Harry D. Rowland

Impact of polymer film thickness and cavity size on polymer flow during embossing: toward process design rules for nanoimprint lithography

This paper presents continuum simulations of polymer flow during nanoimprint lithography (NIL). The simulations capture the underlying physics of polymer flow from the nanometer to millimeter length scale and examine geometry and thermophysical process quantities affecting cavity filling. Variations in embossing tool geometry and polymer film thickness during viscous flow distinguish different flow driving mechanisms. Three parameters can predict polymer deformation mode: cavity width to polymer thickness ratio, polymer supply ratio and capillary number. The ratio of cavity width to initial polymer film thickness determines vertically or laterally dominant deformation. The ratio of indenter width to residual film thickness measures polymer supply beneath the indenter which determines Stokes or squeeze flow. The local geometry ratios can predict a fill time based on laminar flow between plates, Stokes flow, or squeeze flow. A characteristic NIL capillary number based on geometry-dependent fill time distinguishes between capillary- or viscous-driven flows. The three parameters predict filling modes observed in published studies of NIL deformation over nanometer to millimeter length scales. The work seeks to establish process design rules for NIL and to provide tools for the rational design of NIL master templates, resist polymers and process parameters.

Polymer deformation and filling modes during microembossing

This work investigates the initial stages of polymer deformation during hot embossing micro-manufacturing at processing temperatures near the glass transition temperature (Tg) of polymer films having sufficient thickness such that polymer flow is not supply limited. Several stages of polymer flow can be observed by employing stamp geometries of various widths and varying imprint conditions of time and temperature to modulate polymer viscosity. Experiments investigate conditions affecting cavity filling phenomena, including apparent polymer viscosity. Stamps with periodic ridges of height and width 4 µm and periodicity 30, 50 and 100 µm emboss trenches into polymethyl methacrylate films at Tg − 10 °C < Temboss < Tg + 20 °C. Imprint parameters of time, temperature and load are correlated with replicated polymer shape, height and imprinted area. Polymer replicates are measured by atomic force microscopy and inspected by scanning electron microscopy. Cavity size and the temperature dependence of polymer viscosity significantly influence the nature of polymer deformation in hot embossing micro-manufacturing and must be accounted for in rational process design.

Molecular Confinement Accelerates Deformation of Entangled Polymers During Squeeze Flow

The squeezing of polymers in narrow gaps is important for the dynamics of nanostructure fabrication by nanoimprint embossing and the operation of polymer boundary lubricants. We measured stress versus strain behavior while squeezing entangled polystyrene films to large strains. In confined conditions where films were prepared to a thickness less than the size of the bulk macromolecule, resistance to deformation was markedly reduced for both solid-glass forging and liquid-melt molding. For melt flow, we further observed a complete inversion of conventional polymer viscosity scaling with molecular weight. Our results show that squeeze flow is accelerated at small scales by an unexpected influence of film thickness in polymer materials.

Simulations of nonuniform embossing: The effect of asymmetric neighbor cavities on polymer flow during nanoimprint lithography

This paper presents continuum simulations of viscous polymer flow during nanoimprint lithography (NIL) for embossing tools having irregular spacings and sizes. Simulations varied non-uniform embossing tool geometry to distinguish geometric quantities governing cavity filling order, polymer peak deformation, and global mold filling times. A characteristic NIL velocity predicts cavity filling order. In general, small cavities fill more quickly than large cavities, while cavity spacing modulates polymer deformation mode. Individual cavity size, not total filling volume, dominates replication time, with large differences in individual cavity size resulting in non-uniform, squeeze flow filling. High density features can be modeled as a solid indenter in squeeze flow to accurately predict polymer flow and allow for optimization of wafer-scale replication. The present simulations make it possible to design imprint templates capable of distributing pressure evenly across the mold surface and facilitating symmetric polymer flow over large areas to prevent mold deformation and non-uniform residual layer thickness.

Variable temperature thin film indentation with a flat punch

We present modifications to conventional nanoindentation that realize variable temperature, flat punch indentation of ultrathin films. The technique provides generation of large strain, thin film extrusion of precise geometries that idealize the essential flows of nanoimprint lithography, and approximate constant area squeeze flow rheometry performed on thin, macroscopic soft matter samples. Punch radii as small as 185 nm have been realized in ten-to-one confinement ratio testing of 36 nm thick polymer films controllably squeezed in the melt state to a gap width of a few nanometers. Self-consistent, compressive stress versus strain measurements of a wide variety of mechanical testing conditions are provided by using a single die-sample system with temperatures ranging from 20 to 125 degrees C and loading rates spanning two decades. Low roughness, well aligned flat punch dies with large contact areas provide precise detection of soft surfaces with standard nanoindenter stiffness sensitivity. Independent heating and thermometry with heaters and thermocouples attached to the die and sample allow introduction of a novel directional heat flux measurement method to ensure isothermal contact conditions. This is a crucial requirement for interpreting the mechanical response in temperature sensitive soft matter systems. Instrumented imprint is a new nanomechanics material testing platform that enables measurements of polymer and soft matter properties during large strains in confined, thin film geometries and extends materials testing capabilities of nanoindentation into low modulus, low strength glassy, and viscoelastic materials.

Measuring Glassy and Viscoelastic Polymer Flow in Molecular-Scale Gaps Using a Flat Punch Mechanical Probe

This paper investigates molecular-scale polymer mechanical deformation during large-strain squeeze flow of polystyrene (PS) films, where the squeeze flow gap is close to the polymer radius of gyration (R(g)). Stress-strain and creep relations were measured during flat punch indentation from an initial film thickness of 170 nm to a residual film thickness of 10 nm in the PS films, varying molecular weight (M(w)) and deformation stress rate by over 2 orders of magnitude while temperatures ranged from 20 to 125 degrees C. In stress-strain curves exhibiting an elastic-to-plastic yield-like knee, the response was independent of M(w), as expected from bulk theory for glassy polymers. At high temperatures and long times sufficient to extinguish the yield-knee, the mechanical response M(w) degeneracy was broken, but no molecular confinement effects were observed during thinning. Creep measurements in films of 44K M(w) were well-approximated by bulk Newtonian no-slip flow predictions. For extrusions down to a film thickness of 10 nm, the mechanical relaxation in these polymer films scaled with temperature similar to Williams-Landel-Ferry scaling in bulk polymer. Films of 9000K M(w), extruded from an initial film thickness of 2R(g) to a residual film thickness of 0.5R(g), while showing stress-strain viscoelastic response similar to that of films of 900K M(w), suggestive of shear-thinning behavior, could not be matched to a constitutive flow model. In general, loading rate and magnitude influenced subsequent creep extrusion depth of high-M(w) films, with deeper final extrusions for high loading rates than for low loading rates. The measurements suggest that, for high-resolution nanoimprint lithography, mold flash or final residual film thickness can be reduced for high strain and strain rate loading of high-M(w) thin films.

Microsystems manufacturing via embossing of photodefinable thermally sacrificial materials

Substantial recent interest in microelectronics manufacturing has motivated significant work on non-traditional processes such as embossing-based lithography. This work has been generally limited to manufacturing conventional microelectronics, producing two dimensional patterned surfaces and structures. To date, little work has been done to produce microelectromechanical systems (MEMS), which can require production of complex three-dimensional and possibly free standing structures. This paper reports a novel method for manufacturing three-dimensional microstructures that can be freely standing and/or fully released. The method involves the use of thermally sacrificial polymers, i.e. materials that can be cleanly decomposed to gaseous products upon heating at elevated temperatures. Such sacrificial polymers can be directly embossed and subsequently overcoated with a variety of materials including other polymers, dielectrics, semiconductors, and metals. Following the deposition of the overcoat layer, further processing can be performed on the overcoat layer (e.g. selective etching or deposition of additional materials). Finally, the entire structure is heated to the decomposition temperature of the sacrificial polymer which results in the “dry” removal of the sacrificial layer, thus releasing the desired structures. The various sacrificial materials that have been investigated are polynorbornenes and polycarbonates, and the overlayer materials include polyimides, silicon oxide, and metals. This paper discusses the various properties of these sacrificial materials, the printing and processing conditions for these materials, and the use of this method for the fabrication of a MEMS based microfluidic system with free standing and suspended obstructions. This novel manufacturing technique meets the needs of MEMS manufacturing in that it can produce three dimensional and free standing microstructures. It permits the fabrication of devices and systems in only a few process steps that would otherwise be either substantially more complicated or impossible to achieve. This process of coating, embossing, and overcoating can also be repeated to build-up complex multi-layered structures.

Micro- and Nanomanufacturing via Molding

Molding is a simple manufacturing process that enables fabrication of feature sizes ranging from 1 nm to 1 m at high volume and low cost. This chapter introduces micro- and nanomolding applications, processes, and design rules. Micro-and nanomolding processes have created high resolution lithographic patterns and fabricated functional applications in microfluidics, optics, and other areas. Analysis of polymer flow during local cavity filling and nonuniform long range polymer transport makes it possible to predict the physical driving mechanism governing flow and develop guidelines for optimized processing via micro- and nanomolding. Micro- and nanomolding processes offer a low cost, scalable alternative to silicon based microfabrication that capitalize on the high resolution, ease of processing, and wide range of mechanical, optical, or chemical properties of polymers. Successful high resolution, high yield micro- and nanomolding processes can enable widespread fabrication of nanotechnology-related products.

Transport During Hot Embossing Micro-Manufacturing Studied via Stylus Profilometry and SEM

This work investigates processing parameters affecting replicated feature size during hot embossing micro-manufacturing. Silicon micromachined masters were heated and pressed into polymer layers of different thermophysical properties. Imprinting with loads ranging from 20–35 MPa, load rates from 1–15 MPa/sec, load times from 90–115 sec, and imprint temperatures at, below, and above the polymer glass transition temperature (Tg ) replicated features in polymer with varying degrees of conformity. Replicated features were measured by profilometry and inspected by scanning electron microscopy, revealing polymer feature heights ranging from 25–100% conformal matching of silicon master features and polymer feature widths closely matching the period of features on the silicon master. Statistical analysis determined replicated feature height was positively dependent on tip sharpness, master feature height, temperature, and load rate while negatively dependent on master feature width. Replicated feature width was found to depend positively on master feature height and width, temperature, load rate, and load time. Optimization of imprint parameters during hot embossing micro/nano-manufacturing can possibly lead to a high-throughput manufacturing process offering nanometer resolution.Copyright