Surface texturing of polytetrafluoroethylene by hot embossing

In this study, hot embossing by reusable Ni mold with features in the form of rectangular diffraction gratings of 4 μm period was successfully employed for surface texturing of polytetrafluoroethylene (PTFE) film above the glass transition temperature of PTFE amorphous phase with the aim to enhance surface hydrophobicity. Imprint pressure was set to 0.5 MPa and it was at least tenfold lower than reported by other authors using cold stamping. Embossed gratings were clearly seen on the surface of all imprinted samples even after the annealing at 140 °C and aging for 1 month at room temperature. The best results were achieved when imprint temperature was 150 °C. Measurements of the water contact angle on imprinted PTFE surfaces have showed that increase of the average contact angle for the current test setup was 8°. Using imprint stamp with the more favorable features may lead to somewhat higher hydrophobicity.     

Computer simulation of nanoindentation into polymer films

We present computer simulations of nanoindentation into amorphous polymer films. The bulk polymer is treated through a united atom model in connection with molecular dynamics methods. The dynamics of the indenter is modeled as overdamped, such that the indentation velocity is proportional to the difference between the external force acting onto the tool and the resistance force built up in the polymer film. We concentrate on the initial, kinetic stage of the indentation process and give results for the motion of the indenter, the deformation field of the polymer film, the stress field, and the field of total monomer energy. We propose an effective coefficient as a new measure for the resistivity of a surface against indentation. Its value can be determined in an experiment with constant indentation velocity. In addition, we investigate the free drift behavior when the external driving force has been set to zero and the tool is expelled from the polymer film. For different polymer chain lengths, the tool’s motion is exponential in time and we determine the relaxation scale.     

摩擦导致的聚合物表层微观结构改变

应用大规模分子动力学方法, 模拟了锥形探头在非晶态聚合物薄膜表面的滑动摩擦过程, 研究了摩擦导致的聚合物薄膜表层微观结构改变, 以及探头与基体间黏着作用、滑动速度和分子链长度对基体表层微观结构改变的影响. 当探头与基体之间为黏着作用时, 摩擦导致基体表面滑痕区域的键取向沿滑动方向重新取向, 导致表层分子链回转半径沿滑动方向伸长, 并且这些表层微观结构的改变程度随滑动速度的减小而增大. 在摩擦导致结构改变的过程中, 链端单体和链中单体的贡献作用不同, 形成了不同的分子链拉伸变形机制. 当样本缠结度较大或探头滑动速度较小时, 相比于链中单体, 探头对链端单体的拖曳作用使更多分子链发生拉伸变形. 研究还发现, 在探头与聚合物薄膜系统中, 使薄膜表层微观结构发生改变是摩擦能量耗散的重要途径.     

Demolding temperature in thermal nanoimprint lithography

In thermal nanoimprint lithography, temperature is one of the most important process parameters. Temperature is not only important for the flow of resist during molding but also for demolding, the process by which the imprint stamp is removed from the molded resist/substrate. This is because thermal stress and friction and adhesion forces generated at the stamp/resist interface and the mechanical strength of the resist are all dependent on temperature. In this paper, we demonstrate via both experimentation and numerical simulation that an optimal temperature (T _d) leading to minimal deformation of molded resist exists for demolding. The ease of demolding was directly accessed by measuring demolding force at different T _d for a Si stamp/PMMA/Si substrate system of 4-in.-diameter using a mechanical tester. Numerically, the demolding process for a simple two-dimensional model of a Si stamp/poly(methyl methacrylate) (PMMA) resist/Si substrate system was simulated using a finite-element method for different T _d, assuming viscoelasticity of the PMMA resist and temperature dependence of friction coefficients at the stamp/PMMA interface. We found that a temperature leading to the minimum in both the demolding force and the normalized stress vs. T _d curves exists below the glass transition temperature of the PMMA resist, from which the optimal T _d was derived.     

Biomimetic, hierarchical structures on polymer surfaces by sequential imprinting

Thermal nanoimprint lithography (NIL) is based on the thermo-mechanical deformation of a polymer film above the glass transition temperature (T_g) and at an applied pressure. Sequential imprinting extends the process of thermal NIL to create hierarchical structures by carrying out secondary and tertiary imprintings at temperatures below the T_g of a polymer. In this work, we demonstrate the use of sequential imprinting technique to fabricate two- and three-level hierarchical structures on polystyrene (PS) and poly(methyl methacrylate) (PMMA) films over a temperature range of 70-130 °C, with the aim to mimic the hierarchical structures found in biological systems. By mimicking the hierarchical structure in a plant leaf, the water contact angle of PS film was increased from 95° to 128°, while the water contact angle of PMMA film was increased from 71° to 104°, without any chemical treatment.     

Issues on nanoimprint lithography with a single-layer resist structure

We summarize our key developments in nanoimprint lithography (NIL) that employs a single layer resist lift-off process: lowering of the imprint temperature (for thermal imprint) and pressure, achieving uniform resist thickness and low residual resist layer thickness in the trenches, and eliminating metal ‘rabbit ears’ for the single-layer lift-off. In thermal NIL, our requirements for lower operating temperature and pressure motivated us to develop an alternative resist that is a viscous fluid at room temperature and cures at a lower temperature of 70 °C than the operating temperature of the conventional thermal NIL (≈200 °C). For UV NIL, we devised a method to dispense the resist onto a hydrophobic mold and use the hydrophilic substrate surface to spread the resist via surface wetting to engineer a continuous and uniform film. We also explored the use of Si(110) substrates as molds to produce features with perfectly vertical side walls, and the use of aqua regia to directly etch away rabbit ears. PACS 86.65.+h; 81.16.Nd; 81.16.Rf     

Confinement-induced nanocrystal alignment of conjugated polymer by the soft-stamped nanoimprint lithography

Soft-stamped nanoimprint lithography(NIL) is considered as one of the most effective processes of nanoscale patterning because of its low cost and high throughput. In this work, this method is used to emboss the poly(9, 9-dioctylfluorene)film. By reducing the linewidth of the nanogratings on the stamp, the orientations of nanocrystals are confined along the grating vector in the nanoimprint process, where the confinement linewidth is comparable to the geometrical size of the nanocrystal. When the linewidth is about 400 nm, the poly(9, 9-dioctylfluorene)(PFO) nanocrystals could be orderly arranged in the nanogratings, so that both pattern transfer and well-aligned nanocrystal arrangement could be achieved in a single step by the soft-stamped NIL. The relevant mechanism of the nanocrystalline alignment in these nanogratings is fully discussed. The modulation of nanocrystal alignment is of benefit to the charge mobilities and other performances of PFO-based devices for the future applications.     

Hot embossing of PTFE: Towards superhydrophobic surfaces

Three types of reusable stamps with features in the form of 2D arrays of pits having lateral dimensions in the range of 2-80 μm and heights of 1.5-15 μm were successfully employed for the hot embossing of PTFE at temperatures up to 50 °C above the glass transition temperature of PTFE amorphous phase. Due to the softening of PTFE at the temperatures used in this study, we were able to decrease imprint pressure significantly when comparing with the imprint conditions reported by other authors. Impact of the imprint temperature, pressure and time on the fidelity of pattern transfer as well as on water repellency was tested. The best results of embossing were achieved by applying pressure of 10 kg/cm² for 2 min at 170 °C. In this case, flattening of a natural PTFE roughness and pretty accurate deep replicas of the stamp patterns were observable on the whole imprinted area. Improvement in water repellency was largest for the samples imprinted by Ni stamp patterned with a 2D array of 2 μm square pits spaced by the same dimension and having a depth of 1.5 μm. Cassie-Baxter wetting regime was observed for the deepest imprints with water contact angles up to the superhydrophobic limit.     

Cracks and crazes: on calculating the macroscopic fracture energy of glassy polymers from molecular simulations

We combine molecular dynamics simulations of deformation at the submicron scale with a simple continuum fracture mechanics model for the onset of crack propagation to calculate the macroscopic fracture energy of amorphous glassy polymers. Key ingredients in this multiscale approach are the elastic properties of polymer crazes and the stress at which craze fibrils fail through chain pullout or scission. Our results are in quantitative agreement with dimensionless ratios that describe experimental polymers and their variation with temperature, polymer length, and polymer rigidity.     

Laser-induced forward transfer technique for maskless patterning of amorphous V2O5 thin film

A laser-induced forward transfer technique has been applied for the maskless patterning of amorphous V₂O₅ thin films. A sheet beam of a frequency doubled (SHG) Q-switched Nd:YAG laser was irradiated on a transparent glass substrate (donor), the rear surface of which was pre-coated with a vacuum-deposited V₂O₅ 180 nm thick film was either in direct contact with a second glass substrate (receiver) or a 0.14 mm air-gap was maintained between the donor film and the receiving substrate. Clear, regular stripe pattern of the laser-induced transferred film was obtained on the receiver. The pattern was characterized using X-ray diffraction (XRD), optical absorption spectroscopy, scanning electron microscopy (SEM), energy dispersive analysis of X-ray (EDAX), atomic force microscopy (AFM), etc.     

Fabrication of structures with tunable morphologies and sizes by soft molding

This paper presents a simple and versatile patterning method to fabricate polymer patterns with different morphologies and sizes by utilizing soft molding. When a patterned elastomeric stamp was placed on the polymer solution dropped on the substrate, the polymer solution will fill into the grooves of the stamp under capillary force. Through the modulation of the polymer concentration, it is possible to produce highly regular and reproducible polymer patterns with tunable morphologies and sizes using the same microscopic patterned mold. The gained polymer patterns can be further transferred to produce second-generation stamps.     

Micro via and line patterning for PCB using imprint technique

Today’s electronic devices such as mobile phones, PDA, computers, etc. have more functions in a smaller size. Thus conducting lines and via holes of PCB (printed circuit board) which has a role of land for all kinds of electronic components are getting finer. In this study, the conducting lines and via holes are produced using thermal imprint technique rather than the conventional photo-lithography process. Imprint technique is a press process that transfers patterns of stamp to resins. Imprint technique is used to produce micro size trench lines and via holes in epoxy resins.Resins used in this work are silica (SiO₂) reinforced epoxy. Resins were imprinted using 10 * 10 mm size Ni or polymer stamp. Line/space of pattern is 10/10 μm while diameter of via hole is 30 μm. The depths of lines and via holes are 15 and 30 μm, respectively. The anti-sticking treated stamp and epoxy resins were pressed at 100 °C for 30 min in vacuum. The stamp was released after resins were cured for 1 h at 130 °C. All patterns of stamp were successfully transferred with high fidelity and any noticeable defect was not observed within imprinted area. Imprinted resins were de-smeared to remove the residue at the bottom of via holes and to enhance the adhesion of resins with Cu. Electro/less copper plating was followed to fill in the imprinted patterns. Since the excess Cu layer was formed on the resins during Cu plating, the planarization process was introduced to obtain isolated lines and via holes.     

Macromolecular nanoelectronics

We have explored new organic materials and fabrication methods to fabricate organic photodiodes and light emitting diodes. Grafting of a fullerene derivative to a polythiophene backbone yielded an integrated acceptor-donor polymer that we used as the active material in organic photodiodes. Using a method of soft lithography, soft embossing, we fabricated submicron structures to be used as organic light emitting diodes. Employing a silicone rubber replica (stamp) of an optical diffraction grating we transferred the grating pattern to an organic resist layer by placing the stamp in conformal contact with the resist. The transferred pattern was subsequently used as an etch mask for the processing of the device. The structures were successfully utilized as light emitting diodes and photodiodes, with device characteristics influenced by the imposed structure.     

退火温度对高分子薄膜中掺杂小分子的结晶和光谱学响应特性的影响

研究了小分子材料苝(EPPTC)在高分子材料聚芴衍生物(F8BT)薄膜中的结晶特性随温度的变化规律,以及由此引起的两种材料构成的异质结中激发复合体荧光发射特性的变化。实验结果表明,退火温度的升高会加强小分子与高分子材料在固体薄膜中的相分离。而小分子相在析出过程中,会在分子间作用力诱导下发生π—π团聚而结晶。晶体的尺度在达到小分子材料相变温度之前基本上随温度升高而增大。这一过程将破坏异质结结构,减小小分子与高分子间的接触面积,从而降低激发复合体的形成及其荧光发射强度。同时,由高分子向小分子发生的能量转移过程被显著减弱,而小分子晶相的荧光发射成分提高。这对于调控有机半导体异质结结构,进而改善光伏器件性能具有重要意义。     

钼掺杂氧化锌薄膜的结构、光学和表面等离子体特性研究

室温下,通过直流磁控反应溅射在石英衬底上制备一系列钼掺杂氧化锌薄膜。分别采用X射线衍射(XRD)、原子力显微镜(AFM)、分光光度计及拉曼光谱仪研究了钼掺杂浓度对氧化锌薄膜结构、表面形貌、光学性能和表面等离子体特性的影响。XRD测试结果表明,零掺杂氧化锌薄膜结晶良好,呈c轴择优取向,掺杂后薄膜缺陷增多,结晶质量下降,当掺杂浓度达到3.93 Wt%时,薄膜由c轴择优取向的晶态转变为非晶态。AFM测试结果表明非晶态掺钼氧化锌薄膜表面光滑,粗糙度最低可达489 pm。透射光谱表明所有薄膜样品在可见光范围(400～760 nm)平均透过率均达到80%,禁带宽度随着掺杂浓度的提高从3.28 eV单调增加至3.60 eV。吸收光谱表明氧化锌薄膜表面等离子体共振吸收峰随钼掺杂量的增大发生蓝移,而拉曼光谱表明Mo重掺杂时ZnO薄膜表面拉曼散射信号强度显著降低。通过Mo掺杂获得非晶态氧化锌薄膜,拓宽了氧化锌薄膜材料的应用领域,同时研究了Mo掺杂浓度对氧化锌薄膜表面等离子体的调控作用,这对制备氧化锌基光子器件具有重要参考价值。     

Transfer bonding technology for batch fabrication of SMA microactuators

Currently, the broad market introduction of shape memory alloy (SMA) microactuators and sensors is hampered by technological barriers, since batch fabrication methods common to electronics industry are not available. The present study intends to overcome these barriers by introducing a wafer scale transfer process that allows the selective transfer of heat-treated and micromachined shape memory alloy (SMA) film or foil microactuators to randomly selected receiving sites on a target substrate. The technology relies on a temporary adhesive bonding layer between SMA film/foil and an auxiliary substrate, which can be removed by laser ablation. The transfer technology was tested for microactuators of a cold-rolled NiTi foil of 20 μm thickness, which were heat-treated in free-standing condition, then micromachined on an auxiliary substrate of glass, and finally selectively transferred to different target substrates of a polymer. For demonstration, the new technology was used for batch-fabrication of SMA-actuated polymer microvalves.     

Force-induced desorption and unzipping of semiflexible polymers

The thermally assisted force-induced desorption of semiflexible polymers from an adhesive surface or the unzipping of two bound semiflexible polymers by a localized force are investigated. The phase diagram in the force-temperature plane is calculated both analytically and by Monte Carlo simulations. Force-induced desorption and unzipping of semiflexible polymers are first order phase transitions. A characteristic energy barrier for desorption is predicted, which scales with the square root of the polymer bending rigidity and governs the initial separation process before a plateau of constant separation force is reached. This leads to activated desorption and unzipping kinetics accessible in single molecule experiments.     

准分子激光增强高分子材料粘着力的机理研究

 由热方程计算激光与液体薄膜材料相互作用时的温度场,分析高分子材料表面熔化及材料表面液体膜汽化产生的材料的表面粗化;近一步分析高分子的断裂、F原子 替代等光化学反应;从而提出激光增强高分子材料的粘着力的表面粗化和光化学反应的机理。     

Plastic deformation transfer through the amorphous intercrystallite phase in nanoceramics

A three-dimensional model is proposed for plastic deformation transfer through the amorphous intercrystallite phase in mechanically loaded nanoceramics. In this model, glide dislocation loops are pressed against amorphous intercrystallite boundaries by the applied local shear stress and initiate in them local longitudinal plastic shears, which causes emission of new glide dislocation loops into neighboring grains. The energy characteristics of these processes and the critical applied stress required for barrierless nucleation of grainboundary and intragrain loops are calculated. As an example, a nanoceramic based on cubic silicon carbide is considered. It is shown that plastic deformation transfer through the amorphous intercrystallite phase in such nanoceramics is energetically favorable and can occur athermically over wide ranges of values of the applied stress and the structural characteristics of the material.     

High-speed residue-free transfer of two-dimensional materials using PDMS stamp and water infiltration

A high-speed residue-free transfer method using PDMS (polydimethylsiloxane) stamp and water infiltration between graphene and a hydrophilic surface is reported. Monolayer graphene was transferred from an enhanced fluorinated Al₂O₃ surface using PDMS. Water infiltration dramatically reduced the time required to separate the graphene from the Al₂O₃ substrate to a few minutes. The graphene was then successfully transferred to a target substrate (SiO₂) using the PDMS stamp. Atomic force microscopy and lateral force microscopy was used to confirm the absence of residue on the transferred graphene surface.