Robert Kirchner

Novel 3D micro- and nanofabrication method using thermally activated selective topography equilibration (TASTE) of polymers

Micro- and nanostructures with three-dimensional (3D) shapes are needed for a variety of applications in optics and fluidics where structures with both smooth and sharp features enhance the performance and functionality. We present a novel method for the generation of true 3D surfaces based on thermally activated selective topography equilibration (TASTE). This technique allows generating almost arbitrary sloped, convex and concave profiles in the same polymer film with dimensions in micro- and nanometer scale. We describe its principal mechanism exemplified by pre-patterned poly (methyl methacrylate) resist which is exposed to high energy electrons prior to a thermal annealing step enabling the selective transformation of stepped contours into smooth surfaces. From this we conclude, that TASTE not only offers an enormous degree of freedom for future process variations, but also will advance the patterning capabilities of current standard 3D micro- and nanofabrication methods.

High fidelity 3D thermal nanoimprint with UV curable polydimethyl siloxane stamps

A two-step replication process chain is developed for a microlens array structure with deep three dimensional (3D) reliefs and sharp features enabling the transfer of a photocured acrylic resist patterns into thermoplastic poly-methyl methacrylate (PMMA) with the same structural polarity via an intermediate stamp. By using ultraviolet (UV)-curable polydimethyl siloxane (PDMS), high fidelity negatives were cast from the original microstructures made by two-photon-polymerization and subsequently replicated into PMMA using thermal imprint. The mechanical properties of the new UV-PDMS (X-34-4184, Shin-Etsu Chemical Company, Ltd.), along with its nearly zero process shrinkage, proved to be highly suitable to replicate both 50 μm high concave features and sharp tips with an apex diameter of 500 nm. The results prove that silicone rubber, despite its elasticity, has specific advantages in thermal imprint in structures where both tall microstructures and submicron surface structures have to be replicated. This wa...

Mobility based 3D simulation of selective, viscoelastic polymer reflow using surface evolver

This work demonstrates implementation of the main effects of viscoelastic thermal polymer reflow in an efficient energy and mobility based simulation. The concept is based on a finite-element, soap-film method using the free software SURFACE EVOLVER. Properties of a homogeneous 3D volume are thereby represented by a corresponding 2D surface. The simulation only requires the contact angle between polymer and substrate for infinite long reflow times, obtained from fingerprint experiments, and a mobility value as input. The mobility value is a measure for the polymer-chain mobility and is directly linked to the polymer viscosity. This concept allows for an accurate and fast treatment of the thermomechanically complex polymer behavior close to the glass transition. The simulation time scale is linearly related to the experimental time scale allowing for accelerated-time simulations. Simulation and experiment showed a very good agreement. As a generalized concept, the approach presented here can be used for fast and full 3D shape computation during any complex, energy driven geometry optimization process like polymer reflow, viscoelastic wetting or dewetting and droplet coagulation. This simulation may facilitate a faster uptake of grayscale reflow technologies for industrial processes. Supplementary material supports a quick grasp of the simulation approach.

Direct UV-Imprinting of Hybrid-Polymer Photonic Microring Resonators and Their Characterization

The direct patterning of hybrid-polymer microring resonators with minimal residual layers by UV-assisted nanoimprint lithography is reported. The proposed stamp-and-repeat technology requires no post-processing. The imprint polymer was applied by spin-coating as a 130-150 nm thin initial film for an optimized processing. The importance of the initial film thickness is discussed in detail. Aspect ratios of more than 5:1 were realized with 2 μm high ridge-waveguides and sub-400 nm coupling gaps on maximal 130 nm thin residual layers. The achieved ratio of structure height to residual layer thickness of 15.4 (2 μm versus 130 nm) was much larger than the typical values in high-resolution imprinting and superseded the removal of the residual layer completely. The resonators are thought as biosensor transducers. High quality devices with Q-factors up to 13000 were produced with a minimal set of process steps.

Degradation of Perfluorotrichlorosilane Antisticking Layers: The Impact on Mold Cleaning, Ultraviolet-Nanoimprinting, and Bonded Ultraviolet-Nanoimprint Molds

A reduction of the adhesion between imprint resist and mold is crucial for defect free imprints and is commonly achieved by silane based antisticking layers. Highly stable antisticking layers are required for high throughputs and long imprint mold lifetimes. Hybrid nanoimprint molds avoid the imprint inherent residual polymer layer in UV-assisted nanoimprinting. Such hybrid molds have chemically heterogeneous surfaces of silica and, e.g., chromium oxide regions. The chemical stability of vapor-coated 1H,1H,2H,2H-perfluorodecyltrichlorosilane antisticking layers against acetone, acidic piranha, reactive ion etching and UV-assisted nanoimprinting was investigated. To evaluate the behavior of hybrid mold surfaces, flat silica and antireflective chromium-oxynitride surfaces were used. The antisticking layer on both surfaces was highly chemical resistant against acetone. A continuous antisticking layer degradation with a surface free energy increase of 0.9mN/m per 10min piranha treatment and 1.2mN/m per 10 subsequent UV-assisted imprints was found for silica surfaces. On the chromium surfaces, the antisticking layer quality was much lower than on fused silica and degraded much faster. The surface free energy of silane coated chromium surfaces was increased by 2.3mN/m after 10 imprints and the antisticking layer was completely degraded after a single 10min piranha cleaning step. The lower antisticking layer quality on antireflective chromium was attributed to the surface itself. Additionally, the high chemical resistance of the vapor coated silane was used to successfully protect the adhesive joints of cost-efficient, adhesively bonded nanoimprint molds from being degraded by acidic piranha during mold cleaning. This can significantly increase the life-time of such bonded molds. # 2011 The Japan Society of Applied Physics

How post-processing by selective thermal reflow can reduce the roughness of 3D lithography in micro-optical lenses

Most polymeric refractive micro-optics simultaneously demand ultra-smooth 3D topographies and precise geometry for high optical performance and low stray light. We have established a surface selective smoothening for thermoplastic polymers that does not affect the designed optical geometry. For example, high curvature corners required for a 50 μm tall optical diffuser device were maintained while the surface roughness was reduced to about 10 nm RMS. 3D master structures were fabricated using direct write laser-lithography with two-photon absorption. Master structures were then replicated into poly(methyl methacrylate) through a poly(dimethyl siloxane) intermediate copying step and subsequently smoothed-out by high-energy photon exposure and thermal post-processing. The smoothening results in a lower roughness compared to a direct writing strategy using even about 50 nm vertical discretization steps still enables 10 times faster writing times.

Benchmarking surface selective vacuum ultraviolet and thermal postprocessing of thermoplastics for ultrasmooth 3-D-printed micro-optics

Abstract. State-of-the-art, polymeric, refractive micro-optics simultaneously require an ultrasmooth three-dimensional (3-D) surface and a precise geometry for excellent optical performance with minimal stray light. In earlier work, we have established a surface finishing process for thermoplastic polymer master structures that is only effective on the surface and does not affect the designed optical geometry, thus enabling polishing without touching. Therewith, the high curvature corners of a 50-μm-tall optical diffuser device were maintained while the surface roughness was reduced to about 10-nm root mean square. For this, 3-D master structures were first fabricated by direct write laser-lithography with two-photon polymerization. The master structures were replicated into poly(methyl methacrylate) through a poly(dimethyl siloxane) intermediate replication stamp. Finally, all structures were surface-polished by selective high-energy photon exposure and thermal postprocessing. In this work, we focus on the comparison of the surface smoothening using either postprocessing or dedicated direct writing strategies. For this comparison, strategies for modifying the exposed voxel size and the writing discretization being the primary source of roughness were tested by sweeping the laser exposure dose for two different resist materials and objectives. In conclusion, the postprocessing smoothening resulted in a lower roughness compared to a direct writing strategy—even when 50-nm vertical discretization steps were used—and still enabled 10 times shorter writing times.

mr-PosEBR - A novel positive tone resist for high resolution electron beam lithography and 3D surface patterning

In this contribution, we present the results of a systematic material variation for the development of a resist material for high resolution positive tone electron beam lithography (EBL). Several acrylic copolymer materials with different compositions, that is varying mass fractions of the comonomers and different molecular weights, were synthesized and – as resist solutions – evaluated in terms of EBL performance at acceleration voltages of 30 kV and 100 kV. The resist material exhibiting the best combination of the desired properties, named mr-PosEBR, is two times more sensitive than PMMA 495k and performs comparably to the known high resolution resist ZEP520A at 30 kV. For example, a grating pattern with 29 nm wide lines with a period of 100 nm could be lithographically generated in films of mr-PosEBR with an area dose of 100 μC/cm2. In terms of resolution, single lines of only 35 nm width could be fabricated via metal liftoff. Furthermore, the dry etch stability of mr-PosEBR in a CF4/SF6 process is similar to the one of ZEP520A. Consequently, via dry etching nano patterns in mr-PosEBR could be smoothly transferred into the underlying Si substrate with high fidelity. Moreover, mr-PosEBR was evaluated as electron beam grayscale patterning and reflow resist. It was shown that the resist exhibits a good grayscale and reflow performance very similar to PMMA 120k and ZEP520A. Via these well controllable processes the generation of a wide variety of features and applications is possible.

Surface smoothening of the inherent roughness of micro-lenses fabricated with 2-photon lithography

Two-photon polymerization by direct laser writing enables to write refractive micro-optical elements with sub-μm precision. The trajectories and layering during the direct writing process often result in roughness in the range of the writing increment, which has adverse effects for optical applications. Instead of increasing overlap between adjacent voxels, roughness in the range of 100 nm can be smoothed out by post-processing. For this a method known as TASTE was developed, which allows polishing of surfaces without changing the structural details or the overall shape. It works particularly well with thermoplastic polymers and enables sub-10 nm roughness. The optical quality was confirmed for an array with several 100 microlenses.

Reducing the roughness of 3D micro-optics

Polymer microlenses are used in various modern devices, including high-manufacturing-volume products such as mobile smartphones. Since these lenses are so small, they have to be processed with the use of novel 3D lithographic methods such as two-photon direct-write laser (2PP-DWL) lithography. With such techniques, a scanning approach is used to build the lenses out of thin, discrete layers, i.e., a laser beam is scanned through the photosensitive material.1, 2 The trajectories and layering during such DWL processes, however, often give rise to roughness (in the range of the writing increment, i.e., 100–200nm) that causes adverse effects for optical applications (it is typically much more desirable to achieve sub-20nm roughness levels for transmission with a low amount of stray light). Surface smoothing is thus often required, which can be achieved through various techniques. Most of these approaches involve optimization of the writing strategy. For instance, a small increment of overlapping trajectories reduces roughness. The excessive writing time required, however, is not acceptable for current micro-optical systems. In contrast, increasing the overlap of two adjacent beams (e.g., by blurring the writing beam or by using special resists) compromises the high-resolution capabilities of 2PP-DWL and is particularly useful for systems with low-aspect-ratio structures.3, 4 If a surface has to be subsequently smoothed out, a polishing method is thus required. Such postprocessing steps, however, must only modify the surface and not change the structural details or the overall shape. We have thus developed a new method for the fabrication of microand nanoscale lenses. Our technique—known as thermally activated selective topography equilibrium (TASTE)— works particularly well with thermoplastic polymers such as poly(methyl methacrylate), PMMA,5, 6 and involves selective modification of material properties in only part of the sample of Figure 1. Scanning electron microscope (SEM) image of a 3 3 microlens array (each segment is 50 50 m), with a 40 m sag, fabricated using the two-photon direct-write laser (2PP-DWL) lithography technique in a viscous resist material (IpDip).