Generation of electron spin polarization in disordered organic semiconductors

The generation mechanisms of electron spin polarization (ESP) of charge carriers (electrons and holes, called "doublets") in doublet-doublet recombination and triplet-doublet quenching in disordered organic semiconductors are analyzed in detail. The ESP is assumed to result from quantum transitions between the states of the spin Hamiltonian of the pair of interacting particles. The value of the ESP is essentially determined by the mechanism of relative motion of particles. In our work we have considered the cage and free diffusion models. The effect of possible attractive spin-independent interactions between particles is also analyzed. Estimation with obtained formulas shows that the proposed mechanisms can lead to a fairly strong ESP much larger than the thermal one (at room temperatures)Comment: 10 pages, 3 figure

Magnetic field effects on electron-hole recombination in disordered organic semiconductors

Characteristic properties of magnetic field effects on spin selective geminate and bulk electron-hole polaron pair (PP) recombination are analyzed in detail within the approach based on the stochastic Liouville equation. Simple expressions for the magnetic field (B) dependence of recombination yield and rate are derived within two models of relative PP motion: free diffusion and diffusion in the presence of well (cage). The spin evolution of PPs is described taking in account the relaxation induced by hyperfine interaction, anisotropic part of the Zeeman interaction induced, as well as $\Delta g$-mechanism. A large variety of the $B$-dependences of the recombination yield $Y(B)$ and rate $K(B)$ is obtained depending on the relative weights of above-mentioned mechanisms. The proposed general method and derived particular formulas are shown to be quite useful for the analysis of recent experimental results.Comment: 12 pages, 3 figure

n-CdSe/p-ZnTe based wide band-gap light emitters: Numerical simulation and design

The only II‐VI/II‐VI wide band‐gap heterojunction to provide both good lattice match and p‐ and n‐type dopability is CdSe/ZnTe. We have carried out numerical simulations of several light emitter designs incorporating CdSe, ZnTe, and Mg alloys. In the simulations, Poisson’s equation is solved in conjunction with the hole and electron current and continuity equations. Radiative and nonradiative recombination in bulk material and at interfaces are included in the model. Simulation results show that an n‐CdSe/p‐ZnTe heterostructure is unfavorable for efficient wide band‐gap light emission due to recombination in the CdSe and at the CdSe/ZnTe interface. An n‐CdSe/Mg_(x)Cd_(1−x)Se/p‐ZnTe heterostructure significantly reduces interfacial recombination and facilitates electron injection into the p‐ZnTe layer. The addition of a Mg_(y)Zn_(1−y)Te electron confining layer further improves the efficiency of light emission. Finally, an n‐CdSe/Mg_(x)Cd_(1−x)Se/Mg_(y)Zn_(1−y)Te/p‐ZnTe design allows tunability of the wavelength of light emission from green into the blue wavelength regime

X-ray photoelectron spectroscopy measurement of valence-band offsets for Mg-based semiconductor compounds

We have used x-ray photoelectron spectroscopy to measure the valence-band offsets for the lattice matched MgSe/Cd0.54Zn0.46Se and MgTe/Cd0.88Zn0.12Te heterojunctions grown by molecular beam epitaxy. By measuring core level to valence-band maxima and core level to core level binding energy separations, we obtain values of 0.56+/-0.07 eV and 0.43+/-0.11 eV for the valence-band offsets of MgSe/Cd0.54Zn0.46Se and MgTe/Cd0.88Zn0.12Te, respectively. Both of these values deviate from the common anion rule, as may be expected given the unoccupied cation d orbitals in Mg. Application of our results to the design of current II-VI wide band-gap light emitters is discussed

Measurement of Endogenous versus Exogenous Formaldehyde-Induced DNA-Protein Crosslinks in Animal Tissues by Stable Isotope Labeling and Ultrasensitive Mass Spectrometry

DNA-protein crosslinks (DPCs) arise from a wide range of endogenous and exogenous chemicals, such as chemotherapeutic drugs and formaldehyde. Importantly, recent identification of aldehydes as endogenous genotoxins in Fanconi anemia has provided new insight into disease causation. Due to their bulky nature, DPCs pose severe threats to genome stability, but previous methods to measure formaldehyde-induced DPCs were incapable of discriminating between endogenous and exogenous sources of chemical. In this study, we developed methods that provide accurate and distinct measurements of both exogenous and endogenous DPCs in a structurally-specific manner. We exposed experimental animals to stable isotope-labeled formaldehyde ([13CD2]-formaldehyde) by inhalation and performed ultrasensitive mass spectrometry to measure endogenous (unlabeled) and exogenous (13CD2-labeled) DPCs. We found that exogenous DPCs readily accumulated in nasal respiratory tissues, but were absent in tissues distant to the site of contact. This observation together with the finding that endogenous formaldehyde-induced DPCs were present in all tissues examined suggests that endogenous DPCs may be responsible for increased risks of bone marrow toxicity and leukemia. Furthermore, the slow rate of DPC repair provided evidence for persistence of DPCs. In conclusion, our method for measuring endogenous and exogenous DPCs presents a new perspective for the potential health risks inflicted by endogenous formaldehyde, and may inform improved disease prevention and treatment strategies

N 6 -Formyllysine as a Biomarker of Formaldehyde Exposure: Formation and Loss of N 6 -Formyllysine in Nasal Epithelium in Long-Term, Low-Dose Inhalation Studies in Rats

Exposure to both endogenous and exogenous formaldehyde has been established to be carcinogenic, likely by virtue of forming nucleic acid and proteins adducts such as N6-formyllysine. To better assess N6-formyllysine as a biomarker of formaldehyde exposure, we studied accumulation of N6-formyllysine adducts in tissues of rats exposed by inhalation to 2 ppm [13C2H2]-formaldehyde for 7, 14, 21, and 28 days (6 h/day) and investigated adduct loss over a 7-day postexposure period using liquid chromatography-coupled tandem mass spectrometry. Our results showed formation of exogenous adducts in nasal epithelium and to some extent in trachea but not in distant tissues of lung, bone marrow, or white blood cells, with a 2-fold increase over endogenous N6-formyllysine over a 3-week exposure period. Postexposure analyses indicated a biexponential decay of N6-formyllysine in proteins extracted from different cellular compartments, with half-lives of ∼25 and ∼182 h for the fast and slow phases, respectively, in cytoplasmic proteins. These results parallel the behavior of DNA adducts and DNA-protein cross-links, with protein adducts cleared faster than DNA-protein cross-links, and point to the potential utility of N6-formyllysine protein adducts as biomarkers of formaldehyde

Molecular dosimetry of DNA and hemoglobin adducts in mice and rats exposed to ethylene oxide.

Experiments involving ethylene oxide (ETO) have been used to support the concept of using adducts in hemoglobin as a surrogate for DNA adducts in target tissues. The relationship between repeated exposures to ETO and the formation of N-(2-hydroxyethyl)valine (HEtVal) in hemoglobin and 7-(2-hydroxyethyl)guanine (7-HEG) in DNA was investigated in male rats and mice exposed by inhalation to 0, 3, 10, 33, or 100 ppm ETO for 6 hr/day for 4 weeks, or exposed to 100 ppm (mice) or 300 ppm (rats) for 1, 3, 5, 10, or 20 days (5 days/week). HEtVal was determined by Edman degradation, and 7-HEG was quantitated by HPLC separation and fluorescence detection. HEtVal formation was linear between 3 and 33 ppm ETO and increased in slope above 33 ppm. The dose-response curves for 7-HEG in rat tissues were linear between 10 and 100 ppm ETO and increased in slope above 100 ppm. In contrast, only exposures to 100 ppm ETO resulted in significant accumulation of 7-HEG in mice. Hemoglobin adducts were lost at a greater rate than predicted by normal erythrocyte life span. The loss of 7-HEG from DNA was both species and tissue dependent, with the adduct half-lives ranging from 2.9 to 5.8 days in rat tissues (brain, kidney, liver, lung, spleen, testis) and 1.0 to 2.3 days in all mouse tissues except kidney (t1/2 = 6.9 days). The concentrations of HEtVal were similar in concurrently exposed rats and mice, whereas DNA from rats had at least 2-fold greater concentrations of 7-HEG than DNA from mice.(ABSTRACT TRUNCATED AT 250 WORDS

Schottky-based band lineups for refractory semiconductors

An overview is presented of band alignments for small-lattice parameter, refractory semiconductors. The band alignments are estimated empirically through the use of available Schottky barrier height data, and are compared to theoretically predicted values. Results for tetrahedrally bonded semiconductors with lattice constant values in the range from C through ZnSe are presented. Based on the estimated band alignments and the recently demonstrated p-type dopability of GaN, we propose three novel heterojunction schemes which seek to address inherent difficulties in doping or electrical contact to wide-gap semiconductors such as ZnO, ZnSe, and ZnS