High-energy ion (He+, Si++, Ga+, Au++) interactions with PMMA in ion beam lithography.

Resist-based ion beam lithography has been studied by exposing different species of ions (He+, Si++, Ga+ and Au++) on 700 and 2000 Å thick poly(methyl methacrylate) (or PMMA) films supported on Si substrates. By comparing the resist sensitivities to different ions and the cross-sectional shapes of the developed features with the simulation outputs from the TRIM (TRansport of Ions in Matter) software, long-chain scissoring in PMMA can be largely attributed to ion-initiated electron cascades (as evaluated by ion energy loss to the electrons) and recoil atom cascades (as evaluated by vacancy distribution in TRIM). The ion-initiated electron cascades contribute more to the resist sensitivity for the lighter ions, while the recoil atom cascades are more important for the heavier ions. A proportional relation between the resist sensitivity and the product of the ion energy loss to electrons and vacancy number is obtained semi-empirically for heavy ions. The He+ ion is the only ion species that can travel through and therefore expose the entire 2000-Å thick PMMA resist film, while the heaviest ion, Au++, provides the highest resist sensitivity. The effective energy and momentum impartment to the resist by the ion, as revealed by recoil atom cascades and vacancy formation, is important to significantly expanding the material types suitable for ion beam lithography.

Interfacial micropore defect formation in PEDOT:PSS-Si hybrid solar cells probed by TOF-SIMS 3D chemical imaging.

Conducting p-type polymer layers on n-type Si have been widely studied for the fabrication of cost-effective hybrid solar cells. In this work, time-of-flight secondary ion mass spectrometry (TOF-SIMS) is used to provide three-dimensional chemical imaging of the interface between poly(3,4-ethylene-dioxythiophene):polystyrenesulfonate (PEDOT:PSS) and SiOx/Si in a hybrid solar cell. To minimize structural damage to the polymer layer, an Ar cluster sputtering source is used for depth profiling. The present result shows the formation of micropore defects in the interface region of the PEDOT:PSS layer on the SiOx/Si substrate. This interfacial micropore defect formation becomes more prominent with increasing thickness of the native oxide layer, which is a key device parameter that greatly affects the hybrid solar cell performance. Three-dimensional chemical imaging coupled with Ar cluster ion sputtering has therefore been demonstrated as an emerging technique for probing the interface of this and other polymer-inorganic systems.

Defect-Rich Dopant-Free ZrO2 Nanoclusters and Their Size-Dependent Ferromagnetism.

As an intermediate form of matter between a single atom or molecule and the bulk, nanoclusters (NCs) provide novel properties because of their high surface area-to-volume ratios and distinct physical and electronic structures. These ultrasmall NCs offer a new approach to advance charge-spin manipulation for novel devices, including spintronics and magnetic tunneling junctions. Here, we deposit monosized ZrO2 NCs over a large area by using gas-phase aggregation followed by in situ size selection by a quadrupole mass filter. These size-specific NCs exhibit sub-oxide photoemission features at binding energies that are dependent on the cluster size (from 3 to 9 nm), which are attributed to different oxygen vacancy defect states. These dopant-free ZrO2 NCs also show strongly size-dependent ferromagnetism, which provides distinct advantages in solubility and homogeneity of magnetism when compared to traditional dilute magnetic semiconductors. A defect-band hybridization-induced magnetic polaron model is proposed to explain the origin of this size-dependent ferromagnetism. This work demonstrates a new protocol of magnetization manipulation by size control and promises potential applications based on these defect-rich size-selected NCs.

Charge Transfer in Nanowire-Embedded PEDOT:PSS and Planar Heterojunction Solar Cells.

Hybrid metallic nanowire-embedded, highly conductive poly(3,4-ethylenedioxy thiophene):polystyrenesulfonate (PEDOT:PSS) with synergetic properties is indispensable for enhancing the performances of conductive polymer-based electronic devices. Here, we report embedment of silver nanowires (AgNWs), with diameter ∼100 nm and a high concentration (500 mg/mL) of nanowires dispersed in either ethanol or isopropanol, in PEDOT:PSS and compare the effects of the nanowire-dispersing solvents as well as its thicker diameter and high concentration on the overall properties and particularly its charge transfer characteristics and planar heterojunction solar cell (HSC) properties. Furthermore, electrostatic force microscopy is applied to elucidate the direct charge transfer from AgNWs to the PEDOT:PSS matrix. The AgNW-embedded PEDOT:PSS-based planar HSCs show a very high open-circuit voltage of over 638 mV and a high power conversion efficiency greater than 15.3% and without any significant influence from the AgNW dispersing solvents. While charge transfer in PEDOT:PSS without AgNWs occurs through the conducting PEDOT grains, enhanced charge transfer is realized in AgNW-embedded PEDOT:PSS with charge transport from PEDOT grains to AgNWs and then to PEDOT grains before reaching the top electrode in the HSC. The AgNW-embedded PEDOT:PSS hybrid materials pave a simple way to enhance the charge transfer performance in not only HSCs but also other hybrid or heterojunction electronics.

Highly Conducting Hybrid Silver-Nanowire-Embedded Poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate) for High-Efficiency Planar Silicon/Organic Heterojunction Solar Cells.

Embedding nanowires, such as silver nanowires (AgNWs), in a transparent conductive polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) to enhance its conductivity is technologically important for improving the performances of devices comprising transparent conductive layers. Addition of nanowires in the highly conducting form of cosolvent (ethylene glycol) or mixed-cosolvent (ethylene glycol and methanol) modified PEDOT:PSS could change the nanowire structure and significantly alter the conductivity. Here, we report a simple method to embed AgNWs in PEDOT:PSS efficiently to improve its conductivity. By incorporating nanowires in the mixed cosolvent matrix prior to addition into PEDOT:PSS, this method preserves the structure of the nanowires while enabling conductivity enhancement. In contrast, the addition of AgNWs into cosolvent-premodified PEDOT:PSS leads to breaking of nanowires and conductivity impediment. The hybrid films with efficiently embedded AgNWs and mixed-cosolvent-modified PEDOT:PSS show a sheet resistance of 104 Ω/□, which is among the lowest ever reported for the as-deposited films, with conductivity enhancement of 33% relative to that of mixed-cosolvent-modified PEDOT:PSS. The resulting planar heterojunction solar cell (HSC) based on AgNW-embedded PEDOT:PSS exhibits a power conversion efficiency of greater than 15%. This demonstrates the importance of reducing sheet resistance by integrating nanowires into the PEDOT:PSS matrix as effective charge-transfer conduits interconnecting the highly conducting quinoid chains. The present approach to efficiently embed AgNWs in PEDOT:PSS could be readily extended to other nanowires or nanoparticles for improving the performance of PEDOT:PSS for applications in not just HSCs but indeed other electronic devices that require both transparent and highly conductive layers.

High-Performance Single-Active-Layer Memristor Based on an Ultrananocrystalline Oxygen-Deficient TiOx Film.

The theoretical and practical realization of memristive devices has been hailed as the next step for nonvolatile memories, low-power remote sensing, and adaptive intelligent prototypes for neuromorphic and biological systems. However, the active materials of currently available memristors need to undergo an often destructive high-bias electroforming process in order to activate resistive switching. This limits their device performance in switching speed, endurance/retention, and power consumption upon high-density integration, due to excessive Joule heating. By employing a nanocrystalline oxygen-deficient TiOx switching matrix to localize the electric field at discrete locations, it is possible to resolve the Joule heating problem by reducing the need for electroforming at high bias. With a Pt/TiOx/Pt stacking architecture, our device follows an electric field driven, vacancy-modulated interface-type switching that is sensitive to the junction size. By scaling down the junction size, the SET voltage and output current can be reduced, and a SET voltage as low as +0.59 V can be obtained for a 5 × 5 µm2 junction size. Along with its potentially fast switching (over 105 cycles with a 100 µs voltage pulse) and high retention (over 105 s) performance, memristors based on these disordered oxygen-deficient TiOx films promise viable building blocks for next-generation nonvolatile memories and other logic circuit systems.

Performance Enhancement by Secondary Doping in PEDOT:PSS/Planar-Si Hybrid Solar Cells.

Solar cells depend on effectively absorbing light and converting it into electrical current. It is therefore essential to increase conductivity and to limit both reflection and parasitic absorbance to achieve higher photoconversion efficiency. Here, we examine the effect of post-treatment on the absorbance and conductivity of hybrid solar cells comprised of p-type poly(3,4-ethylene-dioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) on an n-type silicon substrate. Three sets of cells based on pristine PEDOT:PSS film, cosolvent enhanced PEDOT:PSS film using ethylene glycol as a cosolvent, and post-treated PEDOT:PSS film using a novel 1:1 binary mixture of ethylene glycol and methanol have been studied. Markedly different film conductivities have been found for the pristine (∼0.8 S/cm), cosolvent added (637 S/cm), and post-treated films (1334 S/cm). The photoconversion efficiency obtained over a large set of samples (72 cells) was used to evaluate the cosolvent addition and post-treatment. Post-treatment is found to reproducibly provide films with not only the highest conductivities but also the highest efficiencies along with higher open-circuit voltage and fill factor but lower short-circuit current density when compared to those of the cosolvent added films. The decrease in the latter is attributed to the increase in absorbance in the PEDOT:PSS film. The present work illustrates the delicate challenge in improving the conductivity and carrier collection efficiency of the cells not at the expense of other properties such as absorption.

Reversible structural transformation and enhanced performance of PEDOT:PSS-based hybrid solar cells driven by light intensity.

Hybrid solar cells made of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) ( PEDOT: PSS) and appropriate amounts of a cosolvent and a fluorosurfactant on planar n-type silicon substrates showed a photoconversion efficiency (PCE) of above 13%. These cells also exhibited stable, reproducible, and high external quantum efficiency (EQE) that was not sensitive to light-bias intensity (LBI). In contrast, solar cells made of pristine PEDOT: PSS showed low PCE and high EQE only under certain measurement conditions. The EQE was found to degrade with increasing LBI. Here we report that the LBI-sensitive variation of EQE of the low-PCE cells is related to a reversible structural transformation from a quinoid to a benzoid structure of PEDOT.

Size-selected TiO2 nanocluster catalysts for efficient photoelectrochemical water splitting.

Nanoclusters (NCs) are of great interest because they provide the link between the distinct behavior of atoms and nanoparticles and that of bulk materials. Here, we report precisely controlled deposition of size-selected TiO2 NCs produced by gas-phase aggregation in a special magnetron sputtering system. Carefully optimized aggregation length and Ar gas flow are used to control the size distribution, while a quadrupole mass filter provides precise in situ size selection (from 2 to 15 nm). Transmission electron microscopy studies reveal that NCs larger than a critical size (∼8 nm) have a crystalline core with an amorphous shell, while those smaller than the critical size are all amorphous. The TiO2 NCs so produced exhibit remarkable photoelectrochemical water splitting performance in spite of a small amount of material loading. NCs of three different sizes (4, 6, and 8 nm) deposited on H-terminated Si(100) substrates are tested for the photoelectrochemical catalytic performance, and significant enhancement in photocurrent density (0.8 mA/cm(2)) with decreasing NC size is observed with a low saturation voltage of -0.22 V vs Ag/AgCl (0.78 V vs RHE). The enhanced photoconductivity could be attributed to the increase in the specific surface area and increase in the number of active (defect) sites in the amorphous NCs. The unique advantages of the present technique will be further exploited to develop applications based on tunable, size-selected NCs.

Near-surface oxidized sulfur modifications and self-assembly of thiol-modified aptamer on Au thin film substrates influenced by piranha treatment.

Self-assembly of thiol-modified oligonucleotides on Au films has great importance for biosensor applications. Prior to the self-assembly, a piranha treatment (PT) is commonly used to clean the Au surface. Here we report that near-surface oxidized sulfur modifications on Au thin films by PT for longer than 60 s have serious effects on the self-assembled monolayer (SAM) formation of thiol-modified single-stranded thrombin binding aptamer (s-TBA), and a PT time of 10-30 s is optimal for s-TBA SAM formation. These results have important implication to SAM formation of biomolecules, especially for the thiol-modified ones where a careful consideration of this key step could significantly enhance the SAM formation and biosensor performance.