Principles of Semiconductor Surface Reconstruction

Semiconductor surfaces are known to reconstruct, i.e., their surface atomic geometries differ from those of the corresponding surface planes in the bulk material. For clean tetrahedrally coordinated semiconductors, these reconstructed geometries are shown to be predicted by five simple principles. These principles are illustrated by the specific examples of Si(100)-(2x1), Si(111)-(2x1), GaAs(100)-c(2x8), GaAs(111)-(2x2), and relaxed zincblende (110) surfaces. The concept of universal (i.e., material independent) semiconductor surface structures is introduced and shown to be characteristic of the cleavage surfaces of tetrahedrally coordinated compound semiconductors. The role of scanning tunneling microscopy in identifying and validating these principles is highlighted

Growth of epitaxial silicon layers by ion beam sputtering

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Growth and characterisation of MnSb thin films and interfaces

The deposition of Mn on to reconstructed InSb and GaAs surfaces has been studied by re ection high-energy electron diffraction (RHEED), atomic force microscopy and scanning tunnelling microscopy. On both Ga- and As-terminated GaAs(001), a Mn-induced (2x2) reconstruction is observed. In contrast, there are no well defined Mn-induced surface reconstructions on InSb. Islands are observed to form on all of the surfaces studied, with islands on the Group III-rich surfaces composed of elemental Mn and of an alloy on the Group V-rich surfaces. The conversion from Group III(V)-rich to Group V(III)-rich surfaces are discussed in terms of basic thermodynamic quantities and a number of models for surface atom substitution are proposed as pathways for MnAs and MnSb island formation. A high resolution X-ray diffraction study (HRXRD) has been performed on niccolite, cubic and wurtzite crystallites present within MnSb thin films grown on GaAs(111) substrates. It is observed that the lattice parameters of the polymorphs do not depend on the film thickness or the time-corrected beam ux ratio, J. The niccolite phase is found to relax rapidly (within 3 nm) and the average c lattice parameter of these films is 5.791(1) A. Variations in the c lattice parameter indicate that the average stoichiometry of the films varies on a per sample basis and this may act to promote the formation of polymorphs. Cubic MnSb crystallites exhibit a large strain dispersion of approximately 1 % and a rhombohedral or trigonal distortion is believed to be the origin. Quantitative analysis of asymmetric reciprocal space maps reveals that films grown using the optimised conditions have the highest concentration of the cubic polymorph, with lower values of J in the optimised range promoting this polymorph. The growth of MnSb on Ge(001) and Ge(111) substrates has been investigated. On Ge(001) growth proceeds through the formation of three dimensional islands and no dependence on the growth conditions is observed. Evidence for (1102) and (1120) crystallites is seen in XRD and RHEED, respectively. The interface between the MnSb islands and the Ge(001) substrate is sharp with no evidence for interfacial reactivity. The epitaxial growth of MnSb on Ge(111) is reported for the first time. The growth orientation is confirmed to be (0001) by X-ray diffraction while the layers are found to be ferromagnetic with a Curie temperature in excess of 300 K

Surface Chemical Reactions at the Atomic Scale: Gas Reactions with Semiconductors Studied with Scanning Tunneling Microscopy

The vacuum tunneling microscope has been extensively utilized in the study of the surface atomic configuration of conducting materials. Analysis of features in both the tunneling images and in the tunnel junction I-V characteristic yields insight into a wide variety of processes occurring at surfaces. In the last few years, elementary chemical reactions occurring at surfaces have been examined in this manner, principally adsorption of simple gas species such as H2, O2, and NH3 on semiconductors and metals. Adsorption sites have been deduced from changes brought about in surface configuration subsequent to gas exposure. The relationship of these sites with one another and their evolution as a function of exposure has been utilized to constrain mechanisms for the adsorption process. More recently, work has been performed where the scanning tunneling microscope (STM) takes on an active role. Hydrogen terminated silicon surfaces have been prepared and imaged with the STM. The tunneling images and infrared absorption spectra showed that configurations of both the terraces and steps are radically changed due to hydrogen capping. Moreover, the low-energy high-current density electron source, which is formed by the STM tip, has been used to selectively desorb this species from the surface. This process results in configuration changes which are derived from both the desorption kinetics and the long-range configuration of the initial surface

Reflection High-Energy Electron Diffraction Studies of Indium Phosphide (100) and Growth on Indium and Indium Nitride on Silicon (100)

Study of the effects of atomic hydrogen exposure on structure and morphology of semiconductor surfaces is important for fundamental properties and applications. In this dissertation, the electron yield of a hydrogen-cleaned indium phosphide (InP) surface was measured and correlated to the development of the surface morphology, which was monitored by in situ reflection high-energy electron diffraction (RHEED). Atomic hydrogen treatment produced a clean, well-ordered, and (2x4)-reconstructed InP(100) surface. The quantum efficiency, after activation to negative electron affinity, and the secondary electron emission were shown to increase with hydrogen cleaning time. RHEED patterns of low-index InP(100) surface were modified by the step structure and resulted in splitting of the specular beam at the out-of-phase diffraction condition. Quantitative RHEED showed reduction in the average terrace width and a decrease of the adatom-vacancy density with hydrogen exposure. This suggests that atomic hydrogen etching occurs preferentially at terrace edges, and thermal diffusion on the surface causes changes in the terrace edge morphology, which result in the observed decrease in the average terrace width. The results show that the decrease in the surface disorder, measured from the RHEED intensity-to-background ratio, correlated with the increased quantum efficiency. The growth of group-III metals on Si surfaces has become an attractive area of research because of its scientific importance and great potential in technological applications. In this work, the growth dynamics, structure, and morphology of indium (In) on a vicinal Si(100)-(2×1) surface by femtosecond pulsed laser deposition (fsPLD) were studied using in situ RHEED and ex situ atomic force microscopy. Indium was found to grow on Si(100) by the Stranski-Krastanove mode. At room temperature, the initial growth formed strained two-dimensional (2D) layers in the In(2×1) structure followed by growth of three-dimensional islands. During the 2D growth, the surface diffusion coefficient of deposited In on the In(2×1) layer was estimated to be in the order of 10−14 cm2/s, from recovery of the RHEED intensity. This was attributed to surface diffusion of In clusters by step flow mode. The results suggest that fsPLD of In removed the reconstruction of the Si(100)-(2×1) surface in the early growth and resulted in the initial In(2x1) structure. Next, growth of In on Si(100)-(2×1) was studied at temperature of 350–420°C and showed formation of In(4×3) structure. The growth stages, probed by RHEED intensity relaxation, proceed in a two-step process, formation of small In clusters and surface diffusion to the terrace step edges with activation energy of 1.4±0.2 eV and diffusion rate constant of 1.0±0.1x1011 s −1. The terrace width dynamics and the related surface processes were studied during growth of the In(4×3) phase with increase in film coverage. Finally, the fsPLD was used to grow nitride films of InN on Si(100) substrates. A buffer layer of In was grown on Si(100) by fsPLD prior to growth of InN and different nitridation procedures were used

Croissance épitaxiale des matériaux semi-conducteurs III-V et IV sur graphène pour des applications optoélectroniques

L’hétéroépitaxie conventionnelle permet la croissance épitaxiale de couches cristallines de haute qualité sur des substrats compatibles. Cependant, en raison des désaccords de maille/thermique, la formation de défauts cristallins tels que les dislocations dans les couches hétéroépitaxiales entrave fortement l’hétérointégration de divers semi-conducteurs et le développement de dispositifs de haute performance. Alternativement, l’épitaxie Van der Waals (VdWE), un nouveau paradigme de croissance épitaxiale permet la croissance des semiconducteurs cristallins sur des matériaux 2D sans les contraintes susmentionnées. Ce nouveau concept d’hétéroépitaxie mettant en œuvre de faibles interactions de type VdW est principalement dicté par les propriétés de la surface des matériaux 2D. Le graphène, combinant la flexibilité mécanique et la faible liaison de surface, s’est avéré être l’un des matériaux 2D les plus populaires pour la croissance épitaxiale VdW. Ce concept a suscité un grand intérêt dans la communauté scientifique, mais sa mise en œuvre est entravée par la compréhension incomplète et immature des processus gouvernant l’étape de nucléation. Ainsi, cette question reste ouverte, car aucune solution viable n’a encore été proposée et il n’y a pas de vision claire sur cette étape fondamentale de la croissance. En effet, la nucléation étant un processus éphémère est très difficile à observer en détail avec les techniques d’analyse conventionnelles post-croissance. En outre, les chercheurs n’ont pas pu fournir de preuves tangibles pour les nombreuses spéculations proposées sur la cinétique des premiers stades de la croissance des semi-conducteurs à 3D sur le graphène (2D). Ce défi a soulevé la question suivante : « Le graphène est-il le substrat ultime pour résoudre les défis fondamentaux de l’hétérointégration des matériaux ayant des désaccords de maille? ». Pour cette raison, les mécanismes gouvernant la nucléation des matériaux sur graphène font l’objet de débats depuis plus d’une décennie. Dans cette thèse, nous avons démontré pour la première fois l’épitaxie VdW de Ge sur monocouche suspendue de graphène (S-SLG) par observation directe à l’intérieur d’un microscope électronique en transmission (TEM). Pour ce faire, la synthèse de couches de graphène de haute qualité a été développée. Le graphène a été synthétisé sur le Ge (100) par CVD en utilisant une voie compatible avec l’intégration verticale avec les semi-conducteurs. Lors de cette étude, nous avons démontré que l’état de surface du substrat joue un rôle crucial dans la qualité du graphène déposé. Ainsi, un traitement de surface efficace, basé sur l’acide bromhydrique (HBr) a été mis au point. En effet, des couches de graphène de haute qualité avec un ratio ID/IG aussi faible que 0,2 ont été obtenues sur substrat de Ge (100). Pour mieux contrôler la nucléation qui est la phase centrale de la croissance cristalline, nous proposons de nouvelles perspectives à partir des observations en temps réel de la croissance in situ de Ge sur graphène en utilisant un TEM à haute résolution (HR). Nous avons étudié les mécanismes clés régissant la nucléation et la croissance du matériau 3D sur la surface du graphène. Alors que la faible énergie de surface du graphène rend difficile la nucléation de Ge sur la surface propre sans défaut, une stratégie en deux étapes a été proposée : Nucléation à basse température (220 °C) et recuit à des températures plus élevées afin d’améliorer la qualité cristalline des cristaux de Ge. À travers les images HRTEM, nous avons déterminé une taille critique de 0,7-1 nm2 permettant la nucléation de Ge sur SLG. Cette taille critique, qui n’a jamais été rapportée avant ce rapport, est cohérente avec celle prédite par la théorie classique de la nucléation. En outre, les données en temps réel ont révélé que, en raison de faibles interactions vdW, les germes Ge peuvent flotter librement à la surface du substrat de graphène, et leuriv coalescence est gouverné par un processus de murissement d’Ostwald extrême rapide. Notre observation majeure, cependant, a été l’implémentation des doubles hétérostructures de Ge/SLG/Ge (3D/2D/3D). Dans les conditions expérimentales employées, nous avons découvert une diffusion verticale (DV) des particules de Ge à travers le réseau hexagonal compact du graphène. Un tel phénomène intrigant ne peut être observé à l’aide des méthodes conventionnelles d’analyse ex situ, qui sont normalement réalisées après la croissance. Ces résultats ont mis en évidence le mécanisme de croissance des semi-conducteurs sur les monocouches de graphène et ont offert une nouvelle voie vers des dispositifs hybrides semiconducteurs/graphène à hautes performances. Finalement, dans l’ambition d’optimiser la croissance de matériaux III-V avec de bonnes propriétés pour la VdWE, une nouvelle approche d’épitaxie hybride a été mise au point et évaluée. Cette technique hybride d’épitaxie, utilisant à la fois des sources solides et gazeuses, est alternative aux techniques standards comme l’épitaxie par faisceaux moléculaires (MBE) et chimiques (CBE). Les résultats expérimentaux de la croissance d’AlInAs et de GaInAs sur substrats d’InP, ont démontré que cette nouvelle approche est efficace pour croitre des couches avec d’excellentes propriétés cristallines, optiques et à faible dopage résiduel.Abstract : Conventional heteroepitaxy allows epitaxial growth of highly crystalline layers onto compatible substrates. However, due to the lattice/thermal mismatch, the formation of crystalline defects such as dislocations in heteroepitaxial layers severely impede the heterointegration of various semiconductors with complementary properties and the development of high-performance devices. Alternatively, Van der Waals epitaxy (vdWE), a new paradigm of epitaxial growth can enable the growth of crystalline semiconductors on 2D materials without the aforementioned constraints. This new concept of heteroepitaxy, mediated by weak VdW interactions, is mainly dictated by the surface properties of emerging 2D materials, which also have many novel electrical, optical, thermal, and mechanical properties. Graphene, a 2D material that combines mechanical flexibility and weak surface bonding, is found to be one of the most popular for VdW epitaxial growth. This is currently the subject of intense research in the community, but tangible exploitation of such a compelling phenomenon is impeded by the immature and incomplete understanding of the nucleation and growth processes. Therefore, the question remains open as no viable solution was reached yet and there is no clear picture of the nucleation step. In fact, the nucleation process, which is a fleeting event is very difficult to observe in detail by using conventional ex situ analyses. Besides, researchers could not provide hard evidence for the several speculations involving the kinetics of threedimensional (3D) crystal growth over 2D graphene, at early stages of growth process. This challenge raised the following question: “Is graphene the ultimate substrate to solve fundamental challenges of heterointegration of mismatched materials?” For matters as such, governing mechanisms for nucleation on graphene has been debated for more than a decade now; however, despite the promises of VdW epitaxy, the lack of understanding of basic phenomena is still a major obstacle to the new applications. In this thesis, we demonstrated for the first time, in-situ TEM observation of VdWE of Ge on freestanding single layer graphene suspended graphene monolayers (S-SLG). To do this, the synthesis of high-quality graphene layers was developed. Using a compatible approach for the monolithic integration of 3D semiconductors on 2D materials, graphene was synthesized on germanium (Ge) (100) by CVD. In this study, we demonstrated that the physical and chemical surface state of the substrate play a crucial role in the quality of deposited graphene layers. Thus, an effective surface treatment, based on hydrobromic acid (HBr) has been developed. Highquality graphene layers with an ID/IG ratio as low as 0.2 were obtained on Ge (100). To better control the nucleation that is the central phase of crystalline growth, we offer new perspectives from real-time observations of Ge's in situ growth on graphene using a highresolution TEM. Through meticulous analysis of the collected video data, we investigated the key mechanisms governing the nucleation and the growth of sp3-bonded 3D material on the weakly interacting graphene surfaces. Whereas the low surface energy of the graphene layer prevented the nucleation of Ge over pristine and defect-free graphene, a two-step strategy consists of nucleating at low temperature (220 °C) and annealing at higher temperatures, resulted in growth of highly crystalline quality Ge. In view of the high-resolution TEM images, we determined a critical size of 0.7-1 nm2 enabling the nucleation of Ge on SLG. This critical size, which has never been reported prior to this report, is consistent with the one predicted by the classical nucleation theory. Moreover, the real-time data revealed that, due to weak VdW interactions, the Ge germs can freely float on the surface of graphene substrate,vi making the coarsening process of Ge layer to be dominated by a very fast Ostwald ripening process. Our major finding, however, was achieved by examining the 3D/2D/3D (2D/2D/2D) configuration of the Ge/graphene/Ge double heterostructures. Under the experimental conditions employed in our work, we recorded a vertical diffusion (VD) of Ge particles through the closely packed hexagonal ring of single layers of graphene. Such an intriguing and yet unexplored phenomenon cannot be obtained by means of the conventional ex situ analysis methods, which are normally carried out after the growth of material. These findings highlighted the growth mechanism of semiconductors on graphene monolayers and provided a new path to high-performance semiconductor/graphene hybrid devices. Finally, in the ambition to optimize the growth of III-V materials with good properties for VdWE, a new hybrid epitaxy approach has been proposed and evaluated. This hybrid epitaxy technique, using both solid and gaseous sources, is an alternative approach to standard techniques such as molecular beam epitaxy (MBE) and chemical beam epitaxy (CBE). Experimental results of the growth of AlInAs and GaInAs on InP substrates showed that this new approach is effective in growing layers with excellent crystalline, optical properties, and low residual doping

Ge quantum dot arrays grown by ultrahigh vacuum molecular beam epitaxy on the Si(001) surface: nucleation, morphology and CMOS compatibility

Issues of morphology, nucleation and growth of Ge cluster arrays deposited by ultrahigh vacuum molecular beam epitaxy on the Si(001) surface are considered. Difference in nucleation of quantum dots during Ge deposition at low (<600 deg C) and high (>600 deg. C) temperatures is studied by high resolution scanning tunneling microscopy. The atomic models of growth of both species of Ge huts---pyramids and wedges---are proposed. The growth cycle of Ge QD arrays at low temperatures is explored. A problem of lowering of the array formation temperature is discussed with the focus on CMOS compatibility of the entire process; a special attention is paid upon approaches to reduction of treatment temperature during the Si(001) surface pre-growth cleaning, which is at once a key and the highest-temperature phase of the Ge/Si(001) quantum dot dense array formation process. The temperature of the Si clean surface preparation, the final high-temperature step of which is, as a rule, carried out directly in the MBE chamber just before the structure deposition, determines the compatibility of formation process of Ge-QD-array based devices with the CMOS manufacturing cycle. Silicon surface hydrogenation at the final stage of its wet chemical etching during the preliminary cleaning is proposed as a possible way of efficient reduction of the Si wafer pre-growth annealing temperature.Comment: 30 pages, 11 figure

The Influence of Metal Substrates on the Electronic States of Metal Overlayers

The aim of this paper is to provide an introduction to the electronic structure of very thin film (one to ten monolayers) overlayers using examples from studies of Hg overlayers on Ag(100) and Fe thin film overlayers. Interracial states as a result of the interaction of the substrate and overlayer, as well as the new electronic states of the overlayer caused by a new crystallographic structure can modify the overlayer metal electronic structure. Additional changes in the overlayer electronic structure arise from the reduced dimensionality (2 dimensionality as opposed to 3 dimensionality) of the thin film. We discuss the photoemission techniques for determining the electronic structures of thin metal over layers. Layer by layer growth of the overlayer is important for such studies as is knowledge of the overlayer structure. We have summarized our current understanding of metal overlayers in tables and attempt to demonstrate that further progress in combining structural and photoemission studies is necessary for better fundamental understanding of metal overlayers

Heteroepitaxy of 3-5 compound semiconductors on insulating substrates Interim report

Heteroepitaxial growth of GaAs films on aluminum oxide substrates by trimethylgallium-arsine proces