By Jan H. Schut
After nearly 30 years of R&D, nano molding may be too small to see, but it’s real. Nano details that are so small they can’t even be seen under a microscope are being injection molded. They’re read by electron microscopes or by defraction using a laser pointer. Molded nano features include invisible logos on parts to prevent counterfeiting, functional surfaces like radar deflection, and hologram-like iridescence.
The original technology was developed in the 1980s by what is now the Karlsruhe Institute of Technology in Germany (www.kit.edu) to make nozzles for uranium enrichment for atomic energy. Called LIGA, short for lithography, electroplating and molding in German, it uses concentrated X-rays to cure successive layers of PMMA to make highly precise, straight-sided parts, which are then electroplated with nickel alloys or gold.
But X-ray LIGA has drawbacks for nano molding. Vertical walls are hard to demold, so it would only work for shallow nano surfaces. The technology also requires a costly, colossal X-ray concentrating machine called a synchrotron. KIT’s is the size of a very large warehouse. An even larger one in Switzerland is the size of a small stadium. Only two companies use X-ray LIGA commercially – Microworks GmbH in Eggenstein-Leopoldshafen, Germany (www.micro-works.de), a spinoff from KIT in 2007, and HT MicroAnalytical Inc., Albuquerque, NM (www.htmicro.com). Neither has made an injection mold insert.
Nano-featured injection mold inserts are beginning to be made by UV-cured LIGA, which is less expensive than X-ray, and by nano imprint lithography. Both lithography technologies have been used for over a decade to emboss nano features on film, but only recently tried for injection molding. Mimotec SA in Sion, Switzerland (www.mimotec.ch), was founded in 1998 to develop UV LIGA for micron-scale molding technology, as the name says. Instead Mimotec’s market turned out to be direct production of electroplated watch parts. Mimotec only made its first commercial nano mold insert with UV LIGA three years ago for a French office supply company. The insert, mounted on an ejector pin, puts an invisible logo on parts for authentication.
Mimotec’s patented UV-LIGA technology (EP 2855737) exposes up to three layers of polymer to make a nano feature. First a flat silicon substrate is coated with an epoxy-based photo-sensitive polymer called “SU8.” Then the reverse of the part is exposed to UV laser light using a mask. After UV exposure it takes a week for each layer to harden unless a curing agent is used. Once the layers harden, uncured polymer is washed away, and the cavity is sent out for electroplating with nickel, nickel phosphorous or gold. Electroplating is up to 0.8 mm thick, much thicker than conventional electroplating, which is only microns thick.
Mimotec’s sister company, Sigatec SA in the same location (www.sigatec.ch), engraves directly on an oxidized surface layer of silicon to make functional nano-features. Sigatec’s Deep Reactive Ion Etching was used to emboss film, for example for a medical part for DNA analysis with 42 million truncated cones on the surface, each 3 microns in diameter by 3.5 microns high.
Tecan Precision Ltd. in Weymouth, Dorset, U.K. (www.tecan.co.uk), founded in the 1970s, is also an early user of UV LIGA, making metal masks for vacuum deposition for electronics with micro features. Tecan has also taken customers’ nano-structured masters and replicated them to make injection mold shims 200-300 microns thick, electroplated with sulphamate nickel.
NEWER VARIATIONS ON LIGA
Two other companies offer equipment for mask-less UV LIGA for nano mold inserts, which is reportedly less expensive and faster than using a mask. LPKF Laser & Elektronics AG, Garbsen, Germany (www.lpkf.com), a maker of laser equipment for printed circuits, offers Laser Direct Imaging technology, which guides a UV laser with what LPKF calls a “2D acoustic/optic deflector.” LPKF’s ProtoLaser LDI exposes photo resists by positioning the laser spot with “better than 1 nanometer precision,” using a UV laser wave length of 375 nanometers at a maximum speed of 100,000 spots per second. It targets molding microfluidic parts like lab-on-a-chip medical devices for blood testing and can even create rounded nano structures.
Nanoscribe GmbH in Eggenstein-Leopoldshaven, Germany (www.nanoscribe.de), another spinoff from KIT founded in 2007, makes a commercial mask-less 3D printer for nano parts, called the “Photonic Professional GT.” Nanoscribe’s patented light absorption reaction (U.S. Pat. Applic. # 20120218535) uses electromagnetic radiation to trigger a local photo reaction in the coating with either positive or negative-tone photo resist. Nanoscribe also has a patented LIGA process (U.S. Pat. # 8986563) that uses AZ MiR 701 polymer from Merck Performance Materials GmbH, Darmstadt, Germany (www.emd-performance-materials.com), for positive photo resist and SU8 epoxy for negative resist. Parts can then be electroplated.
Temicon GmbH in Dortmund, Germany (www.temicon.com), founded in 2005, uses Laser Interference Lithography and UV LIGA to make shims for micro embossing down to 0.2-micron details like a “moth eye” anti-reflective film for laminated display screens. Temicon is developing customized injection mold inserts for lab-on-a-chip parts, which Temicon can injection mold in-house. Temicon merged in 2014 with Holotools GmbH in Freiburg im Breisgau, Germany (www.holotools.com), a spinoff in 2001 from the Fraunhofer Institute for Solar Energy Systems in Freiburg (www.ise.fraunhofer.de). Holotools specializes in large area nano-structures without seam lines for embossing down to 200 nanometers.
FIRST NANO IMPRINT LITHOGRAPHY FOR MOLDS
At least five companies also use processes loosely called “nano imprint lithography” or NIL, including two with technology for steel molds, not electroplated shims. (An electroplated nickel shim is typically good for only a few 100,000 injection shots, but the original LIGA part can be used multiple times to make new molds.) NIL Technology ApS (www.nilt.com), a spinoff from the Danish Technical University in Lyngby, Denmark in 2009, uses patent-applied-for technology (U.S. Pat. Applic. # 20120244246) to put nano patterns onto a non-planar existing mold. NIL Technology first etches a nano pattern down to 80 nanometers onto a silicon wafer, then uses the wafer to emboss the pattern on film. Nano-featured film is then applied to a coated mold and electroplated. NIL Technology’s first commercial nano patterned injection mold was sold in 2014 to mold a package with a hologram.
NANO 4 U Group in Karlsruhe, Germany, and Sarnen, Switzerland (www.nano4u.net), founded in 2008, also directly builds nano structured steel molds, not nickel shims. Its steel molds can form more than a million parts “without severe quality reduction of the nano-structured end products,” NANO 4 U says. Patent-pending technology applies a surface onto an existing steel mold, and then etches into the surface to create nano features. The company’s first commercial application of the technology in an injection mold was in 2009. Main applications are hologram-like logos for branding and authentication in food, pharmaceuticals and medical devices.
Molecular Imprints Inc., Austin, TX (www.molecularimprints.com), founded in 2001 by two professors from the University of Texas, developed patented “Jet and Flash” imprint lithography that ink jets a low viscosity resist onto a silicon substrate. In 2014 Molecular Imprints sold the technology to Canon Inc., Tokyo, Japan, for use in equipment for the semi-conductor industry. Molecular Imprints is now developing other uses for the technology including nano imprint stamps on silicon, targeting lab-on-a-chip and other medical parts.
The EV Group, St. Florian am Inn, Austria (www.evgroup.com), founded in 1980 to build production equipment for semi-conductors, also builds commercial UV nano imprint lithography printers to make nano detailed parts, which can be electroplated into shims. EVG works with CEA Tech-Leti, a nano technology research institute in Grenoble, France (www.leti.fr).
LEAP Co. Ltd., Kanagawa, Japan (www.leap-leap.co.jp), founded in 2000, worked with Waseda University in Japan to develop patent pending “self-assembled monolayer” surface technology, or SAM, which covers surfaces with nano holes or pillars with high aspect ratio.