Laser printing and characterization of semiconducting polymers for organic electronics

Hybrid organic/inorganic thin-film transistors (TFTs) with bottom-contact configuration were fabricated using the Laser Induced Forward Transfer (LIFT) process. The semiconducting polymer P3HT was laser printed from a donor to a receiver substrate in order to form the active layer of the TFTs. With a single laser pulse, P3HT pixels were successfully printed. The printed material was analyzed morphologically by means of Optical Microscopy and its thickness was measured by profilometry. In addition, structural characterization of P3HT thin films before and after laser printing took place by using UV-Visible absorption spectroscopy and X-Ray Diffraction. It was found that the crystallinity of the investigated films is improved upon annealing. An organic thin-film transistor (OTFT) with laser printed P3HT pixel as a channel layer was then fabricated. The OTFTs indicated a field-effect mobility up to 2.23?10^?4 cm²/Vs and an on/off ratio on the order of 10–100.     

Multi-layered Ag film pattern printed by spatially modulated pulsed laser beam

Ag film solution-deposited on the glass source substrate was selectively transferred onto a receiver substrate by a spatially modulated pulsed ultraviolet laser beam. After printing a line pattern, an additional layer was orthogonally printed over the first layer. It was found that the thickness of the first layer is a crucial factor affecting the mechanical stability of the overall pattern. When the first layer was thicker than 0.7 μm, the second layer was cracked at the junction edges regardless of its thickness. This is attributed to the vertical elongation of the second layer at the edge areas. As long as the first layer remains below 0.7 μm thick, however, a very thick additional layer could be printed without any cracks. The printed patterns were mechanically robust and exhibited good electrical contact between the layers. The threshold pulse energy density for printing was measured to be 10 mJ/cm² and this threshold level made it possible to print over square centimeters by a single pulse.     

Laser induced forward transfer of conducting polymers

We report on laser printing of conducting polymers directly from the solid phase. Laser induced forward transfer is employed to deposit P3HT:PCBM films on glass/ITO/PEDOT:PSS substrates. P3HT:PCBM is widely used as the active material in organic solar cells. Polyaniline films, which are also printed by laser induced forward transfer, find many applications in the field of biotechnology. Laser printing parameters are optimized and results are presented. To apply solid-phase laser printing, P3HT:PCBM films are spun cast on quartz substrates, while aniline is in-situ polymerized on quartz substrates.     

Novel materials for electronic device fabrication using ink-jet printing technology

Novel materials and a metallization technique for the printed electronics were studied. Insulator inks and conductive inks were investigated. For the conductive ink, the nano-sized copper particles were used as metallic sources. These particles were prepared from a copper complex by a laser irradiation process in the liquid phase. Nano-sized copper particles were consisted of a thin copper oxide layer and a metal copper core wrapped by the layer. The conductive ink showed good ink-jettability. In order to metallize the printed trace of the conductive ink on a substrate, the atomic hydrogen treatment was carried out. Atomic hydrogen was generated on a heated tungsten wire and carried on the substrate. The temperature of the substrate was up to 60 °C during the treatment. After the treatment, the conductivity of a copper trace was 3 μΩ cm. It was considered that printed wiring boards can be easily fabricated by employing the above materials.     

Selective ablation with UV lasers of a-Si:H thin film solar cells in direct scribing configuration

Monolithical series connection of silicon thin-film solar cells modules performed by laser scribing plays a very important role in the entire production of these devices. In the current laser process interconnection the two last steps are developed for a configuration of modules where the glass is essential as transparent substrate. In addition, the change of wavelength in the employed laser sources is sometimes enforced due to the nature of the different materials of the multilayer structure which make up the device. The aim of this work is to characterize the laser patterning involved in the monolithic interconnection process in a different configurations of processing than the usually performed with visible laser sources. To carry out this study, we use nanosecond and picosecond laser sources working at 355 nm of wavelength in order to achieve the selective ablation of the material from the film side. To assess this selective removal of material has been used EDX (energy dispersive using X-ray) analysis, electrical measurements and confocal profiles. In order to evaluate the damage in the silicon layer, Raman spectroscopy has been used for the last laser process step. Raman spectra gives information about the heat affected zone in the amorphous silicon structure through the crystalline fraction calculation. The use of ultrafast sources, such as picoseconds lasers, coupled with UV wavelength gives the possibility to consider materials and substrates different than currently used, making the process more efficient and easy to implement in production lines. This approach with UV laser sources working from the film side offers no restriction in the choice of materials which make up the devices and the possibility to opt for opaque substrates.     

Selective growth of ZnO nanowires on substrates patterned by photolithography and inkjet printing

Zinc oxide nanowires (ZnO NWs) were grown by a two-step growth method, involving the deposition of a patterned ZnO thin seeding layer and the chemical vapor deposition (CVD) of ZnO NWs. Two ways of patterning the seed layer were performed. The seeding solution containing ZnO precursors was deposited by sol–gel/spin-coating technique and patterned by photolithography. In the other case, the seeding solution was directly printed by inkjet printing only on selected portion of the substrate areas. In both cases, crystallization of the seed layer was achieved by thermal annealing in ambient air. Vertically aligned ZnO NWs were then grown by CVD on patterned, seeded substrates. The structure and morphology of ZnO NWs was analyzed by means of X-ray diffraction and field emission scanning electron microscopy measurements, respectively, while the vibrational properties were evaluated through Raman spectroscopy. Results showed that less-defective, vertically aligned, c-axis oriented ZnO NWs were grown on substrates patterned by photolithography while more defective nanostructures were grown on printed seed layer. A feature size of 30 µm was transferred into the patterned seed layer, and a good selectivity in growing ZnO NWs was obtained.     

Substrate pre-treatment of flexible material for printed electronics with carbon nanotube based ink

In this work, an innovative solution was developed in order to make paper-based material, used traditionally in the packaging and labelling industries, compatible with the printing of functional conductive inks. In order to avoid the deterioration of the ink functionalities due to different paper properties, a UV-curing inkjettable primer layer was developed. This pre-treatment enables homogeneous surface properties such as smoothness, absorption capacity and surface energy to be obtained, for almost all the examined substrates. To confirm the positive impact of such pre-treatment, conductivity has been measured when using a new conductive ink, combining the processability of the PEDOT-PSS conductive polymer with the high electrical properties of carbon nanotubes (CNTs). Significant improvement has been measured for all paper materials and similar conductivity (close to reference PET film) has been obtained whatever the substrate involved. This pre-treatment now makes it possible to consider paper-based material as a potential substrate for printed electronics. In this case, the substrate adaptation technique offers an innovative solution to produce low-cost and flexible electronics.     

基于聚(4-乙烯基苯酚)衬底修饰层喷墨打印的小分子有机半导体薄膜制备和表征

采用旋涂法预先在SiO₂衬底表面形成一层聚（4-乙烯基苯酚）（PVP）作为表面修饰层,以喷墨打印的6,13-双（三异丙基甲硅烷基乙炔基）并五苯（TIPS并五苯）作为有源层制作有机薄膜晶体管,有效改善了有机半导体薄膜的形貌。采用真空热蒸镀工艺制备源漏电极,形成底栅顶接触结构的有机薄膜晶体管（OTFT）器件。作为对比,在未经过表面修饰的SiO₂衬底上采用相同条件打印TIPS并五苯薄膜晶体管,发现在经过PVP修饰的SiO₂衬底上打印的单点厚度更均匀,咖啡环效应被抑制或被消除;而通过多点交叠打印形成的矩形薄膜的晶粒尺寸更大,相应的OTFT器件具有更高的场效应迁移率。在有PVP修饰层的衬底上制作的OTFT,器件在饱和区的平均场效应迁移率达到了0.065 cm²·V^-1·s^-1;而直接在SiO₂衬底上制作的器件,相应的平均场效应迁移率仅为0.02 cm²·V^-1·s^-1。     

悬浮二维晶体材料反射光谱和光致发光光谱的周期性振荡现象

研究了在二氧化硅/硅衬底上制备的悬浮石墨烯以及二硫化钼的反射光谱以及悬浮二硫化钼的光致发光光谱.研究发现:悬浮多层石墨烯的反射光谱表现出明显的振荡现象,并且该振荡具有一定的周期性;振荡周期的大小不依赖于悬浮多层石墨烯的层数,而是随着衬底上沉孔深度(空气层厚度)的增加而减小.利用多重光学干涉模型可以解释这种振荡现象以及振荡周期随沉孔深度改变的变化趋势.该模型计算结果表明,只有当沉孔深度达到微米量级时这种振荡现象才会显著出现;并且可由振荡周期定量地确定出沉孔深度.对于悬浮的二硫化钼样品,其反射光谱和光致发光光谱也出现了类似的振荡现象.这表明这种振荡现象是在各种衬底上悬浮二维材料反射光谱和光致发光光谱的一种普遍性结果,也预示悬浮二维材料器件的电致发光光谱也会出现类似的振荡现象,对悬浮二维晶体材料的物理性质和器件性能研究具有一定的参考价值.     

Surface-enhanced Raman scattering active substrates by liquid flame spray deposited and inkjet printed silver nanoparticles

Surface-enhanced Raman scattering (SERS) active substrates were made via liquid flame spray deposition and inkjet printing of silver nanoparticles. Both processes are suitable for cost-effective fabrication of large-area SERS substrates. Crystal violet (CV) solutions were used as target molecules and in both samples the detection limit was approximately 10 nM. In addition, sintering temperature of the inkjet printed silver nanoparticles was found to have a large effect on the SERS activity with the higher curing temperature of 200 °C resulting in contamination layer on silver and cancelation of the SERS signal. This layer was characterized using an X-ray photoelectron spectroscopy (XPS).     

Liquids microprinting through a novel film-free femtosecond laser based technique

Laser-induced forward transfer (LIFT) is a high resolution microprinting technique in which small amounts of material are transferred from a previously prepared donor thin film to a receptor substrate. The application of LIFT to liquid donor films allows depositing complex and fragile materials in solution or suspension without compromising the integrity of the deposited material. However, the main drawback of LIFT is the preparation of the donor material in thin film form, being difficult to obtain reproducible thin films with thickness uniformity and good stability.In this work we present a laser microprinting technique that is able to overcome the drawbacks associated with the preparation of the liquid film, allowing the deposition of well-defined uniform microdroplets with high reproducibility and resolution. The droplet transfer mechanism relies on the highly localized absorption of strongly focused femtosecond laser pulses underneath the free surface of the liquid contained in a reservoir.An analysis of the influence of laser pulse energy on the morphology of the printed droplets is carried out, revealing a clear correlation between the printed droplet dimensions and the laser pulse energy. Such correlation is interpreted in terms of the dynamics of the liquid displaced by a laser-generated cavitation bubble close to the free surface of the liquid. Finally, the feasibility of the technique for the production of miniaturized biosensors is tested.     

Laser printing of conformal and multi-level 3D interconnects

A crucial challenge in three-dimensional multi-chip assemblies is to establish electrical connections between discrete devices. Here, we apply laser printing of congruent voxels of silver nanopaste for the fabrication of conformal and 3D multi-level interconnects. By controlling laser fluence, various 3D electrodes including freestanding tabs and side contacts over vertical walls can be directly printed without the need for sacrificial layers, chemical etching or electroplating. The electrical characteristics of the printed interconnects are similar to those currently in use by the semiconductor industry. These results are a promising step forward in the generation of customized interconnects for 3D microelectronics.     

Electric and ferroelectric properties of PZT/BLT multilayer films prepared by photochemical metal-organic deposition

The electric and ferroelectric properties of lead zirconate titanate (PZT) and lanthanum-substituted bismuth titanate (BLT) multilayer films prepared using photosensitive precursors were characterized. The electric and ferroelectric properties were investigated by studying the effect of the stacking order of four ferroelectric layers of PZT or BLT in 4-PZT, PZT/2-BLT/PZT, BLT/2-PZT/BLT, and 4-BLT multilayer films. The remnant polarization values of the 4-BLT and BLT/2-PZT/BLT multilayer films were 12 and 17 μC/cm², respectively. Improved ferroelectric properties of the PZT/BLT multilayer films were obtained by using a PZT intermediate layer. The films which contained a BLT layer on the Pt substrate had improved leakage currents of approximately two orders of magnitude and enhanced fatigue resistances compared to the films with a PZT layer on the Pt substrate. These improvements are due to the reduced number of defects and space charges near the Pt electrodes. The PZT/BLT multilayer films prepared by photochemical metal-organic deposition (PMOD) possessed enhanced electric and ferroelectric properties, and allow direct patterning to fabricate micro-patterned systems without dry etching.     

Laser printing of polythiophene for organic electronics

We report on the development of hybrid organic/inorganic thin-film transistors using regioregular poly-3-hexylthiophene (P3HT) semiconductor material deposited by means of the solid-phase Laser Induced Forward Transfer (LIFT) technique. P3HT pixels were LIFT-printed onto Au/Ti source and drain electrodes formed on silicon dioxide/p⁺-type Si substrate. Deposition of the P3HT pixels was investigated as a function of the laser fluence using donor substrates with and without a dynamic release layer. Device electrical characterization reveals efficient field-effect action of the bottom gate on the organic channel. The transfer I_DS-V_GS characteristics exhibit well-defined sub-threshold, linear and saturation regimes designating LIFT as a promising technique for hybrid organic/inorganic transistor technology.     

无机厚膜发光器件绝缘层的研究

采用丝网印刷技术,在Al2O3陶瓷基板上印刷、高温烧结内电极及绝缘层,制备出陶瓷厚膜基板,进而制备了新型厚膜电致发光显示器(TDEL)。整个器件结构为陶瓷基板/内电极/厚膜绝缘层/发光层/薄膜绝缘层/ITO透明电极。研究不同结构的无机厚膜发光器件对器件性能的影响,并对器件的亮度—电压、亮度—频率进行测量。结果显示绝缘层在无机发光器件中不是单纯的保护作用,它对器件的性能有十分重要的影响。主要是对注入电子的加速作用,从而提高发光亮度。绝缘层本身对无机厚膜发光器件的发光机理没有关系。     

Multilayers as defect barriers

A multilayer structure consisting of undoped GaAs and AlAs layers was incorporated into a buffer layer on GaAs substrates. This reduces the spreading of impurities from the substrate (e.g. tellurium) into layers deposited on top of the multilayer system as observed by SIMS and C/V profiling. Incorporation coefficients for tellurium in GaAs, AlAs and multilayers were calculated.     

Laser printing of enamels on tiles

A Nd:YAG laser beam is used as a tool to print patterns of coloured enamels on tile substrates. For this, the laser beam is scanned over a layer of raw enamel previously sprayed on the tile surface. The possibility to focus the laser energy to heat a small zone without affecting the rest of the piece presents some advantages in front of traditional furnace techniques in which the whole piece has to be heated; among them, energy saving and the possibility to apply enamels with higher melting temperatures than those of the substrate. In this work, we study the effects of laser irradiation of a green enamel, based in chromium oxide pigment and lead frit, deposited on a white tile substrate. Lines obtained with different combinations of laser beam power and scan speeds were investigated with the aim to optimize the process from the point of view of the quality of the patterns. For this purpose, the morphology of the lines and their cross-sections is studied. The results show that lines with good visual properties can be printed with the laser. The characteristics of the marked lines were found to be directly related with the accumulated energy density delivered. Moreover, there is a linear relationship between the accumulated energy density and the volume of melted material. A minimum accumulated energy density is required to melt a shallow zone of the glazed substrate to allow the adhesion of the enamelled lines.     

Fabrication of multilayer metamaterials by femtosecond laser‐induced forward‐transfer technique

A novel method based on femtosecond laser‐induced forward transfer for high‐throughput and efficient fabrication of periodic multilayer plasmonic metamaterials is demonstrated. With precisely controlling laser raster path applied on sputtered multilayer thin films, the laser‐ablated materials can be transferred to another substrate leaving the fabricated multilayer structure on the original substrate. Subsequently, three‐dimensional metamaterials can be made by multilayer structuring. Moreover, all the experimental results show that to create such multilayer split resonant rings (SRRs) with uniform profile, the laser fluence should be fine controlled under proper conditions. The optical property of fabricated multilayer SRR array is investigated by optical measurements and finite‐difference time‐domain simulations, showing various resonant modes in the middle‐IR region. The calculated induced current distributions exhibit rich resonance properties of the structures as well. This work markedly extends the laser direct writing technique to a wide application in fabricating complicated metamaterials and plasmonic devices efficiently.     

Cost-effective fabrication of memristive devices with ZnO thin film using printed electronics technologies

A prototype memristive device has been presented in this paper, for which the top and bottom electrodes have been fabricated through a simple and cost-effective technique, i.e. electrohydrodynamic printing. For deposition of the bottom electrode pattern, a silver ink containing 60 wt% silver by content was subjected to controlled flow through a metal capillary exposed to an electric field at the ambient temperature to generate an electrohydrodynamic jet, thereby depositing uniform patterns of silver on glass substrate at a constant substrate speed. The top electrode has been deposited in a similar fashion. In between the top and bottom electrodes, a uniform layer of ZnO is fabricated using spin-coating technique. The nanoscale ZnO memristor stack has a channel length of 370 μm and channel width of 82 μm. A memristor thus fabricated was characterized and its current voltage curves were analyzed. The device showed a typical nonvolatile resistive switching behavior present in memristor devices thus highlighting the EHD printed patterning as a reliable method for the fabrication of memory devices.     

Laser-induced forward transfer of single-walled carbon nanotubes

The objective of this work is the application of laser-induced forward transfer (LIFT) for the fabrication of chemiresistor sensors. The receiver substrate is an array with metal electrodes and the active materials placed by LIFT are single-walled carbon nanotubes (SWCNT). The functionality of such sensors depends on the geometry of the active material onto the metallic electrodes. First the best geometry for the sensing materials and electrodes was determined, including the optimization of the process parameters for printing uniform pixels of SWCNT onto the sensor electrodes. The sensors were characterized in terms of their sensing characteristics, i.e., upon exposure to ammonia, proving the feasibility of LIFT.