained perovskite oxide thin films are a key factor for determining their structure phases and physical properties.     

Thin Films of Dendritic Anatase Titania Nanowires Enable Effective Hole‐Blocking and Efficient Light‐Harvesting for High‐Performance Mesoscopic Perovskite Solar Cells

To achieve high‐performance perovskite solar cells, especially with mesoscopic cell structure, the design of the electron transport layer (ETL) is of paramount importance. Highly branched anatase TiO₂ nanowires (ATNWs) with varied orientation are grown via a facile one‐step hydrothermal process on a transparent conducting oxide substrate. These films show good coverage with optimization obtained by controlling the hydrothermal reaction time. A homogeneous methyl­ammonium lead iodide (CH₃NH₃PbI₃) perovskite thin film is deposited onto these ATNW films forming a bilayer architecture comprising of a CH₃NH₃PbI₃ sensitized ATNW bottom layer and a CH₃NH₃PbI₃ capping layer. The formation, grain size, and uniformity of the perovskite crystals strongly depend on the degree of surface coverage and the thickness of the ATNW film. Solar cells constructed using the optimized ATNW thin films (220 nm in thickness) yield power conversion efficiencies up to 14.2% with a short‐circuit photocurrent density of 20.32 mA cm^?2, an open‐circuit photovoltage of 993 mV, and a fill factor of 0.70. The dendritic ETL and additional perovskite capping layer efficiently capture light and thus exhibit a superior light harvesting efficiency. The ATNW film is an effective hole‐blocking layer and efficient electron transport medium for excellent charge separation and collection within the cells.     

Growth of Heteroepitaxial ZnO Thin Films on GaN‐Buffered Al2O3 (0001) Substrates by Low‐Temperature Hydrothermal Synthesis at 90 °C

Heteroepitaxial ZnO films are successfully grown on nondoped GaN‐buffered Al₂O₃ (0001) substrates in water at 90 °C using a two‐step process. In the first step, a discontinuous ZnO thin film (ca. 200 nm in thickness) consisting of hexagonal ZnO crystallites is grown in a solution containing Zn(NO₃)·6 H₂O and NH₄NO₃ at ca. pH 7.5 for 24 h. In the second step, a dense and continuous ZnO film (ca. 2.5 μm) is grown on the first ZnO thin film in a solution containing Zn(NO₃)·6 H₂O and sodium citrate at ca. pH 10.9 for 8 h. Scanning electron microscopy, X‐ray diffraction, UV‐vis absorption spectroscopy, photoluminescence spectroscopy, and Hall‐effect measurement are used to investigate the structural, optical, and electrical properties of the ZnO films. X‐ray diffraction analysis shows that ZnO is a monocrystalline wurtzite structure with an epitaxial orientation relationship of (0001)[11 0]_ZnO∥(0001)[11 0]_GaN. Optical transmission spectroscopy of the two‐step grown ZnO film shows a bandgap energy of 3.26 eV at room temperature. A room‐temperature photoluminescence spectrum of the ZnO film reveals only a main peak at ca. 380 nm without any significant defect‐related deep‐level emissions. The electrical property of ZnO film showed n‐type behavior with a carrier concentration of 3.5 × 10¹⁸ cm^–3 and a mobility of 10.3 cm² V^–1 s^–1.     

Understanding the Mechanism of Solvent‐Mediated Adhesion of Vacuum Deposited Au and Pt Thin Films onto PMMA Substrates

The adhesion of vapor deposited Au and Pt thin films onto poly(methyl methacrylate) (PMMA) substrates can be significantly enhanced by either spin‐casting or vapor‐exposure to hydrohalocarbon solvents prior to metal deposition. X‐ray photoelectron spectroscopy (XPS) and evolved gas analysis Fourier transform infrared spectroscopy detect residual halogenated solvent at the PMMA surface which chemically activates the surface. Density functional theory (DFT) calculations show that the solvent molecules form a Lewis acid‐base adduct with the ester oxygens in PMMA. DFT predicts that the deposited metal atom (M) inserts into the C–halogen (X) bond on either CHCl₃ or CHBr₃ to form a O–M–X interaction. This is consistent with M–X bonding observed in high resolution XPS. A model is proposed in which the bond energy of the C–X bond of the solvent must be weak enough so that it can be cleaved by the metal atom to form a M–X bond. A negative control of PMMA exposed to CHF₃ is shown to have no effect on Au or Pt adhesion since the bond dissociation energy of the C–F bond is stronger than the C–Cl and C–Br bond energy compared to the metal halide bond energies.     

Enhanced Electrical Switching and Electrochromic Properties of Poly(p‐phenylenebenzobisthiazole) Thin Films Embedded with Nano‐WO3

The electrical switching and electrochromic phenomena of a novel nanocomposite comprising poly(p‐phenylenebenzobisthiazole) (PBZT) and tungsten oxide (WO₃) nanoparticles are investigated as a function of the nanoparticle loading. Both dissolving PBZT and doping PBZT backbone structure with acid are achieved by one simple step. Chlorosulfonic acid (CSA) is used as a solvent and spontaneously transformed to sulfuric acid upon exposure to moisture. The formed sulfuric acid serves as doping agent to improve the electrical conductivity of PBZT. The most significant enhancement of electrical switching is observed in the nanocomposites with low weight fraction (5%). The electrical conductivity of 5% WO₃/PBZT nanocomposite thin film is increased by about 200 times and 2 times, respectively, as compared to those of the as‐received PBZT and PBZT/CSA thin films. As the nanoparticle loading increases to 20% and 30%, the nanocomposites follow an ohmic conduction mechanism. Stable electrical conductivity switching is observed before and after applying a bias on the pristine PBZT and WO₃/PBZT nanocomposite thin films. Electrochromic phenomena of both PBZT and WO₃/PBZT nanocomposite thin films with high contrast ratio are observed after applying a bias (3 V). The mechanisms of the nanoparticles in enhancing the electrical switching and electrochromic properties are proposed.     

Assessing Antisite Defect and Impurity Concentrations in Bi2Te3 Based Thin Films by High‐Accuracy Chemical Analysis

In Bi₂Te₃‐based materials charge‐carrier densities are determined by antisite defects and controlling these defects is a key issue for thermoelectric and topological insulator materials. Bi‐Te thin films with high‐quality thermoelectric properties are deposited using a nano‐alloying approach by molecular beam epitaxy (MBE) and sputtering. The in‐plane transport properties are measured at room temperature as a function of charge‐carrier density. High‐accuracy chemical analysis by wavelength‐dispersive X‐ray spectrometry (WDX) is applied for the first time to these Bi₂Te₃‐based thin films. The acquisition conditions for WDX spectrometry are established using Monte Carlo simulations for the electron trajectories, which guarantees a high lateral resolution and rules out stray radiation generated in the substrate of the films. In contrast to energy‐dispersive X‐ray spectrometry (EDX), which is usually applied, WDX offers unprecedented accuracy for measuring antisite defect concentrations and thus has a high impact on improving the quality of thin films. The charge‐carrier densities are calculated from the WDX results according to the point‐defect model of Miller and Li and the thermopower and electrical conductivity are calculated for different charge‐carrier densities by solving the linearized Boltzmann transport equation. A good quantitative agreement is found for the dependence of the thermopower on stoichiometry, whereas the electrical conductivity is sensitively affected by contaminants.     

室温下脉冲激光沉积制备高取向度AlN薄膜

用脉冲激光沉积(PLD)方法,在p-Si(100)衬底上、室温下和不同N2氛围中制备了高度取向的AlN薄膜,并利用X射线衍射(XRD)仪、傅立叶变换红外(FTIR)光谱仪和扫描电子显微镜(SEM)对样品的特征进行了研究.结果表明,在从5×10-6～5.0 Pa的N2气压范围内,制备的薄膜都呈现h＜100＞晶向,并且随着气压的升高,样品的结晶度有明显的提高.另外,随着N2浓度的增大,Al-N键的结合度增强,AlN晶粒的尺寸增大,在样品表面出现杂散晶粒,薄膜的粗糙度增大.     

Systematic Control of Nucleation Density in Poly(3‐Hexylthiophene) Thin Films

While molecular ordering via crystallization is responsible for many of the impressive optoelectronic properties of thin‐film semiconducting polymer devices, crystalline morphology and its crucial influence on performance remains poorly controlled and is usually studied as a passive result of the conditions imposed by film deposition parameters. A method for systematic control over crystalline morphology in conjugated polymer thin films by very precise control of nucleation density and crystal growth conditions is presented. A precast poly(3‐hexylthiophene) film is first swollen into a solution‐like state in well‐defined vapor pressures of a good solvent, while the physical state of the polymer chains is monitored using in situ UV–vis spectroscopy and ellipsometry. Nucleation density is selected by a controlled deswelling of the film or by a self‐seeding approach using undissolved crystalline aggregates that remain in the swollen film. Nucleation densities ranging successively over many orders of magnitude are achieved, extending into the regime of spherulitic domains 10 to 100 μm in diameter, a length scale highly relevant for typical probes of macroscopic charge transport such as field‐effect transistors. This method is presented as a tool for future systematic study of the structure‐function relation in semicrystalline semiconducting polymers in a broad range of applications.     

溅射沉积AlN薄膜结构与基片种类的关系

采用高真空直流磁控反应溅射成功地在５种基片上制备出多晶择优取向的ＡＩＮ薄膜。结果表明,５种基片均可生长（１００）面掺优取向的ＡＩＮ薄膜,并且具有良好的纵向组成均匀性,表面粗造度小,晶粒均匀致密。在金属电极和Ｓｉ片上沉积的ＡＩＮ薄膜结晶度、取向性、衍射强度差别较小,两者的结构均优于在盖玻片上的沉积的ＡＩＮ薄膜。     

A Large Magnetoresistance Effect in p–n Junction Devices by the Space‐Charge Effect

The finding of an extremely large magnetoresistance effect on silicon based p–n junction with vertical geometry over a wide range of temperatures and magnetic fields is reported. A 2500% magnetoresistance ratio of the Si p–n junction is observed at room temperature with a magnetic field of 5 T and the applied bias voltage of only 6 V, while a magnetoresistance ratio of 25 000% is achieved at 100 K. The current‐voltage (I–V) behaviors under various external magnetic fields obey an exponential relationship, and the magnetoresistance effect is significantly enhanced by both contributions of the electric field inhomogeneity and carrier concentrations variation. Theoretical analysis using classical p–n junction transport equation is adapted to describe the I–V curves of the p–n junction at different magnetic fields and reveals that the large magnetoresistance effect origins from a change of space‐charge region in the p–n junction induced by external magnetic field. The results indicate that the conventional p–n junction is proposed to be used as a multifunctional material based on the interplay between electronic and magnetic response, which is significant for future magneto‐electronics in the semiconductor industry.