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.     

Study of the laser-induced forward transfer of liquids for laser bioprinting

Laser-induced forward transfer (LIFT) is a direct-writing technique that allows printing patterns of diverse materials with a high degree of spatial resolution. In conventional LIFT a small fraction of a solid thin film is vaporized by means of a laser pulse focused on the film through its transparent holder, and the resulting material recondenses on the receptor substrate. It has been recently shown that LIFT can also be used to transfer materials from liquid films. This widened its field of application to biosensors manufacturing, where small amounts of biomolecules-containing solutions have to be deposited with high precision on the sensing elements. However, there is still little knowledge on the physical processes and parameters determining the characteristics of the transfers.In this work, different parameters and their effects upon the transferred material were studied. It was found that the deposited material corresponds to liquid droplets which volume depends linearly on the laser pulse energy, and that a minimum threshold energy has to be overcome for transfer to occur. The liquid film thickness was varied and droplets as small as 10 μm in diameter were obtained. Finally, the effects of the variation of the film to substrate distance were also studied and it was found that there exists a wide range of distances where the morphology of the transferred droplets is independent of this parameter, what provides LIFT with a high degree of flexibility.     

Jet formation in the laser forward transfer of liquids

The dynamics of the laser-induced forward transfer (LIFT) of an aqueous solution is investigated through time-resolved imaging. The experiment is carried out at conditions under which droplets are deposited on a receptor substrate. The obtained images reveal that after an initial balloon-like stage, a uniform jet with a very long length and high aspect ratio is formed, which advances at constant speed until it finally becomes unstable and breaks into several droplets. This dynamics demonstrates that the deposition process of well-defined droplets through LIFT results from the contact of the liquid jet with the receptor substrate, and not from a flying droplet.     

Printing biological solutions through laser-induced forward transfer

Laser-induced forward transfer (LIFT) is a direct-writing technique adequate for the high-resolution printing of a wide range of materials, including biological molecules. In this article, the preparation through LIFT of microarrays of droplets from a solution containing rabbit antibody immunoglobulin G (IgG) is presented. The microarrays were prepared at different laser pulse energy conditions, obtaining microdroplets with a circular and well-defined contour. The transfer process has a double threshold: a minimum energy density required to generate an impulsion on the liquid film, and a minimum pulse energy, which corresponds to the onset for material ejection. In addition, it was demonstrated that the transfer process can be correctly described through a simple model which relates the energy density threshold with the amount of released material. Finally, a fluorescence assay was carried out in which the preservation of the activity of the transferred biomolecules was demonstrated.     

Smart beam shaping for the deposition of solid polymeric material by laser forward transfer

Laser-induced forward transfer (LIFT) has been investigated for the transfer of a polymeric material. This study focuses on the comparison of the printing process using conventional LIFT printing with a simple square mask and an optimized LIFT technique using a double mask setup, i.e. smart beam shaping (SBS). The purpose is to optimize the energy repartition on the donor layer using a beam profile with over-intensities at the edges and low intensities in the center. This allows the incoming irradiation fluence on the donor layer to be kept as low as possible in the central area, thus preventing the organic pixels being damaged by laser irradiation. The influence of the film’s thickness on the SBS efficiency is discussed.     

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.     

Laser-induced forward transfer of focussed ion beam pre-machined donors

In this paper we report femtosecond laser-induced forward transfer (LIFT) of pre-machined donor films. 1 μm thick zinc oxide (ZnO) films were first machined using the focussed ion beam (FIB) technique up to a depth of 0.8 μm. Debris-free micro-pellets of ZnO with extremely smooth edges and surface uniformity were subsequently printed from these pre-machined donors using LIFT. Printing results of non-machined ZnO donor films and films deposited on top of a polymer dynamic release layer (DRL) are also presented for comparison, indicating the superior quality of transfer achievable and utility of this pre-machining technique.     

Laser induced forward transfer of SnO2 for sensing applications using different precursors systems

This paper presents the transfer of SnO₂ by laser induced forward transfer (LIFT) for gas sensor applications. Different donor substrates of SnO₂ with and without triazene polymer (TP) as a dynamic release layer were prepared. Transferring these films under different conditions were evaluated by optical microscopy and functionality. Transfers of sputtered SnO₂ films do not lead to satisfactory results and transfers of SnO₂ nanoparticles are difficult. Transfers of SnO₂ nanoparticles can only be achieved when applying a second laser pulse to the already transferred material, which improves the adhesion resulting in a complete pixel. A new approach of decomposing the transfer material during LIFT transfer was developed. Donor films based on UV absorbing metal complex precursors namely, SnCl₂(acac)₂ were prepared and transferred using the LIFT technique. Transfer conditions were optimized for the different systems, which were deposited onto sensor-like microstructures. The conductivity of the transferred material at temperatures of about 400 ^°C are in a range usable for SnO₂ gas sensors. First sensing tests were carried out and the transferred material proved to change conductivity when exposed to ethanol, acetone, and methane.     

A novel laser transfer process for direct writing of electronic and sensor materials

MAPLE direct write (MAPLE DW) is a new laser-based direct-write technique which combines the basic approach employed in laser-induced forward transfer (LIFT) with the unique advantages of matrix-assisted pulsed-laser evaporation (MAPLE). MAPLE DW utilizes an optically transparent substrate coated on one side with a matrix consisting of the material to be transferred mixed with a polymer or organic binder. As in LIFT, the laser is focused through the transparent substrate onto the matrix. When a laser pulse strikes the matrix, the binder decomposes and aids the transfer of the material of interest to an acceptor substrate placed parallel to the matrix surface. MAPLE DW is a maskless deposition process which operates in air and at room temperature. Powders of Ag, BaTiO₃, SrTiO₃, and Y₃Fe₅O₁₂ with average diameters of 1 7m were transferred onto the surfaces of alumina, glass, silicon, and printed circuit board substrates. Parallel-plate and interdigitated capacitors and flat inductors were produced by MAPLE DW over Rogers RO4003 substrates. MAPLE DW was also used to transfer polymer composites for the fabrication of gas sensor chemoresistors. One such composite chemoresistor fabricated with polyepichlorohydrin/graphite was used to detect organic vapors with a sensitivity of parts per million.     

Aluminum film microdeposition at 775 nm by femtosecond laser-induced forward transfer

Micro-deposition of an aluminum film of 500-nm thickness on a quartz substrate was demonstrated by laserinduced forward transfer (LIFT) using a femtosecond laser pulse. With the help of atomic force microscopy (AFM) and scanning electron microscopy (SEM), the dependence of the morphology of deposited aluminum film on the irradiated laser pulse energy was investigated. As the laser fluence was slightly above the threshold fluence, the higher pressure of plasma for the thicker film made the free surface of solid phase burst out, which resulted in that not only the solid material was sputtered but also the deposited film in the liquid state was made irregularly.     

Aryltriazene photopolymer thin films as sacrificial release layers for laser-assisted forward transfer systems: study of photoablative decomposition and transfer behavior

Thin films of a tailor-made photodecomposible aryltriazene polymer were applied in a modified laser-induced forward transfer (LIFT) process as sacrificial release layers. The photopolymer film acts as an intermediate energy-absorbing dynamic release layer (DRL) that decomposes efficiently into small volatile fragments upon UV laser irradiation. A fast-expanding pressure jet is generated which is used to propel an overlying transfer material from the source target onto a receiver. This DRL-assisted laser direct-write process allows the precise deposition of intact material pixels with micrometer resolution and by single laser pulses. Triazene-based photopolymer DRL donor systems were studied to derive optimum conditions for film thickness and laser fluences necessary for a defined transfer process at the emission wavelength of a XeCl excimer laser (308 nm). Photoablation, surface detachment, delamination and transfer behavior of aryltriazene polymer films with a thickness from 25 nm to ∼400 nm were investigated in order to improve the process control parameters for the fabrication of functional thin-film devices of microdeposited heat- and UV-sensitive materials.     

A study on the pulsed laser printing of liquid-phase exfoliated graphene for organic electronics

The aim of this work is the pulsed laser printing of liquid-phase exfoliated graphene in the nanosecond regime and the optimization of the printing process on Si/SiO₂ and flexible polymer substrates (polyethylene naphthalate) via the laser-induced forward transfer technique (LIFT). The laser printing conditions and the optimum energy fluence window for reproducible deposition have been investigated, while the deposited graphene features have been studied morphologically and structurally by means of optical microscopy, micro-Raman spectroscopy and electrical characterization. LIFT experiments were carried out using the fourth harmonic (266 nm) of a pulsed ns Nd:YAG laser combined with a high-power imaging micromachining system to monitor the printing process throughout the experiments. The irradiation of our graphene solution resulted in the deposition of well-resolved patterns on different surfaces, highlighting LIFT as an alternative technique for the printing and patterning of liquid-phase exfoliated graphene for organic electronics applications.     

Optimization of laser printing of nanoparticle suspensions for microelectronic applications

Digital printing of interconnects for electronic devices requires processes capable of delivering controlled amounts of conductive inks in a fast and accurate way. Laser-induced forward transfer (LIFT) is an emerging technology that enables controlled printing of voxels of a wide range of inks with micrometer resolution. Its use with high solids content nanoparticle suspensions results in the deposition of voxels shaped as the impinging laser beam. This allows higher processing speeds, increasing the throughput of the technique. However, the optimum conditions for printing spot-like voxels have not been determined, yet. In this work, we perform a systematic study of the main experimental parameters, including laser pulse energy, laser beam dimensions, and gap distance, in order to understand the role that these parameters play in laser printing. Based on these results, we find that there is a narrow fluence range at distances close to the receiving substrate where spot-like voxels are deposited. We also provide a detailed discussion of the possible mechanisms that may lead to the observed features.     

A sensor for adenosine triphosphate fabricated by laser-induced forward transfer of luciferase onto a poly(dimethylsiloxane) microchip

Laser-induced forward transfer (LIFT) of the enzyme luciferase was explored as a potential technique to be used in the fabrication of a microchip adenosine triphosphate (ATP) sensor. Poly(dimethylsiloxane) (PDMS) was selected as the substrate for deposition of the luciferase. In comparison with other solid substrates, such as glass and polystyrene, it was found that the flexibility of PDMS made it a superior substrate for the immobilization of micro-spots of luciferase. LIFT of luciferase onto a PDMS substrate using a 355 nm laser was successfully carried out, while the bioactivity of the enzyme was maintained. Yellow luminescence ascribed to luciferase was observed from a transferred spot on the PDMS chip from the enzymatic reaction between luciferin and ATP. A microchip ATP sensor was also fabricated by attaching a small photodiode to the PDMS chip. On the basis of the fabricated microchip, the Michaelis-Menten relation between the luminescence intensity from the spot, and the ATP concentration was confirmed. The potential for fabricating biosensors using a combination of the LIFT technique with a PDMS substrate was shown to be very good.     

Nanoscale laser-induced forward transfer through patterned Cr films

The resolution enhancement of laser-induced forward transfer (LIFT) is investigated through the pre-patterning of Cr on the donor substrate. 85 nm dots are first patterned on a microscope slide, and an 800 nm wavelength and 130 fs pulse laser with a beam waist of ～9 μm is used to transfer the Cr dots to an acceptor substrate. The threshold fluence is found to be ～0.15 the threshold fluence of a similar continuous film, which is thought to be due to the fact that no force is needed to tear away Cr from the film itself, unlike in a continuous film experiment. Since the volume of the material limits the transfer feature sizes instead of the laser parameters, as in a continuous film system, minimum transferable feature diameters are significantly lower compared to the continuous film case. Also, the transferred feature diameters are not dependent on the laser parameters, so the diameters are consistent across a wide range of fluences. The force per unit area generated by the laser at threshold fluence is estimated to be ～3 GPa, which is consistent with previous results in the literature. The simplified model that our pre-patterned Cr LIFT experiment represents would make it an ideal case for benchmarking molecular dynamics simulations of femtosecond laser ablation.     

Study of liquid deposition during laser printing of liquids

Laser-induced forward transfer (LIFT) is a direct-writing technique which can be used to successfully print various complex and sensitive materials with a high degree of spatial resolution. However, the optimization of its performances requires a deep understanding of the LIFT dynamics. Such understanding should allow correlating the phenomena underlying the liquid transfer process with the morphology of the obtained deposits. To this end, in this work it is presented a study related to two aspects: first, the correlation of the morphological characteristics of the transferred droplets with the variation of the film thickness combined with laser fluence; and second, a correlation of the dependences observed with the dynamics of the transfer process. The work is focused on the understanding of the observed dependences for which the information provided by time-resolved analysis on liquid transfer dynamics has proved to be crucial.     

Atomized spraying of liquid metal droplets on desired substrate surfaces as a generalized way for ubiquitous printed electronics

A direct electronics printing technique through atomized spraying for patterning room-temperature liquid metal droplets on desired substrate surfaces is proposed and experimentally demonstrated for the first time. This method is highly flexible and capable of fabricating electronic components on various target objects, with either flat or rough surfaces, made of different materials, or having different orientations from 2D to 3D geometrical configurations. With a pre-designed mask, the liquid metal ink can be directly deposited on the substrate to form various specific patterns which lead to the rapid prototyping of electronic devices. Further, extended printing strategies were also suggested to illustrate the adaptability of the method. For example, it can be used for making transparent conductive film with an optical transmittance of 47 % and a sheet resistance of 5.167Ω/□ due to natural porous structure. Different from the former direct writing technology where large surface tension and poor adhesion between the liquid metal and the substrate often impede the flexible printing process, the liquid metal here no longer needs to be pre-oxidized to guarantee its applicability on target substrates. One critical mechanism was that the atomized liquid metal microdroplets can be quickly oxidized in the air due to its large specific surface area, resulting in a significant increase of the adhesion capacity and thus firm deposition of the ink to the substrate. This study paved a generalized way for pervasively and directly printing electronics on various substrates which are expected to be significant in a wide spectrum of electrical engineering areas.     

Polymer-coated compliant receivers for intact laser-induced forward transfer of thin films: experimental results and modelling

In this study, we investigate both experimentally and numerically laser-induced forward transfer (LIFT) of thin films to determine the role of a thin polymer layer coating the receiver with the aim of modifying the rate of deceleration and reduction of material stress preventing intact material transfer. A numerical model of the impact phase during LIFT shows that such a layer reduces the modelled stress. The evolution of stress within the transferred deposit and the substrate as a function of the thickness of the polymer layer, the transfer velocity and the elastic properties of the polymer are evaluated. The functionality of the polymer layer is verified experimentally by LIFT printing intact 1- \(\upmu \) m-thick bismuth telluride films and polymeric light-emitting diode pads onto a layer of 12- \(\upmu \) m-thick polydimethylsiloxane and 50-nm-thick poly(3,4-ethylenedioxythiophene) blended with poly(styrenesulfonate) (PEDOT:PSS), respectively. Furthermore, it is demonstrated experimentally that the introduction of such a compliant layer improves adhesion between the deposit and its substrate.     

Improved laser-induced forward transfer of organic semiconductor thin films by reducing the environmental pressure and controlling the substrate–substrate gap width

Laser-induced forward transfer (LIFT) has been investigated for bilayer transfer material systems: silver/organic film (Alq₃ or PFO). The LIFT process uses an intermediate dynamic release layer of a triazene polymer. This study focuses on the effect of introducing a controlled donor–receiver substrate gap distance and the effect of doing the transfer at reduced air pressures, whilst varying the fluence up to ∼200 mJ/cm². The gap between ‘in-contact’ substrates has been measured to be a minimum of 2–3 μm. A linear variation in the gap width from ‘in contact’ to 40 μm has been achieved by adding a spacer at one side of the substrate–substrate sandwich. At atmospheric pressure, very little transfer is achieved for Alq₃, although PFO shows some signs of successful doughnut transfer (with a large hole in the middle) in a narrow fluence range, at gaps greater than 20 μm. For the transfer of Ag/PFO bilayers at atmospheric pressure, the addition of a PFO layer onto the receiver substrate improved the transfer enormously at smaller gaps and higher fluences. However, the best transfer results were obtained at reduced pressures where a 100% transfer success rate is obtained within a certain fluence window. The quality of the pixel morphology at less than 100 mbar is much higher than at atmospheric pressure, particularly when the gap width is less than 20 μm. These results show the promise of LIFT for industrial deposition processes where a gap between the substrates will improve the throughput.     

Laser direct writing of biomolecule microarrays

Protein-based biosensors are highly efficient tools for protein detection and identification. The production of these devices requires the manipulation of tiny amounts of protein solutions in conditions preserving their biological properties. In this work, laser induced forward transfer (LIFT) was used for spotting an array of a purified bacterial antigen in order to check the viability of this technique for the production of protein microarrays. A pulsed Nd:YAG laser beam (355 nm wavelength, 10 ns pulse duration) was used to transfer droplets of a solution containing the Treponema pallidum 17 kDa protein antigen on a glass slide. Optical microscopy showed that a regular array of micrometric droplets could be precisely and uniformly spotted onto a solid substrate. Subsequently, it was proved that LIFT deposition of a T. pallidum 17 kDa antigen onto nylon-coated glass slides preserves its antigenic reactivity and diagnostic properties. These results support that LIFT is suitable for the production of protein microarrays and pave the way for future diagnostics applications. PACS 87.14.Ee; 81.15.Fg; 07.07.Df