Hyungchul Kim

Stability of inverted organic solar cells with ZnO contact layers deposited from precursor solutions

We report on investigations of the stability of inverted organic solar cells with ZnO electron collecting interlayer that are solution-processed from zinc acetate (ZnAc) or diethylzinc (deZn) precursors. Characterization of the respective solar cells suggests that the two materials initially function similarly in devices, however, we find that devices with ZnO from the deZn precursor are more stable under long-term illumination and load than devices with ZnO from the ZnAc precursor. A dipolar phosphonic acid that reduces the ZnO work function also improved device performance and stability when compared with unmodified ZnAc-based ZnO, but was problematic for deZn-based ZnO. The long-term device degradation analyses shows that the improved devices had increased and significantly more stable open-circuit voltage and fill factor characteristics. Chemical analyses suggests that defects in the ZnO films, most likely interstitial zinc, may be responsible for the observed disparities in stability within organic solar cells.

Micro- and mesoporous carbide-derived carbon prepared by a sacrificial template method in high performance lithium sulfur battery cathodes

Polymer-based carbide-derived carbons (CDCs) with combined micro- and mesopores are prepared by an advantageous sacrificial templating approach using poly(methylmethacrylate) (PMMA) spheres as the pore forming material. Resulting CDCs reveal uniform pore size and pore shape with a specific surface area of 2434 m2 g−1 and a total pore volume as high as 2.64 cm3 g−1. The bimodal CDC material is a highly attractive host structure for the active material in lithium–sulfur (Li–S) battery cathodes. It facilitates the utilization of high molarity electrolytes and therefore the cells exhibit good rate performance and stability. The cathodes in the 5 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) electrolyte show the highest discharge capacities (up to 1404 mA h gs−1) and capacity retention (72% after 50 cycles at C/5). The unique network structure of the carbon host enables uniform distribution of sulfur through the conductive media and at the same time it facilitates rapid access for the electrolyte to the active material.

Defect‐Driven Interfacial Electronic Structures at an Organic/Metal‐Oxide Semiconductor Heterojunction

The electronic structure of the hybrid interface between ZnO and the prototypical organic semiconductor PTCDI is investigated via a combination of ultraviolet and X-ray photoelectron spectroscopy (UPS/XPS) and density functional theory (DFT) calculations. The interfacial electronic interactions lead to a large interface dipole due to substantial charge transfer from ZnO to 3,4,9,10-perylenetetracarboxylicdiimide (PTCDI), which can be properly described only when accounting for surface defects that confer ZnO its n-type properties.

Improving the stability of atomic layer deposited alumina films in aqueous environments with metal oxide capping layers

Alumina (Al2O3) films deposited through atomic layer deposition (ALD) are known to be effective permeation barriers due to their uniformity and pinhole-free morphology. However, they suffer from process-induced defects that inhibit their stability in aqueous and hygroscopic environments. We explore the water stability of ALD deposited alumina barrier films capped with nickel oxide (NiOx) and titanium oxide (TiOx) thin films deposited through e-beam or ALD deposition. The performance of the barriers was evaluated by measuring their ability to protect zinc oxide (ZnO) thin film sensors immersed in deionized (DI) water. X-ray photoelectron spectroscopy (XPS) was used to determine the composition of the barrier films with the various capping layers. The characteristic photoluminescence (PL) peak for the ZnO sensor was used as a marker to study changes in peak intensity due to degradation of the barrier films as a function of water immersion time. The TiOx capped films showed remarkable stability when immersed in DI water for 10 days. These results show that TiOx capping layers can offer superior protection to mitigate the water degradation of ALD alumina barrier films. Such composite laminates will enable a wider range of applications for ALD deposited alumina barrier films including aqueous environments.

Bandgap bowing in BGaN thin films

We report on the bandgap variation in thin films of BxGa1−xN grown on AlN/sapphire substrates using metal-organic vapor phase epitaxy. Optical transmission, photoluminescence, and x-ray diffraction were utilized to characterize the materials’ properties of the BxGa1−xN films. In contrast to the common expectation for the bandgap variation, which is based on the linear interpolation between the corresponding GaN and BN values, a significant bowing (C=9.2±0.5u2002eV) of the bandgap was observed. A decrease in the optical bandgap by 150 meV with respect to that of GaN was measured for the increase in the boron composition from 0% to 1.8%.We report on the bandgap variation in thin films of BxGa1−xN grown on AlN/sapphire substrates using metal-organic vapor phase epitaxy. Optical transmission, photoluminescence, and x-ray diffraction were utilized to characterize the materials’ properties of the BxGa1−xN films. In contrast to the common expectation for the bandgap variation, which is based on the linear interpolation between the corresponding GaN and BN values, a significant bowing (C=9.2±0.5u2002eV) of the bandgap was observed. A decrease in the optical bandgap by 150 meV with respect to that of GaN was measured for the increase in the boron composition from 0% to 1.8%.

Systematic Reliability Study of Top-Gate p- and n-Channel Organic Field-Effect Transistors

We report on a systematic investigation on the performance and stability of p-channel and n-channel top-gate OFETs, with a CYTOP/Al2O3 bilayer gate dielectric, exposed to controlled dry oxygen and humid atmospheres. Despite the severe conditions of environmental exposure, p-channel and n-channel top-gate OFETs show only minor changes of their performance parameters without undergoing irreversible damage. When correlated with the conditions of environmental exposure, these changes provide new insight into the possible physical mechanisms in the presence of oxygen and water. Photoexcited charge collection spectroscopy experiments provided further evidence of oxygen and water effects on OFETs. Top-gate OFETs also display outstanding durability, even when exposed to oxygen plasma and subsequent immersion in water or operated under aqueous media. These remarkable properties arise as a consequence of the use of relatively air stable organic semiconductors and proper engineering of the OFET structure.

Engineering the mechanical properties of ultrabarrier films grown by atomic layer deposition for the encapsulation of printed electronics

Direct deposition of barrier films by atomic layer deposition (ALD) onto printed electronics presents a promising method for packaging devices. Films made by ALD have been shown to possess desired ultrabarrier properties, but face challenges when directly grown onto surfaces with varying composition and topography. Challenges include differing nucleation and growth rates across the surface, stress concentrations from topography and coefficient of thermal expansion mismatch, elastic constant mismatch, and particle contamination that may impact the performance of the ALD barrier. In such cases, a polymer smoothing layer may be needed to coat the surface prior to ALD barrier film deposition. We present the impact of architecture on the performance of aluminum oxide (Al2O3)/hafnium oxide (HfO2) ALD nanolaminate barrier films deposited on fluorinated polymer layer using an optical calcium (Ca) test under damp heat. It is found that with increasing polymer thickness, the barrier films with residual tensile stre...

Disrupted Attosecond Charge Carrier Delocalization at a Hybrid Organic/Inorganic Semiconductor Interface

Despite significant interest in hybrid organic/inorganic semiconductor interfaces, little is known regarding the fate of charge carriers at metal oxide interfaces, particularly on ultrafast time scales. Using core-hole clock spectroscopy, we investigate the ultrafast charge carrier dynamics of conductive ZnO films at a hybrid interface with an organic semiconductor. The adsorption of C60 on the ZnO surface strongly suppresses the ultrafast carrier delocalization and increases the charge carrier residence time from 400 attoseconds to nearly 30 fs. Here, we show that a new hybridized interfacial density of states with substantial molecular character is formed, fundamentally altering the observed carrier dynamics. The remarkable change in the dynamics sheds light on the fate of carriers at hybrid organic/inorganic semiconductor interfaces relevant to organic optoelectronics and provides for the first time an atomistic picture of the electronically perturbed near-interface region of a metal oxide.

Hybridization-Induced Carrier Localization at the C60/ZnO Interface

Electronic coupling and ground-state charge transfer at the C60 /ZnO hybrid interface is shown to localize carriers in the C60 phase. This effect, revealed by resonant X-ray photoemission, arises from interfacial hybridization between C60 and ZnO. Such localization at carrier-selective electrodes and interlayers may lead to severely reduced carrier harvesting efficiencies and increased recombination rates in organic electronic devices.

Hydrogen-related, deeply bound excitons in Mg-doped GaN films

Luminescence in the near band-edge spectral region of Mg-doped GaN films grown by metalorganic chemical vapor deposition has been studied at liquid-helium temperatures. Radiative transitions at 3.37 and 3.416u2009eV were observed to evolve in cathodoluminescence spectra during electron-beam irradiation at 5u2009kV. The intensity of the 3.37u2009eV peak correlates monotonically with the resistivity of the films. By annealing the films in N2 and N2/H2 atmospheres, the 3.37 and 3.416u2009eV transitions are shown to be related to hydrogen.