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The quality and the stability of devices prepared from polycrystalline layers of organic–inorganic perovskites highly depend on the grain sizes prevailing. Tuning of the grain size is either done during layer preparation or in a post-processing step. Our investigation refers to thermal imprint as the post-processing step to induce grain growth in perovskite layers, offering the additional benefit of providing a flat surface for multi-layer devices. The material studied is MAPbBr3; we investigate grain growth at a pressure of 100 bar and temperatures of up to 150 °C, a temperature range where the pressurized stamp is beneficial to avoid thermal degradation. Grain coarsening develops in a self-similar way, featuring a log-normal grain size distribution; categories like ‘normal’ or ‘secondary’ growth are less applicable as the layers feature a preferential orientation already before imprint-induced grain growth. The experiments are simulated with a capillary-based growth law; the respective parameters are determined experimentally, with an activation energy of Q ≈ 0.3 eV. It turns out that with imprint as well the main parameter relevant to grain growth is temperature; to induce grain growth in MAPbBr3 within a reasonable processing time a temperature of 120 °C and beyond is advised. An analysis of the mechanical situation during imprint indicates a dominance of thermal stress. The minimization of elastic energy and surface energy together favours the development of grains with (100)-orientation in MaPbBr3 layers. Furthermore, the experiments indicate that the purity of the materials used for layer preparation is a major factor to achieve large grains; however, a diligent and always similar preparation of the layer is equally important as it defines the pureness of the resulting perovskite layer, intimately connected with its capability to grow. The results are not only of interest to assess the potential of a layer with respect to grain growth when specific temperatures and times are chosen; they also help to rate the long-term stability of a layer under temperature loading, e.g. during the operation of a device.

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.

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 preparation of nanostructures by guiding the phase separation of a block copolymer (BCP) is an attractive technique to overcome the limitations of conventional lithography. Well-established methods for guiding are to provide a topographical pattern (grapho-epitaxy) or a chemical pattern (chemo-epitaxy) on the substrate before BCP application. This paper reports on an alternative technique, the guiding of the BCP without pre-patterning the substrate, by providing the guiding pattern from the top, by nanoimprint. This approach offers the benefit of a multiple use of the same stamp. In the work reported here, we use an elastomeric stamp and examine capillary force lithography (CFL) with respect to guiding. The processing temperature is chosen high in order to provide fast phase separation. For the control of the surface energy of the substrate, a silane deposition from the gas phase is utilized. The ordering behavior of a lamellar polystyrene–polymethylmethacrylate BCP with CFL is studied. In particular, the issues specific with phase separation in an imprint situation are addressed, the locally differing layer thickness and the fact that two surface energies contribute to the ordering process, the one of the substrate and the one of the stamp. Though further optimization is required to make use of CFL for efficient guiding, the first results reported here indicate the potential of this technique for stamp-induced guiding of BCPs. As it allows a multiple use of the stamp, such guiding is interesting and may replace the time- and cost-consuming pre-patterning of each substrate.

Low-pressure imprint is interesting to avoid stamp deformation, stamp failure as well as polymer recovery. When large-area stamps are prepared with a stepping procedure, low pressure is required to optimize the stitching. However, with low-pressure imprint, conformal contact between stamp and substrate is critical. Admittedly, the imprint pressure required for conformal contact depends on the stamp material and its thickness. To get an idea to which extent the imprint pressure can be reduced with a flexible stamp, we compared different stamp materials and stamp architectures, single-layer stamps and two-layer stamps. The two-layer stamps are replica stamps, where the structures were replicated in a thin layer of OrmoStamp, fixed by a backplane. On the background of plate theory, we deduce the pressure reduction compared to a Si stamp by calculating the respective pressure ratio, independent from geometries. In addition, temperature-induced issues are addressed which are of relevance for a thermal imprint process. These issues are related to the mismatch between the thermal expansion coefficients of the stamp and the substrate, and in case of a two-layer stamp, to the mismatch between the backplane material and the top layer. The latter results in temperature-induced stamp bending. On the basis of simple analytical calculations, the potential of single-layer stamps and two-layer stamps with respect to thermal imprint at reduced pressure is discussed and guidelines are provided to assess the imprint situation when replica stamps are used for imprint. The results demonstrate the attractiveness of two-layer stamps for reduced pressure nanoimprint, even in a temperature-based process.

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.

When nanoimprint is not used for lithography purposes (NIL), but for the direct patterning of polymeric layers, high aspect ratio patterns may be of interest for a number of applications. The definition of such patterns in a nanoimprint process deals with two aspects, a successful filling of the high aspect ratio cavities of the stamp used, followed by a successful separation of the high aspect ratio structures defined in the polymeric layer on the substrate, from the stamp. These two aspects are addressed by shedding light to the impact of capillary effects during the filling of high aspect ratio cavities, and to the deformation processes involved in the separation of the stamp from the polymeric structures, where adhesional energies have to be overcome without cohesional failure. Both aspects are discussed in terms of the geometries involved, the stamp geometries as well as the polymeric layer thickness, and correlations with thermally-assisted (T-NIL) and UV-assisted (UV-NIL) processing are deduced. The aspects discussed are typical of a nanoimprint situation with thin polymeric layers on hard substrates.

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.