Synthesis and characterization of copper ink and direct printing of copper patterns by inkjet printing for electronic devices

Among the conventional metallic inks used in the printing process, silver exhibits high conductivity and thermal stability. Nevertheless, due to the high cost of silver, it cannot be extensively used for the fabrication of inks. As a competitive alternative, copper can be considered as a substitute for silver; however, copper ink oxidizes under certain atmospheric conditions. To meet these shortcomings, a cost effective, highly conductive, and oxidation-free copper-based ink has been synthesized in this study, wherein, oxidation of the copper particles in the copper-based ink was prevented by using copper complexes. The copper ink thus fabricated was printed on chemically treated Si/SiO₂ substrates followed by the characterization of the printed copper films. The results of this study confirmed that the synthesized copper ink exhibited properties suitable for its use in the inkjet printing process for fabrication of various electronic devices.     

A promising approach to conductive patterns with high efficiency for flexible electronics

A promising approach for conductive patterns with high efficiency for flexible electronics was developed by direct-writing, silver(I) solution (silver nitrate, acetate silver, etc.) with no solid particles as a conductive ink, conductive pen as a writing implement, and polyimide (PI) film as a substrate. The physical properties of the conductive ink were investigated by a dynamic contact angle system, ubbelohde viscometer and surface tension instrument. Conductive properties of silver ink film were investigated by 4-point probe, scanning electron microscope (SEM) and surface profilometer. It is demonstrated how the design of solvent composition in conductive ink affects surface morphology, and conductivity of silver ink films. It can be obtained that conductive patterns drawn on PI substrate not only have good mechanical/electrical fatigue properties, but also have low resistivity. Especially, when the sintering condition is 200 °C for 60 min, the resistivity can be down to 6.6 μΩ cm, 4.25 times the silver bulk resistivity.     

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.     

Selective laser processing of ink-jet printed nano-scaled tin-clad copper particles

The deposition of tin-clad nano-size copper particles was carried out by means of ink-jet printing. Curing the particles on Polyimide (PI) turned them into soldered structures using an Nd-YAG laser. Area coverage of 55% was achieved for a single-layer print. Subsequent laser sintering increased this value to 95%. A Butanol-based copper ink and an aqueous tin (Sn)-clad Copper (Cu) ink were produced and were ink-jetted in this work. These nano-metallic inks showed excellent suspension stability with particle weight concentrations as high as 5%. The ink components were examined by measuring the particle size distribution in a dispersed condition, and the melting temperature. A piezo ink-jet print head was used to deposit the inks onto a moveable substrate. The thermal effect of the laser irradiation allowed approaching and connecting adjacent particles by melting the particle’s tin coating. The results were examined with regard to structure and soldering properties using EDX, SEM and optical microscopy.     

Crystal morphology variation in inkjet-printed organic materials

The recent commercialization of piezoelectric-based drop-on-demand inkjet printers provides an additive processing platform for producing and micropatterning organic crystal structures. We report an inkjet printing approach where macro- and nano-scale energetic composites composed of cyclotrimethylenetrinitramine (RDX) crystals dispersed in a cellulose acetate butyrate (CAB) matrix are produced by direct phase transformation from organic solvent-based all-liquid inks. The characterization of printed composites illustrates distinct morphological changes dependent on ink deposition parameters. When 10 pL ink droplets rapidly formed a liquid pool, a coffee ring structure containing dendritic RDX crystals was produced. By increasing the substrate temperature, and consequently the evaporation rate of the pooled ink, the coffee ring structure was mitigated and shorter dendrites from up to ∼1 to 0.2 mm with closer arm spacing from ∼15 to 1 μm were produced. When the nucleation and growth of RDX and CAB were confined within the evaporating droplets, a granular structure containing nanoscale RDX crystals was produced. The results suggest that evaporation rate and microfluidic droplet confinement can effectively be used to tailor the morphology of inkjet-printed energetic composites.     

Effects of dodecylamine and dodecanethiol on the conductive properties of nano-Ag films

Nano-Ag particles, with dodecylamine (DDA) and dodecanethiol (DDT) as the protective agent, were prepared and studied in order to investigate the effect of protective agent in the post heat-treatment of nano-Ag films. Results of electrical resistivity, micro-structural evolution and thermal analysis showed that the Ag-DDA films require a lower treatment temperature to convert into conductive materials compared to that of the Ag-DDT films. And the Ag-DDA films also have lower final electrical resistivity as well as more uniform and dense microstructure in comparison with the Ag-DDT films. Further study indicated that Ag-DDA films are thermodynamically unstable and the sinter of Ag-DDA particles could occur spontaneously even at room temperature. FT-IR, ¹H NMR and X-ray diffraction determinations revealed that both DDA and DDT molecules coordinate to the surface of nano-Ag particles through their head-groups. The bonding energy of Ag-S is higher than that of Ag-N and the alkyl chains ordering of chemisorbed DDT is also higher than that of chemisorbed DDA. It is implied that the post heat-treatment temperature and final resistivity of nano-Ag films are associated with the bonding energy and configuration of different capping molecules. Finally the conductive ink was prepared with well dispersed Ag-DDA nanoparticles and the ink-jet printed patterns on PI films show a sheet resistance of 166 mΩ/□ after heat-treating at 140 °C for 60 min.     

Laser sintering of Cu paste film printed on polyimide substrate

We here show that highly conductive copper films are obtainable from Cu paste by laser sintering. The Cu paste synthesized using an organo-metallic compound was screen-printed onto polyimide substrate and the printed films were scanned by an ultraviolet laser beam at 355 nm under nitrogen atmosphere. Very compact microstructure was observed throughout the whole thickness and the sintered films were mechanically robust. Although Cu is known susceptible to oxidation, no Cu oxides were incorporated into the film during laser sintering. An electrical resistivity of 1.86 × 10⁻⁵ Ω cm was obtained. This resistivity is several orders of magnitude lower than those reported for the copper nanoparticle paste thermally sintered under N₂ or H₂ atmosphere.     

无颗粒型银导电墨水的制备及其印刷成膜研究

以柠檬酸银为导电金属前驱体化合物,仲丁胺为络合剂,并添加乙醇调节粘度和表面张力等物性参数,制备了无颗粒型银导电墨水。该导电墨水可以采用凹版印刷方式印刷在PET片基上,并且在较低的热处理温度下即可获得导电性较好的银导电膜。利用X射线光电子能谱仪、同步热分析仪、红外光谱仪、X射线衍射仪、扫描电子显微镜和四探针测试仪对柠檬酸银、导电墨水以及银导电膜进行表征。结果表明导电墨水在132 ℃时残留质量即达到恒重,远低于柠檬酸银的210 ℃;经150 ℃热处理之后,银导电膜由均匀致密、纯度高的纳米银颗粒组成;经150 ℃热处理50 min后得到的银导电膜的方块电阻值为1.83 Ω·□-1。     

Direct fabrication of copper patterns by reactive inkjet printing

Reactive inkjet printing (RIP) was applied to fabricate arbitrary copper (Cu) patterns. RIP prints reactive inks which can provide desired materials after the reaction on a substrate. Here, Cu precursors and reducing agents were dissolved together in one solution as a printable ink instead of conventional Cu nanoparticle inks. The prepared reactive ink was applied to the RIP method to provide dot arrays, lines, and films of Cu. The synthesis of Cu was confirmed to occur successfully by thorough analysis. The RIP method can reduce the process cost and resolve critical drawbacks of the conventional inkjet printing such as a nozzle clogging problem. Furthermore, utilizing reactive precursor inks broadens the choice of materials that can be processed by inkjet printing.     

Characteristics of ZnO-Cu-ZnO multilayer films on copper layer properties

ZnO/Cu/ZnO multilayers on glass with different copper layer thickness were prepared by simultaneous RF magnetron sputtering of ZnO and dc magnetron sputtering of Cu. Different optimization procedure were used for good transparent conductive film. Several analytical tools such as spectrophotometer, scanning electron microscope (SEM), four point probes were used to explore the causes of the changes in electrical and optical properties. The sheet resistance of the structure was severely influenced by the deposition condition of both top ZnO and intermediate Cu layer. Effect of substrate temperature and annealing treatment on ZnO and Cu layer was analyzed. A sheet resistance of 10 Ω/sq and transmittance over 85% at 580 nm wavelength was achieved and could be reproduced by controlling the preparation process parameter. The results of an optimization condition of both oxide layers and metallic Cu layers are illustrated.     

Fabrication and adhesion performance of gold conductive patterns on silicon substrate by laser sintering

Laser sintering of gold-microparticle ink was examined in this study. Laser-sintered gold conductive patterns were characterized by using scanning electron microscope (SEM), energy-dispersive spectrometer (EDS), cross-cut tape test and destructive bond wire pull tests. The effects of laser power on microstructure and adhesion of gold conductive patterns were investigated. It was found that the microstructure of gold conductive patterns became denser with increase of laser power. The gold conductive patterns treated with laser power of 2 W showed poor adhesiveness of 2B in accordance with ASTM D3359-08. The adhesion level of gold conductive patterns increased to 5B by elevating laser power to 8 W. The adhesion mechanism of gold conductive patterns on silicon substrate was discussed and wire bonding test was also performed on gold conductive patterns. Wire breakage took place at the practical pull strength of around 5 gf.     

GaN-based light-emitting diode with ZnO nanotexture layer prepared using hydrogen gas

ZnO films were deposited on indium tin oxide (ITO), which formed the transparent conductive layer (TCL) of a GaN-based light-emitting diode (LED), by ultrasonic spraying pyrolysis to increase the light output power. The ZnO nanotexture was formed by treating the as-deposited ZnO films with hydrogen. The root mean square (RMS) roughness increased from 4.47 to 7.89 nm before hydrogen treatment to 10.82-15.81 nm after hydrogen treatment for 20 min. Typical current-voltage (I-V) characteristics of the GaN-based LEDs with a ZnO nanotexture layer have a forward-bias voltage of 3.25 V at an injection current of 20 mA. The light output power of a GaN-based LED with a ZnO nanotexture layer improved to as much as about 27.5% at a forward current of 20 mA.     

Low temperature nanoparticle sintering with continuous wave and pulse lasers

New manufacturing methods are being sought for electronics production. Printable electronics is a promising method for producing low cost and large-scale electronics. In printable electronics nanoparticle inks printed on the surface of substrate contain additives, such as dispersing agent and carrier fluids that provide good printing properties by changing the viscosity and separating the nanoparticles of the ink. In the sintering process ink particles are heated to a certain, ink-specific temperature. During the sintering process the carrier fluid and dispersing agents are evaporated from the ink. Additional heating after evaporation causes the nanoparticles to start to agglomerate. A small particle size allows the use of a considerably lower sintering temperature than with bulk silver, for example 220 °C. The sintering process is usually utilized with a convection oven, with a long sintering time, and the thermal load on the surrounding material can become too great as components and patterns are formed from layers of different type inks. Hence, alternative sintering methods are sought. This paper describes tests done with two different types of laser; pulsed and continuous wave lasers. Laser sintering enables short sintering times and selective sintering, making it possible for printed structures to contain fragile active components produced with other technologies.     

Infra-red assisted sintering of inkjet printed silver tracks on paper substrates

In this study, conductive silver features using inkjet printing have been successfully prepared and their sintering studied. Regarding conductivity, metallic inks are the most efficient available conductive inks, even if important drawbacks regarding the use of such inks in inkjet still exist. Indeed, the sintering step is an important limiting factor for the productivity and the substrate choice. An infrared (IR) drying method was experimented to optimize the sintering treatment time. Trials with glass and paper substrates were performed and proved that IR drying is interesting to optimize sintering. Indeed a similar level of resistance was obtained for conventional heating (200 °C, 5 min) and for IR radiations within a shorter treatment time (3 min). Moreover, the substrate temperature during the IR sintering treatment was controlled. The substrate appears to be a relevant parameter to optimize sintering because its thermal behaviour directly impacts on the treatment duration. And for the first time a sheet resistance of 1.9 Ω sq⁻¹ was obtained on paper substrate after only 2 min of IR treatment without any observation of substrate degradation. The evaluation of an electrical treatment on the sintering of a nanoparticle film was also performed using a corona pre-treatment. This lead appears to be interesting because the study proves that an electrical treatment can initiate the sintering of silver nanoparticles. The current flow generated by the corona electrodes certainly generates a local heating by dissipation of the conductive pattern. Finally, the solutions presented in this article allow reducing the sintering time of silver conductive inkjet inks. However mainly, it proves that using paper as substrate for such inks is now possible.     

In-tandem deposition and sintering of printed gold nanoparticle inks induced by continuous Gaussian laser irradiation

By employing continuous Gaussian laser irradiation in tandem with a specifically designed drop-on-demand jetting system, nanoparticle inks were printed and sintered on glass substrate. A toluene solvent is employed as the carrier of gold nanoparticles possessing a lower melting temperature than that of bulk gold. Marangoni flow due to radial surface tension gradient combined with a moving substrate displaces nanoparticle ink in front of and around the laser spot. Experiments were carried out changing incident laser power, focused beam waist, and translation speed, and resulting phenomena at different conditions were explained. Strong coalescence occurred from 9000–14000 W/cm², and a gold line with 8 m of width was demonstrated. PACS 81.16.Mk; 85.40.Ls; 44.10.+i; 47.20.Dr     

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.     

Copper reduction and hydroxyl formation by hydrogen process in alumino-silicate glasses

The process of nanometric copper (Cu⁰) precipitation by hydrogen in alumino-silicate glasses was studied regarding the simultaneous formation of hydroxyl bonding. Firstly, copper-ion-doped alumino-silicate glasses were melt-quenched and then heat-treated in the presence of hydrogen gas, which allowed copper ions to be reduced into nanometric metal particles. Along with the metallic copper formation, there was also formed the hydroxyl groups as a byproduct of the reaction. From spectroscopic studies, it was revealed that the reduction process was kinetically controlled by the hydrogen diffusion into the glasses. After the Cu⁰ precipitation, in particular, at temperatures higher than 700 °C or for reduction times longer than 5 h the copper metal was found to move towards the surface, creating a copper metal rich surface. Moreover, an increase in hydrogen permeation with the treatment time was also observed and this tendency was more intense for the matrix, which allowed higher copper reduction.     

Laser ablation of multilayers of ink from a paper substrate for tactile printing

This paper reports the effects of laser ablation upon multiple-layered coloured inks which have been printed on an ordinary white paper. The aim of this work is to examine the feasibility of generating a fully tactile three-coloured image by selectively removing ink layers to reveal underlying layers of a different colour. In this paper laser ablation has been carried out upon four layered ink samples consisting of white/cyan/white/black layers. Ablation was carried out using a Q-switched Nd : YAG laser. The results show that it is possible to selectively remove the inks to expose both the top white and the cyan layers, although charring occurs with deeper ablation. An evaporation/decomposition mechanism is proposed to describe process of ink ablation.     

Characterisation of molybdenum intermediate layers in Cu-C system with SIMS method

In the design of new high-speed chip generations a huge problem is bleeding off process heat during their operation. The installation of heat sinks onto such chips is necessary. Possible materials are copper-coated carbon composites. They combine high thermal conductivity with low density and a tailorable coefficient of thermal expansion (CTE). The low wettability of copper onto carbon necessitates a surface pretreatment.Flat slices of nitrogen-plasma etched vitreous carbon (Sigradur G) made up as a model system for carbon fiber material. The later serial fabrication of these fibers includes a hot pressing step after the deposition joining them to solid composites. It is simulated by a heat treatment step of the compound. The first sample series consisted of samples with 100 nm molybdenum and 500 nm copper layers (sputter deposited), as deposited and heat treated. The second run concludes samples without molybdenum layer but an additional 50 nm cap layer deposited after heat treatment.All samples were investigated with secondary ion mass spectrometry (SIMS), showing a diffusion of carbon into the molybdenum layer. Measuring MCs⁺ secondary ions, both matrix elements and trace elements were detectable sufficiently.     

Evaluation of copper ion of antibacterial effect on Pseudomonas aeruginosa, Salmonella typhimurium and Helicobacter pylori and optical, mechanical properties

Antibacterial effect on Pseudomonas aeruginosa, Salmonella typhimurium and Helicobacter pylori of copper ion was researched. Also, additional effects of copper ion coating on optical and mechanical properties were researched as well. Copper ion was coated on glass substrate as a thin film to prevent bacteria from growing. Cupric nitrate was used as precursors for copper ion. The copper ion contained sol was deposited by spin coating process on glass substrate. Then, the deposited substrates were heat treated at the temperature range between 200 °C and 250 °C. The thickness of deposited copper layer on the surface was 63 nm. The antibacterial effect of copper ion coated glass on P. aeruginosa, S. typhimurium and H. pylori demonstrated excellent effect compared with parent glass. Copper ion contained layer on glass showed a similar value of transmittance compared with value of parent glass. The 3-point bending strength and Vickers hardness were 209.2 MPa, 540.9 kg/mm² which were about 1.5% and 1.3% higher than the value of parent glass. From these findings, it is clear that copper ion coating on glass substrate showed outstanding effect not only in antibacterial activity but also in optical and mechanical properties as well.