Ryan Wagner

Development of the metrology and imaging of cellulose nanocrystals

The development of metrology for nanoparticles is a significant challenge. Cellulose nanocrystals (CNCs) are one group of nanoparticles that have high potential economic value but present substantial challenges to the development of the measurement science. Even the largest trees owe their strength to this newly appreciated class of nanomaterials. Cellulose is the worlds most abundant natural, renewable, biodegradable polymer. Cellulose occurs as whisker-like microfibrils that are biosynthesized and deposited in plant material in a continuous fashion. The nanocrystals are isolated by hydrolyzing away the amorphous segments leaving the acid resistant crystalline fragments. Therefore, the basic raw material for new nanomaterial products already abounds in nature and is available to be utilized in an array of future materials. However, commercialization requires the development of efficient manufacturing processes and nanometrology to monitor quality. This paper discusses some of the instrumentation, metrology and standards issues associated with the ramping up for production and use of CNCs.

Vibrational shape tracking of atomic force microscopy cantilevers for improved sensitivity and accuracy of nanomechanical measurements

Contact resonance atomic force microscopy (CR-AFM) methods currently utilize the eigenvalues, or resonant frequencies, of an AFM cantilever in contact with a surface to quantify local mechanical properties. However, the cantilever eigenmodes, or vibrational shapes, also depend strongly on tip-sample contact stiffness. In this paper, we evaluate the potential of eigenmode measurements for improved accuracy and sensitivity of CR-AFM. We apply a recently developed, in situ laser scanning method to experimentally measure changes in cantilever eigenmodes as a function of tip-sample stiffness. Regions of maximum sensitivity for eigenvalues and eigenmodes are compared and found to occur at different values of contact stiffness. The results allow the development of practical guidelines for CR-AFM experiments, such as optimum laser spot positioning for different experimental conditions. These experiments provide insight into the complex system dynamics that can affect CR-AFM and lay a foundation for enhanced nanomechanical measurements with CR-AFM.

Mechanical properties of cellulose nanomaterials studied by contact resonance atomic force microscopy

Quantification of the mechanical properties of cellulose nanomaterials is key to the development of new cellulose nanomaterial based products. Using contact resonance atomic force microscopy we measured and mapped the transverse elastic modulus of three types of cellulosic nanoparticles: tunicate cellulose nanocrystals, wood cellulose nanocrystals, and wood cellulose nanofibrils. These modulus values were calculated with different contact mechanics models exploring the effects of cellulose geometry and thickness on the interpretation of the data. While intra-particle variations in modulus are detected, we did not observe a measureable difference in modulus between the three types of cellulose particles. Improved practices and experimental complications for the characterization of cellulosic nanomaterials with atomic force microscopy are discussed.

Spatial spectrograms of vibrating atomic force microscopy cantilevers coupled to sample surfaces

Many advanced dynamic Atomic Force Microscopy (AFM) techniques such as contact resonance, force modulation, piezoresponse force microscopy, electrochemical strain microscopy, and AFM infrared spectroscopy exploit the dynamic response of a cantilever in contact with a sample to extract local material properties. Achieving quantitative results in these techniques usually requires the assumption of a certain shape of cantilever vibration. We present a technique that allows in-situ measurements of the vibrational shape of AFM cantilevers coupled to surfaces. This technique opens up unique approaches to nanoscale material property mapping, which are not possible with single point measurements alone.

Photothermally excited force modulation microscopy for broadband nanomechanical property measurements

We demonstrate photothermally excited force modulation microscopy (PTE FMM) for mechanical property characterization across a broad frequency range with an atomic force microscope (AFM). Photothermal excitation allows for an AFM cantilever driving force that varies smoothly as a function of drive frequency, thus avoiding the problem of spurious resonant vibrations that hinder piezoelectric excitation schemes. A complication of PTE FMM is that the sub-resonance cantilever vibration shape is fundamentally different compared to piezoelectric excitation. By directly measuring the vibrational shape of the cantilever, we show that PTE FMM is an accurate nanomechanical characterization method. PTE FMM is a pathway towards the characterization of frequency sensitive specimens such as polymers and biomaterials with frequency range limited only by the resonance frequency of the cantilever and the low frequency limit of the AFM.

Detection of atomic force microscopy cantilever displacement with a transmitted electron beam

The response time of an atomic force microscopy (AFM) cantilever can be decreased by reducing cantilever size; however, the fastest AFM cantilevers are currently nearing the smallest size that can be detected with the conventional optical lever approach. Here, we demonstrate an electron beam detection scheme for measuring AFM cantilever oscillations. The oscillating AFM tip is positioned perpendicular to and in the path of a stationary focused nanometer sized electron beam. As the tip oscillates, the thickness of the material under the electron beam changes, causing a fluctuation in the number of scattered transmitted electrons that are detected. We demonstrate detection of sub-nanometer vibration amplitudes with an electron beam, providing a pathway for dynamic AFM with cantilevers that are orders of magnitude smaller and faster than the current state of the art.