The working curve measurement in photopolymer additive manufacturing is a ubiquitous measure of the cure depth of a printing resin as a function of radiant exposure of light. The fit parameters from this measurement (the depth of light penetration D p and the critical exposure E c) are used to evaluate and report a resin's printability, optimize processing parameters, and inform print and resin quality control. Despite its widespread use, the working curve lacks a standard measurement method. Following up on our paper "Results of an Interlaboratory Study on the Working Curve in Vat Photopolymerization" from last year, an interlaboratory study on the working curve was performed using calibrated, reproducible, bandpass filtered light sources. With these light sources, the variability between labs in measured working curves was dramatically reduced from the initial interlaboratory study. Aggregate data from this experiment produced reliable D p and E c measurements at 385 nm of 39.2 ± 3.7 μm and 12.3 ± 3.0 mJ cm-2, respectively. At 405 nm the values of D p and E c are 69.3 ± 3.8 μm and 17.9 ± 2.3 mJ cm-2, respectively. The results are agnostic to the thickness measurement tool utilized by participants, ensuring broad applicability across laboratories. We also tested the generalizability of the proposed method of using a filtered light source by filtering a commercial 405 nm light source and obtaining a working curve in agreement with the aggregate data from the interlaboratory study. This interlaboratory study provides a basis for a documentary standard for the working curve, so that the entire photopolymer additive manufacturing industry can share reproducible and interoperable working curve data.

Vat photopolymerization (VP) additive manufacturing enables fabrication of complex 3D objects by using light to selectively cure a liquid resin. Developed in the 1980s, this technique initially had few practical applications due to limitations in print speed and final part material properties. In the four decades since the inception of VP, the field has matured substantially due to simultaneous advances in light delivery, interface design, and materials chemistry. Today, VP materials are used in a variety of practical applications and are produced at industrial scale. In this perspective, we trace the developments that enabled this printing revolution by focusing on the enabling themes of light, interfaces, and materials. We focus on these fundamentals as they relate to continuous liquid interface production (CLIP), but provide context for the broader VP field. We identify the fundamental physics of the printing process and the key breakthroughs that have enabled faster and higher-resolution printing, as well as production of better materials. We show examples of how in situ print process monitoring methods such as optical coherence tomography can drastically improve our understanding of the print process. Finally, we highlight areas of recent development such as multimaterial printing and inorganic material printing that represent the next frontiers in VP methods.

The working curve informs resin properties and print parameters for stereolithography, digital light processing, and other photopolymer additive manufacturing (PAM) technologies. First demonstrated in 1992, the working curve measurement of cure depth vs radiant exposure of light is now a foundational measurement in the field of PAM. Despite its widespread use in industry and academia, there is no formal method or procedure for performing the working curve measurement, raising questions about the utility of reported working curve parameters. Here, an interlaboratory study (ILS) is described in which 24 individual laboratories performed a working curve measurement on an aliquot from a single batch of PAM resin. The ILS reveals that there is enormous scatter in the working curve data and the key fit parameters derived from it. The measured depth of light penetration Dp varied by as much as 7x between participants, while the critical radiant exposure for gelation Ec varied by as much as 70x. This significant scatter is attributed to a lack of common procedure, variation in light engines, epistemic uncertainties from the Jacobs equation, and the use of measurement tools with insufficient precision. The ILS findings highlight an urgent need for procedural standardization and better hardware characterization in this rapidly growing field.

Thermal phenomena in many biological systems offer an alternative detection opportunity for quantifying relevant sample properties. While there is substantial prior work on thermal characterization methods for fluids, the push in the biology and biomedical research communities towards analysis of reduced sample volumes drives a need to extend and scale these techniques to these volumes of interest, which can be below 100 pl. This work applies the 3ω technique to measure the temperature-dependent thermal conductivity and heat capacity of de-ionized water, silicone oil, and salt buffer solution droplets from 24 to 80 °C. Heater geometries range in length from 200 to 700 μm and in width from 2 to 5 μm to accommodate the size restrictions imposed by small volume droplets. We use these devices to measure droplet volumes of 2 μl and demonstrate the potential to extend this technique down to pl droplet volumes based on an analysis of the thermally probed volume. Sensitivity and uncertainty analyses provide guidance for relevant design variables for characterizing properties of interest by investigating the tradeoffs between measurement frequency regime, device geometry, and substrate material. Experimental results show that we can extract thermal conductivity and heat capacity with these sample volumes to within less than 1% of thermal properties reported in the literature.

The continued efforts in the biological community to optimize methodologies such as PCR and to characterize biological reactions and processes are motivating reductions in sample volume. There is a growing need for the detection of thermal phenomena in these small volumes, such as the heat released by recombination and the effective conductivities and capacities in extremely small fluidic regions. While past work has focused largely on heat transport in essentially bulk fluid volumes, there is a need to scale these techniques to the much smaller volumes of interest for biological and biomedical research.” This work applies the 3ω measurement technique to μL volumes by using heaters with dimensions of 200–700μm in lengths and 2–5μm in widths. We investigate fluid samples of DI water, silicone oil, and a salt buffer solution to experimentally determine their temperature-dependent thermal properties from 25°C to 80°C. Validation is achieved through comparison of these values of thermal conductivity κ and volumetric heat capacity Cν to literature. The work also demonstrates the device capability to conduct temperature-dependent measurements down to pL droplet volumes by conducting a volume analysis given the dimensions of heaters used, independent of droplet boundary conditions. Sensitivity and uncertainty analyses based on these heater dimensions and surrounding material stack show the detection capabilities of these heaters, as they are optimally designed to maximize signal while accommodating the size restrictions of small volume droplets.

Reliably routing heat to and from conversion materials is a daunting challenge for a variety of innovative energy technologies--from thermal solar to automotive waste heat recovery systems--whose efficiencies degrade due to massive thermomechanical stresses at interfaces. This problem may soon be addressed by adhesives based on vertically aligned carbon nanotubes, which promise the revolutionary combination of high through-plane thermal conductivity and vanishing in-plane mechanical stiffness. Here, we report the data for the in-plane modulus of aligned single-walled carbon nanotube films using a microfabricated resonator method. Molecular simulations and electron microscopy identify the nanoscale mechanisms responsible for this property. The zipping and unzipping of adjacent nanotubes and the degree of alignment and entanglement are shown to govern the spatially varying local modulus, thereby providing the route to engineered materials with outstanding combinations of mechanical and thermal properties.

The extremely high thermal conductivities of carbon nanotubes have motivated a wealth of research. Progress includes innovative conduction metrology based on microfabricated platforms and scanning thermal probes as well as simulations exploring phonon dispersion and scattering using both transport theory and molecular dynamics. This article highlights these advancements as part of a detailed review of heat conduction research on both individual carbon nanotubes and nanostructured films consisting of arrays of nanotubes or disordered nanotube mats. Nanotube length, diameter, and chirality strongly influence the thermal conductivities of individual nanotubes and the transition from primarily diffusive to ballistic heat transport with decreasing temperature. A key experimental challenge, for both individual nanotubes and aligned films, is the separation of intrinsic and contact resistances. Molecular dynamics simulations have studied the impacts of specific types of imperfections on the nanotube conductance and its variation with length and chirality. While the properties of aligned films fall short of predictions based on individual nanotube data, improvements in surface engagement and postfabrication nanotube quality are promising for a variety of applications including mechanically compliant thermal contacts.

Thermal conduction in periodic multilayer composites can be strongly influenced by nonequilibrium electron-phonon scattering for periods shorter than the relevant free paths. Here we argue that two additional mechanisms-quasiballistic phonon transport normal to the metal film and inelastic electron-interface scattering-can also impact conduction in metal/dielectric multilayers with a period below 10 nm. Measurements use the 3ω method with six different bridge widths down to 50 nm to extract the in- and cross-plane effective conductivities of Mo/Si (2.8 nm/4.1 nm) multilayers, yielding 15.4 and 1.2 W/mK, respectively. The cross-plane thermal resistance is lower than can be predicted considering volume and interface scattering but is consistent with a new model built around a film-normal length scale for phonon-electron energy conversion in the metal. We introduce a criterion for the transition from electron to phonon dominated heat conduction in metal films bounded by dielectrics.

Extreme ultraviolet (EUV) lithography requires nanostructured optical components, whose reliability can be influenced by radiation absorption and thermal conduction. Thermal conduction analysis is complicated by sub-continuum electron and phonon transport and the lack of thermal property data. This paper measures and interprets thermal property data, and their evolution due to heating exposure, for Mo/Si EUV mirrors with 6.9 nm period and Mo/Si thickness ratios of 0.4/0.6 and 0.6/0.4. We use time-domain thermoreflectance and the 3ω method to estimate the thermal resistance between the Ru capping layer and the Mo/Si multilayers (RRu-Mo/Si = 1.5 m2 K GW−1), as well as the out-of-plane thermal conductivity (kMo/Si 1.1 W m−1 K−1) and thermal anisotropy (η = 13). This work also reports the impact of annealing on thermal conduction in a co-deposited MoSi2 layer, increasing the thermal conductivity from 1.7 W m−1 K−1 in the amorphous phase to 2.8 W m−1 K−1 in the crystalline phase.

Silicon-rich and rare-earth-doped nitride materials are promising candidates for silicon-compatible photonic sources. This work investigates the thermal conductivity and photoluminescence (PL) of light emitting samples fabricated with a range of excess silicon concentrations and annealing temperatures using time-domain picosecond thermoreflectance and time-resolved photoluminescence. A direct correlation between the thermal conductivity and photoluminescence dynamics is demonstrated, as well as a significant reduction of thermal conductivity upon incorporation of erbium ions. These findings highlight the role of annealing and stoichiometry control in the optimization of light emitting microstructures suitable for the demonstration of efficient Si-compatible light sources based on the silicon nitride platform.

The nanoscale features in silicon nanowires (SiNWs) can suppress phonon propagation and strongly reduce their thermal conductivities compared to the bulk value. This work measures the thermal conductivity along the axial direction of SiNW arrays with varying nanowire diameters, doping concentrations, surface roughness, and internal porosities using nanosecond transient thermoreflectance. For SiNWs with diameters larger than the phonon mean free path, porosity substantially reduces the thermal conductivity, yielding thermal conductivities as low as 1 W/m/K in highly porous SiNWs. However, when the SiNW diameter is below the phonon mean free path, both the internal porosity and the diameter significantly contribute to phonon scattering and lead to reduced thermal conductivity of the SiNWs.

Tantalum Nitride (TaN) films carry high heat fluxes in a variety of applications including diffusion barriers in magnetoresistive random access memory and buffer/absorbers in extreme ultraviolet masks. The thicknesses of these films are usually of the same order as the thermal energy carrier mean free path, which complicates the study of heat conduction. This paper presents thermal (cross-plane) and electrical (in-plane) conductivity measurements on TaN films with thicknesses of 50, 75, and 100 nm. Picosecond thermoreflectance is used to extract the thermal boundary resistance between TaN and Al and the intrinsic thermal conductivity of TaN for temperatures of 300–700 K. The data and the relative importance of boundary resistances, electron-boundary scattering, and electron-defect scattering are interpreted using the electrical and thermal transport data. These data facilitate comparison of the phonon and electron contributions to thermal conduction in TaN.

The programming current required to switch a phase-change memory cell depends upon the thermal resistances in the device. In many designs, significant heat loss occurs through the electrode. This letter investigates the thermal properties of a multilayer electrode stack. This material offers greater thermal resistance than single-material electrodes due to the presence of multiple thermal boundary resistances (TBRs), reducing heat loss from the device and potentially lowering the programming current. Picosecond time-domain thermoreflectance interrogates the temperature-dependent thermal conductivity of three as-deposited and postannealed electrode materials: carbon, titanium nitride, and tungsten nitride. These data are used to extract the temperature-dependent, as-deposited, and postannealed TBR in two multilayer electrode stacks: carbon-titanium nitride and tungsten-tungsten nitride. The C-TiN stacks demonstrate an as-deposited TBR of 4.9 m(2)K/GW, increasing to 11.9 m(2)K/GW postanneal. The W-WN(x) stacks demonstrate an as-deposited TBR of 3.9 m(2)K/GW, decreasing to 3.6 m(2)K/GW postanneal. These resistances are equivalent to electrode films with thickness on the order of tens of nanometers.

Nanostructured composites containing aligned carbon nanotubes (CNTs) are very promising as interface materials for electronic systems and thermoelectric power generators. We report the first data for the thermal conductivity of densified, aligned multiwall CNT nanocomposite films for a range of CNT volume fractions. A 1 vol % CNT composite more than doubles the thermal conductivity of the base polymer. Denser arrays (17 vol % CNTs) enhance the thermal conductivity by as much as a factor of 18 and there is a nonlinear trend with CNT volume fraction. This article discusses the impact of CNT density on thermal conduction considering boundary resistances, increased defect concentrations, and the possibility of suppressed phonon modes in the CNTs.