Quantitative nanopatterning of fg-scale liquids with dip-pen nanolithography.

The ability to precisely pattern nanoscale amounts of liquids is essential for biotechnology and high-throughput chemistry, but controlling fluid flow on these scales is very challenging. Scanning probe lithography methods such as dip-pen nanolithography (DPN) provide a mechanism to write fluids at the nanoscale, but this is an open loop process as methods to provide feedback while patterning sub-pg features have yet to be reported. Here, we demonstrate a novel method for programmably nanopatterning liquid features at the fg-scale through a combination of ultrafast atomic force microscopy probes, the use of spherical tips, and inertial mass sensing. We begin by investigating the required probe properties that would provide sufficient mass responsivity to detect fg-scale mass changes and find ultrafast probes to be capable of this resolution. Further, we attach a spherical bead to the tip of an ultrafast probe as we hypothesize that the spherical tip could hold a drop at its apex which both facilitates interpretation of inertial sensing and maintains a consistent fluid environment for reliable patterning. We experimentally find that sphere-tipped ultrafast probes are capable of reliably patterning hundreds of features in a single experiment. Analyzing the changes in the vibrational resonance frequency during the patterning process, we find that drift in the resonance frequency complicates analysis, but that it can be removed through a systematic correction. Subsequently, we quantitatively study patterning using sphere-tipped ultrafast probes as a function of retraction speed and dwell time to find that the mass of fluid transferred can be modulated by greater than an order of magnitude and that liquid features as small as 6 fg can be patterned and resolved. Taken together, this work addresses a persistent concern in DPN by enabling quantitative feedback for nanopatterning of aL-scale features and lays the foundation for programmably nanopatterning fluids.

Experimental observation of metal-organic framework-polymer interaction forces and intercalation.

We attach a MOF crystallite to an atomic force microscope cantilever to realize a system for rapidly and quantitatively studying the interaction between single-crystal MOFs and polymer films. Using this method, we find evidence of polymer intercalation into MOF pores. This approach can accelerate composite design.

Closed-Loop Nanopatterning of Liquids with Dip-Pen Nanolithography.

The ability to reliably manipulate small quantities of liquids is the backbone of high-throughput chemistry, but the continual drive for miniaturization necessitates creativity in how nanoscale samples of liquids are handled. Here, we describe a closed-loop method for patterning liquid samples on pL to sub-fL scales using scanning probe lithography. Specifically, we employ tipless scanning probes and identify liquid properties that enable probe-sample transport that is readily tuned using probe withdrawal speed. Subsequently, we introduce a novel two-harmonic inertial sensing scheme for tracking the mass of liquid on the probe. Finally, this is combined with a fluid mechanics-based iterative control scheme that selects printing conditions to meet a target feature mass to enable closed-loop patterning with better than 1% accuracy and ∼4% precision in terms of mass. Taken together, these advances address a pervasive issue in scanning probe lithography, namely, real-time closed-loop control over patterning, and position scanning probe lithography of liquids as a candidate for the robust nanoscale manipulation of liquids for advanced high-throughput chemistry.

High-resolution measurement of atomic force microscope cantilever resonance frequency.

The atomic force microscope (AFM) is widely used in a wide range of applications due to its high scanning resolution and diverse scanning modes. In many applications, there is a need for accurate and precise measurement of the vibrational resonance frequency of a cantilever. These frequency shifts can be related to changes in mass of the cantilever arising from, e.g., loss of fluid due to a nanolithography operation. A common method of measuring resonance frequency examines the power spectral density of the free random motion of the cantilever, commonly known as a thermal. While the thermal is capable of reasonable measurement resolution and speed, some applications are sensitive to changes in the resonance frequency of the cantilever, which are small, rapid, or both, and the performance of the thermal does not offer sufficient resolution in frequency or in time. In this work, we describe a method based on a narrow-range frequency sweep to measure the resonance frequency of a vibrational mode of an AFM cantilever and demonstrate it by monitoring the evaporation of glycerol from a cantilever. It can be seamlessly integrated into many commercial AFMs without additional hardware modifications and adapts to cantilevers with a wide range of resonance frequencies. Furthermore, this method can rapidly detect small changes in resonance frequency (with our experiments showing a resolution of ∼0.1 Hz for cantilever resonances ranging from 70 kHz to 300 kHz) at a rate far faster than with a thermal. These attributes are particularly beneficial for techniques such as dip-pen nanolithography.