Self-regulated charge transfer and band tilt in nm-scale polar GaN films

To date, the generic polarization of Bernardini, Fiorentini and Vanderbilt (PBFV) has been widely used to address the issue of polarity in III-V nitride semiconductors, but improvements in nitride materials and the performance of optoelectronic devices have been limited. The current first-principles calculation for the electronic structures of nm-scale [0001] GaN films show that the internal electric fields and the band tilt of these films are in opposite direction to those predicted by PBFV. Additionally, it is determined that an intrinsic self-regulated charge transfer across the film limits the electrostatic potential difference across the film, which renders the local conduction band energy minimum (at the Ga-terminated surface) approximately equal to the local valence band energy maximum (at the N-terminated surface). This effect is found to occur in films thicker than ~4nm

Non-linear macroscopic polarization in III-V nitride alloys

We study the dependence of macroscopic polarization on composition and strain in wurtzite III-V nitride ternary alloys using ab initio density-functional techniques. The spontaneous polarization is characterized by a large bowing, strongly dependent on the alloy microscopic structure. The bowing is due to the different response of the bulk binaries to hydrostatic pressure, and to internal strain effects (bond alternation). Disorder effects are instead minor. Deviations from parabolicity (simple bowing) are of order 10 % in the most extreme case of AlInN alloy, much less at all other compositions. Piezoelectric polarization is also strongly non-linear. At variance with the spontaneous component, this behavior is independent of microscopic alloy structure or disorder effects, and due entirely to the non-linear strain dependence of the bulk piezoelectric response. It is thus possible to predict the piezoelectric polarization for any alloy composition using the piezoelectricity of the parent binaries.Comment: RevTex 7 pages, 7 postscript figures embedde

K-band ESR studies of structural anisotropy in P3HT and P3HT/PCBM blend polymer solid films: Paramagnetic defects after continuous wave Xe-lamp photolysis

K-band electron spin resonance (ESR) technique was employed to study films of regioregular poly(3-hexylthiophene) (P3HT) and P3HT/PCBM ([6,6]-phenyl- C61-butyric acid methyl ester) blends to estimate their structural macroscopic anisotropy. As for nematic liquids (or liquid crystals) our consideration was based on the approach that the free energy of self-organised polymer molecules of P3HT is a function of molecular orientation and therefore chains in polymer films exhibit some degree of orientational order. The lamellar molecular orientation of the films was confirmed by angular-dependent ESR spectroscopy of polarons, which were considered as a localised paramagnetic centre with an unpaired carbon π-electron of the thiophene ring. The additional ESR signal initiated by the UV/visible CW Xe-lamp illumination of the films at air atmosphere was attributed to the negative polaron (trapped photo-electron) on the polymer chain, as well as to the radical due to chain degradation. © 2009 Elsevier Ltd. All rights reserved

N-Methylmorpholine-N-oxide ring cleavage registration by ESR under heating conditions of the Lyocell process

Thermal cleavage processes of N-methylmorpholine-N-oxide monohydrate (NMMO) were observed in pure NMMO as well as in cellulose/NMMO solutions by ESR at temperatures of the industrial Lyocell process (∼370 K). Generated radicals were attributed to the alkylnitroxyl type radicals -CH2-NO{radical dot}-CH3 in NMMO and additional (and dominated) -CH2-NO{radical dot}-CH2- in cellulose/NMMO solutions. Formation of both radical types formed due to NMMO ring scission is suggested. © 2007 Elsevier B.V. All rights reserved

K-band ESR studies of structural anisotropy in P3HT and P3HT/PCBM blend polymer solid films: Paramagnetic defects after continuous wave Xe-lamp photolysis

K-band electron spin resonance (ESR) technique was employed to study films of regioregular poly(3-hexylthiophene) (P3HT) and P3HT/PCBM ([6,6]-phenyl- C61-butyric acid methyl ester) blends to estimate their structural macroscopic anisotropy. As for nematic liquids (or liquid crystals) our consideration was based on the approach that the free energy of self-organised polymer molecules of P3HT is a function of molecular orientation and therefore chains in polymer films exhibit some degree of orientational order. The lamellar molecular orientation of the films was confirmed by angular-dependent ESR spectroscopy of polarons, which were considered as a localised paramagnetic centre with an unpaired carbon π-electron of the thiophene ring. The additional ESR signal initiated by the UV/visible CW Xe-lamp illumination of the films at air atmosphere was attributed to the negative polaron (trapped photo-electron) on the polymer chain, as well as to the radical due to chain degradation. © 2009 Elsevier Ltd. All rights reserved

Degradation processes in the cellulose/N-methylmorpholine-N-oxide system studied by HPLC and ESR. Radical formation/recombination kinetics under UV photolysis at 77 K

Degradation processes of N-methylmorpholine-N-oxide monohydrate (NMMO), cellulose and cellulose/NMMO solutions were studied by high performance liquid chromatography (HPLC) and electron spin resonance (ESR) spectroscopy. Kinetics of radical accumulation processes under UV (λ = 248 nm) excimer laser flash photolysis was investigated by ESR at 77 K. Beside radical products of cellulose generated and stabilized at low temperature, radicals in NMMO and cellulose/NMMO solutions were studied for the first time in those systems and attributed to nitroxide type radicals ∼CH2- NO•∼-CH2∼ and/or ∼CH2 NO•-CH3∼ at the first and methyl •CH3 and formyl -CHO radicals at the second step of the photo-induced reaction. Kinetic study of radicals revealed that formation and recombination rates of radical reaction depend on cellulose concentration in cellulose/NMMO solutions and additional ingredients, e.g., Fe(II) and propyl gallate. HPLC measurements showed that the concentrations of ring degradation products, e.g., aminoethanol and acetaldehyde, are determined by the composition of the cellulose/NMMO solution. Results based on HPLC are mainly maintained by ESR that supports the assumption concerning a radical initiated ring-opening of NMMO. © Springer Science+Business Media B.V. 2007

Polarity in GaN and ZnO: Theory, measurement, growth, and devices

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Appl. Phys. Rev. 3, 041303 (2016) and may be found at https://doi.org/10.1063/1.4963919.The polar nature of the wurtzite crystalline structure of GaN and ZnO results in the existence of a spontaneous electric polarization within these materials and their associated alloys (Ga,Al,In)N and (Zn,Mg,Cd)O. The polarity has also important consequences on the stability of the different crystallographic surfaces, and this becomes especially important when considering epitaxial growth. Furthermore, the internal polarization fields may adversely affect the properties of optoelectronic devices but is also used as a potential advantage for advanced electronic devices. In this article, polarity-related issues in GaN and ZnO are reviewed, going from theoretical considerations to electronic and optoelectronic devices, through thin film, and nanostructure growth. The necessary theoretical background is first introduced and the stability of the cation and anion polarity surfaces is discussed. For assessing the polarity, one has to make use of specific characterization methods, which are described in detail. Subsequently, the nucleation and growth mechanisms of thin films and nanostructures, including nanowires, are presented, reviewing the specific growth conditions that allow controlling the polarity of such objects. Eventually, the demonstrated and/or expected effects of polarity on the properties and performances of optoelectronic and electronic devices are reported. The present review is intended to yield an in-depth view of some of the hot topics related to polarity in GaN and ZnO, a fast growing subject over the last decade

Theory of coherent acoustic phonons in InGaN/GaN multi-quantum wells

A microscopic theory for the generation and propagation of coherent LA phonons in pseudomorphically strained wurzite (0001) InGaN/GaN multi-quantum well (MQW) p-i-n diodes is presented. The generation of coherent LA phonons is driven by photoexcitation of electron-hole pairs by an ultrafast Gaussian pump laser and is treated theoretically using the density matrix formalism. We use realistic wurzite bandstructures taking valence-band mixing and strain-induced piezo- electric fields into account. In addition, the many-body Coulomb ineraction is treated in the screened time-dependent Hartree-Fock approximation. We find that under typical experimental conditions, our microscopic theory can be simplified and mapped onto a loaded string problem which can be easily solved.Comment: 20 pages, 17 figure

TRESR study of the photo-induced electron transfer in P3DDT/maleic anhydride blend in THF solution under UV flash photolysis

Photo-induced electron transfer (PET) between a poly(3-dodecylthiophene) (P3DDT) and maleic anhydride (MA) in their blend in liquid solution of tetrahydrofuran was observed by the time-resolved electron spin resonance (TRESR) under UV flash photolysis at 308 nm. The observed spectra were identified as free-radical signals of positive polarons on polymer chains and MA anion radicals. Their emissive chemical induced dynamic electron polarization (CIDEP) originated mainly from excited triplet states (triplet mechanism of CIDEP). Analysis of radical spectra integral intensity distribution shows at the influence of radical pair mechanism (RPM) of CIDEP with the positive sign of the exchange interaction constant (J > 0). The last is attributed to Coulombic interaction between geminately formed polarons and MA anion radicals. The spin relaxation times of radicals were determined by fitting the time evolution of the TRESR signal at near-resonance positions of the field using the Bloch equations and direct Fourier transform analysis. © 2008 Elsevier B.V. All rights reserved

Accurate calculation of polarization-related quantities in semiconductors

We demonstrate that polarization-related quantities in semiconductors can be predicted accurately from first-principles calculations using the appropriate approach to the problem, the Berry-phase polarization theory. For III-V nitrides, our test case, we find polarizations, polarization differences between nitride pairs, and piezoelectric constants quite close to their previously established values. Refined data are nevertheless provided for all the relevant quantities.Comment: RevTeX 4 pages, no figure