Two-dimensional (2D) materials have attracted extensive research interest in recent years. Among them, graphene and the semiconducting transition metal dichalcogenides (TMDs) are considered as promising candidates for future device applications due to their unique atomic thickness and outstanding properties. The study on graphene and TMDs has demonstrated great potential to further push the scaling of devices into the sub-10 nanometer regime and enable endless opportunities of novel device architectures for the next generation. In this thesis, crucial challenges facing 2D materials are investigated from material synthesis to electronic applications. A comprehensive review of the direct synthesis of graphene on arbitrary substrates with an emphasis on the metal-catalyst-free synthesis is given, followed by a detailed study of the contact engineering in TMDs with a focus on the strategies to lower the contact resistance. Effective approaches have been demonstrated to solve these issues. These include: (1) metal-catalyst-free synthesis of graphene on various insulating substrates; (2) Fermi level pinning observed in TMDs and integration of graphene contact to lower the contact resistance; and (3) application of metal-insulator-semiconductor (MIS) contact in TMD field-effect transistors (FETs). First, a direct low-temperature synthesis of graphene on insulators without any metal catalysts has been realized. The effects of carbon sources, NH3/H2 concentrations, and insulating substrates on the material synthesis have been systematically investigated. Graphene transistors based on the as-grown material have been fabricated to study the electronic properties, which can further confirm the nitrogen-doped graphene has been synthesized from the electrical characterizations. Then electronic devices focusing on the semiconducting TMDs has been studied. The Fermi level pinning has been observed and studied in WS2 FETs with four metal materials. A novel method of using graphene as an insertion layer between the metal and TMDs has been proven to effectively reduce the contact resistance. Owing to the benefit of tuning the graphene work function via the electric field, the contact resistance can further be reduced. Finally, the effectiveness of MIS contacts in WS2 FETs has been demonstrated. A thickness dependence research has been conducted to find the optimal thickness of the inserted insulator. Moreover, the possible physical mechanism of how this MIS contact reduces the contact resistance in 2D materials has been discussed.

This thesis is a sandwich thesis composed of three papers that are published in refereed journals or conferences. The first paper is a systematic experimental study conducted to identify the first phase to form during cobalt germanidation. Hexagonal β-Co5Ge3 was the first phase to form at temperatures as low as 227°C followed by monoclinic CoGe as the second phase at the same temperature. We also report for the first time that both phases that formed were highly ordered partial epitaxial crystal orientations suggesting that both of those low-temperature phases could potentially serve as high quality contacts for germanium based devices with a very low thermal budget which is advantageous for the process design. Those results contributed to a better understanding of cobalt germanidation leading to the first multiphase technology computer aided design model presented in the second paper. This kinetic model for cobalt germanide growth can predict the resulting phase based on anneal time, temperature, and ambient. The model has been calibrated to experimental results. This predictive model can help in the design of cobalt germanide contacts with low resistance and can serve as a general modeling framework for multiphase solid state reaction binary systems. A comprehensive survey of the experimental results for formation of cobalt germanides is discussed and the data are reconciled in the third paper. Factors affecting the resulting phases and their quality are identified and some optimum choices for the experimental parameters are pointed based on the survey. The role of germanium crystal orientation in ohmic and Schottky properties of the contact is analyzed. Fermi level pinning plays a role mainly on metal/(100) n-type Ge interfaces and its role is minimal on p-type Ge and other crystalline orientations. Schottky Barrier Heights for cobalt germanide contacts reported in the literature are surveyed. Crystalline cobalt germanides, forming when Co is deposited at high temperatures, are expected to have lower interface resistivities compared to those reported. The work is important because contact resistance has become one of the most important factors in advanced complementary metal oxide semiconductor (CMOS) technology and advanced devices already include germanium (Ge) in the source/drain regions of devices. It is also important because heating at the interface due to contact resistance is one of the key challenges in power devices and cobalt germanide can be used both for Si and Ge based devices as well as for gallium nitride (GaN) devices. The latter application is possible because cobalt germanide is lattice-matched to GaN. / Thesis / Doctor of Philosophy (PhD) / The main goal of this thesis is to create predictive empirical, mathematical, and physical models to help the designer of the semiconductor process technology to design high quality electric contacts, namely cobalt germanides, to their semiconductor devices, germanium based. The choice of cobalt germanides is motivated by their expected superior quality given the possibility of growing them in crystalline form. We settled a theoretical and experimental controversy regarding the first phase to form by conducting experiments demonstrating that low-temperature forming cobalt germanide phases are highly ordered and could serve as high quality contacts. A predictive physical based mathematical model was developed to assist the designer in obtaining the desired cobalt germanide phase for its needed electrical properties by design. Factors affecting the quality of the germanide were identified based on an extensive survey and the optimum choices for the parameters to obtain high quality contact were pointed.

Silicon carbide is a promising wide bandgap semiconductormaterial for high-temperature, high-power, and high-frequencydevice applications. However, there are still a number offactors that are limiting the device performance. Among them,one of the most important and critical factors is the formationof low resistivity Ohmic contacts and high-temperature stableSchottky diodes on silicon carbide. In this thesis, different metals (TiW, Ti, TiC, Al, and Ni)and different deposition techniques (sputtering andevaporation) were suggested and investigated for this purpose.Both electrical and material characterizations were performedusing various techniques, such as I-V, C-V, RBS, XRD, XPS,LEED, SEM, AFM, and SIMS. For the Schottky contacts to n- and p-type 4H-SiC, sputteredTiW Schottky contacts had excellent rectifying behavior afterannealing at 500 ºC in vacuum with a thermally stableideality factor of 1.06 and 1.08 for n- and p-type,respectively. It was also observed that the SBH for p-type SiC(ΦBp) strongly depends on the choice the metal with alinear relationship ΦBp= 4.51 - 0.58Φm, indicating no strong Fermi-level pinning.Finally, the behavior of Schottky diodes was investigated byincorporation of size-selected Au nano-particles in Ti Schottkycontacts on silicon carbide. The reduction of the SBH isexplained by using a simple dipole layer approach, withenhanced electric field at the interface due to the small sizeof the circular patch (Au nano-particles) and large differenceof the barrier height between two metals (Ti and Au) on both n-and p-SiC. For the Ohmic contacts, titanium carbide (TiC) was used ascontacts to both n- and p-type 4H-SiC epilayers as well as onAl implanted layers. The TiC contacts were epitaxiallydeposited using a co-evaporation method with an e-beam Tisource and a Knudsen cell for C60, in a UHV system at low substrate temperature(500 ºC). In addition, we extensively investigatedsputtered TiW (weight ratio 30:70) as well as evaporated NiOhmic contacts on both n- and p-type epilayers of SiC. The bestOhmic contacts to n-type SiC are annealed Ni (&gt;950ºC)with the specific contact resistance of ≈ 8× 10-6Ω cm2with doping concentration of 1.1 × 10-19cm-3while annealed TiW and TiC contacts are thepreferred contacts to p-type SiC. From long-term reliabilitytests at high temperature (500 ºC or 600 ºC) invacuum and oxidizing (20% O2/N2) ambient, TiW contacts with a platinum cappinglayer (Pt/Ti/TiW) had stable specific contact resistances for&gt;300 hours. <b>Keywords</b>: silicon carbide, Ohmic and Schottky contacts,co-evaporation, current-voltage, capacitance-voltagemeasurement, power devices, nano-particles, Schottky barrierheight lowering, and TLM structures.

<p>Silicon carbide is a promising wide bandgap semiconductormaterial for high-temperature, high-power, and high-frequencydevice applications. However, there are still a number offactors that are limiting the device performance. Among them,one of the most important and critical factors is the formationof low resistivity Ohmic contacts and high-temperature stableSchottky diodes on silicon carbide.</p><p>In this thesis, different metals (TiW, Ti, TiC, Al, and Ni)and different deposition techniques (sputtering andevaporation) were suggested and investigated for this purpose.Both electrical and material characterizations were performedusing various techniques, such as I-V, C-V, RBS, XRD, XPS,LEED, SEM, AFM, and SIMS.</p><p>For the Schottky contacts to n- and p-type 4H-SiC, sputteredTiW Schottky contacts had excellent rectifying behavior afterannealing at 500 ºC in vacuum with a thermally stableideality factor of 1.06 and 1.08 for n- and p-type,respectively. It was also observed that the SBH for p-type SiC(Φ_Bp) strongly depends on the choice the metal with alinear relationship Φ_Bp= 4.51 - 0.58Φ_m, indicating no strong Fermi-level pinning.Finally, the behavior of Schottky diodes was investigated byincorporation of size-selected Au nano-particles in Ti Schottkycontacts on silicon carbide. The reduction of the SBH isexplained by using a simple dipole layer approach, withenhanced electric field at the interface due to the small sizeof the circular patch (Au nano-particles) and large differenceof the barrier height between two metals (Ti and Au) on both n-and p-SiC.</p><p>For the Ohmic contacts, titanium carbide (TiC) was used ascontacts to both n- and p-type 4H-SiC epilayers as well as onAl implanted layers. The TiC contacts were epitaxiallydeposited using a co-evaporation method with an e-beam Tisource and a Knudsen cell for C₆₀, in a UHV system at low substrate temperature(500 ºC). In addition, we extensively investigatedsputtered TiW (weight ratio 30:70) as well as evaporated NiOhmic contacts on both n- and p-type epilayers of SiC. The bestOhmic contacts to n-type SiC are annealed Ni (>950ºC)with the specific contact resistance of ≈ 8× 10^-6Ω cm²with doping concentration of 1.1 × 10^-19cm^-3while annealed TiW and TiC contacts are thepreferred contacts to p-type SiC. From long-term reliabilitytests at high temperature (500 ºC or 600 ºC) invacuum and oxidizing (20% O₂/N₂) ambient, TiW contacts with a platinum cappinglayer (Pt/Ti/TiW) had stable specific contact resistances for>300 hours.</p><p><b>Keywords</b>: silicon carbide, Ohmic and Schottky contacts,co-evaporation, current-voltage, capacitance-voltagemeasurement, power devices, nano-particles, Schottky barrierheight lowering, and TLM structures.</p>

Táto práca sa zaoberá technikou výroby samousporiadaných nanoštruktúr pre elektrické aplikácie. Prototypy boli pripravené anodickou oxidáciou v dvoch dĺžkach a tromi rôznymi tepelnými úpravami. Štrukturálna charakterizácia bola spravená pomocou techniky SEM, TEM a EDX a vyhodnotenie nielen z štrukturálneho, ale aj z materiálového hľadiska. Jedinečná koreňová štruktúra samousporiadaných nanotyčiniek bola vyhodnotená a porovnaná po troch rôznych tepelných úpravách: po anodizácii, po vákuovom žíhaní, a po žíhaní vo vzduchu. Všetky prototypy obsahujú nanotyčinky s amorfnou štruktúrou, ale našli sa však aj nanokryštály pod koreňovými štruktúrami. Elektrická charakterizácia prototypov ukázala: odporové spínacie správanie (RS), diódové charakteristiky a charakteristiku podobnú pre diódy s kapacitorom. Aktívny povrch pre spínací mechanizmus je v hornej časti nanoštruktúr na rozhraní nanotyčiniek a zlatej elektródy. Výška Schottkyho bariéry na rozhraní Ti / TiO2 bola vypočítaná dvoma spôsobmi a pre všetky tri zariadenia bola nižšia ako 1,11 eV.

Metal-semiconductor contacts have been widely studied in the past 60 years. These structures are of importance in the microelectronics industry. As the scaling down of silicon-based complementary metal-oxide-semiconductor (CMOS) devices becomes more and more challenging, new material and device structures to relax this physical limitation in device scaling are now required. Germanium (Ge) has been proposed as a potential alternative to silicon. In this thesis a systematic study of the thermally induced reaction of transition metals with the n-Ge substrate is outlined. Investigations in the change of the electrical properties of the metal germanide structures is studied in a wide range of temperatures. Current-voltage (I-V), capacitance-voltage (C-V), deep level transient spectroscopy (DLTS) and high-resolution Laplace-DLTS (L-DLTS) techniques have been used for the electrical characterization of the fabricated Schottky contacts. Results obtained indicate the variation of the electrical properties of these Schottky contacts can be attributed to combined effects of interfacial reactions and phase transformation during the annealing process. The barrier height distribution in identically prepared Schottky contacts on n-Ge (100) showed that the barrier heights and ideality factors varied from diode to diode even though they were identically fabricated. The properties of the n-Ge Schottky contacts have revealed a strong dependence on temperature. The current transport mechanism has been shown to be predominantly thermionic emission at high temperatures while at low temperatures, the Schottky contacts have exhibited the dominance of the generation-recombination current mechanism. The variation of the Schottky barrier heights at low temperatures have been attributed to barrier inhomogeneities at the metal-semiconductor (MS) interface. Results from defect characterization by DLTS show that the E-centre is the dominant defect introduced in n-Ge by electron beam deposition during contact fabrication and substitutional related defects are induced during the annealing process. The identification of some of the defects was achieved by using defect properties, defect signature, annealing mechanisms and annealing behaviour and comparing these properties to the results from theoretical defect models. Annealing showed that defects in Ge can be removed by low thermal budget of between 250–350°C. Finally, structural characterization of these samples was performed by scanning electron microscopy (SEM) and Rutherford backscattering spectrometry (RBS) techniques. From the SEM images it can be observed that the onset temperature for agglomeration in the 30 nm Ni/n-Ge (100), and Pt/-, Ir/- and Ru/n-Ge (100) systems occur at 500–600°C and 600–700°C, respectively. / Thesis (PhD)--University of Pretoria, 2010. / Physics / unrestricted

A study of defects in semiconductors is vital as defects tend to influence device operation by modifying their electrical and optoelectronic properties. This influence can at times be desirable in the case of fast switching devices and sometimes undesirable as they may reduce the efficiency of optoelectronic devices. ZnO is a wide bandgap material with a potential for fabricating UV light emitting diodes, lasers and white lighting devices only after the realization of reproducible p-type material. The realization of p-type material is greatly affected by doping asymmetry. The self-compensation behaviour by its native defects has hindered the success in obtaining the p-type material. Hence there is need to understand the electronic properties, formation and annealing-out of these defects for controlled material doping. Space charge spectroscopic techniques are powerful tools for studying the electronic properties of electrically active defects in semiconductors since they can reveal information about the defect “signatures”. In this study, novel Schottky contacts with low leakage currents of the order of 10-11 A at 2.0 V, barrier heights of 0.60 – 0.80 eV and low series resistance, fabricated on hydrogen peroxide treated melt-grown single crystal ZnO samples, were demonstrated. Investigations on the dependence of the Schottky contact parameters on fabrication techniques and different metals were performed. Resistive evaporation proved to produce contacts with lower series resistance, higher barrier heights and low reverse currents compared to the electron-beam deposition technique. Deep level transient spectroscopy (DLTS) and Laplace-DLTS have been employed to study the electronic properties of electrically active deep level defects in ZnO. Results revealed the presence of three prominent deep level defects (E1, E2 and E3) in the as-received ZnO samples. Electron-beam deposited contacts indicated the presence of the E1, E2 and E3 and the introduction of new deep level defects. These induced deep levels have been attributed to stray electrons and ionized particles, present in the deposition system during contact fabrication. Exposure of ZnO to high temperatures induces deep level defects. Annealing samples in the 300°C – 600°C temperature range in Ar + O2 induces the E4 deep level with a very high capture cross-section. This deep level transforms at every annealing temperature. Its instability at room temperature has been demonstrated by a change in the peak temperature position with time. This deep level was broad, indicating that it consists of two or more closely spaced energy levels. Laplace-DLTS was successfully employed to resolve the closely spaced energy levels. Annealing samples at 700°C in Ar and O2 anneals-out E4 and induces the Ex deep level defect with an activation enthalpy of approximately 160 – 180 meV. Vacuum annealing performed in the 400°C – 700°C temperature range did not induce any deep level defects. Since the radiation hardness of ZnO is crucial in space applications, 1.6 MeV proton irradiation was performed. DLTS revealed the introduction of the E4 deep level with an activation enthalpy of approximately 530 meV, which proved to be stable at room temperature and atmospheric pressure since its properties didn’t change over a period of 12 months. / Thesis (PhD)--University of Pretoria, 2013. / Physics / unrestricted

En raison de l'attrait croissant pour les applications haute tension, haute tempé-rature et haute fréquence, le carbure de silicium (SiC) continue d'attirer l'attention du monde entier comme l'un des candidats les plus compétitifs pour remplacer le sili-cium dans le champ électrique de puissance. Entre-temps, il est important de carac-tériser les défauts des semi-conducteurs et d'évaluer leur influence sur les dispositifs de puissance puisqu'ils sont directement liés à la durée de vie du véhicule porteur. De plus, la fiabilité, qui est également affectée par les défauts, devient une question incontournable dans le domaine de l'électricité de puissance.Les défauts, y compris les défauts ponctuels et les défauts prolongés, peuvent introduire des niveaux d'énergie supplémentaires dans la bande passante du SiC en raison de divers métaux comme le Ti, le Fe ou le réseau imparfait lui-même. En tant que méthode de caractérisation des défauts largement utilisée, la spectroscopie à transitoires en profondeur (DLTS) est supérieure pour déterminer l'énergie d'activa-tion Ea , la section efficace de capture Sigma et la concentration des défauts Nt ainsi que le profil des défauts dans la région d'épuisement grâce à ses divers modes de test et son analyse numérique avancée. La détermination de la hauteur de la barrière Schottky (HBS) prête à confusion depuis longtemps. Outre les mesures expérimentales selon les caractéristiques I-V ou C-V, différents modèles ont été proposés, de la distribution gaussienne du HBS au modèle de fluctuation potentielle. Il s'est avéré que ces modèles sont reliés à l'aide d'une hauteur de barrière à bande plate Phi_BF . Le tracé de Richardson basé sur Phi_BF ainsi que le modèle de fluctuation potentielle deviennent un outil puissant pour la caractérisation HBS. Les HBSs avec différents contacts métalliques ont été caractéri-sés, et les diodes à barrières multiples sont vérifiées par différents modèles. Les défauts des électrons dans le SiC ont été étudiés avec des diodes Schottky et PiN, tandis que les défauts des trous ont été étudiés dans des conditions d'injec-tion forte sur des diodes PiN. 9 niveaux d'électrons et 4 niveaux de trous sont com-munément trouvés dans SiC-4H. Une relation linéaire entre le Ea extrait et le log(sigma) indique l'existence de la température intrinsèque de chaque défaut. Cependant, au-cune différence évidente n'a été constatée en ce qui concerne l'inhomogénéité de la barrière à l'oxyde d'éther ou le métal de contact. De plus, les pièges à électrons près de la surface et les charges positives fixes dans la couche d'oxyde ont été étudiés sur des MOSFET de puissance SiC par polarisation de porte à haute température (HTGB) et dose ionisante totale (TID) provoquées par irradiation. Un modèle HTGB-assist-TID a été établi afin d'ex-plain l'effet de synergie. / Due to the increasing appeal to the high voltage, high temperature and high fre-quency applications, Silicon Carbide (SiC) is continuing attracting world’s attention as one of the most competitive candidate for replacing silicon in power electric field. Meanwhile, it is important to characterize the defects in semiconductors and to in-vestigate their influences on power devices since they are directly linked to the car-rier lifetime. Moreover, reliability that is also affected by defects becomes an una-voidable issue now in power electrics. Defects, including point defects and extended defects, can introduce additional energy levels in the bandgap of SiC due to various metallic impurities such as Ti, Fe or intrinsic defects (vacancies, interstitial…) of the cristalline lattice itself. As one of the widely used defect characterization method, Deep Level Transient Spectroscopy (DLTS) is superior in determining the activation energy Ea , capture cross section sigma and defect concentration Nt as well as the defect profile in the depletion region thanks to its diverse testing modes and advanced numerical analysis. Determination of Schottky Barrier Height (SBH) has been confusing for long time. Apart from experimental measurement according to I-V or C-V characteristics, various models from Gaussian distribution of SBH to potential fluctuation model have been put forward. Now it was found that these models are connected with the help of flat-band barrier height Phi_BF . The Richardson plot based on Phi_BF along with the potential fluctuation model becomes a powerful tool for SBH characterization. SBHs with different metal contacts were characterized, and the diodes with multi-barrier are verified by different models. Electron traps in SiC were studied in Schottky and PiN diodes, while hole traps were investigated under strong injection conditions in PiN diodes. 9 electron traps and 4 hole traps have been found in our samples of 4H-SiC. A linear relationship between the extracted Ea and log(sigma) indicates the existence of the intrinsic temper-ature of each defects. However, no obvious difference has been found related to ei-ther barrier inhomogeneity or contact metal. Furthermore, the electron traps near in-terface and fixed positive charges in the oxide layer were investigated on SiC power MOSFETs by High Temperature Gate Bias (HTGB) and Total Ionizing Dose (TID) caused by irradiation. An HTGB-assist-TID model was established in order to ex-plain the synergetic effect.