Machine Intelligence-Centered System for Automated Characterization of Functional Materials and Interfaces.

Classic design of experiment relies on a time-intensive workflow that requires planning, data interpretation, and hypothesis building by experienced researchers. Here, we describe an integrated, machine-intelligent experimental system which enables simultaneous dynamic tests of electrical, optical, gravimetric, and viscoelastic properties of materials under a programmable dynamic environment. Specially designed software controls the experiment and performs on-the-fly extensive data analysis and dynamic modeling, real-time iterative feedback for dynamic control of experimental conditions, and rapid visualization of experimental results. The system operates with minimal human intervention and enables time-efficient characterization of complex dynamic multifunctional environmental responses of materials with simultaneous data processing and analytics. The system provides a viable platform for artificial intelligence (AI)-centered material characterization, which, when coupled with an AI-controlled synthesis system, could lead to accelerated discovery of multifunctional materials.

Analysis of trypsin activity at ß-casein layers formed on hydrophobic surfaces using a multiharmonic acoustic method.

Proteolysis of milk proteins, such as caseins, caused by milk proteases, can change the organoleptic and nutritional characteristics of milk, and therefore it is essential to monitor this enzymatic activity. We used trypsin as a model protease because of its role as a biomarker for pancreatitis. The aim of this work was to demonstrate the detection of proteolysis of ß-casein by trypsin using a multiharmonic quartz crystal microbalance (QCM) biosensor. The ß-casein layer was deposited from a 0.1 mg mL-1 solution on a hydrophobic surface consisting of a self-assembled monolayer of 1-dodecanethiol on the gold electrode of the QCM. The addition of an increasing concentration of trypsin leads to the removal of the casein layer due to proteolysis, and correlates with an increase in the resonant frequency of the QCM. We investigated the effect of trypsin concentrations (0.3-20 nM) on the kinetics of the proteolysis of ß-casein and demonstrated that the frequency increase is proportional to the protease concentration. Consequently, an inverse Michaelis-Menten model was used to estimate the Michaelis-Menten constant (KM = 0.38 ± 0.02 nM) and the limit of detection (LOD = 0.16 ± 0.02 nM). The thickness, mass and viscoelastic properties of the protein adlayer after its formation and following the proteolytic cleavage were evaluated by means of multi-harmonic analysis. We found that ß-casein is preferably adsorbed on the hydrophobic surfaces as an asymmetrical double layer, of which the innermost layer was found to be denser and thinner (about 2.37 nm) and the outermost layer was found to be less tightly bound and thicker (about 3.5 nm).

Exploring Transport Behavior in Hybrid Perovskites Solar Cells via Machine Learning Analysis of Environmental-Dependent Impedance Spectroscopy.

Hybrid organic-inorganic perovskites are one of the promising candidates for the next-generation semiconductors due to their superlative optoelectronic properties. However, one of the limiting factors for potential applications is their chemical and structural instability in different environments. Herein, the stability of (FAPbI3 )0.85 (MAPbBr3 )0.15 perovskite solar cell is explored in different atmospheres using impedance spectroscopy. An equivalent circuit model and distribution of relaxation times (DRTs) are used to effectively analyze impedance spectra. DRT is further analyzed via machine learning workflow based on the non-negative matrix factorization of reconstructed relaxation time spectra. This exploration provides the interplay of charge transport dynamics and recombination processes under environment stimuli and illumination. The results reveal that in the dark, oxygen atmosphere induces an increased hole concentration with less ionic character while ionic motion is dominant under ambient air. Under 1 Sun illumination, the environment-dependent impedance responses show a more striking effect compared with dark conditions. In this case, the increased transport resistance observed under oxygen atmosphere in equivalent circuit analysis arises due to interruption of photogenerated hole carriers. The results not only shed light on elucidating transport mechanisms of perovskite solar cells in different environments but also offer an effective interpretation of impedance responses.

SMART transfer method to directly compare the mechanical response of water-supported and free-standing ultrathin polymeric films.

Intrinsic mechanical properties of sub-100 nm thin films are markedly difficult to obtain, yet an ever-growing necessity for emerging fields such as soft organic electronics. To complicate matters, the interfacial contribution plays a major role in such thin films and is often unexplored despite supporting substrates being a main component in current metrologies. Here we present the shear motion assisted robust transfer technique for fabricating free-standing sub-100 nm films and measuring their inherent structural-mechanical properties. We compare these results to water-supported measurements, exploring two phenomena: 1) The influence of confinement on mechanics and 2) the role of water on the mechanical properties of hydrophobic films. Upon confinement, polystyrene films exhibit increased strain at failure, and reduced yield stress, while modulus is reduced only for the thinnest 19 nm film. Water measurements demonstrate subtle differences in mechanics which we elucidate using quartz crystal microbalance and neutron reflectometry.

Correlation of Spatiotemporal Dynamics of Polarization and Charge Transport in Blended Hybrid Organic-Inorganic Perovskites on Macro- and Nanoscales.

Progress in flexible organic electronics necessitates a full understanding of how local inhomogeneities impact electronic and ionic conduction pathways and underlie macroscopic device characteristics. We used frequency- and time-resolved macro- and nanoprobe measurements to study spatiotemporal characteristics of multiscale charge transport dynamics in a series of ternary-blended hybrid organic inorganic perovskites (HOIPs) (MA0.95-xFAxCs0.05PbI3). We show that A-site cation composition defines charge transport mechanisms across broad temporal (102-10-6 s) and spatial (millimeters-picometers) scales. Ab initio molecular dynamic simulations suggest that insertion of FA results in a dynamic lattice, improved ion transport, and dipole screening. We demonstrate that correlations between macro- and nanoscale measurements provide a pathway for accessing distribution of relaxation in nanoscale polarization and charge transport dynamics of ionically conductive functional perovskites.

Hierarchical TiO2:Cu2O Nanostructures for Gas/Vapor Sensing and CO2 Sequestration.

We investigate the effect of high-surface-area self-assembled TiO2:Cu2O nanostructures for CO2 and relative humidity gravimetric detection using polyethylenimine (PEI), 1-ethyl-3-methylimidazolium (EMIM), and polyacrylamide (PAAm). Introduction of hierarchical TiO2:Cu2O nanostructures on the surface of quartz crystal microbalance sensors is found to significantly improve sensitivity to CO2 and to H2O vapor. The response of EMIM to CO2 increases fivefold for 100 nm-thick TiO2:Cu2O as compared to gold. At ambient CO2 concentrations, the hierarchical assembly operates as a sensor with excellent reversibility, while at higher pressures, the CO2 desorption rate decreases, suggesting possible application for CO2 sequestration under these conditions. The gravimetric response of PEI to CO2 increases by a factor of 3 upon introduction of a 50 nm TiO2:Cu2O layer. The PAAm gravimetric response to water vapor also increases by a factor of 3 and displays improved reversibility with the addition of 50 nm TiO2:Cu2O structures. We found that TiO2:Cu2O can be used to lower the detection limits for CO2 sensing with EMIM and PEI and lower the detection limits for H2O sensing with PAAm by over a factor of 2. Coarse-grained and all-atom molecular dynamics simulations indicate the dissociative character of ionic liquid assembly on TiO2:Cu2O interfaces and different distributions of CO2 and H2O molecules on bare and ionic liquid-coated surfaces, confirming experimental observations. Overall, our results show high potential of hierarchical assemblies of TiO2:Cu2O/room temperature ionic liquid and polymer films for sensors and CO2 sequestration.

Environmental Gating and Galvanic Effects in Single Crystals of Organic-Inorganic Halide Perovskites.

Understanding the impact of environmental gaseous on the surface of organometal halide perovskites (OMHPs) couples to the electronic and ionic transport is critically important. Here, we explore the transport behavior and origins of the gas sensitivity in MAPbBr3 single crystals (SCs) devices using impedance spectroscopy and current relaxation measurements. Strong resistive response occurs when crystals are exposed to different environments. It was shown that SC response to the environment is extremely different at the surface as compared to the bulk due to the disorder surface chemistry. The nonlinear transport properties studied using ultrafast Kelvin probe force microscopy (G-KPFM) to unravel spatio-temporal charge dynamics at SC/electrode interface. The relaxation processes observed in pulse relaxation and G-KPFM measurements along with gas sensitivity of crystals suggest the presence of a triple-phase boundary between environment, electrode, and crystal. Results indicate that the environment is a nontrivial component in the operation of OMHP devices which is reminiscent of fuel cell systems. Furthermore, the triple-phase boundary can play a significant role in the transport properties of OMHPs due to the possibility of the redox processes coupled to the concentration of bulk ionic species. Although instrumental for understanding the device characteristics of perovskites, our studies suggest a new opportunity of coupling the redox chemistry of the Br2-Br- pair that defines the bulk ionic conductivity of MAPbBr3 with the redox chemistry of gaseous (or liquid) environment via a suitable electrocatalytic system to enable new class of energy storage devices and gas sensors.

Multi-modal, ultrasensitive, wide-range humidity sensing with Ti3C2 film.

Gravimetric, direct-current electrical, and electrical impedance sensing modes were used to measure response of high surface area 2D Ti3C2 MXene film to water vapor pressures spanning 3 orders of magnitude (20 mTorr-20 Torr). The Ti3C2 film exhibited reproducible reversible response in 0.1%-95% relative humidity (RH) range with a detection limit of <20 mTorr H2O partial pressure (<0.1% RH). DC electrical current-based sensing with 3 mV operating voltage and 0.8 pW power consumption was demonstrated. The highest normalized sensitivity was shown for gravimetric sensing modalities which scale with the overtone number, reaching highest sensitivity of about 12 Hz/% RH at the 9th crystal overtone (45 MHz oscillation).

Light-Activated Hybrid Nanocomposite Film for Water and Oxygen Sensing.

Oxygen and water vapor sensing properties are investigated in metal-oxide-hybrid polymer nanocomposite thin films generated by infiltration synthesis, which incorporates molecular ZnO into the matrix of SU-8 polymer, a common negative-tone photoresist. The hybrid thin films display 20-fold higher gravimetric responses to oxygen and water vapor than those of control ZnO thin films in the dark. An additional 50-500% enhanced responses are detected under UV irradiation. The overall enhanced gravimetric response in the hybrid film is attributed to the ZnO molecules distributed in the polymer matrix, whereas the UV enhancement is explained by the light-induced, reversible generation of hydrophilic fluoroantimonic acid from triarylsulfonium hexafluoroantimonate photoacids, which leads to the increased surface potential and adsorption energies for oxygen and water. A gravimetric sensor based on a series of ZnO-infiltrated SU-8 films under UV excitation enables 96% accurate classification of water and oxygen environment with sub 10 mTorr detection limits. The results demonstrate UV-induced fully reversible surface hydrophilicity of ZnO/SU-8 hybrid nanocomposites.

Multimodality of Structural, Electrical, and Gravimetric Responses of Intercalated MXenes to Water.

Understanding of structural, electrical, and gravimetric peculiarities of water vapor interaction with ion-intercalated MXenes led to design of a multimodal humidity sensor. Neutron scattering coupled to molecular dynamics and ab initio calculations showed that a small amount of hydration results in a significant increase in the spacing between MXene layers in the presence of K and Mg intercalants between the layers. Films of K- and Mg-intercalated MXenes exhibited relative humidity (RH) detection thresholds of ∼0.8% RH and showed monotonic RH response in the 0-85% RH range. We found that MXene gravimetric response to water is 10 times faster than their electrical response, suggesting that H2O-induced swelling/contraction of channels between MXene sheets results in trapping of H2O molecules that act as charge-depleting dopants. The results demonstrate the use of MXenes as humidity sensors and infer potential impact of water on structural and electrical performance of MXene-based devices.

Multi-mode humidity sensing with water-soluble copper phthalocyanine for increased sensitivity and dynamic range.

Aqueous solubility of copper phthalocyanine-3,4',4″,4″'-tetrasulfonic acid tetrasodium salt (CuPcTs) enables fabrication of flexible electronic devices by low cost inkjet printing. We (1) investigate water adsorption kinetics on CuPcTs for better understanding the effects of relative humidity (RH) on hydrophilic phthalocyanines, and (2) assess CuPcTs as a humidity-sensing material. Reaction models show that H2O undergoes 2-site adsorption which can be represented by a pair of sequentially-occurring pseudo-first order reactions. Using high frequency (300-700 THz) and low frequency (1-8 MHz) dielectric spectroscopy combined with gravimetric measurements and principal component analysis, we observe that significant opto-electrical changes in CuPcTs occur at RH ≈ 60%. The results suggest that rapid H2O adsorption takes place at hydrophilic sulfonyl/salt groups on domain surfaces at low RH, while slow adsorption and diffusion of H2O into CuPcTs crystallites leads to a mixed CuPcTs-H2O phase at RH > 60%, resulting in high frequency dielectric screening of the film by water and dissociation of Na+ from CuPc(SO3-)4 ions. The CuPcTs-H2O interaction can be tracked using a combination of gravimetric, optical, and electrical sensing modes, enabling accurate ( ± 2.5%) sensing in the ~0-95% RH range with a detection limit of less than 0.1% RH.

UV-activated ZnO films on a flexible substrate for room temperature O2 and H2O sensing.

We demonstrate that UV-light activation of polycrystalline ZnO films on flexible polyimide (Kapton) substrates can be used to detect and differentiate between environmental changes in oxygen and water vapor. The in-plane resistive and impedance properties of ZnO films, fabricated from bacteria-derived ZnS nanoparticles, exhibit unique resistive and capacitive responses to changes in O2 and H2O. We propose that the distinctive responses to O2 and H2O adsorption on ZnO could be utilized to statistically discriminate between the two analytes. Molecular dynamic simulations (MD) of O2 and H2O adsorption energy on ZnO surfaces were performed using the large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) with a reactive force-field (ReaxFF). These simulations suggest that the adsorption mechanisms differ for O2 and H2O adsorption on ZnO, and are governed by the surface termination and the extent of surface hydroxylation. Electrical response measurements, using DC resistance, AC impedance spectroscopy, and Kelvin Probe Force Microscopy (KPFM), demonstrate differences in response to O2 and H2O, confirming that different adsorption mechanisms are involved. Statistical and machine learning approaches were applied to demonstrate that by integrating the electrical and kinetic responses the flexible ZnO sensor can be used for detection and discrimination between O2 and H2O at low temperature.

New Insights on Electro-Optical Response of Poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate) Film to Humidity.

Understanding the relative humidity (RH) response of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is critical for improving the stability of organic electronic devices and developing selective sensors. In this work, combined gravimetric sensing, nanoscale surface probing, and mesoscale optoelectronic characterization are used to directly compare the RH dependence of electrical and optical conductivities and unfold connections between the rate of water adsorption and changes in functional properties of PEDOT:PSS film. We report three distinct regimes where changes in electrical conductivity, optical conductivity, and optical bandgap are correlated with the mass of adsorbed water. At low (RH < 25%) and high (RH > 60%) humidity levels, dramatic changes in electrical, optical, and structural properties occur, while changes are insignificant in mid-RH (25 < RH < 60%) conditions. We associate the three regimes with water adsorption at hydrophilic moieties at low RH, diffusion and swelling throughout the film at mid-RH, and saturation of the film by water at high RH. Optical film thickness increased by 150% as RH was increased from 9 to 80%. Low frequency (1 kHz) impedance increased by ∼100%, and film capacitance increased by ∼30% as RH increased from 9 to 80% due to an increase in the film dielectric constant. Changes in electrical and optical conductivities concomitantly decrease across the full range of RH tested.