Daniel J. Gaspar

Application of Surface Chemical Analysis Tools for Characterization of Nanoparticles

AbstractThe important role that surface chemical analysis methods can and should play in the characterization of nanoparticles is described. The types of information that can be obtained from analysis of nanoparticles using Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary-ion mass spectrometry (TOF-SIMS), low-energy ion scattering (LEIS), and scanning-probe microscopy (SPM), including scanning tunneling microscopy (STM) and atomic force microscopy (AFM), are briefly summarized. Examples describing the characterization of engineered nanoparticles are provided. Specific analysis considerations and issues associated with using surface-analysis methods for the characterization of nanoparticles are discussed and summarized, with the impact that shape instability, environmentally induced changes, deliberate and accidental coating, etc., have on nanoparticle properties. FigureAtomic force microscopy image of Cu2O nanodots formed on a SrTiO3 substrate.

Differentiation of Spores of Bacillus subtilis Grown in Different Media by Elemental Characterization Using Time-of-Flight Secondary Ion Mass Spectrometry

ABSTRACT We demonstrate the use of time-of-flight secondary ion mass spectrometry (TOF-SIMS) in a forensics application to distinguish Bacillus subtilis spores grown in various media based on the elemental signatures of the spores. Triplicate cultures grown in each of four different media were analyzed to obtain TOF-SIMS signatures comprised of 16 elemental intensities. Analysis of variance was unable to distinguish growth medium types based on 40Ca-normalized signatures of any single normalized element. Principal component analysis proved successful in separating the spores into groups consistent with the media in which they were prepared. Confusion matrices constructed using nearest-neighbor classification of the PCA scores confirmed the predictive utility of TOF-SIMS elemental signatures in identifying sporulation medium. Theoretical calculations based on the number and density of spores in an analysis area indicate an analytical sample size of about 1 ng, making this technique an attractive method for bioforensics applications.

High-efficiency turquoise-blue electrophosphorescence from a Pt(II)-pyridyltriazolate complex in a phosphine oxide host

We demonstrate high-efficiency turquoise-blue electrophosphorescence from bis[3,5-bis(2-pyridyl)-1,2,4-triazolato]platinum(II) [Pt(ptp)2] doped in 4-(diphenylphosphoryl)-N,N-diphenylaniline(HM-A1). Organic light-emitting diodes (OLEDs) with 5% Pt(ptp)2:HM-A1 attain peak power efficiency of 61.2 lm/W, versus 40.8 lm/W for analogous devices employing the standard turquoise-blue phosphor bis[(4,6-difluorophenyl)-pyridinato-N,C2′](picolinato)iridium(III) (FIrpic). Devices with x% Pt(ptp)2:HM-A1 exhibit blue emission maxima (λmax∼480 nm) with monotonic increase in excimer/monomer intensity ratio at higher doping levels within 1%–10%, causing color shift toward green and less charge balance. This work represents a significant step toward optimizing future white OLEDs from the same phosphor via combination of low-doped and higher-doped or neat films.

Highly efficient blue organic light emitting device using indium-free transparent anode Ga:ZnO with scalability for large area coating

Organic light emitting devices have been achieved with an indium-free transparent anode, Ga doped ZnO (GZO). A large area coating technique was used (RF magnetron sputtering) to deposit the GZO films onto glass. The respective organic light emitting devices exhibited an operational voltage of 3.7 V, an external quantum efficiency of 17%, and a power efficiency of 39 lm/W at a current density of 1 mA/cm2. These parameters are well within acceptable standards for blue OLEDs to generate a white light with high enough brightness for general lighting applications. It is expected that high-efficiency, long-lifetime, large area, and cost-effective white OLEDs can be made with these indium-free anode materials.

Surface decontamination of simulated chemical warfare agents using a nonequilibrium plasma with off-gas monitoring

InnovaTek, Inc., Richland, WA, is developing a surface decontamination technology that utilizes active species generated in a nonequilibrium corona plasma. The plasma technology was tested against dimethyl-methyl phosphonate (DMMP), a simulant for the chemical agent Sarin. Gas chromatograph mass spectrometry analysis showed that a greater than four log/sub 10/ destruction of the DMMP on an aluminum surface was achieved in a 10-min treatment. An ion-trap mass spectrometer was utilized to collect time-resolved data on the treatment off-gases. These data indicate that only nontoxic fragments of the broken down DMMP molecule were present in the gas phase. The technology is being further refined to develop a product that will not only decontaminate surfaces but that will also sense when decontamination is complete.

Tuning the optical properties of mesoporous TiO2 films by nanoscale engineering.

The optical properties of spin-coated titanium dioxide films have been tuned by introducing mesoscale pores into the inorganic matrix. Differently sized pores were templated using Pluronic triblock copolymers as surfactants in the sol-gel precursor solutions and adjusted by varying the process parameters, such as the polymer concentration, annealing temperature, and time. The change in refractive index observed for different mesoporous anatase films annealed at 350, 400, or 450 °C directly correlates with changes in the pore size. Additionally, the index of refraction is influenced by the film thickness and the density of pores within the films. The band gap of these films is blue-shifted, presumably due to stress the introduction of pores exerts on the inorganic matrix. This study focused on elucidating the effect different templating materials (Pluronic F127 and P123) have on the pore size of the final mesoporous titania film and on understanding the relation of varying the polymer concentration (taking P123 as an example) in the sol-gel solution to the pore density and size in the resultant titania film. Titania thin film samples or corresponding titanium dioxide powders were characterized by X-ray diffraction, cross-section transmission electron microscopy, nitrogen adsorption, ellipsometery, UV/vis spectrometry, and other techniques to understand the interplay between mesoporosity and optical properties.

7,7,8,8-Tetracyanoquinodimethane-Based Molecular Dopants for p-Type Doping of OLEDs: A Theoretical Investigation

The array of organic conductivity dopants used for organic light-emitting devices (OLEDs) to reduce the operating voltage and improve power efficiency is extremely limited. Here we report a comparative theoretical study between newly proposed analogues and the standard state-of-the-art conductivity dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ). We used density functional theory to determine the bond lengths, bond angles, and electronic properties, such as the energy of the highest occupied molecular orbital (E(HOMO)) and the lowest unoccupied molecular orbital (E(LUMO)) states. The ground state structures of the proposed molecules were optimized at the B3LYP/6-31G* level. The results show that substitution of one or two fluorine groups in the F4-TCNQ core with a substituted phenyl ring or other electron-withdrawing moieties, will not substantially affect the geometry of the molecule or its electronic ability to accept electrons. The most significant finding was that the phenyl substitutions onto the TCNQ core are nearly perpendicular to the TCNQ plane, and thus there is no electronic communication between the two rings. This is extremely important, as such extension of the π conjugated system would negatively affect the E(LUMO) and thus the electron affinity of the molecule.

Synthesis and characterization of p-type conductivity dopant 2-(3-(adamantan-1-yl)propyl)-3,5,6-trifluoro-7,7,8,8-tetracyanoquinodimethane

We report the synthesis and characterization of 2-(3-(adamantan-1-yl)propyl)-3,5,6-trifluoro-7,7,8,8-tetracyanoquinodimethane (F3TCNQ-Ad1), a substituted analog of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), designed for p-type conductivity doping. The dopant is designed as a model for substituted alternatives to F4TCNQ that maintain similar electronic properties with the goal of engineering dopants with superior fabrication characteristics over F4TCNQ. We describe the design strategy for F3TCNQ-Ad1 based on molecular modeling predictions that substitution of a single fluorine atom of F4TCNQ has little effect on the electronic properties of the molecule. Photophysical and electrochemical characterization reveal that the adamantyl substituent in F3TCNQ-Ad1 does not significantly alter the electronic properties of the substituted dopant relative to F4TCNQ. Unfortunately, F3TCNQ-Ad1 degrades under standard sublimation conditions, preventing sublimation deposition processing. Instead, hole-only devices were made via solution-processing of the p-doped films with the structure glass/ITO/2.3 × 103 A PVK:(MTDATA:dopant)/2.0 × 102 A Au/1.0 × 103 A Al, where dopant is either F4TCNQ or F3TCNQ-Ad1. We demonstrate that F3TCNQ-Ad1 increased the conductivity of the films by at least 1000 times compared to an undoped device.

Blue phosphorescent organic light-emitting devices utilizing cesium–carbonate-doped 2,4,6-tris(2′,4′-difluoro-[1,1′-biphenyl]-4-yl)-1,3,5-triazine

We report an alternative, high-yielding synthesis for the known compound 2,4,6-tris(2′,4′-difluoro-[1,1′-biphenyl]-4-yl)-1,3,5-triazine (tris-(dFB)Tz). The energy of the lowest unoccupied molecular orbital (ELUMO) for tris-(dFB)Tz is estimated to be −3.5 eV from electrochemical measurements. The deep ELUMO of tris-(dFB)Tz affords a material with excellent electron acceptor characteristics for use in n-doped electron transport layers. Tris-(dFB)Tz shows a four order of magnitude increase in the number of carriers on doping with 8 wt. % Cs2CO3. Enhanced electron injection was also observed on doping with Cs2CO3, which eliminated the necessity for a separate LiF electron injection layer. Blue phosphorescent organic light-emitting devices (OLEDs) were fabricated using n-doped tris-(dFB)Tz electron transport layers. OLEDs with thick (700-A) Cs2CO3-doped tris-(dFB)Tz electron transport layers had lower operating voltages than OLEDS with an undoped electron transport layer of bis(diphenylphosphoryl)dibenzothiophene (PO15), which has previously been used in low-voltage, high-efficiency OLEDs. The tris-(dFB)Tz results indicate that aromatic substituted triazines may be promising materials for use as electron acceptors in n-doped organic electronic systems.

Tuning charge balance in PHOLEDs with ambipolar host materials to achieve high efficiency

The efficiency and stability of blue organic light emitting devices (OLEDs) continue to be a primary roadblock to developing organic solid state white lighting. For OLEDs to meet the high power conversion efficiency goal, they will require both close to 100% internal quantum efficiency and low operating voltage in a white light emitting device.1 It is generally accepted that such high quantum efficiency, can only be achieved with the use of organometallic phosphor doped OLEDs. Blue OLEDs are particularly important for solid state lighting. The simplest (and therefore likely the lowest cost) method of generating white light is to down convert part of the emission from a blue light source with a system of external phosphors.2 A second method of generating white light requires the superposition of the light from red, green and blue OLEDs in the correct ratio. Either of these two methods (and indeed any method of generating white light with a high color rendering index) critically depends on a high efficiency blue light component.3