Nanoimprint of ordered ferro/piezoelectric P(VDF-TrFE) nanostructures

The next generation of portable computing and communication devices tremendously depend on the technologies that enable the rapid manipulation, caching and high-density non-volatile data storage. The recent development of organic electronics requires high-quality organic memory compatible with other devices, which will eventually lead to the realization of all organic electronic systems. The challenge of the organic electronics application is to find less degradative ways of fabricating ferroelectric polymer nanostructures. In this work, we applied the nanoimprint technique to fabricate ferroelectric poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] copolymer line and dot nanostructures and compared the ferroelectric properties and domain formation in these two nanostructures.     

朗缪尔铁电聚合物薄膜的电学特性:高热释电系数和低介电常数

研究了利用朗缪尔技术(LB)生长在柔性基底上的聚偏氟乙烯和三氟乙烯的共聚物(P(VDF-TrFE))薄膜的电学性质.通过测量相对介电常数和热释电系数,发现薄膜在室温1kHz时的优值因子达到1.4 Pa~(-1/2).这表明利用LB技术生长的P(VDF-TrFE)薄膜是热释电探测器的优良候选材料.优值因子的提高可能来源于LB薄膜的良好结晶性和分子链在平面内的高度有序性.     

Facile and solvent-free fabrication of highly oriented ferroelectric copolymer thin films and its application in ferroelectric field effect transistors

An environmentally friendly and solvent-free method was reported for fabrication of ferroelectric copolymer P(VDF-TrFE) thin films directly from their molten mass. Friction-transferred poly(tetrafluoroethylene) (PTFE) templates were used for epitaxy during solidification process. The obtained films showed highly-oriented crystallite structure and improved degree of crystallinity. Electrical measurement indicated that these films presented good ferroelectric property with remnant polarization comparable to those solution deposited and epitaxially processed films. A ferroelectric field effect transistor (FeFET) was constructed with one oxide semiconductor as an active layer and P(VDF-TrFE) as a ferroelectric layer. The memory device showed an ON/OFF ratio as high as 10⁵ and good retention performance during the whole experimental duration. This work developed a new route for environmentally friendly fabrication of organic ferroelectric devices.     

Topography engineering of ferroelectric crystalline copolymer film

Effects of surface roughness as well as crystallinity onto functionalities of crystalline copolymer films were studied using a dipping method to inject the crystalline grains into voids among crystalline nano-rods. Differently from a widely-used fabrication method such as spin-coating of solution, we achieved a smooth surface and high crystallinity in ferroelectric P(VDF-TrFE) films, simultaneously. Varying dipping temperature and time, remnant polarization and relative dielectric constant values increased by 20% and 75% with a decrease of surface roughness from 20 nm to 7 nm in root mean square value, respectively. The ferroelectric stabilities of P(VDF-TrFE) film capacitors were found to be strongly dependent on the crystallinity.     

Size effect on polarization switching kinetics of P(VDF-TrFE) copolymer nanodots

We demonstrate polarization switching kinetics of poly(vinylidene fluoride-ran-trifluoroethylene) P(VDF-TrFE) nanodots depending on their sizes. Ferroelectric copolymer P(VDF-TrFE) nanodots, ranging from 20 to 250 nm in lateral size, were deposited on a Nb-doped SrTiO₃ substrate by a position-controlled dip-pen nanolithography technique. Ferroelectric switching characteristics of P(VDF-TrFE) nanodots was investigated by piezoresponse force microscopy. Asymmetric switching behavior was observed during switching process, indicating that the threshold electric fields for polarization reversal were measured differently under the same conditions according to the switching polarity. Significantly, when the size of P(VDF-TrFE) nanodot approached around 250 nm, electric fields for polarization switching were compatible with those of the P(VDF-TrFE) thin film. We suggest that the electric fields required for polarization reversal of the P(VDF-TrFE) nanodots present asymmetric switching behaviors, and asymptotic behavior be observed as the nanodots increase in lateral size.     

Preparation and Dielectric Characteristics of Semitransparent CoFe2O4–P(VDF-TrFE) Nanocomposite Films

Polymer–ceramic nanocomposites play an important role in embedded capacitors. However, polymer–ceramic dielectrics are limited for commercial applications due to their low transmittance, poor adhesion, and poor thermal stress reliability at high filler loadings. Thus, materials design and processing is critical to prepare films with improved dielectric properties and low filler loading. In this work, we use a spin coating-assisted method to fabricate poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF-TrFE)]–CoFe₂O₄ (CFO) nanocomposite films. Magnetic CFO nanoparticles in the size range of 10 nm to 40 nm were successfully synthesized using a hydrothermal process. The dispersion of the nanoparticles, the dielectric properties, and the transmittance of the nanocomposite films were studied. The dielectric constant of the nanocomposite films increased by about 45% over the frequency range of 100 Hz to 1 MHz, compared with that of pristine P(VDF-TrFE) film. Optical measurements indicated that the transmittance of the films remains above 60% in the visible range, indicating a relatively low content of CFO in the polymer matrix. Our experimental results suggest that spin coating-assisted dispersion may be a promising route to fabricate dielectric polymer–ceramic nanocomposite films of controllable thickness.     

P(VDF-TrFE)/Ag复合薄膜的铁电以及介电性能研究

利用旋涂法制备并采用氢气退火处理得到P(VDF-TrFE)/Ag复合薄膜,在XRD图像上可以观察到在2θ=38.1°的Ag(111)相的衍射峰,同样在SEM图像上观察到银纳米粒子的存在.在薄膜的红外透射光谱上可以观察到β相特征峰的蓝移,这可归结为银纳米粒子与偶极子的相互作用.银纳米粒子的掺杂增强了薄膜的铁电和介电性能.与传统退火方式处理的纯P(VDF-TrFE)薄膜相比,纳米银掺杂比例为10％的P(VDF-TrFE)/Ag复合薄膜的铁电剩余极化强度和介电常数分别提高了32.5％和13.3％.介电损耗不随纳米银掺杂比例的增加而变化的现象不符合渗流理论.     

Enhanced organic ferroelectric field effect transistor characteristics with strained poly(vinylidene fluoride-trifluoroethylene) dielectric

Poly(vinylidene fluoride-trifluoroethylene) (70–30 mol%) was used as the functional dielectric layer in organic ferroelectric field effect transistors (FeFET) for non-volatile memory applications. Thin P(VDF-TrFE) film samples spin-coated on metallized plastic substrates were stretch-annealed to attain a topographically flat-grain structure and greatly reduce the surface roughness and current leakage of semi-crystalline copolymer film, while enhancing the preferred β-phase of the ferroelectric films. Resultant ferroelectric properties (P_R = |10| μC/cm², E_C = |50| MV/m) for samples simultaneously stretched (50–70% strain) and heated below the Curie transition (70 ^oC) were comparable to those resulting from high temperature annealing (>140 ^oC). The observed enhancements by heating and stretching were studied by vibration spectroscopy and showed mutual complementary effects of both processes. Organic FeFET fabricated by thermal evaporating pentacene on the smooth P(VDF-TrFE) films showed substantial improvement of semiconductor grain growth and enhanced electrical characteristics with promising non-volatile memory functionality.     

Molecular Weight‐Induced Structural Transition of Liquid‐Crystalline Polymer Semiconductor for High‐Stability Organic Transistor

In order to fabricate polymer field‐effect transistors (PFETs) with high electrical stability under bias‐stress, it is crucial to minimize the density of charge trapping sites caused by the disordered regions. Here we report PFETs with excellent electrical stability comparable to that of single‐crystalline organic semiconductors by specifically controlling the molecular weight (MW) of the donor‐acceptor type copolymer semiconductors, poly (didodecylquaterthiophene‐alt‐didodecylbithiazole). We found that MW‐induced thermally structural transition from liquid‐crystalline to semi‐crystalline phases strongly affects the device performance (charge‐carrier mobility and electrical bias‐stability) as well as the nanostructures such as the molecular ordering and the morphological feature. In particular, for the polymer with a MW of 22 kDa, the transfer curves varied little (ΔV_th = 3～4 V) during a period of prolonged bias stress (about 50 000 s) under ambient conditions. This enhancement of the electrical bias‐stability can be attributed to highly ordered liquid‐crystalline nanostructure of copolymer semiconductors on dielectric surface via the optimization of molecular weights.     

Novel Direct Nanopatterning Approach to Fabricate Periodically Nanostructured Perovskite for Optoelectronic Applications

While indirectly patterned organic–inorganic hybrid perovskite nanostructures have been extensively studied for use in perovskite optoelectronic devices, it is still challenging to directly pattern perovskite thin films because perovskite is very sensitive to polar solvents and high‐temperature environments. Here, a simple and low‐cost approach is proposed to directly pattern perovskite solid‐state films into periodic nanostructures. The approach is basically perovskite recrystallization through phase transformation with the presence of a periodic mold on an as‐prepared solid‐state perovskite film. Interestingly, this study simultaneously achieves not only periodically patterned perovskite nanostructures but also better crystallized perovskites and improved optical properties, as compared to its thin film counterpart. The improved optical properties can be attributed to the light extraction and increased spontaneous emission rate of perovskite gratings. By fabricating light‐emitting diodes using the periodic perovskite nanostructure as the emission layers, approximately twofold higher radiance and lower threshold than the reference planar devices are achieved. This work opens up a new and simple way to fabricate highly crystalline and large‐area perovskite periodic nanostructures for low‐cost production of high‐performance optoelectronic devices.     

The possibility of polarization recovery in fatigued ferroelectric vinylidene fluoride and trifluoroethylene copolymer films

Simple treatments were made to study the possibility of polarization recovery in fatigued P(VDF-TrFE) films. Annealing at a temperature below or above the Curie point of ferroelectric films would not improve the ferroelectric property of fatigued films, while a long-time rest would induce partially or even fully polarization recovery, though P-E loops obtained from recovered films showed a rounded shape. Some discussions were also given to explain our observations.     

PVDF/P（VDF-TrFE）混合薄膜形貌的原子力显微镜研究

利用原子力显微镜研究PVDF/P（VDF-TrFE）混合薄膜的结晶形貌受退火温度的影响,发现随着退火温度的升高,两种成份的结晶情况各异,并受到分子链间的作用而互相影响。α相的PVDF大球晶结构受P（VDF-TrFE）分子链的影响不易转化成β相的小球晶。在P（VDF-TrFE）的熔融温度以上退火后,P（VDF-TrFE）结晶成长纤维状晶体,并随着退火温度的升高而长大。共混薄膜中发生了两种类型的相分离,P（VDF-TrFE）的结晶可以使整个混合薄膜的宏观相容性得到提高,使两种成份的分层现象消失。     

Absorption-Dominant Electromagnetic Interference Shielding through Electrical Polarization and Triboelectrification in Surface-Patterned Ferroelectric Poly[(vinylidenefluoride-co-trifluoroethylene)-MXene] Composite

Extensive utilization of electronic devices and wireless equipment require human to take affirmative measures to weaken unwanted electromagnetic wave radiations. Herein, a ferroelectric poly[(vinylidenefluoride-co-trifluoroethylene) (P(VDF-TrFE)-MXene]-poly(3,4-ethylenedioxythiophene) (PEDOT) multilayered film is developed that can increase electromagnetic interference (EMI) shielding performance through electrical polarization. The MXene is encapsulated by a P(VDF-TrFE) matrix, which inhibits oxidation, and a highly conductive MXene is created conductive network resulting in enhancement EMI shielding effectiveness (EMI SE). Furthermore, the surface pattern inducing multiple scattering and PEDOT layer contributes to the increasing absorption due to the electrically conductive PEDOT. Thanks to the electrically polarized and negatively charged P(VDF-TrFE)-MXene, the composite film demonstrates superior EMI SE and absolute EMI SE (SSE_t) are exhibited remarkable ≈61 dB and 15230 dB cm²g⁻¹ with high absorptivity (0.87) at thickness of 120 µm in X-band. Additionally, P(VDF-TrFE)-MXene composite film is applicable to motion and thermo-resistive sensor due to the negatively charged P(VDF-TrFE) and thermo-resistive property of PEDOT, respectively, for multifunctionality. This work provides a feasible avenue for flexible absorption dominant EMI shielding materials via electrical polarization with remarkable EMI shielding performance.     

Influences of embossing technology on Pb(Zr0.3,Ti0.7)O3 ferroelectric thin film

The ferroelectric random access memory (FRAM) which uses ferroelectric thin film as memory material is considered to be a candidate for the next generation memory application. In this work, we apply nano-embossing technology to fabricate Pb(Zr_0.3,Ti_0.7)O₃ (PZT) ferroelectric thin film nanostructures and investigate the influence of the patterning process on the material and ferroelectric properties by using SEM, XRD and Precision Ferroelectric Tester. Embossing process has been optimized for embossing depth and pattern profile. It was found that embossing will result in (1 0 0) preferred orientation of the PZT thin film. The electrical characteristics of patterned and un-patterned PZT films have been also studied for comparison.     

氧化物缓冲层制备Si(111)基GaN纳米线

采用氧化物缓冲层,通过射频磁控溅射系统依次在n型Si(111)衬底上沉积Ga2O3/ZnO(Ga2O3/MgO)薄膜,然后将薄膜于950℃氨化合成GaN纳米结构,氨化时间为15min。采用X射线衍射(XRD)、傅里叶红外吸收谱(FTIR)和高分辨透射电镜(HRTEM)对样品的结构进行了分析,结果显示两种缓冲层下制备的样品均为六方纤锌矿单晶GaN纳米结构,且缓冲层的取向对纳米线的生长方向有很大影响;采用扫描电镜(SEM)对样品的形貌进行了测试,发现纳米线表面光滑,长度可达几十微米,表明采用氧化物缓冲层制备了高质量的GaN线。同时对GaN纳米线的生长机理进行了简单讨论。     

（英）界面极化层引起P(VDF-TrFE)电容器的电容-电压的不对称

通过研究Au/P(VDF-TrFE)/Al 电容器的变温(200 K 到310 K)电容-电压曲线,室温下观察到两个极化方向下的电容不对称,这个现象可以应用于非挥发性存储器.电容不对称程度随着温度的降低而变小,当温度低于230 K,电容不对称现象消失.P(VDF-TrFE)与Al电极之间的界面极化层可以解释观察到的电容不对称现象.     

Global excitation and local probing of ferroelectric domains

In this work, the macroscopic polarization of a ferroelectric capacitor is correlated with the local domain morphology. To this end, a ferroelectric capacitor of the random copolymer poly(vinylidenefluoride-trifluoroethylene) [P(VDF-TrFE)] is poled to a set polarization state in a Sawyer-Tower setup. After chemically removing the top electrode, the exposed ferroelectric is locally probed with piezoresponse force microscopy. The domains without the top electrode are thermodynamically stable for weeks in ambient environment, as proven by comparing the remanent polarization measured before etching away and after re-depositing the top electrode. Out-of-plane PFM phase images show a random distribution of domains with up and down polarity. We unambiguously demonstrate a linear correlation between the mean PFM phase and the macroscopic polarization. As a demonstration of the insights that the global excitation and local probing method can provide, we show how thermal and electrical depoling can result in identical macroscopic polarization yet completely different domain morphologies.     

Polymer nanocomposite dielectric based on P(VDF-TrFE)/PMMA/BaTiO3 for TIPs-pentacene OFETs

TIPs-pentacene OFETs were fabricated on a plastic substrate using polymer nanocomposite dielectric. The blend polymer P(VDF-TrFE)/PMMA (30 wt%) was used as polymer matrix and BaTiO₃ nanoparticles modified by 3-glycidoxypropyltrimethoxysilane (GPTMS) were dispersed as ceramic fillers. The effects of different loadings of BaTiO₃ on the surface morphology and electrical properties of dielectric films were investigated. The formulation of screen-printable dielectric ink of P(VDF-TrFE)/PMMA/BaTiO₃/Silica (SII) was achieved by adding fumed silica as the viscosity modifier. TIPs-pentacene OFETs using SII as the gate dielectric features a mobility of 0.01 cm²/V s, and having a threshold voltage of −6 V. This screen-printable dielectric ink is promising for low operating-voltage fully-printed OFETs.     

Profile Control in Block Copolymer Nanostructures using Bilayer Thin Films for Enhanced Pattern Transfer Processes

Although control over the domain orientation and long‐range order of block copolymer nanostructures self‐assembled in thin films has been achieved using various directed self‐assembly techniques, more challenging but equally important for many lithographic applications is the ability to precisely control the shape of the interface between domains. Here, a novel layer‐by‐layer approach is reported for controlling the interface profile of block copolymer nanostructures and the application of an undercut sidewall profile for an enhanced metal lift‐off process for pattern transfer is demonstrated. Bilayer films of lamellar‐forming poly(styrene‐block‐methyl methacrylate) are assembled and thermally cross‐linked on wafer substrates in a layer‐by‐layer process. The top layer, while being directed to self‐assemble on the lamellae of the underlying layer, has a tunable composition and polystyrene domain width independent of that of the bottom layer. Undercut or negative sidewall profiles in the PS nanostructures are proven to provide better templates for the lift‐off of Au nanowires by achieving complete and defect‐free pattern transfer more than three times faster than comparable systems with vertical sidewall profiles. More broadly, the layer‐by‐layer approach presented here provides a pathway to achieving sophisticated interface profiles and user‐defined 3D block copolymer nanostructures in thin films.     

Microcavity polymer electroluminescent devices with solution-processed dielectric distributed Bragg reflectors utilizing inorganic copper (I) thiocyanate and insulating polymers

The concept of using printed inorganic/organic hybrid distributed Bragg reflectors (DBRs) utilizing inorganic semiconductor and insulating polymers in microcavity polymer electroluminescent devices is introduced to provide an approach to achieve the spectral narrowing and the strong forward directionality. The large refractive index contrast of approximately 0.5 (0.44) between inorganic copper(I) thiocyanate, CuSCN, and insulating polymer of poly(vinylidene fluoride-trifluoroethylene), P(VDF-TrFE) (cellulose acetate, CA) results in the fabrication of solution-processed inorganic-organic hybrid dielectric DBRs with high reflectivity (>90%) from nanostructures consisting of only four (five) bilayers. For DBRs composed of CuSCN/CA alternative dielectric layers, all-solution processed microcavity polymer light-emitting diode based on highly conductive poly(ethylenedioxythiophene):poly(styrenesulfonate) anode except for Ag cathode exhibits the narrowing of EL spectrum with a full width at half maximum of approximately 25 nm and the maximum luminance of above 10,000 cd/m². From the viewpoint of dielectric DBRs based on ferroelectric polymer P(VDF-TrFE) with both low refractivity and high permittivity, we demonstrate a microcavity AC voltage-driven polymer electroluminescent device (μcACEL) which exhibits the spectral narrowing and the strong forward directionality. This work is anticipated to be useful for the development of solution-processed μcACEL with unique device architecture.