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NMC thick films were prepared by tape-casting and subsequent ultrafast laser-structuring. The lithium distribution in electrochemically cycled and unstructured or fs laser-structured NMC cathodes was investigated by using Laser-Induced Breakdown Spectroscopy (LIBS). The main goal is to develop an optimized three dimensional cell architecture with improved electrochemical properties based on studies of the homogeneity of the local State-of-Charge. LIBS experiments were carried out using a LIBS workstation equipped with a mode-locked diode pumped solid state Nd:YAG laser operating at a wavelength of 1063 nm. The element distribution was investigated using two different techniques: element mapping and element depth-profiling of the unstructured / fs laser-structured electrode surface. Results achieved from post-mortem studies using LIBS will be presented.

Lithium manganese oxide composite cathodes are realized by laser-printing. The printed cathode is a composite and consists of active powder, binder and conductive agents. Laser-printed cathodes are first calendered and then laser structured using femtosecond-laser radiation in order to form three-dimensional (3D) micro-grids in the cathode material. Three-dimensional micro-grids in calendered/laser structured cathodes exhibit improved discharge capacity retention at a 1 C discharging rate. Calendered but unstructured cathodes indicate the poorest cycling behavior at 1 C discharge. The improved capacity retention and the reduced degradation of calendered/structured cathodes can be attributed to both the increased electrical contact through calendering as well as shortened Li-ion pathways due to laser-induced 3D microgrids.

LiFePO 4 is a very promising material to be used as positive electrode for future lithium-ion batteries. Nevertheless, a reduced rate capability at high discharging and charging currents is the main drawback. In this work, a 3D structure was made in LiFePO 4 composite electrodes by applying ultrafast laser ablation. The change of the electrochemical properties in a lithium-ion half-cell due to laser structuring was studied in detail and will be discussed. The main challenging goal is to correlate cell properties such as capacity retention with laser parameters and laser generated microstructure. For microstructuring electrode materials an ultrafast as well as a ns fiber laser were used. The pulse duration was varied in the range from 350 fs to 200 ns. With ultrashort laser radiation, the ablation efficiency was increased. Electrochemical characterisations were performed. For this purpose, Swagelok® test cells with lithium metal as counter electrode were assembled. Main electrochemical parameters such as specific capacity and cycle stability were determined for the cells with structured and unstructured cathodes. It was shown that the rate capability for the cells with structured cathodes in comparison to cells with unstructured cathodes was significantly enhanced, especially for high charging and discharging rates.

Three-dimensional (3D) battery architectures are under current scientific investigation since they can achieve large areal energy capacities while maintaining high power densities. A main objective of surface patterning is the enhancement of lithium-ion diffusion which is often a limiting factor in lithium-ion cells. By using a rather new approach, laser material processing of thick-film electrodes has been investigated for the precise adjustment of 3D surface topography. Besides lithium-ion diffusion in electrode materials as an electrochemically limited process, a critical step in lithium-ion pouch cell manufacturing is the homogeneous electrolyte wetting of stacked electrodes and separators. This process requires cost expensive and time-consuming vacuum and storage processes at elevated temperatures. A new and cost efficient laser process has been successfully applied in order to significantly improve the electrode wetting and the battery operation. Preliminary investigations for testing the process on pouch cell geometry revealed higher capacities and increased cell life-time compared to standard cells without storage processes at elevated temperatures. The laser structuring process can be applied to commercial electrode materials and integrated into existing production lines.

Laser induced forward transfer (LIFT) process was used to print thick-film electrodes (LiCoO2 cathode and carbon anode) and solid-state polymer membranes for Li-ion microbatteries. Their electrochemical behaviors were characterized by cyclic voltammograms, capacity measurement and cycling performance. Microbatteries based on these laser-printed thick-film electrodes showed significantly higher discharge capacities than those made by sputter-deposited thin film techniques. This enhanced performance is attributed to the high surface area porous structure of the laser-printed electrodes that allows improved diffusion of the Li-ions across the 100 μm-thick electrodes without a significant internal resistance. In addition, a laser structuring process was used to prepare three-dimensional microstructures on the laserprinted thick-film electrodes to further improve battery performance by increasing the active surface area. These results indicate that the laser processing techniques are a viable approach for developing Li-ion microbatteries in microelectronic devices. This paper will show examples of Li-ion microbatteries fabricated with various polymer separators and structured electrodes using a combination of LIFT and excimer laser structuring processes.

The increasing need for long-life lithium-ion batteries requires the further development of electrode materials. Especially on the cathode side new materials or material composites are needed to increase the cycle lifetime. On the one hand, spinel-type lithium manganese oxide is a promising candidate to be used as cathode material due to its non-toxicity, low cost and good thermal stability. On the other hand, the spinel structure suffers from change in the oxidation state of manganese during cycling which is also accompanied by loss of active material into the liquid electrolyte. The general trend is to enhance the active surface area of the cathode in order to increase lithium-ion mobility through the electrode/electrolyte interface, while an enhanced surface area will also promote chemical degradation. In this work, laser microstructuring of lithium manganese oxide thin films was applied in a first step to increase the active surface area. This was done by using 248 nm excimer laser radiation and chromium/quartz mask imaging techniques. In a second step, high power diode laser-annealing operating at a wavelength of 940 nm was used for forming a cubic spinel-like battery phase. This was verified by means of Raman spectroscopy and cyclic voltammetric measurements. In a last step, the laser patterned thin films were coated with indium tin oxide (ITO) layers with a thickness of 10 nm to 50 nm. The influence of the 3D surface topography as well as the ITO thickness on the electrochemical performance was studied by cyclic voltammetry. Post-mortem studies were carried out by using scanning electron microscopy and focused ion beam analysis.

Rechargeable lithium-ion batteries have emerged as an attractive power source for a wide variety of applications, in particular for portable electronics. The development and modification of electrode materials is a major issue for the improvement of energy density and power density of lithium-ion batteries. For this purpose, laser-induced self-organizing surface structures were generated using UV-excimer laser radiation with a wavelength of 248 nm and a pulse width of 4-6 ns. The self-organization process was applied for thin films made of lithium cobalt oxide with a thickness of about 3 μm. In order to identify the chemical changes due to laser processing time-of-flight secondary ion mass spectroscopy measurements were performed. It was found that this process can be linked to a decomposition of the electrode material forming a lithium oxide surface layer. Similar self-organized surface structures could also be obtained for thick film electrode materials consisting of LiCoO 2 powder mixed with binder and carbon black which were tape-casted onto aluminium foils. The thickness of these films was in the range of 50 - 100 μm.

The further development of energy storage devices especially of lithium-ion batteries plays an important role in the ongoing miniaturization process towards lightweight, flexible mobile devices. To improve mechanical stability and to increase the power density of electrode materials while maintaining the same footprint area, a three-dimensional battery design is necessary. In this study different designs of three-dimensional cathode materials are investigated with respect to the electrochemical performance. Lithium cobalt oxide is considered as a standard cathode material, since it has been in use since the first commercialization of lithium-ion batteries. Various electrode designs were manufactured in lithium cobalt oxide electrodes via laser micro-structuring. Laser ablation experiments in ambient air were performed to obtain hierarchical and high aspect surface structures. Laser structuring using mask techniques as well as the formation of self-organized conical surface structures were studied in detail. In the latter case a density of larger than twenty million microstructures per square centimeter was obtained with a significant increase of active surface area. Laser annealing was applied for the control of the average grain size and the adjustment of a crystalline phase which exhibits electrochemical capacities in the range of the practical capacity known for lithium cobalt oxide. An investigation of cycling stability with respect to annealing parameters such as annealing time and temperature was performed using a diode laser operating at 940 nm. Information on the phase and crystalline structure were obtained using Raman spectroscopy and X-ray diffraction analysis. The electrochemical performance of the laser modified cathodes was studied via cyclic voltammetry and galvanostatic testing using a lithium anode and a standard liquid electrolyte.

Three-dimensional cathode architectures for rechargeable lithium-ion cells can provide better Li-ion diffusion due to larger electrochemical active surface area and therefore, may stabilize the cycling behaviour of an electrochemical cell. This features show great importance when aiming for long-life batteries, e.g. in stationary or portable power devices. In this study, lithium manganese oxide thin films were used as cathode material with the goal to stabilize their cycling behavior and to counter degradation effects which come up within the lithium manganese oxide system. Firstly, appropriate laser ablation parameters were selected in order to achieve defined three-dimensional structures with features sizes down to micro- and sub-micrometer scale by using mask imaging technique. Laser annealing was also applied onto the laser structured material in a second step in order to form an electrochemically active phase. Process development led to a laser annealing strategy for a flexible adjustment of crystallinity and grain size. Laser annealing was realized using a high power diode laser system operating at a wavelength of 940 nm. Information on the surface composition, chemistry and topography as well as studies on the crystalline phase of the material were obtained by using Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy and X-ray diffraction analysis. The electrochemical activity of the laser modified lithium manganese oxide cathodes was explored by cyclic voltammetry measurements and galvanostatic testing by using a lithium anode and standard liquid electrolyte.

The development of future battery systems is mainly focused on powerful rechargeable lithium-ion batteries. To satisfy this demand, current studies are focused on cathodes based on nano-composite materials which lead to an increase in power density of the LIB primarily due to large electrochemically active surface areas. Electrode materials made of lithium manganese oxides (Li-Mn-O) are assumed to replace commonly used cathode materials like LiCoO2 due to less toxicity and lower costs. Thin films in the Li-Mn-O system were synthesized by non-reactive r.f. magnetron sputtering of a LiMn 2 O 4 target on silicon and stainless steel substrates. In order to enhance power density and cycle stability of the cathode material, direct laser structuring methods were investigated using a laser system operating at a wavelength of 248 nm. Therefore, high aspect ratio micro-structures were formed on the thin films. Laser annealing processes were investigated in order to achieve an appropriate crystalline phase for unstructured and structured thin films as well as for an increase in energy density and control of grain size. Laser annealing was realized via a high power diode laser system. The effects of post-thermal treatment on the thin films were studied with Raman spectroscopy, X-ray diffraction and scanning electron microscopy. The formation of electrochemically active and inactive phases was discussed. Surface chemistry was investigated via X-ray photoelectron spectroscopy. Interaction between UV-laser radiation and the thin film material was analyzed through ablation experiments. Finally, to investigate the electrochemical properties, the manufactured thin film cathodes were cycled against a lithium anode. The formation of a solid electrolyte interphase on the cathode side was discussed.

The material development for advanced lithium-ion batteries plays an important role in future mobile applications and energy storage systems. It is assumed that electrode materials made of nano-composited materials will improve battery lifetime and will lead to an enhancement of lithium diffusion and thus improve battery capacity and cyclability. A major problem concerning thin film electrodes is, that increasing film thickness leads to an increase in lithium diffusion path lengths and thereby a decrease in power density. To overcome this problem, the investigation of a 3D-battery system with an increased surface area is necessary. UV-laser micromachining was applied to create defined line or grating structures via mask imaging. SnO 2 is a highly investigated anode material for lithium-ion batteries. Yet, the enormous volume changes occurring during electrochemical cycling lead to immense loss of capacity. The formation of micropatterns via laser ablation to create structures which enable the compensation of the volume expansion was investigated in detail. Thin films of SnO 2 were deposited in Ar:O 2 atmosphere via r.f. magnetron sputtering on silicon and stainless steel substrates. The thin films were studied with X-ray diffraction to determine their crystallinity. The electrochemical properties of the manufactured films were investigated via electrochemical cycling against a lithium anode.

The material development for advanced lithium ion batteries plays an important role in future mobile applications and energy storage systems. It is assumed that electrode materials made of nano-composited materials will improve battery lifetime and will lead to an enhancement of lithium diffusion and thus improve battery capacity and cyclability. Lithium cobalt oxide (LiCoO 2 ) is commonly used as a cathode material. Thin films of this electrode material were synthesized by non-reactive r.f. magnetron sputtering of LiCoO 2 targets on silicon or stainless steel substrates. For the formation of the high temperature phase of LiCoO 2 (HT-LiCoO 2 ), which exhibits good electrochemical performance with a specific capacity of 140 mAh/g and high capacity retention, a subsequent annealing treatment is necessary. For this purpose laser annealing of thin film LiCoO 2 was investigated in detail and compared to conventional furnace annealing. A high power diode laser system operating at a wavelength of 940 nm with an integrated pyrometer for temperature control was used. Different temperatures (between 200°C and 700°C) for the laser structured and unstructured thin films were applied. The effects of laser treatment on the LiCoO 2 thin films studied with Raman spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction to determine their stoichiometry and crystallinity. The development of HT-LiCoO 2 and also the formation of a Co 3 O 4 phase were discussed. The electrochemical properties of the manufactured films were investigated via electrochemical cycling against a lithium anode.

Two types of laser patterning are of interest for application in microsystem technology: direct ablation of polymer material for the generation of two or three dimensional shapes such as microfluidic channels, curved shapes or micro-holes and alternatively photo-induced change of chemical or physical properties. An appropriate choice of laser and process parameters enables new approaches for the fabrication of lab-on-chip devices with integrated functionalities. We will present our current research results in laser-assisted ablation and modification of polystyrene (PS) with respect to the fabrication of polymer devices for high throughput planar patch clamping. Patch clamping is a highly sensitive technique used to measure the electrical activity of a cell. It is used in applications which include drug screening where there is demand for high throughput systems (HTS). While there are a few commercially available HTS patch clamping systems on the market using traditional patch clamping materials, there are no systems on the market using novel materials, or for dealing with cell networks - a physiologically important consideration for the developing fields of tissue engineering and understanding cell to cell interactions. This paper presents potential design approaches and processes for producing a polymer based automated patch clamping system. For this purpose laser micro-drilling of PS and subsequent surface functionalization was investigated as function of laser and process parameters. A high power ArF-excimer laser radiation source with pulse length of 20 ns (repetition rate up to 40 Hz) as well as high repetition ArF- and KrF-excimer laser sources with pulse lengths of 4-6 ns (repetition rates up to 500 Hz) were used in order to study the influence of laser pulse length on laser drilling and laser-induced surface modification. Micro-drilling of PS with diameters down to 1.5 μm were demonstrated. Furthermore the localized formation of chemical structures suitable for improved adhesion of single cells and cell networks was achieved on PS surfaces. A photolytic activation of specific areas of the polymer surface and subsequent oxidization in oxygen or ambient air leads to a chemically modified polymer surface bearing carboxylic acid groups well-suited for controlled competitive protein adsorption or protein immobilization. Finally, distinct areas for cell growth and adhesion are obtained. The combination of laser ablation and modification will be discussed for the laser-assisted fabrication of polymer devices for patch clamping.

Selective Laser Melting (SLM) is a generative manufacturing procedure mainly known for the application with metal powders. From these, metallic structures are produced in a layer-by-layer way. This layer-related procedure is comparable to the stereolithographic manufacturing of polymer devices. On a base plate, a thin layer of metal powder is spread. The powder is locally completely melted by the application of a focused laser beam. The base plate is then lowered by a value defined by the thickness of the metal layer, metal powder is spread again, and the local melting process is re-initiated. The complete procedure is continued as described, until the device is manufactured in the defined way. Commercially available metal powder can be used as base material. In principle, the SLM process should be suitable for the generation of metallic microstructures. The main precondition for the generation of microstructures by SLM is that the spatial resolution of the laser focus is small and precise enough to generate microstructure walls of around 100μm thickness in a reproducible way by melting metal powder. The walls should be gas- and leak-tight. In this publication, experimental results of the generation of metallic microstructure devices by SLM will be given. The process will be described in details. Process parameters for the generation of stainless steel devices having wall thicknesses in the range of about 100μm will be given. Examples for microstructure devices made by SLM will be shown. The devices can be manufactured in a reproducible way. Moreover, very first preliminary results on the use of ceramic powder as base material will be presented.

Laser-assisted patterning of polymers is investigated for the direct fabrication of polymeric lab-on-a-chip devices in microsystem technology for capillary electrophoresis chips in bio-analytical applications. In many cases the laser process induces a chemical, physical and topographical change in the laser treated surface. This material modification significantly influences the lab-on-a-chip-functionalities. We will present our current research results in laser-assisted modification of polystyrene (PS) and polymethylmethacrylate (PMMA) with respect to applications in micro-optics, micro-fluidics and cell culture applications. For this purpose the refractive index change, the wettability and the adsorption of proteins and the adhesion of animal cells were investigated as function of laser- and processing parameters. The possible change of surface chemistry was characterized by X-ray photoelectron spectroscopy. The local UV-laser-assisted formation of chemical structures suitable for improved cell adhesion was realized on two- and three-dimensional PS and polycarbonate (PC) surfaces. Above and below the laser ablation threshold two different mechanisms were detected. In one case the produced debris was responsible for improved cell adhesion, while in the other case a photolytical activation of the polymer surface including a subsequent oxidization in oxygen or ambient air leads to a highly localized alteration of protein adsorption from cell culture media and increased cell adhesion. The highly localized control of wettability on polymeric surfaces was investigated for PS and PMMA. In the case of PS the dynamic advancing contact angle could be adjusted between 2° and 150°. This was possible for a suitable exposure dose and an appropriate choice of processing gas (helium or oxygen). A similar but not so significant effect was observed for PMMA below the laser ablation threshold. For PMMA the dynamic advancing contact angle could be adjusted between nearly 50° and 80°. The adjustment of wettability for microfluidic application will be discussed. For the integration of integrated optical waveguides in micro-fluidic devices new approaches for a rapid manufacturing of optical singlemode waveguides made of PMMA were investigated. For this purpose a high repetition excimer laser radiation source was used in combination with a flexible mask technology. The waveguides were characterized for the visible optical range and for 1559 nm. The obtained structures reveal absorption losses of 0.7 dB/cm in the visible range.

In this contribution experimental studies on the laser-assisted welding of transparent polymers with diode laser (wavelength 940 nm) are presented to discuss their potential for the fabrication of micro-devices for micro-chemical engineering and life science. Micro-channel devices such as capillary electrophoresis chips, heat exchangers or static mixers for liquids and gases consist of different micro-patterned sheets with structural details in the range of a few μm. In micro-chemical engineering, in general the sheets of micro-devices are made of metals. In our approaches the use of transparent and micro-patterned polymers such as polyvinylidene fluoride (PVDF) is investigated. For the development of micro-devices in life science the use of sheets made of transparent polymers such as polymethylmethacrylate (PMMA) is presented, e.g., in capillary electrophoresis chips. Devices are built up by stacks of micro-patterned sheets which have to be joined. These sheets are patterned by micro-milling, CO 2 -laser cutting or hot embossing. Laser-assisted polymer welding of transparent and opaque materials is well established. But the welding of only transparent components is still a challenge in micro-system technology, especially if micro-structures are included. For this purpose very thin absorbing layers with a thickness of about 5nm to 20nm are used in order to establish a welding process between transparent and micro-patterned polymers. The strength of the bonding is characterized by tensile tests as function of absorbing layer thickness, temperature, laser scan velocity and laser scan overlap. The topography is investigated with atomic force microscopy and low voltage scanning electron microscopy.

In this work the fabrication of integrated polymer waveguide components (waveguides, S-bends, splitters) by means of several approaches is reported. Fabrication of one type of waveguide involves laser-assisted micro-patterning of small grooves in (Polymethylmethacrylat) PMMA substrates which are subsequently filled with index-matched materials. Another type of waveguide is realized by local physical modification of PMMA in a laser direct writing process. The transmission characteristics of the waveguide were studied at the optical communication wavelengths of 1520-1620 nm. Fabrication of filled waveguides with oil as waveguide medium yielded low loss of 2.6 dB/cm and single-mode behavior for 10 μm wide grooves. Filling of 20 μm grooves with PMMA/MMA/dye mixture and subsequent polymerization yielded multi-mode waveguides with higher loss of 5.9 dB/cm. The laser direct writing (Nd:YAG, 266 nm) of waveguides showed loss of 6.3 dB/cm and multi-mode behavior indicating a need for further process optimization. Two Y-splitters fabricated by laser patterning and filling with branch radii of 10 mm and 25 mm showed device loss of 16 dB and 19 dB for a 25 mm device length. These results are compared to the performance of reference Y-splitters fabricated by UV-lithography, where parametric studies of the device geometry revealed the best branch radius of 20 mm.

In the microscopic world the need of functional prototypes increases, e.g. as a precondition for a mould insert fabrication for micro-injection moulding. In this work the direct fabrication of prototypes made from polymers with an accuracy down to the micrometer range will be presented. For this purpose the direct patterning or modification of polymers with UV-laser radiation is performed for applications in fluidic and micro-optics. Different UV laser sources such as excimer and frequency-multiplied Nd:YAG were used. In the case of complex designs for fluidic applications it is powerful to use Nd:YAG laser radiation as patterning tool because of their high laser repetition rates: CAD data from complex fluidic designs were transmitted directly via CAM module into the polymeric surface. Because of the very small laser pulse duration of about 400-500 ps the thermal-induced damage during ablation decreases significantly. Process parameters, ablation rates and attainable surface qualities for capillary-electrophoreses chips will be presented. With the aid of a motorised aperture or a rotating mask system, excimer laser radiation is used to enable a well defined patterning of grooves with sharp edges and smooth sidewalls. The direct ablation of polymethylmethacrylate (PMMA), as well as the laser induced modification of the polymeric chemistry is used for the preparation of passive integrated-optical waveguides. Two types of concepts of waveguides are discussed: 1. Laser patterned grooves are filled with index matched materials which leads either to an increase or a decrease of the refractive index relative to pure PMMA. 2. Localised laser-induced polymer modification leads immediately to an integrated waveguide with higher refractive index. Both types of waveguides-concepts are characterised by their optical properties, which will be discussed in detail.

The rapid fabrication of microcomponents made from polymers will be presented. The whole fabrication process is divided into three main steps: First, direct patterning of polymers with excimer laser radiation enables the fabrication of first prototypes. Second, laser assisted micromachining using Nd:YAG and KrF-Excimer laser allows a rapid manufacturing of microstructured mold inserts. Third, the application of light induced reaction injection molding (UV-RIM) gives the access to the replication of the previously fabricated mold insert. The fabrication of prototypes made of polymer is carried out highly precisely with excimer laser radiation. With the aid of a motorised aperture mask, CAD data are transmitted directly into the polymeric surface. With an appropriate pretreatment of the polymer surface the debris formation can be drastically reduced. A promising method of micropatterning of mold inserts made of steel is called laser microcaving. This processing technique enables a clean patterning process with only a small amount of debris and melt. The etch rate and surface quality strongly depend on the chemical composition of the steel and the process parameters. Surface qualities with a roughness of about 300 nm can be achieved. Microstructures composed of polymers or ceramic-composites are successfully demolded by using the UV-RIM technique with aspect ratios up to 10. Capillary Electrophoresis-Chips made of PMMA are fabricated, and the functionality of the CE-Chips is demonstrated.© (2001) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.

In the macroscopic world different 'rapid'-technologies like Rapid Prototyping, Rapid Manufacturing or Rapid Tooling have been established for a fast prototype or molding tool development. In all cases CAD-data can be transformed in a model or prototype directly using a laser which polymerizes reactive resin layer by layer to a final 3D mold within a short period. In this work the rapid fabrication of micro components made from polymers or composites will be presented. The whole fabrication process is divided into two main steps: Firstly laser assisted micro machining using Nd:YAG and KrF-Excimer laser allows a rapid manufacturing of micro structured cemented carbide or steel mold inserts. Secondly the application of light induced reaction injection molding using reactive monomer/polymer resins gives access to the replication of the previously fabricated mold insert. The total processing period starting from CAD until the modeled micro structured part is less than one week.

Dry etching and micromachining with laser radiation of short wavelength and pulse length are investigated to present their process capabilities for the production of surface structures within precision silicon components. The laser dry etching processing with excimer laser radiation is modified by using a microwave-excited processing gas. Furthermore, methylmethacrylate is additionally used to study the influence of polymerization on the etched structures. The micromachining with frequency-doubled Nd:YLF laser radiation is performed yielding more precise structures during drilling and caving due to the lower heat and pressure load during the interaction time. The processes involved in dry etching and micromachining with laser radiation are studied by high-speed photography, mass spectroscopy and optical spectroscopy, whereas the produced structures are analyzed by profilometry, optical and electron microscopy as well as electron spectroscopy such as XPS and AES. The results are discussed in view of applications for surface patterning of precision silicon components.