Development of the Tele-Measurement of Plasma Uniformity via Surface Wave Information (TUSI) Probe for Non-Invasive In-Situ Monitoring of Electron Density Uniformity in Plasma Display Fabrication Process.

The importance of monitoring the electron density uniformity of plasma has attracted significant attention in material processing, with the goal of improving production yield. This paper presents a non-invasive microwave probe for in-situ monitoring electron density uniformity, called the Tele-measurement of plasma Uniformity via Surface wave Information (TUSI) probe. The TUSI probe consists of eight non-invasive antennae and each antenna estimates electron density above the antenna by measuring the surface wave resonance frequency in a reflection microwave frequency spectrum (S11). The estimated densities provide electron density uniformity. For demonstration, we compared it with the precise microwave probe and results revealed that the TUSI probe can monitor plasma uniformity. Furthermore, we demonstrated the operation of the TUSI probe beneath a quartz or wafer. In conclusion, the demonstration results indicated that the TUSI probe can be used as an instrument for a non-invasive in-situ method for measuring electron density uniformity.

Observation of prior light emission before arcing development in a low-temperature plasma with multiple snapshot analysis.

Arcing is a ubiquitous phenomenon and a crucial issue in high-voltage applied systems, especially low-temperature plasma (LTP) engineering. Although arcing in LTPs has attracted interest due to the severe damage it can cause, its underlying mechanism has yet to be fully understood. To elucidate the arcing mechanism, this study investigated various signals conventionally used to analyze arcing such as light emission, arcing current and voltage, and background plasma potential. As a result, we found that light emission occurs as early as 0.56 µs before arcing current initiation, which is a significant indicator of the explosive development of arcing as well as other signals. We introduce an arcing inducing probe (AIP) designed to localize arcing on the tip edge along with multiple snapshot analysis since arcing occurs randomly in space and time. Analysis reveals that the prior light emission consists of sheath and tip glows from the whole AIP sheath and the AIP tip edge, respectively. Formation mechanisms of these emissions based on multiple snapshot image analysis are discussed. This light emission before arcing current initiation provides a significant clue to understanding the arcing formation mechanism and represents a new indicator for forecasting arcing in LTPs.

Investigation into SiO2 Etching Characteristics Using Fluorocarbon Capacitively Coupled Plasmas: Etching with Radical/Ion Flux-Controlled.

SiO2 etching characteristics were investigated in detail. Patterned SiO2 was etched using radio-frequency capacitively coupled plasma with pulse modulation in a mixture of argon and fluorocarbon gases. Through plasma diagnostic techniques, plasma parameters (radical and electron density, self-bias voltage) were also measured. In this work, we identified an etching process window, where the etching depth is a function of the radical flux. Then, pulse-off time was varied in the two extreme cases: the lowest and the highest radical fluxes. It was observed that increasing pulse-off time resulted in an enhanced etching depth and the reduced etching depth respectively. This opposing trend was attributed to increasing neutral to ion flux ratio by extending pulse-off time within different etching regimes.

Influence of Additive N2 on O2 Plasma Ashing Process in Inductively Coupled Plasma.

One of the cleaning processes in semiconductor fabrication is the ashing process using oxygen plasma, which has been normally used N2 gas as additive gas to increase the ashing rate, and it is known that the ashing rate is strongly related to the concentration of oxygen radicals measured OES. However, by performing a comprehensive experiment of the O2 plasma ashing process in various N2/O2 mixing ratios and RF powers, our investigation revealed that the tendency of the density measured using only OES did not exactly match the ashing rate. This problematic issue can be solved by considering the plasma parameter, such as electron density. This study can suggest a method inferring the exact maximum condition of the ashing rate based on the plasma diagnostics such as OES, Langmuir probe, and cutoff probe, which might be useful for the next-generation plasma process.

Development of a High-Linearity Voltage and Current Probe with a Floating Toroidal Coil: Principle, Demonstration, Design Optimization, and Evaluation.

As the conventional voltage and current (VI) probes widely used in plasma diagnostics have separate voltage and current sensors, crosstalk between the sensors leads to degradation of measurement linearity, which is related to practical accuracy. Here, we propose a VI probe with a floating toroidal coil that plays both roles of a voltage and current sensor and is thus free from crosstalk. The operation principle and optimization conditions of the VI probe are demonstrated and established via three-dimensional electromagnetic wave simulation. Based on the optimization results, the proposed VI probe is fabricated and calibrated for the root-mean-square (RMS) voltage and current with a high-voltage probe and a vector network analyzer. Then, it is evaluated through a comparison with a commercial VI probe, with the results demonstrating that the fabricated VI probe achieved a slightly higher linearity than the commercial probe: R2 of 0.9967 and 0.9938 for RMS voltage and current, respectively. The proposed VI probe is believed to be applicable to plasma diagnostics as well as process monitoring with higher accuracy.

Development of the Measurement of Lateral Electron Density (MOLE) Probe Applicable to Low-Pressure Plasma Diagnostics.

As the importance of measuring electron density has become more significant in the material fabrication industry, various related plasma monitoring tools have been introduced. In this paper, the development of a microwave probe, called the measurement of lateral electron density (MOLE) probe, is reported. The basic properties of the MOLE probe are analyzed via three-dimensional electromagnetic wave simulation, with simulation results showing that the probe estimates electron density by measuring the surface wave resonance frequency from the reflection microwave frequency spectrum (S11). Furthermore, an experimental demonstration on a chamber wall measuring lateral electron density is conducted by comparing the developed probe with the cutoff probe, a precise electron density measurement tool. Based on both simulation and experiment results, the MOLE probe is shown to be a useful instrument to monitor lateral electron density.

Crossing Frequency Method Applicable to Intermediate Pressure Plasma Diagnostics Using the Cutoff Probe.

Although the recently developed cutoff probe is a promising tool to precisely infer plasma electron density by measuring the cutoff frequency (fcutoff) in the S21 spectrum, it is currently only applicable to low-pressure plasma diagnostics below several torr. To improve the cutoff probe, this paper proposes a novel method to measure the crossing frequency (fcross), which is applicable to high-pressure plasma diagnostics where the conventional fcutoff method does not operate. Here, fcross is the frequency where the S21 spectra in vacuum and plasma conditions cross each other. This paper demonstrates the fcross method through three-dimensional electromagnetic wave simulation as well as experiments in a capacitively coupled plasma source. Results demonstrate that the method operates well at high pressure (several tens of torr) as well as low pressure. In addition, through circuit model analysis, a method to estimate electron density from fcross is discussed. It is believed that the proposed method expands the operating range of the cutoff probe and thus contributes to its further development.

Characteristics of Cobalt Thin Films Deposited by Very High Frequency Plasma Enhanced Atomic Layer Deposition (60 and 100 MHz) Using Cobaltocene (Co(Cp)2)/NH3.

In this study, cobalt films were deposited by plasma enhanced atomic layer deposition (PEALD) with cobaltocene (Co(Cp)2) using two different very high frequency (VHF) NH3 plasmas (60 MHz, 100 MHz), and the effect of different frequencies of VHF on the characteristics of NH3 plasmas and the properties of cobalt films were investigated. It is found that the higher frequency showed the higher plasma density at the same input power and, the NH radicals, which are required to remove the ligands of the cobalt precursor during the plasma exposure step in the ALD cycle, were higher at 100 MHz than those at 60 MHz. The RMS surface roughness and carbon impurity percentage of the deposited cobalt films were lower at the higher frequency possibly indicating denser films due to more active surface reactions at the higher frequency. As a result, it is expected that the cobalt thin films deposited by the higher VHF PEALD will improve the characteristics of deposited thin films.

High-Throughput Screening, Discovery, and Optimization To Develop a Benzofuran Class of Hepatitis C Virus Inhibitors.

Using a high-throughput, cell-based HCV luciferase reporter assay to screen a diverse small-molecule compound collection (∼ 300,000 compounds), we identified a benzofuran compound class of HCV inhibitors. The optimization of the benzofuran scaffold led to the identification of several exemplars with potent inhibition (EC50 < 100 nM) of HCV, low cytotoxicity (CC50 > 25 µM), and excellent selectivity (selective index = CC50/EC50, > 371-fold). The structure-activity studies culminated in the design and synthesis of a 45-compound library to comprehensively explore the anti-HCV activity. The identification, design, synthesis, and biological characterization for this benzofuran series is discussed.

Discovery of desketoraloxifene analogues as inhibitors of mammalian, Pseudomonas aeruginosa, and NAPE phospholipase D enzymes.

Phospholipase D (PLD) hydrolyses cellular lipids to produce the important lipid second messenger phosphatidic acid. A PLD enzyme expressed by Pseudomonas aeruginosa (PldA) has been shown to be important in bacterial infection, and NAPE-PLD has emerged as being key in the synthesis of endocannabinoids. In order to better understand the biology and therapeutic potential of these less explored PLD enzymes, small molecule tools are required. Selective estrogen receptor modulators (SERMs) have been previously shown to inhibit mammalian PLD (PLD1 and PLD2). By targeted screening of a library of SERM analogues, additional parallel synthesis, and evaluation in multiple PLD assays, we discovered a novel desketoraloxifene-based scaffold that inhibited not only the two mammalian PLDs but also structurally divergent PldA and NAPE-PLD. This finding represents an important first step toward the development of small molecules possessing universal inhibition of divergent PLD enzymes to advance the field.

Precise control of quantum dot location within the P3HT-b-P2VP/QD nanowires formed by crystallization-driven 1D growth of hybrid dimeric seeds.

Herein, we report a simple fabrication of hybrid nanowires (NWs) composed of a p-type conjugated polymer (CP) and n-type inorganic quantum dots (QDs) by exploiting the crystallization-driven solution assembly of poly(3-hexylthiophene)-b-poly(2-vinylpyridine) (P3HT-b-P2VP) rod-coil amphiphiles. The visualization of the crystallization-driven growth evolution of hybrid NWs through systematic transmission electron microscopy experiments showed that discrete dimeric CdSe QDs bridged by P3HT-b-P2VP polymers were generated during the initial state of crystallization. These, in turn, assemble into elongated fibrils, forming the coaxial P3HT-b-P2VP/QDs hybrid NWs. In particular, the location of the QD arrays within the single strand of P3HT-b-P2VP can be controlled precisely by manipulating the regioregularity (RR) values of P3HT block and the relative lengths of P2VP block. The degree of coaxiality of the QD arrays was shown to depend on the coplanarity of the thiophene rings of P3HT block, which can be controlled by the RR value of P3HT block. In addition, the location of QDs could be regulated at the specific-local site of P3HT-b-P2VP NW according to the surface characteristics of QDs. As an example, the comparison of two different QDs coated with hydrophobic alkyl-terminated and hydroxyl-terminated molecules, respectively, is used to elucidate the effect of the surface properties of QDs on their nanolocation in the NW.

Carrier lifetime extension via the incorporation of robust hole/electron blocking layers in bulk heterojunction polymer solar cells.

We report the achievement of a power conversion efficiency (PCE) improvement in P3HT:PCBM-based bulk-heterojunction type polymer solar cells using photocrosslinked P3HT (c-P3HT) as the electron blocking/hole extraction layer and titanium oxide nanoparticles (TiO2) as the hole blocking/electron extraction layer. Devices prepared with a 20 nm thick c-P3HT layer showed an improved PCE of 3.4% compared to devices prepared without the c-P3HT layer (PCE = 3.0%). This improvement was attributed to an extension in the carrier lifetime and an enhancement in the carrier mobility. The incorporation of the c-P3HT layer lengthened (by more than a factor of 2) the carrier lifetime and increased (by a factor of 5) the hole mobility. These results suggest that the c-P3HT layer not only prevented non-geminate recombination but it also improved carrier transport. The PCE was further improved to 4.0% through the insertion of a TiO2 layer that acted as an effective hole-blocking layer at the interface between the photoactive layer and the cathode. This work demonstrates that the incorporation of solution-processable hole and electron blocking/extraction layers offers an effective means for preventing nongeminate recombination at the interfaces between a photoactive layer and an electrode in bulk-heterojunction-type polymer solar cells.

Polarity and air-stability transitions in field-effect transistors based on fullerenes with different solubilizing groups.

A series of o-xylene and indene fullerene derivatives with varying frontier molecular orbital energy levels were utilized for assessing the impact of the number of solubilizing groups on the electrical performance of fullerene-based organic-field-effect transistors (OFETs). The charge-carrier polarity was found to be strongly dependent upon the energy levels of fullerene derivatives. The o-xylene C60 monoadduct (OXCMA) and indene C60 monoadduct (ICMA) exhibited unipolar n-channel behaviors with high electron mobilities, whereas the bis- and trisadducts of indene and o-xylene C60 derivatives showed ambipolar charge transport. The OXCMA OFETs fabricated by solution shearing and molecular n-type doping showed an electron mobility of up to 2.28 cm(2) V(-1) s(-1), which is one of the highest electron mobilities obtained from solution-processed fullerene thin-film devices. Our findings systematically demonstrate the relationship between the energy level and charge-carrier polarity and provide insight into molecular design and processing strategies toward high-performance fullerene-based OFETs.

Effect of fullerene tris-adducts on the photovoltaic performance of P3HT:fullerene ternary blends.

Fullerene tris-adducts have the potential of achieving high open-circuit voltages (V(OC)) in bulk heterojunction (BHJ) polymer solar cells (PSCs), because their lowest unoccupied molecular orbital (LUMO) level is higher than those of fullerene mono- and bis-adducts. However, no successful examples of the use of fullerene tris-adducts as electron acceptors have been reported. Herein, we developed a ternary-blend approach for the use of fullerene tris-adducts to fully exploit the merit of their high LUMO level. The compound o-xylenyl C60 tris-adduct (OXCTA) was used as a ternary acceptor in the model system of poly(3-hexylthiophene) (P3HT) as the electron donor and the two soluble fullerene acceptors of OXCTA and fullerene monoadduct (o-xylenyl C60 monoadduct (OXCMA), phenyl C61-butyric acid methyl ester (PCBM), or indene-C60 monoadduct (ICMA)). To explore the effect of OXCTA in ternary-blend PSC devices, the photovoltaic behavior of the device was investigated in terms of the weight fraction of OXCTA (W(OXCTA)). When W(OXCTA) is small (<0.3), OXCTA can generate a synergistic bridging effect between P3HT and the fullerene monoadduct, leading to simultaneous enhancement in both V(OC) and short-circuit current (J(SC)). For example, the ternary PSC devices of P3HT:(OXCMA:OXCTA) with W(OXCTA) of 0.1 and 0.3 exhibited power-conversion efficiencies (PCEs) of 3.91% and 3.96%, respectively, which were significantly higher than the 3.61% provided by the P3HT:OXCMA device. Interestingly, for W(OXCTA) > 0.7, both V(OC) and PCE of the ternary-blend PSCs exhibited nonlinear compositional dependence on W(OXCTA). We noted that the nonlinear compositional trend of P3HT:(OXCMA:OXCTA) was significantly different from that of P3HT:(OXCMA:o-xylenyl C60 bis-adduct (OXCBA)) ternary-blend PSC devices. The fundamental reasons for the differences between the photovoltaic trends of the two different ternary-blend systems were investigated systemically by comparing their optical, electrical, and morphological properties.

Photoinduced charge transfer in donor-acceptor (DA) copolymer: fullerene bis-adduct polymer solar cells.

Polymer solar cells (PSCs) consisting of fullerene bis-adduct and poly(3-hexylthiophene) (P3HT) blends have shown higher efficiencies than P3HT:phenyl C(61)-butyric acid methyl ester (PCBM) devices, because of the high-lying lowest unoccupied molecular orbital (LUMO) level of the fullerene bis-adducts. In contrast, the use of fullerene bis-adducts in donor-acceptor (DA) copolymer systems typically causes a decrease in the device's performance due to the decreased short-circuit current (J(SC)) and the fill factor (FF). However, the reason for such poor performance in DA copolymer:fullerene bis-adduct blends is not fully understood. In this work, bulk-heterojunction (BHJ)-type PSCs composed of three different electron donors with four different electron acceptors were chosen and compared. The three electron donors were (1) poly[(4,8-bis-(2-ethylhexyloxy)benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl-alt-(5-octylthieno[3,4-c]pyrrole-4,6-dione)-1,3-diyl] (PBDTTPD), (2) poly[(4,8-bis-(2-ethylhexyloxy)benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl-alt-(4-(2-ethylhexanoyl)-thieno[3,4-b]thiophene)-2,6-diyl] (PBDTTT-C), and (3) P3HT polymers. The four electron acceptors were (1) PCBM, (2) indene-C(60) monoadduct (ICMA), (3) indene-C(60) bis-adduct (ICBA), and (4) indene-C(60) tris-adduct (ICTA). To understand the difference in the performance of BHJ-type PSCs for the three different polymers in terms of the choice of fullerene acceptor, the structural, optical, and electrical properties of the blends were measured by the external quantum efficiency (EQE), photoluminescence, grazing incidence X-ray scattering, and transient absorption spectroscopy. We observed that while the molecular packing and optical properties cannot be the main reasons for the dramatic decrease in the PCE of the DA copolymers and ICBA, the value of the driving force for charge transfer (ΔG(CT)) is a key parameter for determining the change in J(SC) and device efficiency in the DA copolymer- and P3HT-based PSCs in terms of fullerene acceptor. The low EQE and J(SC) in PBDTTPD and PBDTTT-C blended with ICBA and ICTA were attributed to an insufficient ΔG(CT) due to the higher LUMO levels of the fullerene multiadducts. Quantitative information on the efficiency of the charge transfer was obtained by comparing the polaron yield, lifetime, and exciton dissociation probability in the DA copolymer:fullerene acceptor films.

Solution-phase synthesis of a highly substituted furan library.

A library of furans has been synthesized by iodocyclization and further diversified by palladium-catalyzed coupling processes. The key intermediate 3-iodofurans have been prepared by the electrophilic iodocyclization of 2-iodo-2-alken-1-ones in the presence of various nucleophiles in good to excellent yields under mild reaction conditions. These 3-iodofurans are the key components for library generation through subsequent elaboration by palladium-catalyzed processes, such as Suzuki-Miyaura, Sonagashira, Heck, aminocarbonylation, and carboalkoxylation chemistry to afford a diverse set of 2,3,4,5-tetrasubstituted furans.

Controlling number of indene solubilizing groups in multiadduct fullerenes for tuning optoelectronic properties and open-circuit voltage in organic solar cells.

The ability to tune the lowest unoccupied molecular orbital (LUMO)/highest occupied molecular orbital (HOMO) levels of fullerene derivatives used as electron acceptors is crucial in controlling the optical/electrochemical properties of these materials and the open circuit voltage (V(oc)) of solar cells. Here, we report a series of indene fullerene multiadducts (ICMA, ICBA, and ICTA) in which different numbers of indene solubilizing groups are attached to the fullerene molecule. The addition of indene units to fullerene raised its LUMO and HOMO levels, resulting in higher V(oc) values in the photovoltaic device. Bulk-heterojunction (BHJ) solar cells fabricated from poly(3-hexylthiophene) (P3HT) and a series of fullerene multiadducts-ICMA, ICBA, and ICTA showed V(oc) values of 0.65, 0.83, and 0.92 V, respectively. Despite demonstrating the highest V(oc) value, the P3HT:ICTA device exhibited lower efficiency (1.56%) than the P3HT:ICBA device (5.26%) because of its lower fill factor and current. This result could be explained by the lower light absorption and electron mobility of the P3HT:ICTA device, suggesting that there is an optimal number of the solubilizing group that can be added to the fullerene molecule. The effects of the addition of solubilizing groups on the optoelectrical properties of fullerene derivatives were carefully investigated to elucidate the molecular structure-device function relationship.

Creating opal-templated continuous conducting polymer films with ultralow percolation thresholds using thermally stable nanoparticles.

We propose a novel and robust strategy for creating continuous conducting polymer films with ultralow percolation thresholds using polymer-coated gold nanoparticles (Au NPs) as surfactant. Continuous poly(triphenylamine) (PTPA) films of high internal phase polymeric emulsions were fabricated using an assembly of cross-linked polystyrene (PS) colloidal particles as template. Polymer-coated Au NPs were designed to be thermally stable even above 200 °C and neutral to both the PS and PTPA phases. Therefore, the Au NPs localize at the PS/PTPA interface and function as surfactant to efficiently produce a continuous conducting PTPA polymer film with very low percolation thresholds. The volume fraction threshold for percolation of the PTPA phase with insulating PS colloids (as measured by electron microscopy and conductivity measurements) was found to be 0.20. In contrast, with the addition of an extremely low volume fraction (φ(p) = 0.35 vol %) of surfactant Au NPs, the volume fraction threshold for percolation of the PTPA phase was dramatically reduced to 0.05. The SEM and TEM measurements clearly demonstrated the formation of a continuous PTPA phase within the polyhedral phase of PS colloids. To elucidate the influence of the nanoparticle surfactant on the blend films, the morphology and conductivity of the blends at different PS colloid/PTPA volume ratios were carefully characterized as a function of the Au NP concentration. Our approach provides a methodology for a variety of applications that require a continuous phase for the transport of molecular species, ions, or electrons at low concentrations and a second phase for mechanical support or the conduction of a separate species.

Fluorescent and pH-responsive diblock copolymer-coated core-shell CdSe/ZnS particles for a color-displaying, ratiometric pH sensor.

A color distinctive, ratiometric pH sensor was demonstrated using pH responsive and fluorescent (PyMMP-b-P2VP) diblock copolymer coated CdSe/ZnS QDs. Due to the change in the P2VP conformations in response to pH change, the color of QDs in solution changes distinctly from blue to red.

Parallel synthesis of a desketoraloxifene analogue library via iodocyclization/palladium-catalyzed coupling.

For a future structure-activity relationship (SAR) study, a library of desketoraloxifene analogues has been prepared by parallel synthesis using iodocyclization and subsequent palladium-catalyzed coupling reactions. Points of desketoraloxifene diversification involve the two phenolic hydroxyl groups and the aliphatic amine side chain. This approach affords oxygen-bearing 3-iodobenzo[b]thiophenes 4 in excellent yields, which are easily further elaborated using a two-step approach involving Suzuki-Miyaura and Mitsunobu coupling reactions to give multimethoxy-substituted desketoraloxifene analogues 6. Various hydroxyl-substituted desketoraloxifene analogues 7 were subsequently generated by demethylation with BBr(3).