Multifunctional lipid multilayer stamping.

Nanostructured lipid multilayers on surfaces are a promising biofunctional nanomaterial. For example, surface-supported lipid multilayer diffraction gratings with optical properties that depend on the microscale spacing of the grating lines and the nanometer thickness of the lipid multilayers have been fabricated previously by dip-pen nanolithography (DPN), with immediate applications as label-free biosensors. The innate biocompatibility of such gratings makes them promising as biological sensor elements, model cellular systems, and construction materials for nanotechnology. Here a method is described that combines the lateral patterning capabilities and scalability of microcontact printing with the topographical control of nanoimprint lithography and the multimaterial integration aspects of dip-pen nanolithography in order to create nanostructured lipid multilayer arrays. This approach is denoted multilayer stamping. The distinguishing characteristic of this method is that it allows control of the lipid multilayer thickness, which is a crucial nanoscale dimension that determines the optical properties of lipid multilayer nanostructures. The ability to integrate multiple lipid materials on the same surface is also demonstrated by multi-ink spotting onto a polydimethoxysilane stamp, as well as higher-throughput patterning (on the order of 2 cm(2) s(-1) for grating fabrication) and the ability to pattern lipid materials that could not previously be patterned with high resolution by lipid DPN, for example, the gel-phase phospholipid 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) or the steroid cholesterol.

High-throughput optical quality control of lipid multilayers fabricated by dip-pen nanolithography.

Surface supported phospholipid multilayers are promising materials for nanotechnology because of their tendency to self-organize, their innate biocompatibility, the possibility to encapsulate other materials within the multilayers, and the ability to control the multilayer thickness between ∼ 2 and 100 nm during fabrication. Dip-pen nanolithography (DPN) is an atomic force microscopy (AFM) based fabrication method that allows high-throughput fabrication and integration of a variety of micro- and nanostructured materials including lipid multilayers, with areal throughputs on the scale of cm(2) min(-1). Although multilayer thickness is a critical feature that determines the functionality of the lipid multilayer structures (for instance as carriers for other materials as well as optical scattering properties), reliable height characterization by AFM is slow (on the order of µm(2) min(-1)) and a bottleneck in the lithographic process. Here we describe a novel optical method to reliably measure the height of fluorescent multilayers with thicknesses above 10 nm, and widths above the optical diffraction limit based on calibrating the fluorescence intensity using one-time AFM height measurements. This allows large surface areas to be rapidly and quantitatively characterized using a standard fluorescence microscope. Importantly, different pattern dimensions (0D dots, 1D lines or 2D squares) require different calibration parameters, indicating that shape influences the optical properties of the structured lipid multilayers. This method has general implications in the systematic and high-throughput optical characterization of nanostructure-function relationships.

Site-specific dual ink dip pen nanolithography.

The ability to deposit different materials with nanoscale precision at user-specified locations is a very important attribute of dip pen nanolithography (DPN). However, the potential of DPN goes beyond simple deposition since DPN used in conjunction with lateral force microscopy (LFM) allows site-specific investigations of nanoscale properties. In this work, we use two different inks, 16-mercaptohexadecanoic acid (MHA) and 1-octadecanethiol (ODT) to show site-specific dual ink DPN enabled exclusively by our proprietary software. A diamond-dot pattern was created by using a layer-to-layer alignment (LLA) algorithm, which enables a MHA pattern (diamond) to be written concentric with another ODT (central dot) pattern. This simple demonstration of multi-ink DPN is not specific to alkanethiol ink systems, but is also applicable to other multi-material patterning, interaction, and exchange studies.

Dip Pen Nanolithography: a "Desktop Nanofab" approach using high-throughput flexible nanopatterning.

The ability to perform controllable nanopatterning with a broad range of "inks" at ambient conditions is a key aspect of the dip pen nanolithography (DPN) technique. The traditional ink system to demonstrate DPN is n-alkanethiols on a gold substrate, but the DPN method has found numerous other applications since. This article is meant to outline recent advances in the DPN toolkit, both in terms of research and patterning technology, and to discuss applications of DPN as a viable nanofabrication method. We will summarize new DPN developments, and introduce our concept of the "Desktop Nanofab." In addition, we outline our efforts to commercialize DPN as a viable nanofabrication technique by demonstrating massively parallel nanopatterning with the 55,000 tip 2D nano PrintArray. This demonstrates our ability to overcome the serial nature of DPN patterning and enable high-throughput nanofabrication.

Relative humidity effects in dip-pen nanolithography of alkanethiol mixtures.

In the dip-pen nanolithography of a binary alkanethiol mixture of mercaptohexadecanoic acid (MHA) and 1-octadecanethiol (ODT) at a relative humidity (RH) of less than 80%, two distinct phases of MHA and ODT were patterned. However, on ramping up the RH to greater than 80%, only MHA was observed to pattern. This effect was reversible, as shown by the fact that two distinct thiol regions were again patterned on lowering the RH. This segregation could be exploited for generating exclusive MHA (hydrophilic) templates for subsequent architectures from a mixture of alkanethiols driven solely by the RH.

Evidence of meniscus interface transport in dip-pen nanolithography: An annular diffusion model.

Ring shaped dots were patterned with mercaptohexadecanoic acid ink by dip-pen nanolithography. These dots have an ink-free inner core surrounded by an inked annular region, making them different from the filled dots usually obtained. This suggests a different transport mechanism than the current hypothesis of bulk water meniscus transport. A meniscus interface ink transport model is proposed, and its general applicability is demonstrated by predicting the patterned dot radii of chemically diverse inks.