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The manufacturing of devices from methylammonium-based perovskites asks for reliable and scalable processing. As solvent engineering is not the option of choice to obtain homogeneous layers on large areas, our idea is to ‘upgrade’ a non-perfect pristine layer by recrystallization in a thermal imprint step (called ‘planar hot pressing’) and thus to reduce the demands on the layer formation itself. Recently, imprint has proven both its capability to improve the crystal size of perovskite layers and its usability for large area manufacturing. We start with methylammonium lead bromide layers obtained from a conventional solution-based process. Acetate is used as a competitive lead source; even under perfect conditions the resulting perovskite layer then will contain side-products due to layer formation besides the desired perovskite. Based on the physical properties of the materials involved we discuss the impact of the temperature on the status of the layer both during soft-bake and during thermal imprint. By using a special imprint technique called ‘hot loading’ we are able to visualize the upgrade of the layer with time, namely a growth of the grains and an accumulation of the side-products at the grain boundaries. By means of a subsequent vacuum exposition we reveal the presence of non-perovskite components with a simple inspection of the morphology of the layer; all experiments are supported by X-ray and electron diffraction measurements. Besides degradation, we discuss recrystallization and propose post-crystallization to explain the experimental results. This physical approach towards perovskite layers with large grains by post-processing is a key step towards large-area preparation of high-quality layers for device manufacturing.

Thermal management in devices like solar cells, light-emitting diodes, and lasers based on hybrid halide perovskite thin films is expected to be of paramount importance for optimal performance and reliability. As of yet, experimental data of thermal properties of non-iodine-based hybrid halide perovskites is very scarce. Here the thermal conductivity of methylammonium lead halide perovskite (CH3NH3PbX3 X= I, Br, and Cl) single crystals and thin films is analyzed by scanning near-field thermal microscopy. The thermal conductivity of CH3NH3PbX3 single crystals with X= I, Br, and Cl is found to be 0.34 ± 0.12, 0.44 ± 0.08, and 0.50 ± 0.05 W/(mK) at room temperature, respectively. Strikingly, similar thermal conductivities are determined for the corresponding thin-film samples. The thermal conductivity of MAPbI3 in the cubic phase (T > 55 °C) increases to (1.1 ± 0.1) W/(mK). In addition, the temperature dependence of the thermal conductivities and of thermal expansion coefficients of MAPbI3 around the phase t...

The directed self-assembly (DSA) of block copolymers (BCP) has attracted high interest for the definition of nanostructures in an almost self-forming way when adequate boundary conditions are given. At present, grapho- and chemo-epitaxy are the workhorses but they require precisely patterned substrates to serve as the guiding pattern. Nanoimprint may replace this laborious pre-patterning of each substrate by employing an adequate stamp that can be used multiple times, inducing the guided DSA from the top of the film. Here, the DSA of BCPs is revisited in view of the specific nanoimprint situation. As a consequence, the BCP layer is imprinted in a partial cavity-filling mode, using a stamp of sufficient height provided with a conventional anti-sticking layer; substrate pre-treatment is minimized or rather avoided. Even with a highly preferential substrate it is possible to obtain vertical lamellae that are largely oriented in parallel to the stamp edges in PS-b-PMMA (polystyrene-block-polymethyl methacrylate) already after 3min of imprint. The vertical lamellae are at least 70nm high, freestanding on the substrate. Though optimization is required the results indicate the high potential of nanoimprint to simplify the DSA of BCPs for technical applications, also beyond Si technology. Display Omitted Thermal nano imprint with lamellar di block copolymers2 step imprint processFree standing vertical lamellar structuresImpact of a polystyrene brush

Our study refers to the highly stretchable elastomer PDMS (polydimethylsiloxane), a material used with a wide range of applications. Its basic mechanical properties can be tuned, e.g., by varying the curing conditions; moreover, its surface properties can be tuned by modification techniques. We modified our PDMS by irradiating the samples with an excimer lamp at 172 nm. Such a treatment hardens the elastomer at the surface, and it becomes silicalike; the sample changes to a “quasi” two-layer system with a graded interface. When such samples are stretched, surface cracks occur beyond a critical strain. The increase of crack length with increasing strain is evaluated by means of video screenshots. The impact of the curing conditions is addressed by analyzing samples prepared at different cross-linking temperatures, resulting in differing bulk properties but similar surface properties. Crack length and crack velocity are evaluated with each sample based on single randomly chosen cracks. The results are discussed on the basis of theoretical concepts for channeling cracks in multilayer systems with polymeric substrates. Typically, with applications, random cracks should develop at high strain only and, if present, should propagate slowly along the surface but not into the depth of the sample. Our investigation shows that the mechanical material properties of the substrate are vital with respect to such stable cracking, rather than the surface properties. In particular, the curing conditions chosen for the substrate are essential to reduce cracking, a fact less regarded with applications so far.

Flexible composite stamps are commonly used in low pressure and low temperature processes, e.g., UV-assisted nanoimprint, as they provide a good conformal contact between stamp and substrate. The composite stamps investigated here consist of two layers, a thin hard top layer to enable stable nanometre-scaled structures with high aspect ratio and a soft backplane to ensure conformal contact. Stamps with two different material combinations were investigated, OrmoStamp /PDMS (polydimethylsiloxane) and h-PUA/s-PUA (polyurethane acrylate). The stability of both composite stamps was tested under harsh imprint conditions in a process at elevated temperature and pressure. Temperature and pressure loading results in strain in the top layer and may lead to break when the tensile strength is exceeded. To vary the stress level in the top layer, two different stamp designs were investigated, one with a thin backplane and one with a thicker backplane. The experimental results clearly show that a thin stamp (low stress level) is more stable than a thick stamp. Moreover, composite stamps are also suitable for a thermal imprint process when temperature and pressure remain limited.

The morphology of highly regular, semi-crystalline P3HT (poly 3-hexylthiophene-2.5-diyl) after thermal nanoimprint is studied and compared to that of its amorphous counterpart. Differential scanning calorimetry measurements of both materials provide the glass transition temperature (below room temperature) as well as the melting temperature (T m ≈ 235 °C) and the crystallization temperature (T c ≈ 200 °C) of the semi-crystalline polymer. Imprint experiments are performed at temperatures below and above the melting temperature of the crystallites. The samples imprinted with line structures in the range of 135–500 nm are investigated by scanning electron microscopy and transmission measurements. In agreement with T m, the investigations indicate that the crystallites do not melt when semi-crystalline P3HT is imprinted below T m. After imprint above T m, no more indication of the crystallites is found. Furthermore, physical self-assembly only occurred after imprint beyond T m with semi-crystalline P3HT, indicating a fully amorphous state. The morphology observed—the roughness of the surface within partly filled cavities when crystallites are present—correlates well with the results from optical measurements.

The transfer of systems from nature to technical schemes is still a challenge as the fabrication of such complex systems in a cost efficient way while keeping the intended technical functionality requires appropriate materials and fabrication techniques. Here the multi-scale hierarchy of the gecko foot was transferred into membrane-actuated gecko-inspired adhesion elements (AE) to study the adhesion to surfaces. Therefore, a three level hierarchical polydimethylsiloxane (PDMS) structure comprising a membrane for actuating and the micron-patterned AE were mould from a microtechnical fabricated master into PDMS by thermal and UV curing. The micron-patterned AE consist of dot or line micron patterns on top of cuboid posts with 15 µm height that representing the second hierarchical level. For master fabrication lithographic masking, wet and dry etching as well as SU8 3D lithography was applied. The adhesion of such AE on smooth, rough and chemically modified glass surfaces was measured by determining the shear force for several different AE designs and PDMS materials. A slip of the micron sized PDMS AEs at the adhesion test sample surface was measured. This slip of the PDMS elements being in contact to the surface can enhance the accepted shear force and the measured anisotropy of the shear force for linear AEs. The results found can contribute to the optimization of PDMS AE for technical surfaces with chemically and topographically inhomogeneous properties.

Controlled deposition of anti-sticking layers based on the use of evaporation cell.Tuning of process time and uniformity by multiple-cell arrangement.Uniformity of surface energy better than ?4% over 100mm diameter.Low surface energy (?10-15mN/m) obtained after 40min at 120?C. We developed a novel process for the deposition of anti-sticking layers from the gas phase based on the use of evaporation cells. The cells are prepared from Teflon and consist of small silane containers with an orifice. Temperature is used to provide a silane-containing gas phase in the containers; the temperature is well below the boiling point of the silane. The number of cells can be varied to improve the uniformity with respect to surface energy, to scale-up the process to larger diameters and to reduce the processing time required. The impact of cell number, processing temperature and processing time is investigated with respect to uniformity and with respect to the minimum times and temperatures required. The concept works well and shows potential for the control of surface energy beyond anti-sticking purposes.

The copy of structures in the same tone as the original asks at least for a double replication. Each replication generation will suffer from shrinkage of the replication material used, due to curing or thermal contraction. The impact of shrinkage is addressed in a basic study by simulation and experiment. The main replication materials investigated are OrmoStamp and SU-8. Presently, the preparation of anisotropic adhesion elements with hierarchical structures is investigated. The structures are micrometer-sized isolated pads with nanometer-sized self-aligned ripples (laser-induced periodic surface structures) on top. The initial structures are available as isolated photoresist patterns on Si. The double replication of this polymeric master raises questions with respect to its chemical and mechanical stability. The authors report an optimized replication process with an OrmoStamp intermediate template and a final replication in an elastomer. The anisotropic character of the so prepared hierarchical elastomeric adhesion elements is demonstrated by measurement.The copy of structures in the same tone as the original asks at least for a double replication. Each replication generation will suffer from shrinkage of the replication material used, due to curing or thermal contraction. The impact of shrinkage is addressed in a basic study by simulation and experiment. The main replication materials investigated are OrmoStamp and SU-8. Presently, the preparation of anisotropic adhesion elements with hierarchical structures is investigated. The structures are micrometer-sized isolated pads with nanometer-sized self-aligned ripples (laser-induced periodic surface structures) on top. The initial structures are available as isolated photoresist patterns on Si. The double replication of this polymeric master raises questions with respect to its chemical and mechanical stability. The authors report an optimized replication process with an OrmoStamp intermediate template and a final replication in an elastomer. The anisotropic character of the so prepared hierarchical elastom...

Surface-hardened polydimethylsiloxane (PDMS) with random cracks is studied by means of double replication. The PDMS samples are prepared under different curing conditions, resulting in a different Young's modulus of the bulk. To modify the surface, an excimer lamp at 172 nm is used. The samples are stretched uniaxially until the first cracks appear. As an evaluation under strain is hard or rather impossible, the idea is to replicate the cracked sample in a curable material and to characterize the cracks by inspection of the replica. To protect the sample from mechanical loading, this replication is done by molding in OrmoStamp on glass; these replicas are used for optical inspection to determine the crack spacing. As a characterization of the depth and width of the cracks is highly facilitated when cleaving is enabled, a second replication is performed into a thin layer of SU-8 on Si; these second replica are analyzed by secondary electron microscopy of cross sections. They provide a realistic picture of the crack shape. It is found that the curing conditions affect the crack shape; a U-shape occurs with a low bulk modulus, whereas a V-shape occurs with a high bulk modulus. The parameters width, depth, and spacing are largely unaffected by the curing conditions. This work provides a background to understand the behavior of random cracks, which is, e.g., useful to design a system with controlled cracks that remain stable. An important finding is that as soon as cracking occurs at a certain strain, already a number of cracks develop, yet without any further stretching. The cracks behave independently from neighboring cracks. Upon further stretching, new cracks develop, and the crack width and depth remain similar. Therefore, these random cracks are stable, and sample failure does not occur up to a strain of at least 40%.Surface-hardened polydimethylsiloxane (PDMS) with random cracks is studied by means of double replication. The PDMS samples are prepared under different curing conditions, resulting in a different Young's modulus of the bulk. To modify the surface, an excimer lamp at 172 nm is used. The samples are stretched uniaxially until the first cracks appear. As an evaluation under strain is hard or rather impossible, the idea is to replicate the cracked sample in a curable material and to characterize the cracks by inspection of the replica. To protect the sample from mechanical loading, this replication is done by molding in OrmoStamp on glass; these replicas are used for optical inspection to determine the crack spacing. As a characterization of the depth and width of the cracks is highly facilitated when cleaving is enabled, a second replication is performed into a thin layer of SU-8 on Si; these second replica are analyzed by secondary electron microscopy of cross sections. They provide a realistic picture of ...

With residual-free imprint, physical self-assembly of the polymer within partly-filled cavities has to be avoided to ensure the masking capability of nanoimprint when used as a lithography technique. In this regard we investigate the impact of the velocity of pressure application by use of a motor-driven imprint system. Slowing-down the velocity of pressure application maintains a smooth surface of the polymeric layer in the cavities, minimizing the risk of local contact between polymer and stamp with moderate filling levels of the cavities. At a high filling level of the cavities, the formation of self-assembly cannot be avoided, as van der Waals interactions between polymer surface and stamp become effective to drive the formation of instabilities. The experimental results obtained can be understood by stability analysis. Understanding of the processes leading to the formation of physical self-assembly is vital to exploit the full potential of nanoimprint for processing.

Applications in various sectors of microtechnology such as MEMS, microfluidics, and lab on chip call for reliable low-cost joining approaches that are detachable and re-closable, providing a tight fit at the micron level. Dovetail-like structures are a promising approach to realize the female side of such connectors and moulding is a suitable technique to produce the counterpart that completes the joint. Force-displacement measurements were performed for 2x2cm^2 master-replica assemblies, prepared from Si and PDMS (polydimethylsiloxane) and featuring dovetail-like structures with different undercuts. For measurement a miniaturised force-displacement tester was set up. Maximum retention forces of up to about 60mN per trench of 1cm length were measured for lines with [email protected] wide undercuts. Finite element modelling using a linear elastic model was employed to simulate the local distribution of stress and strain in the PDMS under loading with an applied tensile force. The simulation results approximate the measurements well. The quantitative results obtained can be used for designing miniaturized connectors with undercuts.

The replication of 3D structures with undercuts by nanoimprint technologies needs appropriate, rigid masters. The fabrication of 3D microstructured masters with inclined, undercut structures by photolithography and reactive ion beam etching into fused silica is demonstrated. The ion beam incidence angle defines the sidewall inclination of the undercuts and the shape of the structures. Specific characteristics of 3D structures in particular of the undercuts and of the bottoms are the result of the competing processes of polymer deposition and silica etching and the alteration of the average ion current density distribution due to etching depth increasing and mask degradation during the cyclic etching from opposite directions. Optimized structures can be achieved with a high number of short etching cycles.

In a thermal imprint process, contact angles may evolve in two situations, between the stamp and the polymer, when a cavity remains unfilled, or, in cases where the polymer locally dewets the substrate, between the substrate and the polymer. For two polymers of different polarity, such contact angles are determined experimentally and compared to values calculated from surface energy data. In doing so, the specific temperature dependence of surface energies of a thermoplastic polymer as well as the typical course of an imprint process, where cooling times often exceed the imprint times, are considered. The differences between experimental and theoretical values are critically discussed. The results indicate that the respective adhesive layers govern the surface status of the substrate and the stamp as well.

This investigation follows the idea to characterise polymers for thermal imprint, in contrast to the classical rheological characterisation route, directly by means of an imprint process. For this purpose the polymers under investigation, a PS and a PMMA of comparable molecular weight (350kg/mol) are imprinted at different temperatures under conditions of partial cavity filling. The development of characteristic effects, namely physical self-assembly, limited imprint depth and recovery is investigated. Imprintability test results are correlated with parameters obtained from rheology, in particular with the viscosity, the minimum flow time constant and the elastic compliance. In addition, the temperature behaviour is discussed in terms of the WLF-parameters. It turns out, that PMMA requires lower molecular weights than PS for efficient thermal imprint. Differences in the recovery behaviour of both materials can be understood from the elastic compliance and time constants measured. An optimum viscosity for thermal imprint at around 10^6Pas is estimated.

Under mechanical load, the reaction of polymers with a low molecular weight features small time constants. To test their actual behaviour in a thermal imprint, two polystyrenes (PS 10kg/mol, PS 30kg/mol) were imprinted under partial cavity filling conditions. The imprints were inspected regarding recovery and physical self-assembly of the polymer by means of an optical microscope. The results show that such low molecular weight polymers obviously are not suited for thermal imprint. In contrast to polymers with higher molecular weight, physical self-assembly and recovery occur at an identical imprint temperature, so that processing conditions for defect-free imprint cannot be identified. In case of a polymer with higher molecular weight this is possible by adequate choice of the processing temperature.

Semicrystalline Reg-P3HT (regio-regular poly-3-hexylthiophene) is a promising material for organic electronics. It features relatively high charge mobility and enables easy preparation because of its solubility. Due to its high optical and electrical anisotropy, the size, number and orientation of the ordered domains are important for applications. To control these properties without limitation from crystalline domains existing after spin coating, thermal nanoimprint is performed beyond the melting point. The state of the art of measurement to analyze the complex morphology is X-ray diffraction (XRD). We address an alternative measurement method to characterize the material by its optical properties, spectroscopic ellipsometry. It provides information on the degree of order from the typical fingerprint absorption spectrum. In addition, when the material is modeled as a uniaxial layer, an anisotropy factor can be derived. The results obtained from spectroscopic ellipsometry are in accordance with those from XRD. In particular, spectroscopic ellipsometry is able to distinguish between order along the backbone and order in π–π stacking direction, which is important with respect to conductivity.

Thermal imprints into polymer layers, which are thin compared to the structure height of the stamp provide the advantage that minimum residual layers can be achieved. On the other hand, due to the specific properties of thermoplastic polymers, recovery, i.e. a release of stored imprint energy, may occur after separation of sample and stamp. The intensity of this recovery strongly depends on the imprint temperature. Unfortunately a reduction of recovery by means of increased imprint temperature often generates other problems like unwanted physical self-assembly of the polymer. Another parameter that affects the development of recovery is the structure size of the imprinted patterns. This contribution is about the structure size dependency of the intensity of polymer recovery. By means of lift-off imprints of different structure sizes and types are tested after the imprint at two different temperatures.

In order to develop an easy to handle, low-cost procedure to derive imprint-relevant characteristic polymer data from simple imprint experiments, a fingerprint stamp was designed and tested. It contains line and dot structures of different, well-graded sizes in the micron range, where the gaps in between are chosen as to assure independent intrusion of the single patterns into the polymer layer. By imprint of this stamp into a well-characterised polymer, PS 350k, a feasibility test was performed. A pattern size dependent change of the imprint characteristics was observed during the imprint under high-shear into thin layers. This is taken as a hint that polymer characterisation from such experiments is indeed possible. Such data can be adopted to optimise an imprint process for mixed pattern sizes ranging from the micron down to the nanometre scale.

The evolution of the profile of an imprinted line under squeeze-flow dominated thermal nanoimprint is investigated experimentally. The results indicate, that in the very first moment the stamp intrusion into the polymer is fast due to shear thinning at the periphery of the feature, proceeding along with the build-up of internal stress in the feature centre. Relaxation of this stress proceeds according to the flow time constants. At processing times that are short compared to the time constants, stress relaxation will not be completed. Then the polymer recovers its initial shape in parts, and this recovery is responsible for the final profile shape. As time constants can be tuned by temperature, these investigations are helpful to define adequate low temperature imprint conditions when mixed pattern sizes are imprinted into spin-coated layers.

Linear polystyrene of different weight averaged molecular weight (M"w=58kg/mol and 353kg/mol) and a narrow molecular weight distribution was imprinted to point out differences in the flow behaviour caused by the polymer's molecular weight in a typical hot embossing/thermal nanoimprint process. Residual layer thickness and uniformity as well as defects were taken as a measure to qualify the imprint process. Since polymer viscosity is addressed as the main material parameter, a full thermo-mechanical characterisation of the two polymers via parallel plate dynamic viscosimetry was performed prior to imprint. The main process parameter responsible for viscosity, the temperature, was varied from about 30 to 150K above the glass transition. In addition the amount of polymer supplied for the process was varied, i.e. the initial spin-coated polymer layer thickness. Situations representing 'underfilling', 'filling' and 'overfilling' of the stamp cavities in specific regions were investigated. Squeezed flow simulations were performed taking into account the increase of pattern size and the filling of cavities during the ongoing imprint, which have substantial impact on the residual layers obtained. The results show that shear thinning is an issue in a high pressure hot embossing system. It governs the initial phase of the imprint featuring a rapid decrease of the polymer height. From theoretical considerations, a model could be derived for the imprint procedure under shear thinning in a constant pressure system which was able to interpret the observed phenomena. Despite the macroscopic nature of the thermo-mechanical analysis, the standard viscosimetric data for the polymers appeared to be sufficient to understand the experimental results.

Imprint processes can be described by the equations of squeezed flow. In case they account, in a modified form, for the filling of the stamp cavities during the imprint process they predict that the imprint activity virtually stops after complete filling of these cavities and a thick residual layer remains. Without cavity filling no interference of the imprint process occurs and very thin residual layers are obtained. This concept of partial cavity filling is tested during the imprint of fields of periodic 200nm lines, and the imprint temperature was reduced to prevent the formation of self assembly induced defects. Very low residual layers and good aspect ratios were obtained even at temperatures of 130^oC for commercial polystyrene with a glass temperature of 105^oC.

UV curing of resists after imprint is of interest for mix and match applications or when the thermo-mechanical stability of the resist has to be increased. In those cases the imprint into a curable resist like the mr-L 6000XP is followed by a UV exposure. This exposure is different from an exposure during UV lithography, as the pre-patterned resist results in a lateral intensity modulation, depending on the pattern geometries (width, distance, height, residual thickness) and depending on potential polarisation directions as well, which may be induced by reflecting elements within the optical path. We have simulated the exposure of line patterns of different geometries under polarisation of the incident light under directions parallel and perpendicular to the imprinted lines. Corresponding UV curing experiments after imprint suggest that the stabilisation should be feasible at adequate increase of the exposure dose independent from the polarisation direction.

The imprint behaviour of commercial polystyrene, featuring a wide molecular weight distribution, is compared to polymers used as standards with a narrow molecular weight distribution. All polymers were characterised prior to imprint. The differences in their characteristics are discussed, with respect to standard thermo-mechanical behaviour and with respect to nanoimprint in a hot embossing process. Shear rate effects and recovery are discussed. Recovery results in a local non-uniformity of the residual layer within the imprinted features. As long as the reaction time constants of the polymer remain low compared to the embossing time to avoid recovery, the use of shear rate effects during nanoimprint of thermoplastic polymers is favourable for throughput improvement as it allows processing at reduced times and reduced temperatures.

The mechanical state of polymer flows induced by wide area thermal nanoimprint was investigated using instrumented indentation testing. Polystyrene films of narrow distribution molecular weight both slightly above and well above the chain entanglement weight spacing were imprinted with a range of feature shapes under nominally equivalent flow conditions. Following imprint, pristine, unflowed, and flowed regions of the polymer were tested for indentation modulus and hardness using sharp pyramidal and blunt spherical indenters. No difference in mechanical state for these various regions was observed. The implications of these results for the imprint process itself as well as the mechanical testing of imprinted patterns are discussed.

Thickness and uniformity of the residual layer are major global quality criteria for nanoimprint lithography. When the total area of a stamp used in a mechanical replication process like hot embossing is composed of sections with different pattern density, the specific local stamp layout strongly affects residual layer uniformity. Taking the example of a positive stamp with sections of well-defined pattern density the effect of initial layer thickness on uniformity of the residual layer was investigated on the centimetre scale. Long-range uniformity is shown to be a result of local polymer flow in particular between sections of different pattern density. We found the effect to be independent of pattern size. It turned out, that initial layer thickness has to be chosen with regard to the polymer volume locally required for filling of the stamp cavities. Whereas overfilling should be avoided, underfilling may be beneficial for specific applications.

The characteristics and benefits of two types of cross-linking prepolymers with low glass transition temperature (Tg) for nanoimprinting are reported. They are soluble in organic solvents and their solutions can be processed like those of common thermoplastics. The imprinted patterns receive high thermal and mechanical stability through cross-linking polymerization. The course of the polymerization was investigated to determine the appropriate conditions for the imprint process. In thermally cross-linked polymers mr-I 9000, the cross-linking occurs during imprinting. Process time and temperature depend on the polymerization rate. Volume shrinkage during the polymerization does not adversely affect imprinting. Photochemically crosslinked polymers mr-L 6000 make possible imprint temperatures below 100 °C and short imprint times. The Tg of the prepolymer determines the imprint temperature. The cross-linking reaction and structural stabilization is performed after imprinting. 50-nm trenches and sub-50-nm dots confirm the successful application of the polymers.

A preliminary study of the suitability of vacuum chucks for fixing of stamp and sample in a hot embossing lithography process was performed. Four inch test chucks were designed, featuring circular grooves and isolated holes of 0.7 to 2 mm size. The effect of these grooves was tested by imprint into PMMA with an unpatterned stamp. The processed samples showed a polymer thickness variation correlated with the groove locations, which could be measured with a profilometer. The thickness variations found were of different type when polymers of different molecular weight were used. Under realistic embossing conditions, values of up to 70 nm were measured. From the experiments, an allowable groove width of

In order to reduce costs for nanometer-structured templates for hot embossing, potential ways to produce purely thermoset replica to be used as stamps are examined. Thermal expansion of thermosets under realistic process conditions is measured and its influence on the hot embossing of thermoplastic materials is studied. Thermal expansion coefficients of thermosets under different process conditions were found to vary between 3×10−5 and 2×10−4/ °C. Results are presented concerning the imprintability of both curable polymers on thermoset substrates and conventional resist materials on silicon.

Some crucial limiting process steps of ITO/(n)a-Si:H/(p)c-Si solar cell manufacturing were investigated. The influence of amorphous silicon deposition temperature on the efficiency of heterojunction (HJ) solar cells as well as ITO deposition on the properties of ITO/a-Si:H/c-Si interfaces were studied. Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and SIMS measurements were employed for the investigations. It was observed that the decrease in a-Si:H deposition temperature from 230 down to 100°C leads to a reduction in solar cell efficiencies to only 1%. It was found that the ITO deposition process itself can significantly modify the ITO/a-Si:H/c-Si interfaces due to the interaction of oxygen, and In and Sn atoms with silicon at the initial stage. It was concluded that this modification has a more significant impact on the quality of the HJ solar cells than on that of the a-Si:H layer.

This paper presents a study concerning the macroscale deformation of soft stamps for nanoimprint lithography. Composite stamps consisting of two or three layers were prepared with varying process parameters, and the bow of the stamps was investigated with an optical profilometer. Deflection measurements were compared with results from a mechanical model in order to prove its validity. The composite stamps were prepared from polydimethylsiloxane (S-PDMS) and OrmoStamp® layers on different substrate materials (silicon or AF-32-glass). The influence of selected preparation parameters on the deformation was investigated, such as layer thickness, curing, and hardbake temperatures, as well as UV-exposure intensities. It is discussed how an appropriate choice of preparation parameters can reduce the deformation, too. By decreasing the curing intensity of a thin OrmoStamp layer, coated on top of a silicon wafer, from 200 mW/cm2 to 2 mW/cm2, the deformation was reduced from 6 μm to 0. It is shown that the mechanic...

Thermal nanoimprint and sputtering, two low-cost techniques, are combined to define metallic patterns by means of lift-off. The typically positive sidewall angle of imprinted structures in combination with sputtering for layer deposition leads to a continuous metal layer which has to be ruptured at a definite position, at the best along the respective pattern base, so that lift-off can work. This issue is investigated taking polystyrene (PS) as the imprint polymer and toluene as the lift-off solvent. The impact of the geometry factors and the impact of soaking and the power of ultrasonic agitation are addressed both experimentally and analytically to derive the conditions for the successful lift-off of 250nm wide lines over large areas.

Driven by the steadily increasing scale of integration in microelectronics much effort has been made in recent years to establish the technique of nanoimprint lithography (NIL) as a promising approach to time and cost-effective fabrication of nanometer scale patterns. NIL enables high throughput for mass fabrication in a simple way. Experiments have revealed that nanoimprint of small and periodic patterns in the nm range is much easier obtained than for μm scale patterns due to polymer transport phenomena. Thus a combination of NIL with optical lithography is considered to be advantageous for the definition of small patterns adjacent to large patterns. The multifunctionality of the material within one layer offers new routes in device design, in particular as multistep profiles are obtainable. In this contribution a combination of NIL and UV lithography is reported using polymers which are both imprintable and photosensitive. Based on an epoxy type negative tone chemically amplified resist system patterns were easily obtained using both techniques. In the first step a pattern relief was produced through imprinting. In the second step this relief was UV exposed in a contact printer and then developed. In this way three-step profiles could be generated within one single polymer layer.

Using different imprint systems and process conditions, the impact of the visco-elastic properties of polymers on the fidelity of pattern transfer in hot embossing lithography has been studied. The flow behaviour of the polymer, which is a highly viscous liquid at the investigated temperatures, has been shown to be the limiting factor in the replication of micrometer sized features, but does not adversely affect nanometer structuring. This is explained using hydrodynamic considerations. The effects during filling of the cavities formed between stamp and substrate are reported, and explained in accordance with recent publications, where two different types of filling mechanisms have been discussed. Large recessed stamp areas turn out to be much more critical for the process, as they may act as mask defects. They will not restrict the applicability of hot embossing lithography in practice when appropriate imprint conditions are chosen, which have to be enabled by the equipment.

Preparation of a micro-zipper for component assembly requires an efficient anti-sticking layer between the two counterparts during preparation by moulding and during operation as well. In order to deposit a fluorinated silane on the PDMS-type materials used for zipper preparation, a UV-ozone pre-treatment at 172nm was investigated in detail. It was found that already at 2min of irradiation the surface features a sufficient amount of OH-groups for silane binding. Longer irradiation times were found to result in a surface layer of increasing brittleness that would prevent successful zipper operation.

Aromatic polymers based on methacrylates (linear polymers) and multifunctional allylesters (crosslinked polymers) have been prepared. They feature high dry etch resistance and good imprintability in a hot embossing process. The crosslinked polymers and their prepolymers were investigated in detail. Their characteristic molecular weight distribution and thermo-mechanical behaviour were studied with respect to the crosslinking process and compared with those of linear polymers. The thermal stability of imprinted patterns has been investigated for both, linear and crosslinked aromatic polymers. The latter ones show excellent stability up to test temperatures of 200 ^oC directly after the imprint process.

As a simple, low-cost alternative to rheological characterisation of an imprint polymer a novel approach is put forward, the derivation of imprint-relevant characteristic material parameters, here the viscosity, directly from imprint experiments. Imprints are performed at different temperatures with a fingerprint stamp, designed to allow replication of micron-sized linear structures without lateral constraint and independent from their neighbourhood. Under such conditions the squeezed flow theory applies and the viscosity can be determined from the imprint depth. For a typical material in thermal imprint, 25kg/mol PMMA, a broad agreement with rheological viscosity data could be obtained. Though the result requires critical assessment, the simplicity of the approach is appealing. Such procedure is promising for an easy access to material data for imprint process optimisation.

We have studied the suitability of poly(methylmethacrylate) (PMMA) of different molecular weight for large area pattern transfer by embossing structures above the glass transition temperature (Tg) of the specific polymer. The molecular weight covers a range of one order of magnitude (Mw∼5.0×104–8.1×105). This range was chosen in order to obtain information regarding the flow properties that we expect to depend strongly on the molecular weight at a specific temperature. Large area pattern transfer were tested by applying a stamp with both densely packed and isolated features. The feature size ranged from 100 μm down to 450 nm. At a processing temperature of 90°C above Tg we found clear indications that flow is sufficient to transfer large, isolated features even into the polymer with the highest Mw. Problems of incomplete material transport can be related to local inhomogeneities of the imprint due to a lack of parallelism between the stamp and the sample. At 50°C above Tg incomplete flow effects were observed over the whole area and for all molecular weights. This was observed only with large, isolated structures whereas small, periodic features showed a well defined transfer.

The properties of the thermosetting polymer mr-I-9000, developed and used for nanoimprint lithography (NIL), were investigated by means of X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). The spectra of mr-I-9000 were compared with those of PMMA and show the presence of aromatic rings and a high amount of carbon–carbon and carbon–hydrogen bonds. As a consequence, the mask selectivity of mr-I-9000 in an oxygen and tetrafluoromethane reactive ion etching processes is higher than that for PMMA and slightly different for the cross-linked and non-cross-linked state.

Performance and functionality of devices prepared from organic semicrystalline polymers strongly depend on the size and the orientation of the ordered crystalline domains, as the conductivity is distinctly different in the different lattice directions. This investigation addresses the potential of thermal nanoimprint to control the size of the ordered domains as well as their orientation with respect to the substrate. Poly-3-hexylthiophene (P3HT) is chosen as one of the prominent semicrystalline polymers available at high quality. In order to control the ordering of the domains freely, the imprint is performed at a temperature beyond the melting point to eliminate the domains already existing after spin-coating and soft-bake. To avoid a degradation of P3HT at such a high temperature under oxygen contact—the imprint system used operates in air—a novel imprint procedure is employed, where a distinct prepressure is applied already during the heating of the imprint stack (stamp/substrate with P3HT layer). To ...

While researchers of ever more advanced NGL systems are still struggling to demonstrate the feasibility to manufacture features well below 100 nm at an affordable cost and a reasonable throughput, nanoimprint technologies are emerging as a possible answer to these challenges. 100 nm patterns are imprinted with a fully patterned 4 inch diameter stamp in a low-temperature embossing process. In low temperature imprinting processes with polymers having very low glass transition temperatures heating and cooling cycles are minimized. This enables to increase the throughput of a hot embossing process, which is important for potential industrial applications.

Pattern replication into curable imprint resists by hot embossing offers the opportunity to use the replication after crosslinking as a working-stamp. The replications of a 4” Si stamp into the thermoset imprint polymer mr-I 9000R-XP with a commercial hot embossing system (EVGroup) have been coated with an anti-adhesive layer (trichlorosilane) from the gas-phase at ambient pressure. The investigation of the quality and durability of these anti-adhesive coatings reveals that the contact angles and the replication performance of the working-stamps were independent from the fact whether the polymer was already cured or still thermoplastic during the anti-adhesive coating. The prepared 4” working-stamps themselves have been successfully replicated into a low glass transition temperature resist (mr-L 6000.5 XP) and into PMMA.

Sidewall lithography was used as a low cost fabrication process for high aspect ratio stamps for hot embossing. The stamps, featuring up to 1 pm pattern height and an aspect ratio of about 5:1 were tested in a typical hot embossing process at 50 bar. Mechanical stability of the crystalline stamp structures was achieved after optimization of the respective dry etch process. At imprint temperatures of 140°C PMMA was imprinted over areas of four inch diameter. After residual layer removal in the trenches Al electrodes of 500 nm height and 200 nm width could be defined by evaporation and lift off.

One of the key questions concerning the concept of a system for hot embossing lithography is whether or not it should provide for imprinting under vacuum. We have performed experiments comparing the embossing in vacuum and in atmospheric pressure in a semi-automated imprint system. The stamps used were fully patterned, 10 cm diameter with pattern sizes ranging from 400 nm to 100 μm. It turned out that vacuum enhances the large area uniformity of the imprint by avoiding an air cushion remaining between stamp and sample during automated contact after a non-contact assembly and alignment step. Lower molecular weight polymers turned out to be more sensitive to uniformity deviation than higher molecular weight materials. Detailed analysis showed that defects typically found for relatively high processing temperatures, caused by overheated compressed air, remaining solvent in the polymer layer or even beginning polymer decomposition could be reduced substantially under vacuum embossing conditions, where the excess volume of the polymer is evacuated and free to accommodate gaseous constituents. The best result with complete cavity filling and negligible defects was obtained for imprint of a 99 kg/mol polymer at 200°C and 50 bar under vacuum. Residual layers measured across the diameter of the sample were 44.5 nm ± 9.8 nm. The non-uniformity of the residual layer is a result of the locally different pattern sizes and pattern densities of the stamp, typical for all mechanical patterning processes.

Stamp fabrication for nanoimprinting can be significantly simplified, when specialized crosslinking polymers are applied to pattern definition. The polymer patterns can be used as stamps themselves. Two possibilities are reported: (1) An e-beam sensitive resist was developed, which enables the fabrication of polymer-on-silicon stamps. Patterns with a feature size of 70 nm could be created. (2) Full plastic stamps were obtained by a casting-moulding technique, which enable pattern transfer from any conventional mould. The quality of the two stamp variants were proved by imprinting experiments.

Relief of residual stress in an imprinted polymer may affect the replication fidelity by leading to recovery. The level of stress induced in the polymer depends on the method of imprint. For example, a “soft” imprint with an elastomeric stamp uses capillary forces to fill the cavities whereas a “hard” imprint with a rigid stamp relies on external pressure. To study the effect of residual stress after imprint, both methods are applied with different imprint times to vary the level of residual stress, as the stress remaining relaxes with imprint time. To visualize the residual stress a temperature treatment is performed after imprint. This temperature treatment allows recovery within a convenient experimental time. A comparison of the shape of the imprinted structures before and after temperature treatment clearly shows that with a hard imprint at short imprint times a considerable amount of stress remains in the polymer, in particular when the residual layer is thin and the imprinted stamp structures are wide. With a soft imprint residual stress is not evident. Similar results are obtained with a thermoplastic material and a crosslinking material (SU-8); however, with the latter recovery remains limited due to a decrease of mobility during crosslinking. Residual stress is of major importance for the replication fidelity with short imprint processes.

We have studied anti-sticking layers for nanoimprint lithography using different types of polymers, thermoplastic and thermosetting ones. Typically thermosetting polymers have higher mask selectivity in a fluorocarbon dry etch process than the thermoplastic polymers, but replication into these materials is much more complicated. We observe a high tendency for the polymer to adhere to the stamp. To minimize the sticking problem a fluorocarbon coating of the stamp was tested. It was deposited in a radio frequency plasma reactor with C4F8 as a feed gas. The thickness of the coating was several nm. It was characterized by contact angle measurement, XPS and FTIR analysis. Such coatings could successfully reduce sticking effects during an imprint process.© (2000) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.

Replication of the e-beam master into thermosetting polymers was investigated for low cost working stamp fabrication for nanoimprint lithography (NIL). Negative as well as positive replicas from a master were fabricated in a thermal replication step from duroplastic material. Without any further treatment these working stamps were able to imprint thermoplastic polymers. To demonstrate the procedure we used the custom polymers mr-I-8130 and mr-I-9030 as well as PMMA for comparison. All replications were done in a NIL process. The replication quality is excellent when a suitable imprint procedure is used.