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Don't always blame the photons: Relationships between deprotection blur, LER, and shot noise in EUV photoresists

Description: A corner rounding metric has been used to determine the deprotection blur of Rohm and Haas XP 5435, XP 5271, and XP 5496 extreme ultraviolet (EUV) photoresists as base weight percent is varied; an experimental open platform photoresist (EH27) as base weight percent is varied; and TOK EUVR P1123 and FUJI 1195 photoresists as post-exposure bake (PEB) temperature is varied. In the XP 5435, XP 5271, XP 5496, and EH27 resist platforms, a 6 times increase in base weight percent reduces the size of successfully patterned 1:1 lines by over 10 nm and lowers intrinsic line-edge roughness (LER) by over 2.5 nm without changing deprotection blur. In TOK EUVR P1123 photoresist, lowering the PEB temperature from 100 C to 80 C reduces measured deprotection blur (using the corner metric) from 30 nm to 20 nm and reduces the LER of 50 nm 1:1 lines from 4.8 nm to 4.3 nm. These data are used to drive a lengthy discussion about the relationships between deprotection blur, LER, and shot noise in EUV photoresists. We provide two separate conclusions: (1) shot noise is probably not the dominant mechanism causing the 3-4 nm EUV LER floor that has been observed over the past several years; (2) chemical contrast contributes to LER whenever deprotection blur is large relative to the printed half pitch.
Date: June 2, 2008
Creator: Anderson, Christopher N. & Naulleau, Patrick P.
Partner: UNT Libraries Government Documents Department

Water adsorption on alpha-Fe2O3(0001) at near ambient conditions

Description: We have investigated hydroxylation and water adsorption on {alpha}-Fe{sub 2}O{sub 3}(0001) at water vapor pressures up to 2 Torr and temperatures ranging from 277 to 647 K (relative humidity (RH) {<=} 34%) using ambient-pressure x-ray photoelectron spectroscopy (XPS). Hydroxylation occurs at the very low RH of 1 x 10{sup -7}% and precedes the adsorption of molecular water. With increasing RH, the OH coverage increases up to one monolayer (ML) without any distinct threshold pressure. Depth profiling measurements showed that hydroxylation occurs only at the topmost surface under our experimental conditions. The onset of molecular water adsorption varies from {approx}2 x 10{sup -5} to {approx}4 x 10{sup -2}% RH depending on sample temperature and water vapor pressure. The coverage of water reaches I ML at {approx} 15% RH and increases to 1.5 ML at 34% RH.
Date: November 23, 2009
Creator: Yamamoto, Susumu; Kendelewicz, Tom; Newberg, John T.; Ketteler, Guido; Starr, David E.; Mysak, Erin R. et al.
Partner: UNT Libraries Government Documents Department

Major Successes of Theory-and-Experiment-Combined Studies in Surface Chemistry and Heterogeneous Catalysis.

Description: Experimental discoveries followed by theoretical interpretations that pave the way of further advances by experimentalists is a developing pattern in modern surface chemistry and catalysis. The revolution of modern surface science started with the development of surface-sensitive techniques such as LEED, XPS, AES, ISS and SIMS, in which the close collaboration between experimentalists and theorists led to the quantitative determination of surface structure and composition. The experimental discovery of the chemical activity of surface defects and the trends in the reactivity of transitional metals followed by the explanations from the theoretical studies led to the molecular level understanding of active sites in catalysis. The molecular level knowledge, in turn, provided a guide for experiments to search for new generation of catalysts. These and many other examples of successes in experiment-and-theory-combined studies demonstrate the importance of the collaboration between experimentalists and theorists in the development of modern surface science.
Date: November 21, 2009
Creator: Somorjai, Gabor A. & Li, Yimin
Partner: UNT Libraries Government Documents Department

In Situ Spectroscopic Observation of Activation and Transformation of Tantalum Suboxides

Description: Using ambient pressure X-ray Photoelectron Spectroscopy (AP-XPS), we were able to observe the process of oxidation of tantalum with different morphological parameters. Being able to trace surface evolution during oxidation, we evaluated activation energy of oxidation under the influence of strain and grain boundaries. It was found that the metal oxidized through three different stages and there was a transition stage where the phase transformation from suboxides to the equilibrium state of pentoxide. The applied stress and surface defects reduced the activation energy oxidation.
Date: December 16, 2009
Creator: Wang, Ke; Liu, Zhi; Cruz, Tirma Herranz; Salmeron, Miquel & Liang, Hong
Partner: UNT Libraries Government Documents Department

Identity of Passive Film Formed on Aluminum in Li-ion BatteryElectrolytes with LiPF6

Description: The passive film that forms on aluminum in 1:1 ethylene carbonate + ethylmethyl carbonate with 1.2M LiPF{sub 6} and 1:1 ethylene carbonate + dimethyl carbonate with 1.0M LiPF{sub 6} was investigated by a combination of electrochemical quartz crystal microbalance measurements (EQCM), electrochemical impedance spectroscopy (EIS), and x-ray photoelectron spectroscopy. During anodic polarization of aluminum a film of AlF{sub 3} forms on top of the air-formed oxide, creating a duplex, or two-layered film. The thickness of the AlF{sub 3} increases with the applied potential. Independent measurements of film thickness by EQCM and EIS indicate that at a potential of 5.5V vs. Li/Li{sup +}, the thickness of the AlF{sub 3} is approximately 1 nm.
Date: September 1, 2006
Creator: Zhang, Xueyuan & Devine, T.M.
Partner: UNT Libraries Government Documents Department

Examination of the local structure in composite and lowdimensional semiconductor by X-ray Absorption Spectroscopy

Description: X-ray absorption methods have been successfully used to obtain quantitative information about local atomic composition of two different materials. X-ray Absorption Near Edge Structure analysis and X-Ray Photoelectron Spectroscopy allowed us to determine seven chemical compounds and their concentrations in c-BN composite. Use of Extended X-ray Absorption Fine Structure in combination with Transmission Electron Microscopy enabled us to determine the composition and size of buried Ge quantum dots. It was found that the quantum dots consisted out of pure Ge core covered by 1-2 monolayers of a layer rich in Si.
Date: September 25, 2006
Creator: Lawniczak-Jablonska, K.; Demchenko, I.N.; Piskorska, E.; Wolska,A.; Talik, E.; Zakharov, D.N. et al.
Partner: UNT Libraries Government Documents Department

The surface chemistry of Cu in the presence of CO2 and H2O

Description: The chemical nature of copper and copper oxide (Cu{sub 2}O) surfaces in the presence of CO{sub 2} and H{sub 2}O at room temperature was investigated using ambient pressure x-ray photoelectron spectroscopy. The studies reveal that in the presence of 0.1 torr CO{sub 2} several species form on the initially clean Cu, including carbonate CO{sub 3}{sup 2}, CO{sub 2}{sup {delta}-} and C{sup 0}, while no modifications occur on an oxidized surface. The addition of 0.1 ML Zn to the Cu results in the complete conversion of CO{sub 2}{sup {delta}-} to carbonate. In a mixture of 0.1 torr H{sub 2}O and 0.1 torr CO{sub 2}, new species are formed, including hydroxyl, formate and methoxy, with H{sub 2}O providing the hydrogen needed for the formation of hydrogenated species.
Date: July 16, 2008
Creator: Deng, Xingyi; Verdaguer, Albert; Herranz, Tirma; Weis, Christoph; Bluhm, Hendrik & Salmeron, Miquel
Partner: UNT Libraries Government Documents Department

Ion Partitioning at the liquid/vapor interface of a multi-component alkali halidesolution: A model for aqueous sea salt aerosols

Description: The chemistry of Br species associated with sea salt ice and aerosols has been implicated in the episodes of ozone depletion reported at Arctic sunrise. However, Br{sup -} is only a minor component in sea salt, which has a Br{sup -}/Cl{sup -} molar ratio of {approx}0.0015. Sea salt is a complex mixture of many different species, with NaCl as the primary component. In recent years experimental and theoretical studies have reported enhancement of the large, more polarizable halide ion at the liquid/vapor interface of corresponding aqueous alkali halide solutions. The proposed enhancement is likely to influence the availability of sea salt Br{sup -} for heterogeneous reactions such as those involved in the ozone depletion episodes. We report here ambient pressure x-ray photoelectron spectroscopy studies and molecular dynamics simulations showing direct evidence of Br{sup -} enhancement at the interface of an aqueous NaCl solution doped with bromide. The experiments were carried out on samples with Br{sup -}/Cl{sup -} ratios in the range 0.1% to 10%, the latter being also the ratio for which simulations were carried out. This is the first direct measurement of interfacial enhancement of Br{sup -} in a multi-component solution with particular relevance to sea salt chemistry.
Date: December 22, 2008
Creator: Ghosal, Sutapa; Brown, Matthew A.; Bluhm, Hendrik; Krisch, Maria J.; Salmeron, Miquel; Jungwirth, Pavel et al.
Partner: UNT Libraries Government Documents Department

In situ x-ray photoelectron spectroscopy studies of gas/solidinterfaces at near-ambient conditions

Description: X-ray photoelectron spectroscopy (XPS) is a quantitative, chemically specific technique with a probing depth of a few angstroms to a few nanometers. It is therefore ideally suited to investigate the chemical nature of the surfaces of catalysts. Because of the scattering of electrons by gas molecules, XPS is generally performed under vacuum conditions. However, for thermodynamic and/or kinetic reasons, the catalyst's chemical state observed under vacuum reaction conditions is not necessarily the same as that of a catalyst under realistic operating pressures. Therefore, investigations of catalysts should ideally be performed under reaction conditions, i.e., in the presence of a gas or gas mixtures. Using differentially pumped chambers separated by small apertures, XPS can operate at pressures of up to 1 Torr, and with a recently developed differentially pumped lens system, the pressure limit has been raised to about 10 Torr. Here, we describe the technical aspects of high-pressure XPS and discuss recent applications of this technique to oxidation and heterogeneous catalytic reactions on metal surfaces.
Date: December 3, 2007
Creator: Bluhm, Hendrik; Havecker, Michael; Knop-Gericke, Axel; Kiskinova,Maya; Schlogl, Robert & Salmeron, Miquel
Partner: UNT Libraries Government Documents Department

The nature of the water nucleation sites on TiO2(110) surfacesrelvealed by ambient pressure x-ray photoelectron spectroscopy

Description: X-ray photoelectron spectroscopy at ambient conditions of pressure (up to 1.5 Torr) and temperature (265K<T<800K) was used to study the adsorption of water on rutile TiO{sub 2}(110) under conditions of thermodynamic equilibrium. It was found that OH groups in bridging positions, normally present in small amounts due to residual O-vacancies, act as nucleation sites for subsequent water adsorption. The adsorption enthalpy of water binding to these sites is {approx}70 kJ/mol, much stronger than that in the bulk liquid (45 kJ/mol). A model is proposed that relates the structure of the oxide surface to its hydrophilic character.
Date: May 1, 2007
Creator: Ketteler, Guido; Yamamoto, Susumu; Bluhm, Hendrik; Andersson,Klas; Starr, David E.; Ogletree, D. Frank et al.
Partner: UNT Libraries Government Documents Department

Evaluation of the residue from microset on various metal surfaces.

Description: Fast-curing impression materials are sometimes used to cast negative-mold replications of physical defects on material surfaces. The negative-mold impressions can then be used for further measurements to record the nature of the defect. These impression materials have been designed to cure quickly, and with very low adhesion, so that they can be easily removed from the surface leaving little residual contamination. Unfortunately, some contaminant is retained by the substrate material. This investigation seeks to identify the composition and quantity of the remaining material upon removal of Microset Synthetic Rubber Replicating Compound from several material surfaces. Coe-Flex was used as a relative comparison to Microset. On fifteen different substrate materials the Microset leaves no visible trace of contaminant, however, X-ray photoelectron spectroscopy shows evidence of a thin silicone-based contaminant film of approximately 2 nm thickness.
Date: April 1, 2011
Creator: Brumbach, Michael Todd
Partner: UNT Libraries Government Documents Department

Roll measurement of Tevatron dipoles and quadrupoles

Description: In 2003 a simple digital level system was developed to allow for rapid roll measurements of all dipoles and quadrupoles in the Tevatron. The system uses a Mitutoyo digital level and a PC running MS WINDOWS XP and LAB VIEW to acquire data on the upstream and downstream roll of each magnet. The system is sufficiently simple that all 1,000 magnets in the Tevatron can be measured in less than 3 days. The data can be quickly processed allowing for correction of rolled magnets by the Fermilab alignment group. Data will be presented showing the state of the Tevatron in 2003 and the changes in rolls as measured in each shutdown since then.
Date: September 1, 2006
Creator: Volk, J.T.; Elementi, L.; Gollwitzer, K.; Jostlein, H.; Nobrega, F.; Shiltsev, V. et al.
Partner: UNT Libraries Government Documents Department

Hydrogen and oxygen adsorption stoichiometries on silica supported ruthenium nanoparticles

Description: Treatment under H{sub 2} at 300 C of Ru(COD)(COT) dispersed on silica yields 2 nm ruthenium nanoparticles, [Ru{sub p}/SiO{sub 2}], according to EXAFS, HRTEM and XPS. H{sub 2} adsorption measurements on [Ru{sub p}/SiO{sub 2}] in the absence of O{sub 2} show that Ru particles adsorb up to ca. 2 H per surface ruthenium atoms (2H/Ru{sub s}) on various samples; this technique can therefore be used to measure the dispersion of Ru particles. In contrast, O{sub 2} adsorption on [Ru{sub p}/SiO{sub 2}] leads to a partial oxidation of the bulk at 25 C, to RuO{sub 2} at 200 C and to sintering upon further reduction under H{sub 2}, showing that O{sub 2} adsorption cannot be used to measure the dispersion of Ru particles.
Date: December 1, 2008
Creator: Berthoud, Romain; Delichere, Pierre; Gajan, David; Lukens, Wayne; Pelzer, Katrin; Basset, Jean-Marie et al.
Partner: UNT Libraries Government Documents Department

Mechanisms for charge-transfer processes at electrode/solid-electrolyte interfaces.

Description: This report summarizes the accomplishments of a Laboratory-Directed Research and Development (LDRD) project focused on developing and applying new x-ray spectroscopies to understand and improve electric charge transfer in electrochemical devices. Our approach studies the device materials as they function at elevated temperature and in the presence of sufficient gas to generate meaningful currents through the device. We developed hardware and methods to allow x-ray photoelectron spectroscopy to be applied under these conditions. We then showed that the approach can measure the local electric potentials of the materials, identify the chemical nature of the electrochemical intermediate reaction species and determine the chemical state of the active materials. When performed simultaneous to traditional impedance-based analysis, the approach provides an unprecedented characterization of an operating electrochemical system.
Date: November 1, 2011
Creator: Chueh, William; El Gabaly Marquez, Farid; Whaley, Josh A.; McCarty, Kevin F.; McDaniel, Anthony H. & Farrow, Roger L.
Partner: UNT Libraries Government Documents Department

Optimizing Cr(VI) and Tc(VII) remediation through nano-scale biomineral engineering

Description: To optimize the production of biomagnetite for the bioremediation of metal oxyanion contaminated waters, the reduction of aqueous Cr(VI) to Cr(III) by two biogenic magnetites and a synthetic magnetite was evaluated under batch and continuous flow conditions. Results indicate that nano-scale biogenic magnetite produced by incubating synthetic schwertmannite powder in cell suspensions of Geobacter sulfurreducens is more efficient at reducing Cr(VI) than either biogenic nano-magnetite produced from a suspension of ferrihydrite 'gel' or synthetic nano-scale Fe{sub 3}O{sub 4} powder. Although X-ray Photoelectron Spectroscopy (XPS) measurements obtained from post-exposure magnetite samples reveal that both Cr(III) and Cr(VI) are associated with nanoparticle surfaces, X-ray Magnetic Circular Dichroism (XMCD) studies indicate that some Cr(III) has replaced octahedrally coordinated Fe in the lattice of the magnetite. Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES) measurements of total aqueous Cr in the associated solution phase indicated that, although the majority of Cr(III) was incorporated within or adsorbed to the magnetite samples, a proportion ({approx}10-15 %) was released back into solution. Studies of Tc(VII) uptake by magnetites produced via the different synthesis routes also revealed significant differences between them as regards effectiveness for remediation. In addition, column studies using a {gamma}-camera to obtain real time images of a {sup 99m}Tc(VII) radiotracer were performed to visualize directly the relative performances of the magnetite sorbents against ultra-trace concentrations of metal oxyanion contaminants. Again, the magnetite produced from schwertmannite proved capable of retaining more ({approx}20%) {sup 99m}Tc(VII) than the magnetite produced from ferrihydrite, confirming that biomagnetite production for efficient environmental remediation can be fine-tuned through careful selection of the initial Fe(III) mineral substrate supplied to Fe(III)-reducing bacteria.
Date: September 9, 2009
Creator: Cutting, R. S.; Coker, V. S.; Telling, N. D.; Kimber, R. L.; Pearce, C. I.; Ellis, B. et al.
Partner: UNT Libraries Government Documents Department

Molecular Studies of Surfaces under Reaction Conditions; Sum Frequency Generation Vibrational Spectroscopy, Scanning Tunneling Microscopy and Ambient Pressure X-Ray Photoelectron Spectroscopy

Description: Instruments developed in our laboratory permit the atomic and molecular level study of NPs under reaction conditions (SFG, ambient pressure XPS and high pressure STM). These studies indicate continuous restructuring of the metal substrate and the adsorbate molecules, changes of oxidation states with NP size and surface composition variations of bimetallic NPs with changes of reactant molecules.
Date: November 11, 2009
Creator: Somorjai, G.A.
Partner: UNT Libraries Government Documents Department

Real-time observation of the dry oxidation of the Si (100) surface with ambient pressure x-ray photoelectron spectroscopy

Description: We have applied ambient-pressure x-ray photoelectron spectroscopy with Si 2p chemical shifts to study the real-time dry oxidation of Si(100), using pressures in the range of 0.01-1 Torr and temperatures of 300-530 oC, and examining the oxide thickness range from 0 to ~;;25 Angstrom. The oxidation rate is initially very high (with rates of up to ~;;225 Angstrom/h) and then, after a certain initial thickness of the oxide in the range of 6-22 Angstrom is formed, decreases to a slow state (with rates of ~;;1.5-4.0 Angstrom/h). Neither the rapid nor the slow regime is explained by the standard Deal-Grove model for Si oxidation.
Date: September 20, 2007
Creator: Enta, Y.; Mun, B.S.; Rossi, M.; Ross Jr, P.N.; Hussain, Zahid; Fadley, C.S. et al.
Partner: UNT Libraries Government Documents Department

Room temperature reaction of oxygen with gold: an in situ ambient-pressure X-ray photoelectron spectroscopy investigation

Description: Gold is commonly regarded as the most inert element.1 However, the discovery of the exceptional catalytic properties of gold nanoparticles (NPs) for low temperature CO oxidation2 initiated great interest due to its promising applications and spawned a large number of studies devoted to the understanding of the reaction mechanism.3-6 Nevertheless, no consistent and conclusive picture has arisen.7-13
Date: February 1, 2010
Creator: Jiang, Peng; Porsgaard, Soeren; Borondics, Ferenc; Kober, Mariana; Caballero, Alfonso; Bluhm, Hendrik et al.
Partner: UNT Libraries Government Documents Department


Description: Results obtained by means of x-ray photoelectron spectroscopy and internal reflection infrared spectroscopy demonstrate the feasibility of heterogeneous oxidation of sulfur dioxide on soot particles in air. Sulfuric acid formed in this process can be neutralized on basic surface sites of soot particles, resulting in the formation of carbonium and/or oxonium sulfate. Hydrolysis of these salts into cyclic hemiacetals and sulfuric acid is expected.
Date: December 1, 1975
Creator: Chang, S.G. & Novakov, T.
Partner: UNT Libraries Government Documents Department

Electrical Contacts to Individual Colloidal Semiconductor Nanorods

Description: We report the results of charge transport studies on single CdTe nanocrystals contacted via evaporated Pd electrodes. Device charging energy, E{sub c}, monitored as a function of electrode separation drops suddenly at separations below {approx}55 nm. This drop can be explained by chemical changes induced by the metal electrodes. This explanation is corroborated by ensemble X-Ray photoelectron spectroscopy (XPS) studies of CdTe films as well as single particle measurements by transmission electron microscopy (TEM) and energy dispersive X-Rays (EDX). Similar to robust optical behavior obtained when Nanocrystals are coated with a protective shell, we find that a protective SiO2 layer deposited between the nanocrystal and the electrode prevents interface reactions and an associated drop in E{sub c,max}. This observation of interface reactivity and its effect on electrical properties has important implications for the integration of nanocrystals into conventional fabrication techniques and may enable novel nano-materials.
Date: April 1, 2008
Creator: Trudeau, Paul-Emile; Sheldon, Matt; Altoe, Virginia & Alivisatos, A. Paul
Partner: UNT Libraries Government Documents Department

Sum frequency generation and catalytic reaction studies of the removal of the organic capping agents from Pt nanoparticles by UV-ozone treatment

Description: We report the structure of the organic capping layers of platinum colloid nanoparticles and their removal by UV-ozone exposure. Sum frequency generation vibrational spectroscopy (SFGVS) studies identify the carbon-hydrogen stretching modes on poly(vinylpyrrolidone) (PVP) and tetradecyl tributylammonium bromide (TTAB)-capped platinum nanoparticles. We found that the UV-ozone treatment technique effectively removes the capping layer on the basis of several analytical measurements including SFGVS, X-ray photoelectron spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The overall shape of the nanoparticles was preserved after the removal of capping layers, as confirmed by transmission electron microscopy (TEM). SFGVS of ethylene hydrogenation on the clean platinum nanoparticles demonstrates the existence of ethylidyne and di-{sigma}-bonded species, indicating the similarity between single-crystal and nanoparticle systems.
Date: December 10, 2009
Creator: Aliaga, Cesar; Park, Jeong Y.; Yamada, Yusuke; Lee, Hyun Sook; Tsung, Chia-Kuang; Yang, Peidong et al.
Partner: UNT Libraries Government Documents Department