Polycarbonate based non-chemically amplified photoresists for extreme ultraviolet lithography

Some initial EUVL patterning results for polycarbonate based non-chemically amplified resists are presented. Without full optimization the developer a resolution of 60 nm line spaces could be obtained. With slight overexposure (1.4 × E0) 43.5 nm lines at a half pitch of 50 nm could be printed. At 2x E0 a 28.6 nm lines at a half pitch of 50 nm could be obtained with a LER that was just above expected for mask roughness. Upon being irradiated with EUV photons, these polymers undergo chain scission with the loss of carbon dioxide and carbon monoxide. The remaining photoproducts appear to be non-volatile under standard EUV irradiation conditions, but do exhibit increased solubility in developer compared to the unirradiated polymer. The sensitivity of the polymers to EUV light is related to their oxygen content and ways to increase the sensitivity of the polymers to 10 mJ cm-2 is discussed.

Optical coupling of Au nanoparticles on vertical graphenes to maximize SERS response

Gold particle interaction with few-layer graphenes is of interest for the development of numerous optical nanodevices. The results of numerical studies of the coupling of gold nanoparticles with few-layer vertical graphene sheets are presented. The field strengths are computed and the optimum nanoparticle configurations for the formation of SERS hotpots are obtained. The nanoparticles are modeled as 8 nm diameter spheres atop 1.5 nm (5 layers) graphene sheet. The vertical orientation is of particular interest as it is possible to use both sides of the graphene structure and potentially double the number of particles in the system. Our results show that with the addition of an opposing particle a much stronger signal can be obtained as well as the particle separation can be controlled by the number of atomic carbon layers. These results provide further insights and contribute to the development of next-generation plasmonic devices based on nanostructures with hybrid dimensionality.

The collision induced loss of carbon monoxide from deprotonated benzyl benzoate in the gas phase. An anionic 1,2-Wittig type rearrangement

The ion PhCO2--CHPh, upon collision activation, undergoes competitive losses of CO and CO2 of which the former process produces the base peak of the spectrum. Product ion and substituent effect (Hammett) studies indicate that PhCO2--CHPh cyclises to a deprotonated hydroxydiphenyloxirane which ring opens to PhCOCH(O-)Ph. This anion then undergoes an anionic 1,2-Wittig type rearrangement {through [PhCO- (PhCHO)]} to form Ph2CHO- and CO. The mechanism of the 1,2-rearrangement has been probed by an ab initio study [at MP4(SDTQ)/6-31++G(d,p) level] of the model system HCOCH2O- →; MeO- + CO The analogous system RCO2--CHPh (R = alkyl) similarly loses CO, and the migratory aptitudes of the alkyl R groups in this reaction are Bu′ > Me > Et ∼Pri). This trend correlates with the order of anion basicities (i.e. the order of ΔG○acid values of RH), supporting the operation of an anion migration process. The loss of CO2 from PhCO2--CHPh yields Ph2CH- as the anionic product: several mechanistic scenarios are possible, one of which involves an initial ipso nucleophilic substitution.

The loss of CO from the ortho, meta and para forms of deprotonated methyl benzoate in the gas phase

The ortho, meta and para anions of methyl benzoate may be made in the source of a mass spectrometer by the S(N)2(Si) reactions between HO- and methyl (o-, m-, and p-trimethylsilyl)benzoate respectively. All three anions lose CO upon collisional activation to form the ortho anion of anisole in the ratio ortho>>meta > para. The rearrangement process is charge directed through the ortho anion. Theoretical calculations at the B3LYP/6-311++G(d,p)//HF/6-31+G(d) level of theory indicate that the conversion of the meta and para anions to the ortho anion prior to loss of CO involve 1,2-H transfer(s), rather than carbon scrambling of the methoxycarbonylphenyl anion. There are two mechanisms which can account for this rearrangement, viz. (A) cyclisation of the ortho anion centre to the carbonyl group of the ester to give a cyclic carbonyl system in which the incipient methoxide anion substitutes at one of the two equivalent ring carbons of the three membered ring to yield an intermediate which loses CO to give the ortho anion of anisole, and (B) an elimination reaction to give an intermediate benzyne-methoxycarbonyl anion complex in which the MeOCO- species acts as a MeO- donor, which then adds to benzyne to yield the ortho anion of anisole. Calculations at the B3LYP/6-311++G(d,p)//HF/6-31+G(d) level of theory indicate that (i) the barrier in the first step (the rate determining step) of process A is 87 kJ mol(-1) less than that for the synchronous benzyne process B, and (ii) there are more low frequency vibrations in the transition state for benzyne process B than for the corresponding transition state for process A. Stepwise process A has the lower barrier for the rate determining step, and the lower Arrhenius factor: we cannot differentiate between these two mechanisms on available evidence.

Loss of epithelial markers and acquisition of vimentin expression in adriamycin- and vinblastine-resistant human breast cancer cell lines

We have previously observed that breast cancer cell lines could exhibit either epithelial or fibroblastic phenotypes as reflected by their morphologies and intermediate filament protein expression (C. L. Sommers, D. Walker-Jones, S. E. Heckford, P. Worland, E. Valverius, R. Clark, M. Stampfer, and E. P. Gelmann, Cancer Res., 49: 4258-4263, 1989). Fibroblastoid, vimentin-expressing breast cancer cell lines are more invasive in vitro and in vivo (E. W. Thompson, S. Paik, N. Brunner, C. L. Sommers, G. Zugmaier, R. Clarke, T. B. Shima, J. Torri, S. Donahue, M. E. Lippman, G. R. Martin, and R. B. Dickson, J. Cell. Physiol., 150: 534-544, 1992). We hypothesized that a breast cancer cell with an epithelial phenotype could undergo a transition to a fibroblastic phenotype, possibly resulting in more invasive capacity. We now show that two Adriamycin-resistant MCF-7 cell lines and a vinblastine-resistant ZR-75-B cell line have undergone such a transition. Adriamycin-resistant MCF-7 cells express vimentin, have diminished keratin 19 expression, have lost cell adhesion molecule uvomorulin expression, and have reduced formation of desmosomes and tight junctions as determined by reduced immunodetection of their components desmoplakins I and II and zonula occludens (ZO)-1. Other MCF-7 cell lines selected for resistance to vinblastine and to Adriamycin and verapamil did not have these characteristics, indicating that drug selection does not invariably cause these phenotypic changes. In addition, to determine if vimentin expression in MCF-7 cells alone could manifest a fibroblastic phenotype, we transfected the full-length human vimentin complementary DNA into MCF-7 cells. Although vimentin expression was achieved in MCF-7 cells, it did not affect the phenotype of the cells in terms of the distribution of keratins, desmoplakins I and II, ZO-1, or uvomorulin or in terms of in vitro invasiveness. We conclude that vimentin expression is a marker for a fibroblastic and invasive phenotype in breast cancer cells but does not by itself give rise to this phenotype.

The loss of carbon dioxide from activated perbenzoate anions in the gas phase : Unimolecular rearrangement via epoxidation of the benzene ring

The unimolecular reactivities of a range of perbenzoate anions (X-C6H5CO3-), including the perbenzoate anion itself (X=H), nitroperbenzoates (X=para-, meta-, ortho-NO2), and methoxyperbenzoates (X=para-, meta-OCH3) were investigated in the gas phase by electrospray ionization tandem mass spectrometry. The collision-induced dissociation mass spectra of these compounds reveal product ions consistent with a major loss of carbon dioxide requiring unimolecular rearrangement of the perbenzoate anion prior to fragmentation. Isotopic labeling of the perbenzoate anion supports rearrangement via an initial nucleophilic aromatic substitution at the ortho carbon of the benzene ring, while data from substituted perbenzoates indicate that nucleophilic attack at the ipso carbon can be induced in the presence of electron-withdrawing moieties at the ortho and para positions. Electronic structure calculations carried out at the B3LYP/6311++G(d,p) level of theory reveal two competing reaction pathways for decarboxylation of perbenzoate anions via initial nucleophilic substitution at the ortho and ipso positions, respectively. Somewhat surprisingly, however, the computational data indicate that the reaction proceeds in both instances via epoxidation of the benzene ring with decarboxylation resulting-at least initially-in the formation of oxepin or benzene oxide anions rather than the energetically favored phenoxide anion. As such, this novel rearrangement of perbenzoate anions provides an intriguing new pathway for epoxidation of the usually inert benzene ring.

Encouragement of physical activity for weight loss may lead to negative psychological outcomes among girls

PURPOSE To examine correlates and consequences of parents' encouragement of girls' physical activity (PA) for weight loss (ENCLOSS). METHODS Data were collected for 181 girls, mothers and fathers when girls were 9, 11, and 13 years old. Mothers and fathers completed a self-report questionnaire of ENCLOSS (e.g., “I have talked to my daughter about how to exercise to lose weight”). Correlates of ENCLOSS that were assessed include girls' Body Mass Index (BMI) z-score and parents' modeling of and logistic support for PA. Dependent variables assessed at age 13 include girls' self-reported and objectively-measured PA, enjoyment of physical activity, and weight concerns. Associations between ENCLOSS, girls' BMI, and parent's support for PA were assessed using spearman rank correlations. To examine links between ENCLOSS and the outcome variables, scores for ENCLOSS were divided into tertiles at each age. Three groups were created including girls who were in the highest tertile at each age (high ENCLOSS), girls who were in the lowest tertile at each age (low ENCLOSS), and girls who varied in their tertile ranking (mid ENCLOSS). Group differences in the outcome variables were assessed using regression analysis (referent group: low ENCLOSS), controlling for girls' BMI and the outcome variable at age 9. RESULTS Girls' with higher BMI had mothers and fathers who reported higher ENCLOSS (r = .61-. 69, p<. 0001). Parents'reports of ENCLOSS were not associated with modeling of or logistic support for PA. Girls in the high ENCLOSS group reported significantly lower enjoyment of PA and higher weight concerns at age 13, independent of covariates. No differences in PA were noted. CONCLUSION Parents who encourage their daughters to be active for weight loss do not model PA or facilitate girls' PA. Persistent encouragement of PA for weight loss may lead to low enjoyment of PA and higher weight concerns among adolescent girls.

Reactive stepping behaviour in response to forward loss of balance predicts future falls in community-dwelling older adults

Background: a fall occurs when an individual experiences a loss of balance from which they are unable to recover. Assessment of balance recovery ability in older adults may therefore help to identify individuals at risk of falls. The purpose of this 12-month prospective study was to assess whether the ability to recover from a forward loss of balance with a single step across a range of lean magnitudes was predictive of falls. Methods: two hundred and one community-dwelling older adults, aged 65–90 years, underwent baseline testing of sensorimotor function and balance recovery ability followed by 12-month prospective falls evaluation. Balance recovery ability was defined by whether participants required either single or multiple steps to recover from forward loss of balance from three lean magnitudes, as well as the maximum lean magnitude participants could recover from with a single step. Results: forty-four (22%) participants experienced one or more falls during the follow-up period. Maximal recoverable lean magnitude and use of multiple steps to recover at the 15% body weight (BW) and 25%BW lean magnitudes significantly predicted a future fall (odds ratios 1.08–1.26). The Physiological Profile Assessment, an established tool that assesses variety of sensori-motor aspects of falls risk, was also predictive of falls (Odds ratios 1.22 and 1.27, respectively), whereas age, sex, postural sway and timed up and go were not predictive. Conclusion: reactive stepping behaviour in response to forward loss of balance and physiological profile assessment are independent predictors of a future fall in community-dwelling older adults. Exercise interventions designed to improve reactive stepping behaviour may protect against future falls.

Inhibition of the JAK2/STAT3 pathway in ovarian cancer results in the loss of cancer stem cell-like characteristics and a reduced tumor burden

Background Current treatment of ovarian cancer patients with chemotherapy leaves behind a residual tumor which results in recurrent ovarian cancer within a short time frame. We have previously demonstrated that a single short-term treatment of ovarian cancer cells with chemotherapy in vitro resulted in a cancer stem cell (CSC)-like enriched residual population which generated significantly greater tumor burden compared to the tumor burden generated by control untreated cells. In this report we looked at the mechanisms of the enrichment of CSC-like residual cells in response to paclitaxel treatment. Methods The mechanism of survival of paclitaxel-treated residual cells at a growth inhibitory concentration of 50% (GI50) was determined on isolated tumor cells from the ascites of recurrent ovarian cancer patients and HEY ovarian cancer cell line by in vitro assays and in a mouse xenograft model. Results Treatment of isolated tumor cells from the ascites of ovarian cancer patients and HEY ovarian cancer cell line with paclitaxel resulted in a CSC-like residual population which coincided with the activation of Janus activated kinase 2 (JAK2) and signal transducer and activation of transcription 3 (STAT3) pathway in paclitaxel surviving cells. Both paclitaxel-induced JAK2/STAT3 activation and CSC-like characteristics were inhibited by a low dose JAK2-specific small molecule inhibitor CYT387 (1 μM) in vitro. Subsequent, in vivo transplantation of paclitaxel and CYT387-treated HEY cells in mice resulted in a significantly reduced tumor burden compared to that seen with paclitaxel only-treated transplanted cells. In vitro analysis of tumor xenografts at protein and mRNA levels demonstrated a loss of CSC-like markers and CA125 expression in paclitaxel and CYT387-treated cell-derived xenografts, compared to paclitaxel only-treated cell-derived xenografts. These results were consistent with significantly reduced activation of JAK2 and STAT3 in paclitaxel and CYT387-treated cell-derived xenografts compared to paclitaxel only-treated cell derived xenografts. Conclusions This proof of principle study demonstrates that inhibition of the JAK2/STAT3 pathway by the addition of CYT387 suppresses the ‘stemness’ profile in chemotherapy-treated residual cells in vitro, which is replicated in vivo, leading to a reduced tumor burden. These findings have important implications for ovarian cancer patients who are treated with taxane and/or platinum-based therapies. Keywords: Ovarian carcinoma, Cancer stem cell, Metastasis, Ascites, Chemoresistance, Recurrence, JAK2/STAT3 pathway

Deterministic control of structural and optical properties of plasma-grown vertical graphene nanosheet networks via nitrogen gas variation

The effect of nitrogen on the growth of vertically oriented graphene nanosheets on catalyst-free silicon and glass substrates in a plasma-assisted process is studied. Different concentrations of nitrogen were found to act as versatile control knobs that could be used to tailor the length, number density and structural properties of the nanosheets. Nanosheets with different structural characteristics exhibit markedly different optical properties. The nanosheet samples were treated with a bovine serum albumin protein solution to investigate the effects of this variation on the optical properties for biosensing through confocal micro-Raman spectroscopy and UV-Vis spectrophotometry. © 2012 Optical Society of America.

Partial rectification of the plasmon-induced electrical tunnel current in discontinuous thin gold film at optical frequency

The effect of plasmonoscillations, induced by pulsed laserirradiation, on the DC tunnel current between islands in a discontinuous thin goldfilm is studied. The tunnel current is found to be strongly enhanced by partial rectification of the plasmon-induced AC tunnel currents flowing between adjacent gold islands. The DC tunnel current enhancement is found to increase approximately linearly with the laser intensity and the applied DC bias voltage. The experimental data can be well described by an electron tunnelling model which takes the plasmon-induced AC voltage into account. Thermal heating seems not to contribute to the tunnel current enhancement.

Plasma-aided hydrogenation and Al-doping : increasing the conductivity and optical transparency of ZnO transparent conducting oxide

Plasma-assisted magnetron sputtering with varying ambient conditions has been utilised to deposit Al-doped ZnO (AZO) transparent conductive thin films directly onto a glass substrate at a low substrate temperature of 400 °C. The effects of hydrogen addition on electrical, optical and structural properties of the deposited AZO films have been investigated using X-ray diffractometry (XRD), scanning electron microscopy (SEM), Hall effect measurements and UV–vis optical transmission spectroscopy. The results indicate that hydrogen addition has a remarkable effect on the film transparency and conductivity with the greatest effects observed with a hydrogen flux of approximately 3 sccm. It has been demonstrated that the conductivity and the average transmittance in the visible range can increase simultaneously contrary to the effects observed by other authors. In addition, hydrogen incorporation further leads to the absorption edge shifting to a shorter wavelength due to the Burstein–Moss effect. These results are of particular relevance to the development of the next generation of optoelectronic and photovoltaic devices based on highly transparent conducting oxides with controllable electronic and optical properties.

Structural, optical and electrical properties of Al-doped ZnO transparent conducting oxide for solar cell applications

Al-doped zinc oxide (AZO) thin films are deposited onto glass substrates using radio-frequency reactive magnetron sputtering and the improvements in their physical properties by post-synthesis thermal treatment are reported. X-ray diffraction spectra show that the structure of films can be controlled by adjusting the annealing temperatures, with the best crystallinity obtained at 400°C under a nitrogen atmosphere. These films exhibit improved quality and better optical transmittance as indicated by the UV-Vis spectra. Furthermore, the sheet resistivity is found to decrease from 1.87 × 10-3 to 5.63 × 10-4Ω⋅cm and the carrier mobility increases from 6.47 to 13.43 cm2 ⋅ V-1 ⋅ s-1 at the optimal annealing temperature. Our results demonstrate a simple yet effective way in controlling the structural, optical and electrical properties of AZO thin films, which is important for solar cell applications.

Structural, electronic, and optical properties of wurtzite and rocksalt InN under pressure

Structural stability, electronic, and optical properties of InN under high pressure are studied using the first-principles calculations. The lattice constants and electronic band structure are found consistent with the available experimental and theoretical values. The pressure of the wurtzite-to-rocksalt structural transition is 13.4 GPa, which is in an excellent agreement with the most recent experimental values. The optical characteristics reproduce the experimental data thus justifying the feasibility of our theoretical predictions of the optical properties of InN at high pressures.

Diagnostics and two-dimensional simulation of low-frequency inductively coupled plasmas with neutral gas heating and electron heat fluxes

This article presents the results on the diagnostics and numerical modeling of low-frequency (∼460 KHz) inductively coupled plasmas generated in a cylindrical metal chamber by an external flat spiral coil. Experimental data on the electron number densities and temperatures, electron energy distribution functions, and optical emission intensities of the abundant plasma species in low/intermediate pressure argon discharges are included. The spatial profiles of the plasma density, electron temperature, and excited argon species are computed, for different rf powers and working gas pressures, using the two-dimensional fluid approach. The model allows one to achieve a reasonable agreement between the computed and experimental data. The effect of the neutral gas temperature on the plasma parameters is also investigated. It is shown that neutral gas heating (at rf powers≥0.55kW) is one of the key factors that control the electron number density and temperature. The dependence of the average rf power loss, per electron-ion pair created, on the working gas pressure shows that the electron heat flux to the walls appears to be a critical factor in the total power loss in the discharge.