Results of an interlaboratory study on the working curve in vat photopolymerization.

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.

Atom probe tomography using an extreme ultraviolet trigger pulse.

Atom probe tomography (APT) is a powerful materials characterization technique capable of measuring the isotopically resolved three-dimensional (3D) structure of nanoscale specimens with atomic resolution. Modern APT instrumentation most often uses an optical pulse to trigger field ion evaporation-most commonly, the second or third harmonic of a Nd laser is utilized (∼λ = 532 nm or λ = 355 nm). Herein, we describe an APT instrument that utilizes ultrafast extreme ultraviolet (EUV) optical pulses to trigger field ion emission. The EUV light is generated via a commercially available high harmonic generation system based on a noble-gas-filled capillary. The centroid of the EUV spectrum is tunable from around 25 eV (λ = 50 nm) to 45 eV (λ = 28 nm), dependent on the identity of the gas in the capillary (Xe, Kr, or Ar). EUV pulses are delivered to the APT analysis chamber via a vacuum beamline that was optimized to maximize photon flux at the APT specimen apex while minimizing complexity. We describe the design of the beamline in detail, including the various compromises involved. We characterize the spectrum of the EUV light and its evolution as it propagates through the various optical elements. The EUV focus spot size is measured at the APT specimen plane, and the effects of misalignment are simulated and discussed. The long-term stability of the EUV source has been demonstrated for more than a year. Finally, APT mass spectra are shown, demonstrating the instrument's ability to successfully trigger field ion emission from semiconductors (Si, GaN) and insulating materials (Al2O3).

A Data-Driven Approach to Complex Voxel Predictions in Grayscale Digital Light Processing Additive Manufacturing Using U-Nets and Generative Adversarial Networks.

Data-driven U-net machine learning (ML) models, including the pix2pix conditional generative adversarial network (cGAN), are shown to predict 3D printed voxel geometry in digital light processing (DLP) additive manufacturing. A confocal microscopy-based workflow allows for the high-throughput acquisition of data on thousands of voxel interactions arising from randomly gray-scaled digital photomasks. Validation between prints and predictions shows accurate predictions with sub-pixel scale resolution. The trained cGAN performs virtual DLP experiments such as feature size-dependent cure depth, anti-aliasing, and sub-pixel geometry control. The pix2pix model is also applicable to larger masks than it is trained on. To this end, the model can qualitatively inform layer-scale and voxel-scale print failures in real 3D-printed parts. Overall, machine learning models and the data-driven methodology, exemplified by U-nets and cGANs, show considerable promise for predicting and correcting photomasks to achieve increased precision in DLP additive manufacturing.

Characterizing light engine uniformity and its influence on liquid crystal display based vat photopolymerization printing.

Vat photopolymerization (VP) is a rapidly growing category of additive manufacturing. As VP methods mature the expectation is that the quality of printed parts will be highly reproducible. At present, detailed characterization of the light engines used in liquid crystal display (LCD)-based VP systems is lacking and so it is unclear if they are built to sufficiently tight tolerances to meet the current and/or future needs of additive manufacturing. Herein, we map the irradiance, spectral characteristics, and optical divergence of a nominally 405 nm LCD-based VP light engine. We find that there is notable variation in all of these properties as a function of position on the light engine that cause changes in extent of polymerization and surface texture. We further demonstrate through a derived photon absorption figure of merit and through printed test parts that the spatial heterogeneity observed in the light engine is significant enough to affect part fidelity. These findings help to explain several possible causes of variable part quality and also highlight the need for improved optical performance on LCD-based VP printers.

Orientation mapping of graphene using 4D STEM-in-SEM.

A scanning diffraction technique is implemented in the scanning electron microscope. The technique, referred to as 4D STEM-in-SEM (four-dimensional scanning transmission electron microscopy in the scanning electron microscope), collects a diffraction pattern from each point on a sample which is saved to disk for further analysis. The diffraction patterns are collected using an on-axis lens-coupled phosphor/CCD arrangement. Synchronization between the electron beam and the camera exposure is accomplished with off-the-shelf data acquisition hardware. Graphene is used as a model system to test the sensitivity of the instrumentation and develop some basic analysis techniques. The data show interpretable diffraction patterns from monolayer graphene with integration times as short as 0.5 ms with a beam current of 245 pA (7.65×105 incident electrons per pixel). Diffraction patterns are collected at a rate of ca. 100/s from the mm to nm length scales. Using a grain boundary as a 'knife-edge', the spatial resolution of the technique is demonstrated to be ≤5.6nm (edge-width 25 % to 75 %). Analysis of the orientation of the diffraction patterns yields an angular (orientation) precision of ≤0.19∘ (full width at half maximum) for unsupported monolayer graphene. In addition, it is demonstrated that the 4D datasets have the information content necessary to analyze complex and heterogeneous multilayer graphene films.

An algorithm for correcting systematic energy deficits in the atom probe mass spectra of insulating samples.

Improvements in the mass resolution of a mass spectrometer directly correlate to improvements in peak identification and quantification. Here, we describe a post-processing technique developed to increase the quality of mass spectra of strongly insulating samples in laser-pulsed atom probe microscopy. The technique leverages the self-similarity of atom probe mass spectra collected at different times during an experimental run to correct for electrostatic artifacts that present as systematic energy deficits. We demonstrate the method on fused silica (SiO2) and neodymium-doped ceria (CeO2) samples which highlight the improvements that can be made to the mass spectrum of strongly insulating samples.

Field Ion Emission in an Atom Probe Microscope Triggered by Femtosecond-Pulsed Coherent Extreme Ultraviolet Light.

This paper describes initial experimental results from an extreme ultraviolet (EUV) radiation-pulsed atom probe microscope. Femtosecond-pulsed coherent EUV radiation of 29.6 nm wavelength (41.85 eV photon energy), obtained through high harmonic generation in an Ar-filled hollow capillary waveguide, successfully triggered controlled field ion emission from the apex of amorphous SiO2 specimens. The calculated composition is stoichiometric within the error of the measurement and effectively invariant of the specimen base temperature in the range of 25 K to 150 K. Photon energies available in the EUV band are significantly higher than those currently used in the state-of-the-art near-ultraviolet laser-pulsed atom probe, which enables the possibility of additional ionization and desorption pathways. Pulsed coherent EUV light is a new and potential alternative to near-ultraviolet radiation for atom probe tomography.

Transmission imaging with a programmable detector in a scanning electron microscope.

A new type of angularly selective electron detector for use in a scanning electron microscope is presented. The detector leverages a digital micromirror device (DMD) to take advantage of the benefits of two-dimensional (2D) imaging detectors and high-bandwidth integrating detectors in a single optical system. The imaging detector provides direct access to the diffraction pattern, while the integrating detector can be synchronized to the microscope scan generator providing access to a real space image generated by integrating (pixel-by-pixel) a portion of the diffraction pattern as quantitatively defined by the DMD. The DMD, in effect, takes the place of the objective aperture in a transmission electron microscope (TEM) or an annular detector in a scanning transmission electron microscope (STEM), but has the distinct advantage that it can be programmed to take any shape in real time. Proof-of-principle data collected with the detector show diffraction contrast in samples ranging from a polycrystalline gold film to monolayer graphene.

Femtosecond to nanosecond excited state dynamics of vapor deposited copper phthalocyanine thin films.

Vapor deposited thin films of copper phthalocyanine (CuPc) were investigated using transient absorption spectroscopy. Exciton-exciton annihilation dominated the kinetics at high exciton densities. When annihilation was minimized, the observed lifetime was measured to be 8.6 ± 0.6 ns, which is over an order of magnitude longer than previous reports. In comparison with metal free phthalocyanine (H2Pc), the data show evidence that the presence of copper induces an ultrafast relaxation process taking place on the ca. 500 fs timescale. By comparison to recent time-resolved photoemission studies, this is assigned as ultrafast intersystem crossing. As the intersystem crossing occurs ca. 10(4) times faster than lifetime decay, it is likely that triplets are the dominant excitons in vapor deposited CuPc films. The exciton lifetime of CuPc thin films is ca. 35 times longer than H2Pc thin films, while the diffusion lengths reported in the literature are typically quite similar for the two materials. These findings suggest that despite appearing to be similar materials at first glance, CuPc and H2Pc may transport energy in dramatically different ways. This has important implications on the design and mechanistic understanding of devices where phthalocyanines are used as an excitonic material.

Vibrational cooling dynamics of a [FeFe]-hydrogenase mimic probed by time-resolved infrared spectroscopy.

Picosecond time-resolved infrared spectroscopy (TRIR) was performed for the first time on a dithiolate bridged binuclear iron(I) hexacarbonyl complex ([Fe2(µ-bdt)(CO)6], bdt = benzene-1,2-dithiolate) which is a structural mimic of the active site of the [FeFe]-hydrogenase enzyme. As these model active sites are increasingly being studied for their potential in photocatalytic systems for hydrogen production, understanding their excited and ground state dynamics is critical. In n-heptane, absorption of 400 nm light causes carbonyl loss with low quantum yield (<10%), while the majority (ca. 90%) of the parent complex is regenerated with biexponential kinetics (τ1 = 21 ps and τ2 = 134 ps). In order to understand the mechanism of picosecond bleach recovery, a series of UV-pump TRIR experiments were performed in different solvents. The long time decay (τ2) of the transient spectra is seen to change substantially as a function of solvent, from 95 ps in THF to 262 ps in CCl4. Broadband IR-pump TRIR experiments were performed for comparison. The measured vibrational lifetimes (T1(avg)) of the carbonyl stretches were found to be in excellent correspondence to the observed τ2 decays in the UV-pump experiments, signifying that vibrationally excited carbonyl stretches are responsible for the observed longtime decays. The fast spectral evolution (τ1) was determined to be due to vibrational cooling of low frequency modes anharmonically coupled to the carbonyl stretches that were excited after electronic internal conversion. The results show that cooling of both low and high frequency vibrational modes on the electronic ground state give rise to the observed picosecond TRIR transient spectra of this compound, without the need to invoke electronically excited states.

Metal/Phthalocyanine Hybrid Interface States on Ag(111).

A phthalocyanine/Ag(111) interface state is observed for the first time using time- and angle-resolved two-photon photoemission. For monolayer films of metal-free (H2Pc) and iron phthalocyanine (FePc) on Ag(111), the state exists 0.23 ± 0.03 and 0.31 ± 0.03 eV above the Fermi level, respectively. Angle-resolved spectra show the state to be highly dispersive with an effective mass of 0.50 ± 0.15 me for H2Pc and 0.67 ± 0.14 me for FePc. Density functional theory calculations on the H2Pc/Ag(111) surface allow us to characterize this state as being a hybrid state resulting from the interaction between the unoccupied molecular states of the phthalocyanine ligand and the Shockley surface state present on the bare Ag(111) surface. This work, when taken together with the extensive literature on the 3,4,9,10-perylene tetracarboxylic dianhydride/Ag interface state, provides compelling evidence that the hybridization of metal surface states with molecular electronic states is a general phenomenon.

Studying the Dynamics of Photochemical Reactions via Ultrafast Time-Resolved Infrared Spectroscopy of the Local Solvent.

Conventional ultrafast spectroscopic studies on the dynamics of chemical reactions in solution directly probe the solute undergoing the reaction. We provide an alternative method for probing reaction dynamics via monitoring of the surrounding solvent. When the reaction exchanges the energy (in form of heat) with the solvent, the absorption cross sections of the solvent's infrared bands are sensitive to the heat transfer, allowing spectral tracking of the reaction dynamics. This spectroscopic technique was demonstrated to be able to distinguish the differing photoisomerization dynamics of the trans and cis isomers of stilbene in acetonitrile solution. We highlight the potential of this spectroscopic approach for studying the dynamics of chemical reactions or other heat transfer processes when probing the solvent is more experimentally feasible than probing the solute directly.

Femtosecond Trapping of Free Electrons in Ultrathin Films of NaCl on Ag(100).

We report the excited-state electron dynamics for ultrathin films of NaCl on Ag(100). The first three image potential states (IPSs) were initially observed following excitation. The electrons in the spatially delocalized n = 1 IPS decayed on the ultrafast time scale into multiple spatially localized states lower in energy. The localized electronic states are proposed to correspond to electrons trapped at defects in the NaCl islands. Coverage and temperature dependence of the localized states support the assignment to surface trap states existing at the NaCl/vacuum interface. These results highlight the importance of electron trapping in ultrathin insulating layers.

Femtosecond electron solvation at the ionic liquid/metal electrode interface.

Electron solvation is examined at the interface of a room temperature ionic liquid (RTIL) and an Ag(111) electrode. Femtosecond two-photon photoemission spectroscopy is used to inject an electron into an ultrathin film of RTIL 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Bmpyr](+)[NTf2](-)). While much of current literature highlights slower nanosecond solvation mechanisms in bulk ionic liquids, we observe only a femtosecond response, supporting morphology dependent and interface specific electron solvation mechanisms. The injected excess electron is found to reside in an electron affinity level residing near the metal surface. Population of this state decays back to the metal with a time constant of 400 ± 150 fs. Electron solvation is measured as a dynamic decrease in the energy with a time constant of 350 ± 150 fs. We observe two distinct temperature regimes, with a critical temperature near 250 K. The low temperature regime is characterized by a higher work function of 4.41 eV, while the high temperature regime is characterized by a lower work function of 4.19 eV. The total reorganizational energy of solvation changes above and below the critical temperature. In the high temperature regime, the electron affinity level solvates by 540 meV at 350 K, and below the critical temperature, solvation decreases to 200 meV at 130 K. This study will provide valuable insight to interface specific solvation of room temperature ionic liquids.

Time-resolved vibrational spectroscopy of [FeFe]-hydrogenase model compounds.

Model compounds have been found to structurally mimic the catalytic hydrogen-producing active site of Fe-Fe hydrogenases and are being explored as functional models. The time-dependent behavior of Fe(2)(µ-S(2)C(3)H(6))(CO)(6) and Fe(2)(µ-S(2)C(2)H(4))(CO)(6) is reviewed and new ultrafast UV- and visible-excitation/IR-probe measurements of the carbonyl stretching region are presented. Ground-state and excited-state electronic and vibrational properties of Fe(2)(µ-S(2)C(3)H(6))(CO)(6) were studied with density functional theory (DFT) calculations. For Fe(2)(µ-S(2)C(3)H(6))(CO)(6) excited with 266 nm, long-lived signals (τ = 3.7 ± 0.26 µs) are assigned to loss of a CO ligand. For 355 and 532 nm excitation, short-lived (τ = 150 ± 17 ps) bands are observed in addition to CO-loss product. Short-lived transient absorption intensities are smaller for 355 nm and much larger for 532 nm excitation and are assigned to a short-lived photoproduct resulting from excited electronic state structural reorganization of the Fe-Fe bond. Because these molecules are tethered by bridging disulfur ligands, this extended di-iron bond relaxes during the excited state decay. Interestingly, and perhaps fortuitously, the time-dependent DFT-optimized exited-state geometry of Fe(2)(µ-S(2)C(3)H(6))(CO)(6) with a semibridging CO is reminiscent of the geometry of the Fe(2)S(2) subcluster of the active site observed in Fe-Fe hydrogenase X-ray crystal structures. We suggest these wavelength-dependent excitation dynamics could significantly alter potential mechanisms for light-driven catalysis.