Eric S. Muckley

UV-activated ZnO films on a flexible substrate for room temperature O 2 and H 2 O 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.

Multimodal probing of oxygen and water interaction with metallic and semiconducting carbon nanotube networks under ultraviolet irradiation

Abstract. Interaction between ultraviolet (UV) light and carbon nanotube (CNT) networks plays a central role in gas adsorption, sensor sensitivity, and stability of CNT-based electronic devices. To determine the effect of UV light on sorption kinetics and resistive gas/vapor response of different CNT networks, films of semiconducting single-wall nanotubes (s-SWNTs), metallic single-wall nanotubes, and multiwall nanotubes were exposed to O2 and H2O vapor in the dark and under UV irradiation. Changes in film resistance and mass were measured in situ. In the dark, resistance of metallic nanotube networks increases in the presence of O2 and H2O, whereas resistance of s-SWNT networks decreases. UV irradiation decreases the resistance of metallic nanotube networks in the presence of O2 and H2O and increases the gas/vapor sensitivity of s-SWNT networks by nearly a factor of 2 compared to metallic nanotube networks. s-SWNT networks show evidence of delamination from the gold-plated quartz crystal microbalance crystal, possibly due to preferential adsorption of O2 and H2O on gold. UV irradiation increases the sensitivity of all CNT networks to O2 and H2O by an order of magnitude, which demonstrates the importance of UV light for enhancing response and lowering detection limits in CNT-based gas/vapor sensors.

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.

Spatially resolved resistance of NiO nanostructures under humid environment

The spatially resolved electrical response of polycrystalline NiO films composed of 40 nm crystallites was investigated under different relative humidity levels (RH). The topological and electrical properties (surface potential and resistance) were characterized with sub 25nm resolution using Kelvin probe force microscopy (KPFM) and conductive scanning probe microscopy under argon atmosphere at 0%, 50%, and 80% relative humidity. The dimensionality of surface features obtained through autocorrelation analysis of topological maps increased linearly with increased relative humidity, as water was adsorbed onto the film surface. Surface potential decreased from about 280mV to about 100 mV and resistance decreased from about 5 GΩ to about 3 GΩ, in a nonlinear fashion when relative humidity was increased from 0% to 80%. Spatially resolved surface potential and resistance of the NiO films was found to be heterogeneous throughout the film, with distinct domains that grew in size from about 60 nm to 175 nm at 0% and 80% RH levels, respectively. The heterogeneous character of the topological, surface potential, and resistance properties of the polycrystalline NiO film observed under dry conditions decreased with increased relative humidity, yielding nearly homogeneous surface properties at 80% RH, suggesting that the nanoscale potential and resistance properties converge with the mesoscale properties as water is adsorbed onto the NiO film.

Imaging of electrical response of NiOx under controlled environment with sub-25-nm resolution

Abstract. The spatially resolved electrical response of polycrystalline NiOx films, composed of 40 nm crystallites, was investigated under different relative humidity (RH) levels. The topological and electrical properties (surface potential and resistance) were characterized with sub-25-nm resolution using Kelvin probe force microscopy and conductive scanning probe microscopy under argon atmosphere with 0%, 50%, and 80% RH. The dimensionality of surface features obtained through autocorrelation analysis of topological maps increased linearly with increased RH, as water was adsorbed onto the film surface. Surface potential decreased from 280 to 100 mV and resistance decreased from 5  GΩ to 3  GΩ, in a nonlinear fashion when RH was increased from 0% to 80%. Spatially resolved surface potential and resistance of the NiOx films was found to be heterogeneous throughout the film, with distinct surface features that grew in size from 60 to 175 nm at 0% and 80% RH levels, respectively. The heterogeneous character of the topological, surface potential, and resistance properties of the polycrystalline NiOx film observed under dry conditions decreased with increased RH, yielding nearly homogeneous surface properties at 80% RH, suggesting that the nanoscale potential and resistance properties converge with the mesoscale properties as water is adsorbed onto the NiOx film.

Morphology-defined interaction of copper phthalocyanine with O2/H2O

Abstract. Copper phthalocyanine (CuPc) is an important hole transport layer for organic photovoltaics (OPVs), but interaction with ambient gas/vapor may lead to changes in its electronic properties and limit OPV device lifetimes. CuPc films of thickness 25 and 100 nm were grown by thermal sublimation at 25°C, 150°C, and 250°C in order to vary morphology. We measured electrical resistance and film mass in situ during exposure to controlled pulses of O2 and H2O vapor. CuPc films deposited at 250°C showed a factor of 5 higher uptake of O2 as detected by a quartz crystal microbalance (QCM), possibly due to the formation of β-CuPc at T>200°C which allows higher O2 mobility between stacked molecules. While weight-based measurements stabilize after ∼10  min of gas exposure, resistance response stabilizes over times >1  h, suggesting that mass change occurs by rapid adsorption at active surface sites whereas resistive response is dominated by slow diffusion of adsorbates into the bulk film. The 25 nm films exhibit higher resistive response than 100 nm films after an hour of O2/H2O exposure due to fast analyte diffusion down to the film/electrode interface. We found evidence of decoupling of CuPc from the gold-coated QCM crystal due to preferential adsorption of O2/H2O molecules on gold.

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.

Functional two/three-dimensional assembly of monolayer WS2 and nickel oxide

Abstract. Functional assemblies of materials can be realized by tuning the work function and band gap of existing materials. Here we demonstrate the structural assembly of two- and three-dimensional (2-D) and (3-D) nanomaterials and investigate the optical and electronic properties of an assembly of monolayer WS2 on a rough polycrystalline NiO surface. Monolayer WS2 (2-D material) was transferred onto the NiO surface using a polymer-assisted transfer technique and resulted in a surface roughness about 30× greater than that of WS2 on SiO2. Raman maps of WS2 transferred onto NiO display a spatial nonuniformity of the E2g1 (∼352  cm−1) and A1g (∼418  cm−1) peak intensities, indicating that regions of the WS2 exist in a strained condition on the 3-D NiO surface. Kelvin probe force microscopy measurements show that the WS2-SiO2 assembly has a surface potential 62±5  mV lower than that of SiO2, whereas that of WS2-NiO is 11±5  mV higher than NiO, indicating that a monolayer of WS2 is sufficient to modify the surface potential by acting as either an electron donor or acceptor with the underlying surface. Thus, 2-D and 3-D materials can be organized into functional assemblies with electron flow controlled by the WS2 either as the electron donor or acceptor.