Cross-sectional Scanning Tunneling Microscopy Research Articles

Defect formation in InGaAs/AlSb/InAs memory devices

ULTRARAMTM is a novel floating-gate nonvolatile memory in which the oxide barrier of flash is replaced by a triple-barrier resonant tunneling structure comprising of multiple InAs/AlSb heterojunctions. The quality of the triple barrier resonant tunneling heterostructure of an ULTRARAMTM device in terms of interface sharpness and the presence of defects was analyzed by cross-sectional scanning tunneling microscopy. We observed two different types of defects: stacking faults originating in the layers below the triple barrier resonant tunneling structure and AlSb accumulations at the interface between the lower AlSb layer of the triple barrier resonant tunneling structure and the InGaAs channel. The InGaAs surface of a second sample was measured by atomic force microscopy in order to investigate whether its unevenness is caused by deposition of the AlSb layer or it is already present before the AlSb deposition process.

Atomic-scale characterization of single and double layers of InAs and InAlAs Stranski-Krastanov quantum dots

We report a detailed structural characterization of single and double layers of InAs and InAlAs quantum dots (QDs) and their wetting layers (WLs) by atomic force microscopy (AFM) and cross-sectional scanning tunneling microscopy (X-STM). The X-STM analysis with atomic resolution showed that the InAlAs WL consists of two distinct layers: a bottom part where all the Al atoms of the InAlAs alloy settled, and a top part containing exclusively In and Ga atoms. The QDs formed from the InAlAs layer contains no Al atoms at all and lie on top of the Al-rich WL. In the double layers of QDs, the InAlAs QDs were used as a seed to influence the nucleation of the InAs QDs grown on top. A gradual decrease in the density of the top InAs QDs was observed in the AFM images with increasing thickness of the GaAs spacer. The X-STM images showed that both QDs layers were completely intermixed for a 2-nm-thick spacer, while effective strain-induced stacking of both types of QDs was observed for a GaAs spacer thickness of 4 nm. However, both QD layers were completely decoupled for a GaAs spacer thickness of 8 nm and could thus be treated as individual layers.

Control of Morphology and Substrate Etching in InAs/InP Droplet Epitaxy Quantum Dots for Single and Entangled Photon Emitters.

We present a detailed atomic-resolution study of morphology and substrate etching mechanism in InAs/InP droplet epitaxy quantum dots (QDs) grown by metal–organic vapor phase epitaxy via cross-sectional scanning tunneling microscopy (X-STM). Two different etching processes are observed depending on the crystallization temperature: local drilling and long-range etching. In local drilling occurring at temperatures of ≤500 °C, the In droplet locally liquefies the InP underneath and the P atoms can easily diffuse out of the droplet to the edges. During crystallization, the As atoms diffuse into the droplet and crystallize at the solid–liquid interface, forming an InAs etch pit underneath the QD. In long-range etching, occurring at higher temperatures of >500 °C, the InP layer is destabilized and the In atoms from the surroundings migrate toward the droplet. The P atoms can easily escape from the surface into the vacuum, forming trenches around the QD. We show for the first time the formation of trenches and long-range etching in InAs/InP QDs with atomic resolution. Both etching processes can be suppressed by growing a thin layer of InGaAs prior to the droplet deposition. The QD composition is estimated by finite element modeling in combination with X-STM. The change in the morphology of QDs due to etching can strongly influence the fine structure splitting. Therefore, the current atomic-resolution study sheds light on the morphology and etching behavior as a function of crystallization temperature and provides a valuable insight into the formation of InAs/InP droplet epitaxy QDs which have potential applications in quantum information technologies.

Study of Size, Shape, and Etch pit formation in InAs/InP Droplet Epitaxy Quantum Dots

We investigated metal-organic vapor phase epitaxy grown droplet epitaxy (DE) and Stranski–Krastanov (SK) InAs/InP quantum dots (QDs) by cross-sectional scanning tunneling microscopy (X-STM). We present an atomic-scale comparison of structural characteristics of QDs grown by both growth methods proving that the DE yields more uniform and shape-symmetric QDs. Both DE and SKQDs are found to be truncated pyramid-shaped with a large and sharp top facet. We report the formation of localized etch pits for the first time in InAs/InP DEQDs with atomic resolution. We discuss the droplet etching mechanism in detail to understand the formation of etch pits underneath the DEQDs. A summary of the effect of etch pit size and position on fine structure splitting (FSS) is provided via the k · p theory. Finite element (FE) simulations are performed to fit the experimental outward relaxation and lattice constant profiles of the cleaved QDs. The composition of QDs is estimated to be pure InAs obtained by combining both FE simulations and X-STM results. The preferential formation of {136} and {122} side facets was observed for the DEQDs. The formation of a DE wetting layer from As-P surface exchange is compared with the standard SKQDs wetting layer. The detailed structural characterization performed in this work provides valuable feedback for further growth optimization to obtain QDs with even lower FSS for applications in quantum technology.

Kinetically Controlled Epitaxial Growth of Fe3GeTe2 van der Waals Ferromagnetic Films

We demonstrate that kinetics play an important role in the epitaxial growth of Fe$_3$GeTe$_2$ (FGT) van der Waals (vdW) ferromagnetic films by molecular beam epitaxy. By varying the deposition rate, we control the formation or suppression of an initial tellurium-deficient non-van der Waals phase (Fe$_3$Ge$_2$) prior to realizing epitaxial growth of the vdW FGT phase. Using cross-sectional scanning transmission electron microscopy and scanning tunneling microscopy, we optimize the FGT films to have atomically smooth surfaces and abrupt interfaces with the Ge(111) substrate. The magnetic properties of our high quality material are confirmed through magneto-optic, magnetotransport, and spin-polarized STM studies. Importantly, this demonstrates how the interplay of energetics and kinetics can help tune the re-evaporation rate of chalcogen atoms and interdiffusion from the underlayer, which paves the way for future studies of van der Waals epitaxy.

Influence of strain and dislocations on GaSb/GaAs quantum dots: From nested to staggered band alignment

We investigate the influence of strain and dislocations on band alignment in GaSb/GaAs quantum dot systems. Composition profiles from cross-sectional scanning tunneling microscopy images are interpolated onto a finite element mesh in order to calculate the distribution of local elastic strain, which is converted to a spatially varying band alignment using deformation potential theory. Our calculations predict that dislocation-induced strain relaxation and charging lead to significant local variations in band alignment. Furthermore, misfit strain induces a transition from a nested (type I) to a staggered (type II) band alignment. Although dislocation-induced strain relaxation prevents the type I to type II transition, electrostatic charging at dislocations induces the staggered band alignment once again.

Effect of As flux on InAs submonolayer quantum dot formation for infrared photodetectors

The performance of infrared photodetectors based on submonolayer quantum dots was investigated as a function of the arsenic flux. All the devices showed similar figures of merit and a very high specific detectivity above 1 × 1011 cm Hz1/2/W at 12 K, despite the fact that cross-sectional scanning tunneling microscopy images pointed out a strong reduction in the density of such nanostructures with decreasing arsenic flux. This contrast is a consequence of the small size and low In content of the submonolayer quantum dots that lead to a strong delocalization of the electrons wave function and, therefore, reduce the advantage of samples having a very high density of quantum dots. A simple strain model showed that the properties of these nanostructures are limited by the lack of vertical alignment of the small two-dimensional InAs islands resulting from the strong segregation of In atoms. We have proposed some ways to improve the growth of submonolayer quantum dots and believe that, after further optimization, such nanostructures might provide devices with superior performance.

Direct Observations of Uniform Bulk Heterojunctions and the Energy Level Alignments in Nonfullerene Organic Photovoltaic Active Layers.

State-of-the-art organic photovoltaic (OPV) cells rely on the engineering of the energy levels of the organic molecules as well as the bulk-heterojunction nanomorphology to achieve high performance. However, both are difficult to measure inside the active layer where the electron donor and acceptor molecules are mingled. While the energy level alignments of the lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) between the electron donors and acceptors may be altered in the mixed active layer compared to their pure forms, the nanomorphology of the donor and acceptor molecular domains is mostly studied in indirect means. Here, we present the direct observations of the nanomorphology of the molecular domains as well as the energy level alignments in the active layer of a nonfullerene-based OPV (donor: PBDB-T-2F and acceptor: IT-4Cl) using cross-sectional scanning tunneling microscopy and spectroscopy (XSTM/S). It is revealed that (1) the bulk-heterojunction (BHJ) structures are homogeneous and uniform throughout the ∼1.2 μm thick active layer; (2) the energy alignments between the donor-rich and acceptor-rich domains are directly observed; (3) there exist the intermixing domains at the boundaries of the donor-rich and acceptor-rich domains with thickness in the nm scale; (4) the exciton binding energies in PBDB-T-2F and IT-4Cl are estimated to be 0.74 and 0.32 eV, respectively; and (5) there is an ∼0.7 V loss in the open circuit voltage. The results provide a nanoscale understanding of the OPV active layers to guide further improvement of the OPV performance.

Ultrahigh In-Plane Thermoelectric Performance in Self-Assembled PbSe:Au Films With Vertically Aligned Nanopillar

Self-assembled nanocomposites with tunable physical properties have potential applications in advanced devices. In this work, self-assembled PbSe:Au films with vertically aligned nanopillars (VAN) were fabricated by pulsed laser deposition. Detailed heterostructures with atomic-resolution have been investigated by cross-sectional scanning tunnelling microscopy. The results show that self-assembled Au nanopillars in a PbSe matrix is realized. Compared with PbSe matrix, PbSe:Au vertical interface can facilitate energy filter effect and lower the in-plane thermal conductivity. The maximum ZT values for n-type self-assembled VAN film is ~2.6 at 523 K, which is ~400% higher than that of pure PbSe film (ZT=0.5). This study suggests that the vertical interface in the unique VAN provide a viable route to manipulate the thermoelectric properties for the thermoelectric materials.

Atomic-scale study of Si-doped AlAs by cross-sectional scanning tunneling microscopy and density functional theory

Silicon (Si) donors in GaAs have been the topic of extensive studies since Si is the most common and well understood n-type dopant in III-V semiconductor devices and substrates. The indirect bandgap of AlAs compared to the direct one of GaAs leads to interesting effects when introducing Si dopants. Here we present a study of cross-sectional scanning tunneling microscopy (X-STM) and density functional theory (DFT) calculations to study Si donors in AlAs at the atomic scale. Based on their crystal symmetry and contrast strengths, we identify Si donors up to four layers below the (110) surface of AlAs. Interestingly, their short-range local density of states (LDOS) is very similar to Si atoms in the (110) surface of GaAs. Additionally we show high-resolution images of Si donors in all these layers. For empty state imaging, the experimental and simulated STM images based on DFT show excellent agreement for Si donor up to two layers below the surface.

Structural and compositional analysis of (InGa)(AsSb)/GaAs/GaP Stranski\u2013Krastanov quantum dots

We investigated metal-organic vapor phase epitaxy grown (InGa)(AsSb)/GaAs/GaP Stranski–Krastanov quantum dots (QDs) with potential applications in QD-Flash memories by cross-sectional scanning tunneling microscopy (X-STM) and atom probe tomography (APT). The combination of X-STM and APT is a very powerful approach to study semiconductor heterostructures with atomic resolution, which provides detailed structural and compositional information on the system. The rather small QDs are found to be of truncated pyramid shape with a very small top facet and occur in our sample with a very high density of ∼4 × 1011 cm−2. APT experiments revealed that the QDs are GaAs rich with smaller amounts of In and Sb. Finite element (FE) simulations are performed using structural data from X-STM to calculate the lattice constant and the outward relaxation of the cleaved surface. The composition of the QDs is estimated by combining the results from X-STM and the FE simulations, yielding ∼InxGa1 − xAs1 − ySby, where x = 0.25–0.30 and y = 0.10–0.15. Noticeably, the reported composition is in good agreement with the experimental results obtained by APT, previous optical, electrical, and theoretical analysis carried out on this material system. This confirms that the InGaSb and GaAs layers involved in the QD formation have strongly intermixed. A detailed analysis of the QD capping layer shows the segregation of Sb and In from the QD layer, where both APT and X-STM show that the Sb mainly resides outside the QDs proving that Sb has mainly acted as a surfactant during the dot formation. Our structural and compositional analysis provides a valuable insight into this novel QD system and a path for further growth optimization to improve the storage time of the QD-Flash memory devices.

Optimization of the in situ cleavage process for III–V/Si(001) investigations by cross-sectional scanning tunneling microscopy

Interfaces between epitaxial layers forming electronic devices have long been recognized to have an important impact on their functionality. Cross-sectional measurements have, therefore, attained an important role in the characterization of these layers to acquire a deep understanding of their structural and electronic properties. For cross-sectional measurements relying on in situ cleavage, achieving control over the cleavage process is crucial. Particularly, cross-sectional scanning tunneling microscopy relies on atomically flat cleavage surfaces for the investigation of a multitude of material systems with the greatest possible detail. For the investigation of III–V semiconductors grown on Si(001), samples are normally cleaved by applying a force in the [001¯] direction in order to generate and analyze {110} cleavage surfaces. These surfaces are best suited for cross-sectional investigations as they are perpendicular to the growth surface as well as to each other. In this work, we show that for cleaving Si(001) in such a way, sawing rather than notching samples to create a predetermined breaking point results in significantly improved cleavage surfaces. For this purpose, a statistical investigation of the cleavage of Si(001) wafers is presented. We further demonstrate the proficiency of sawing as the sample-preparation method for cross-sectional scanning tunneling microscopy by investigating the interfacial region of high-quality GaP/Si(001) samples as well as a state-of-the-art GaSb/Si(001) sample.

From surface data to bulk properties: a case study for antiphase boundaries in GaP on Si(001)

The orientation, atomic structure, and charge state of defects in crystals have a large influence on the functionality of resultant semiconductor devices. Two-dimensional defects are especially challenging to analyze, as they are embedded within the bulk. We developed a data analysis procedure using information from atomically resolved cross-sectional surface data from two non-parallel surfaces, enabling us to draw conclusions about two-dimensional defects within the bulk. Using antiphase boundaries (APBs) in GaP on Si as a model system, we show that this approach can be applied to any material and microscopy method. For the GaP/Si system and for two-side cross-sectional scanning tunneling microscopy as the experimental tool, the procedure shows that the commonly discussed and APBs do not arise in the investigated sample, whereas the data strongly indicates that previously not recognized APBs are present. Furthermore, a statistical analysis allows a calculation of the net excess charge carrier density introduced into the crystal by the APBs. Its value is negligible compared to the density of wrong bonds that characterize the APBs, since negative and positive excess charges compensate each other almost completely. Moreover, we suggest that controlled enhancement of the formation of APBs may also lead to applications in thermoelectric devices.

Atomic-Scale Characterization of Droplet Epitaxy Quantum Dots.

The fundamental understanding of quantum dot (QD) growth mechanism is essential to improve QD based optoelectronic devices. The size, shape, composition, and density of the QDs strongly influence the optoelectronic properties of the QDs. In this article, we present a detailed review on atomic-scale characterization of droplet epitaxy quantum dots by cross-sectional scanning tunneling microscopy (X-STM) and atom probe tomography (APT). We will discuss both strain-free GaAs/AlGaAs QDs and strained InAs/InP QDs grown by droplet epitaxy. The effects of various growth conditions on morphology and composition are presented. The efficiency of methods such as flushing technique is shown by comparing with conventional droplet epitaxy QDs to further gain control over QD height. A detailed characterization of etch pits in both QD systems is provided by X-STM and APT. This review presents an overview of detailed structural and compositional analysis that have assisted in improving the fabrication of QD based optoelectronic devices grown by droplet epitaxy.

Theoretical explanation of scanning tunneling spectrum of cleaved (110) surface of InGaAs

The cross-sectional (110) surface of In<sub>0.53</sub>Ga<sub>0.47</sub>As/InP hetero-structure grown by molecular beam epitaxy on an InP (001) substrate is characterized by the cross-sectional scanning tunneling microscopy (XSTM). The cleaved (110) surface across the interface between the In<sub>0.53</sub>Ga<sub>0.47</sub>As layer and InP layer is atomically flat but displays slight different image contrast between the two neighbor regions. The scanning tunneling spectroscopy (STS) is used to measure the current/voltage (<i>I-V</i>) spectra. The <i>I-V</i> data of the InGaAs surface and InP (110) surface show the different characteristics. The voltage range of zero-current plateau (apparent band gap) in the <i>I-V</i> spectrum of InP displays the values close to its energy band gaps whereas the plateau ranges in the spectra of In<sub>0.53</sub>Ga<sub>0.47</sub>As are by contrast generally 50% larger than the energy band gap of In<sub>0.53</sub>Ga<sub>0.47</sub>As. The above phenomenon implies the different physical pictures on the tunneling of two surfaces. In the case of InP, the flat band model is feasible since the band edge states existing in the InP (110) surface can prevent the surface from being affected by the tip –induced band bending (TIBB) effect. In contrast, the TIBB effect must be taken into account to explain the <i>I-V</i> spectra of the In<sub>0.53</sub>Ga<sub>0.47</sub>As (110) surface. A statistical analysis of the <i>I-V</i> data of In<sub>0.53</sub>Ga<sub>0.47</sub>As reveals that the width of current plateau in the <i>I-V</i> spectrum is generally between 1.05 eV and 1.20 eV and the current onset points (turn-points) with the plateau for the different spectra are slightly different from each other. We are able to explain quantitatively the above features based on the three-dimensional TIBB model given by Feenstra (<ext-link ext-link-type="uri" xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="http://doi.org/10.1116/1.1606466">2003 <i>J.</i> <i>Vac. Sci. Technol. B</i> <b>21</b> 2080</ext-link>). Our calculation reveals that the parameter of density of surface states (DOSS) is a sensitive parameter responsible for the <i>I-V</i> features mentioned above. According to an appropriate assignment of the value of DOSS, which is generally taken in the scope of (0.8–3.0) × 10<sup>12</sup> (cm<sup>2</sup>·eV)<sup>–1</sup>, we well predict both the width and the onset points of the current-plateau. Moreover, the model also reproduces the line-shapes of the <i>I-V</i> spectra measured on In<sub>0.53</sub>Ga<sub>0.47</sub>As.

Interplay of intrinsic and extrinsic states in pinning and passivation of m-plane facets of GaN n-p-n junctions

Intrinsic and extrinsic pinning and passivation of m-plane cleavage facets of GaN n-p-n junctions were investigated by cross-sectional scanning tunneling microscopy and spectroscopy. On freshly cleaved and clean p-type GaN(101¯0) surfaces, the Fermi level is found to be extrinsically pinned by defect states, whereas n-type surfaces are intrinsically pinned by the empty surface state. For both types of doping, air exposure reduces the density of pinning states and shifts the pinning levels toward the band edges. These effects are assigned to water adsorption and dissociation, passivating intrinsic and extrinsic gap states. The revealed delicate interplay of intrinsic and extrinsic surface states at GaN(101¯0) surfaces is a critical factor for realizing flatband conditions at sidewall facets of nanowires exhibiting complex doping structures.

Cross-sectional scanning tunneling microscopy of InAs/GaAs(001) submonolayer quantum dots

Cross-sectional scanning tunneling microscopy (X-STM) was employed to characterize the InAs submonolayer quantum dots (SMLQDs) grown on top of a Si-doped GaAs(001) substrate in the presence of (2X4) and c(4X4) surface reconstructions. Multiple layers were grown under different conditions to study their effects on the formation, morphology and local composition of the SMLQDs. The morphological and compositional variations in SMLQDs were observed by both filled and emptystate imaging. A detailed analysis of indium segregation in the SMLQDs layers was described by fitting local indium concentration profile with a standard segregation model. A strong influence of arsenic flux over the formation of the SMLQDs and indium incorporation was observed and reported. We investigated the well-width fluctuations of the InGaAs quantum well (QW) in which SMLQDs were formed . The monolayer fluctuations of the well width were negligible compared to the more pronounced compositional fluctuations in all the layers. Keywords: Submonolayer quantum dots, Surface reconstruction, X-STM, Indium segregation

N−nH complexes in GaAs studied at the atomic scale by cross-sectional scanning tunneling microscopy

Hydrogenation of nitrogen (N) doped GaAs allows for reversible tuning of the bandgap and the creation of site controlled quantum dots through the manipulation of N-nH complexes, N-nH complexes, wherein a nitrogen atom is surrounded by n hydrogen (H) atoms. Here we employ cross-sectional scanning tunneling microscopy (X-STM) to study these complexes in the GaAs (110) surface at the atomic scale. In addition to that we performed density functional theory (DFT) calculations to determine the atomic properties of the N-nH complexes. We argue that at or near the (110) GaAs surface two H atoms from N-nH complexes dissociate as an H$_2$ molecule. We observe multiple features related to the hydrogenation process, of which a subset is classified as N-1H complexes. These N-1H related features show an apparent reduction of the local density of states (LDOS), characteristic to N atoms in the GaAs (110) surface with an additional apparent localized enhancement of the LDOS located in one of three crystal directions. N-nH features can be manipulated with the STM tip. Showing in one case a switching behavior between two mirror-symmetric states and in another case a removal of the localized enhancement of the LDOS. The disappearance of the bright contrast is most likely a signature of the removal of an H atom from the N-nH complex.

Probing the local electronic structure of isovalent Bi atoms in InP

Cross-sectional scanning tunneling microscopy (X-STM) is used to experimentally study the influence of isovalent Bi atoms on the electronic structure of InP. We map the spatial pattern of the Bi impurity state, which originates from Bi atoms down to the sixth layer below the surface, in topographic, filled state X-STM images on the natural $\{110\}$ cleavage planes. The Bi impurity state has a highly anisotropic bowtie-like structure and extends over several lattice sites. These Bi-induced charge redistributions extend along the $\left\langle 110\right\rangle$ directions, which define the bowtie-like structures we observe. Local tight-binding calculations reproduce the experimentally observed spatial structure of the Bi impurity state. In addition, the influence of the Bi atoms on the electronic structure is investigated in scanning tunneling spectroscopy measurements. These measurements show that Bi induces a resonant state in the valence band, which shifts the band edge towards higher energies. This is in good agreement to first principles calculations. Furthermore, we show that the energetic position of the Bi induced resonance and its influence on the onset of the valence band edge depend crucially on the position of the Bi atoms relative to the cleavage plane.

Elongated Nanodomains and Molecular Intermixing Induced Doping in Organic Photovoltaic Active Layers with Electric Field Treatment

The effects of the electric-field-assisted annealing on the bulk heterojunction nano-morphology in the P3HT/PCBM active layer of the organic photovoltaic cells (OPVCs) are presented here. It was widely accepted that the electric-field-assisted annealing will facilitate the P3HT, the polar polymer, to be better crystalline to enhance the charge mobility, hence the improvement of the OPVC performance. The influences on the nano-morphology of the electron donor and accepter domains are not well understood. Here, using the cross-sectional scanning tunneling microscopy and spectroscopy (XSTM/S), the electric-field-assisted annealing treatment is found to influence the molecular domains to be elongated with the orientation near the direction of the external electric field. The elongation of the molecular domains is believed to facilitate the domain percolation, which causes higher charge mobility, hence the higher short-circuit current density (Jsc). On the other hand, it was also observed that the electronic properties of the P3HT-rich and PCBM-rich domains in the electric-field-assisted annealed samples showed smaller energy band gaps and smaller molecular orbital offset between the two domains, which is argued to decrease the open circuit voltage (Voc) and negatively impact the OPVC performance. Based on the X-ray diffraction (XRD) and small angle X-ray scattering (SAXS) results, the altered electronic properties are argued to be due to the molecular intermixing induced doping effects. These results point out competing factors affecting the OPVC performance with the electric-field-assisted annealing treatment.