This work establishes a solid foundation for the use of indirect band gap semiconductors for light emitting application and presents the work on development of white light emitting diodes (LEDs) in silicon carbide (SiC). Novel laser doping has been utilized to fabricate white light emitting diodes in 6H-SiC (n-type N) and 4H-SiC (p-type Al) wafers. The emission of different colors to ultimately generate white light is tailored on the basis of donor acceptor pair (DAP) recombination mechanism for luminescence. A Q-switched Nd:YAG pulse laser (1064 nm wavelength) was used to carry out the doping experiments. The p and n regions of the white SiC LED were fabricated by laser doping an n-type 6H-SiC and p-type 4H-SiC wafer substrates with respective dopants. Cr, B and Al were used as p-type dopants (acceptors) while N and Se were used as n-type dopants (donors). Deep and shallow donor and acceptor impurity level states formed by these dopants tailor the color properties for pure white light emission. The electromagnetic field of lasers and non-equilibrium doping conditions enable laser doping of SiC with increased dopant diffusivity and enhanced solid solubility. A thermal model is utilized to determine the laser doping parameters for temperature distribution at various depths of the wafer and a diffusion model is presented including the effects of Fick's diffusion, laser electromagnetic field and thermal stresses due to localized laser heating on the mass flux of dopant atoms. The dopant diffusivity is calculated as a function of temperature at different depths of the wafer based on measured dopant concentration profile. The maximum diffusivities achieved in this study are 4.61x10-10 cm2/s at 2898 K and 6.92x10-12 cm2/s at 3046 K for Cr in 6H-SiC and 4H-SiC respectively. Secondary ion mass spectrometric (SIMS) analysis showed the concentration profile of Cr in SiC having a penetration depth ranging from 80 nm in p-type 4H-SiC to 1.5 [micro]m in n-type 6H-SiC substrates respectively. The SIMS data revealed enhanced solid solubility (2.29x1019 cm-3 in 6H-SiC and 1.42x1919 cm-3 in 4H-SiC) beyond the equilibrium limit (3x1017 cm-3 in 6H-SiC above 2500 [degrees]C) for Cr in SiC. It also revealed similar effects for Al and N. The roughness, surface chemistry and crystalline integrity of the doped sample were examined by optical interferometer, energy dispersive X-ray spectrometry (EDS) and transmission electron microscopy (TEM) respectively. Inspite of the larger atomic size of Cr compared to Si and C, the non-equilibrium conditions during laser doping allow effective incorporation of dopant atoms into the SiC lattice without causing any damage to the surface or crystal lattice. Deep Level Transient Spectroscopy (DLTS) confirmed the deep level acceptor state of Cr with activation energies of Ev+0.80 eV in 4H-SiC and Ev+0.45 eV in 6H-SiC. The Hall Effect measurements showed the hole concentration to be 1.98x1019 cm-3 which is almost twice the average Cr concentration (1x1019 cm-3) obtained from the SIMS data. These data confirmed that almost all of the Cr atoms were completely activated to the double acceptor state by the laser doping process without requiring any subsequent annealing step. Electroluminescence studies showed blue (460-498 nm), blue-green (500-520 nm) green (521-575 nm), and orange (650-690 nm) wavelengths due to radiative recombination transitions between donor-acceptors pairs of N-Al, N-B, N-Cr and Cr-Al respectively, while a prominent violet (408 nm) wavelength was observed due to transitions from the nitrogen level to the valence band level. The red (698-738 nm) luminescence was mainly due to metastable mid-bandgap states, however under high injection current it was due to the quantum mechanical phenomenon pertaining to band broadening and overlapping. This RGB combination produced a broadband white light spectrum extending from 380 to 900 nm. The color space tri-stimulus values for 4H-SiC doped with Cr and N were X = 0.3322, Y = 0.3320 and Z = 0.3358 as per 1931 CIE (International Commission on Illumination) corresponding to a color rendering index of 96.56 and the color temperature of 5510 K. And for 6H-SiC n-type doped with Cr and Al, the color space tri-stimulus values are X = 0.3322, Y = 0.3320 and Z = 0.3358. The CCT was 5338 K, which is very close to the incandescent lamp (or black body) and lies between bright midday sun (5200 K) and average daylight (5500 K) while CRI was 98.32. Similar white LED's were also fabricated using Cr, Al, Se as one set of dopants and B, Al, N as another.

Carbon nanoparticles (CNPs) have drawn great attention in the last few years owing to their unique properties such as excellent water solubility, chemical stability, inertness, low toxicity, good bio-compatibility, and tunable photo physical properties. Recently, researchers have focused on hetero atom (N, S and B) doped CNPs due to their excellent properties. These properties make the CNPs and doped CNPs as potential candidates for a wide range of applications. For example, metal ion detection in aqueous solution, bio-imaging, bio-sensing, photovoltaic devices, cleavage of deoxyribonucleic acid (DNA), and catalysis. Therefore, CNPs are alternative to inorganic semiconductor nanoparticles. However, CNPs with diameter less than 10 nm have been prepared using various approaches including top down and bottom methods. Cutting the bulk carbon from high dimensional to zero dimensional by using either physical or chemical process are classified as top down method. Bottom up method refers the conversion of organic precursor to nano-carbon by using thermal pyrolysis, microwave based hydrothermal method, cage opening of C60 molecules. In the present work, I have dealt with the facile synthesis of CNPs and different hetero atom doped carbon nanoparticles (N-CNPs, B-CNPs, and BN-CNPs) using the hydrothermal method. Based on their intriguing physical and chemical properties, these CNPs/doped-CNPs have been explored for various applications such as (i) metal-free catalysts, (ii) color tunability from red to blue and bio-imaging, (iii) ammonia sensing, (iv) white light generation, and (v) detection of picric acid (PA) in aqueous solution. Finally, I have presented 3D nanodendrites of N-CNPs and Pd NPs and their excellent catalytic mass activity for methanol electro-oxidation and ultra-fast reduction of 4-nitrophenol.

White light emitting diodes (LED) have drawn increasing attention due to their low energy consumption, high efficiency and potential to become primary lighting source by replacing conventional light sources. White light emission is usually generated either by coating yellow phosphor on a blue-LED or blending red, green and blue phosphor in an appropriate ratio. Maintaining appropriate proportions of individual components in the blend is difficult and the major demerit of such system is the overall self-absorption, which changes the solution concentration. This results in uncontrolled changes in the whiteness of the emitted light. Zinc Oxide (ZnO), a wide bandgap semiconductor with a large exciton binding energy at room temperature has been recognized as a promising material for ultraviolet LEDs and laser diodes. Tuning of structural, optical and electrical properties of ZnO thin films by different dopants (Lithium, Indium and Gallium) is dealt in this thesis. The achievement of white light emission from a semiconducting material without using phosphors offers an inexpensive fabrication technology, good luminescence, low turn-on voltage and high efficiency. The present work is organized chapter wise, which has 8 chapters including the summary and future work. Chapter 1: Gives a brief discussion on the overview of ZnO as an optoelectronic material, crystal structure of semiconductor ZnO, the effect of doping, optical properties and its possible applications in optoelectronic devices. Chapter 2: Deals with various deposition techniques used in the present study, includes pulsed laser deposition and thermal evaporation. The experimental set up details and the deposition procedures are described in detail. A brief note on the structural characterization equipments, namely X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and the optical characterization techniques namely Raman spectroscopy, transmission spectroscopy and photoluminescence (PL) spectroscopy is presented. The electrical properties of the films were studied by current- voltage, capacitance - voltage and Hall Effect measurements and the experimental details are discussed. Chapter 3: High quality ZnO/Si heterojunctions fabricated by growing ZnO thin films on p-type Si (100) substrate by pulsed laser deposition without using buffer layers are discussed in this chapter. The crystallinity of the heterojunction was analyzed by high resolution X-ray diffraction and atomic force microscopy. The optical quality of the film was analyzed by room temperature (RT) photoluminescence measurements. The high intense band to band emission confirmed the high quality of the ZnO thin films on Si. The electrical properties of the junction were studied by temperature dependent resistivity, current- voltage measurements and RT capacitance-voltage (C-V) analysis. ZnO thin film showed the lowest resistivity of 6.4x10-3 Ω.cm, mobility of 7 cm2/V.sec and charge carrier concentration of 1.58x1019cm-3 at RT. The charge carrier concentration and the barrier height (BH) were calculated to be 9.7x1019cm-3 and 0.6 eV respectively from the C-V plot. The BH and ideality factor, calculated by using the thermionic emission (TE) model were found to be highly temperature dependent. We observed a much lower value in Richardson constant, 5.19x10-7 A/cm2K2 than the theoretical value (32 A/cm2K2) for ZnO. This analysis revealed the existence of a Gaussian distribution (GD) with a standard deviation of σ2=0.035 V. By implementing GD to the TE, the values of BH and Richardson constant were obtained as 1.3 eV and 39.97 A/cm2K2 respectively from the modified Richardson plot. The obtained Richardson constant value is close to the theoretical value for n-ZnO. These high quality heterojunctions can be used for solar cell applications. Chapter 4: This chapter describes the structural and optical properties of Li doped ZnO thin films and the properties of ZnO/Li doped ZnO multilayered thin film structures. Thin films of ZnO, Li doped ZnO (ZLO) and multilayer of ZnO and ZLO (ZnO/ZLO) were grown on silicon and Corning glass substrates by pulsed laser deposition technique. Single phase formation and the crystalline qualities of the films were analyzed by X-ray diffraction and Li composition in the film was investigated to be 15 Wt % by X-ray photoelectron spectroscopy. Raman spectrum reveals the hexagonal wurtzite structure of ZnO, ZLO and ZnO/ZLO multilayer, confirms the single phase formation. Films grown on Corning glass show more than 80 % transmittance in the visible region and the optical band gaps were calculated to be 3.245, 3.26 and 3.22 eV for ZnO, ZLO and ZnO/ZLO respectively. An efficient blue emission was observed in all films that were grown on silicon (100) substrate by photoluminescence (PL). PL measurements at different temperatures reveal that the PL emission intensity of ZnO/ZLO multilayer was weakly dependent on temperature as compared to the single layers of ZnO and ZLO and the wavelength of emission was independent of temperature. Our results indicate that ZnO/ZLO multilayer can be used for the fabrication of blue light emitting diodes. Chapter 5: This chapter is divided in to two parts. The fabrication and characterization of In doped ZnO thin films grown on Corning glass substrate is discussed in the first section. Zinc Oxide (ZnO) and indium doped ZnO (IZO) thin films with different indium compositions were grown by pulsed laser deposition technique. The effect of indium concentration on the structural, morphological, optical and electrical properties of the film was studied. The films were oriented along the c-direction with wurtzite structure and are highly transparent with an average transmittance of more than 80 % in the visible wavelength region. The energy band gap was found to be decreasing with increasing indium concentration. High transparency makes the films useful as optical windows while the high band gap values support the idea that the film could be a good candidate for optoelectronic devices. The value of resistivity observed to be decreasing initially with doping concentration and subsequently increasing. The XPS and Raman spectrum confirm the presence of indium in indium doped ZnO thin films. The photoluminescence spectrum showed a tunable red light emission with different In concentrations. Undoped and In doped ZnO (IZO) thin films were grown on Pt coated silicon substrates (Pt/Si) to fabricate Pt/ZnO:Inx Schottky contacts (SC) is discussed in the second section. The SCs were investigated by conventional two probe current-voltage (I-V) measurement and by the I-V spectroscopy of conductive atomic force microscopy (C-AFM). X-ray diffraction technique was used to examine the thin film quality. Changes in various parameters like Schottky barrier height (SBH) and ideality factor (IF) as a function of temperature were presented. The estimated BH was found to be increasing and the IF was found to be decreasing with increase in temperature. The variation of SBH and IF with temperature has been explained by considering the lateral inhomogeneities in nanometer scale lengths at metal–semiconductor (MS) interface. The inhomogeneities of SBH in nanometer scale length were confirmed by C-AFM. The SBH and IF estimated from I-V spectroscopy of C-AFM showed large deviation from the conventional two probe I-V measurements. IZO thin films showed a decrease in SBH, lower turn on voltage and an enhancement in forward current with increase in In concentration. Chapter 6: In this chapter the properties of Ga doped ZnO thin films with different Ga concentrations along with undoped ZnO as a reference is discussed. Undoped and Ga doped ZnO thin films with different Ga concentrations were grown on Corning glass substrates by PLD. The structural, optical and electrical properties of Ga doped ZnO thin films are discussed. The XRD, XPS and Raman spectrum reveal the phase formation and successful doping of Ga on ZnO. All the films show good transmittance in the visible region and the photoluminescence of Ga doped ZnO showed a stable emission in the blue- green region. The resistivity of Ga doped ZnO thin films was found to be first decreasing and then increasing with increase in Ga concentrations. Chapter 7: The effect of co-doping to ZnO on the structural, optical and electrical properties was described in this chapter. Ga and In co-doped ZnO (GIZO) thin films together with ZnO, In doped ZnO (IZO), Ga doped ZnO (GZO), IZO/GZO multilayer for comparison, were grown on Corning glass and boron doped Si substrates by PLD. GIZO showed better structural, optical and electrical properties compared with other thin films. The Photoluminescence spectra of GIZO showed a strong white light emission and the current-voltage characteristics showed relatively lower turn on voltage and larger forward current. The CIE co-ordinates for GIZO were observed to be (0.31, 0.33) with a CCT of 6650 K, indicating a cool white light and established a possibility of white light emitting diodes. Finally the chapter 8 presents the summary derived out of the work and a few suggestions on future work.