John E. Northrup

Large modulation of carrier transport by grain-boundary molecular packing and microstructure in organic thin films

Solution-processable organic semiconductors are central to developing viable printed electronics, and performance comparable to that of amorphous silicon has been reported for films grown from soluble semiconductors. However, the seemingly desirable formation of large crystalline domains introduces grain boundaries, resulting in substantial device-to-device performance variations. Indeed, for films where the grain-boundary structure is random, a few unfavourable grain boundaries may dominate device performance. Here we isolate the effects of molecular-level structure at grain boundaries by engineering the microstructure of the high-performance n-type perylenediimide semiconductor PDI8-CN2 and analyse their consequences for charge transport. A combination of advanced X-ray scattering, first-principles computation and transistor characterization applied to PDI8-CN2 films reveals that grain-boundary orientation modulates carrier mobility by approximately two orders of magnitude. For PDI8-CN2 we show that the molecular packing motif (that is, herringbone versus slip-stacked) plays a decisive part in grain-boundary-induced transport anisotropy. The results of this study provide important guidelines for designing device-optimized molecular semiconductors.

Determination of wurtzite GaN lattice polarity based on surface reconstruction

We identify two categories of reconstructions occurring on wurtzite GaN surfaces, the first associated with the N face, (0001), and the second associated with the Ga face, (0001). Not only do these two categories of reconstructions have completely different symmetries, but they also have different temperature dependence. It is thus demonstrated that surface reconstructions can be used to identify lattice polarity. Confirmation of the polarity assignment is provided by polarity-selective wet chemical etching of these surfaces.

Reconstructions of GaN(0001) and (0001̄) surfaces: Ga-rich metallic structures

Reconstructions of GaN(0001) and (0001) surfaces are studied by scanning tunneling microscopy and spectroscopy, by electron diffraction, by Auger electron spectroscopy, and using first-principles theory. Attention is focused on Ga-rich reconstructions for each surface, which are found to have a metallic character involving significant overlap between Ga valence electrons. The electron counting rule is thus violated for these surfaces, but they nonetheless form minimum energy structures.

Surface energetics, pit formation, and chemical ordering in InGaN alloys

We present first-principle calculations of the structure and energetics of the GaN(101_1) surface, and present models for the reconstructions. A strong preference for In surface segregation and occupation of specific surface sites is demonstrated. We argue that inverted pyramid defect formation is enhanced by segregation of In on (101_1) facets. We propose that the chemical ordering recently observed in InGaN alloys is driven by the preference for In incorporation at the sites of reduced N coordination present at step edges during growth on the (0001) and (0001_) surfaces.

Inversion of wurtzite GaN(0001) by exposure to magnesium

Magnesium incorporation during the molecular-beam epitaxy growth of wurtzite GaN is found to invert the Ga-polar (0001) face to the N-polar face. The polarity is identified based on the two different sets of reconstructions seen on the film prior to and after about 1 monolayer Mg exposure. The inversion boundary is seen to lie on the (0001) plane from transmission electron microscopy images, and a structural model is presented for the inversion. On the Ga-polar face, Mg is also seen to stabilize growth in the N-rich regime.

Inversion domains in GaN grown on sapphire

Planar defects observed in GaN films grown on (0001) sapphire have been identified as inversion domain boundaries (IDBs) by a combination of high resolution transmission electron microscopy, multiple dark field imaging, and convergent beam electron diffraction techniques. Films grown by molecular beam epitaxy (MBE), metalorganic vapor deposition (MOCVD), and hydride vapor phase epitaxy (HVPE) were investigated and all were found to contain IDBs. The IDBs in the MBE and HVPE films extended from the interface to the film surface and formed columnar domains that ranged in width from 3 to 20 nm in the MBE films and up to 100 nm in the HVPE films. For the films investigated, the MBE films had the highest density, and the MOCVD films had the lowest density of IDBs. The nucleation of inversion domains (IDs) may result from step‐related inhomogeneities of the GaN/sapphire interface.

Screw dislocations in GaN: The Ga-filled core model

First-principles total energy calculations performed for [0001] screw dislocations in GaN with |b|=c indicate that a model with a helical Ga-filled core is more stable than the hollow core model in Ga-rich conditions. This model gives rise to electronic states dispersed throughout the band gap. Such a dislocation is therefore expected to be a very strong center for nonradiative recombination and a pathway for current leakage.

Structural origin of gap states in semicrystalline polymers and the implications for charge transport

We quantify the degree of paracrystalline disorder in the \ensuremath{\pi}-\ensuremath{\pi} stacking direction of crystallites of a high performing semicrystalline semiconducting polymer with advanced x-ray line-shape analysis. Using density functional theory calculations to provide input to a simple tight-binding model, we obtain the density of states of a system of \ensuremath{\pi}-\ensuremath{\pi} stacked polymer chains with increasing amounts of paracrystalline disorder. We find that, for an aligned film of PBTTT, the paracrystalline disorder is 7.3%. This type of disorder induces a tail of trap states with a breadth of \ensuremath{\sim}100 meV as determined through calculation. This finding agrees with previous device modeling and provides physical justification for the mobility edge model.

Faceted inversion domain boundary in GaN films doped with Mg

Homoepitaxial GaN films, doped with Mg, were grown by rf-plasma molecular-beam epitaxy on Ga-polarity (0001) templates. Convergent-beam electron diffraction analysis establishes that the film polarity changes from [0001] to [0001_] when the Mg flux during growth is approximately 1 ML/s. Secondary ion mass spectrometry indicates a doping concentration of ∼1020 cm−3 in the film where the inversion occurs, and a reduced Mg incorporation in the [0001_] material. Transmission electron microscopy shows that the inversion domain boundary is faceted predominantly along the {0001} and {h,h,−2h,l} planes, with l/h approximately equal to 3. Using first-principles total energy calculations, we show that the {h,h,−2h,l} segments of the boundary are stabilized by the incorporation of Mg in threefold coordinated lattice sites.

GaN(0001) surface structures studied using scanning tunneling microscopy and first-principles total energy calculations

Abstract Surface reconstructions occurring on the (0001) surface of wurtzite GaN are studied using scanning tunneling microscopy, electron diffraction, and Auger electron spectroscopy. The family of reconstructions found on this face includes 2×2, 5×5, 6×4, and ‘1×1’, in order of increasing surface Ga/N ratio. Detailed experimental results are presented for each of these reconstructions. First-principles total energy calculations are employed to identify possible model structures. An adatom model, with N-adatoms occupying H3 sites, is proposed for the 2×2 reconstruction. A model composed of N adatoms, Ga adatoms, and Ga vacancies is proposed for the 5×5 reconstruction.