Improved color purity and efficiency in polyfluorene-based light-emitting diodes

Polyfluorene (PF) is a class of typical blue electroluminescent (EL) material, but it exhibits undesired feature in the green spectral region under operation condition. We investigated the spectral properties of different device structures of poly(9,9-dioctylfluorene) (PFO)-based light-emitting diodes, and found that the interaction between cathode and PFO is the main origination of green emission in EL devices. The general method of inserting a buffer layer between the PFO and cathode can decrease the low energy band emission to purify the color and improve the EL performance of devices.

Improved electron injection in organic light-emitting devices with a lithium acetylacetonate [Li(acac)]/aluminium bilayer cathode

Lithium acetylacetonate [Li(acac)] covered with aluminium was used as an efficient electron injection layer in organic light-emitting devices (OLEDs) consisting of NPB as the hole transport layer and Alq(3) as the electron transport and light emitting layer, resulting in lower turn- on voltage and increased current efficiency. The turn- on voltage (the voltage at a luminance of 1 cd m(-2)) was decreased from 5.5 V for the LiF/Al and 4.4 V for Ca/Al to 4.0 V for Li(acac)/Al, and the device current efficiency was enhanced from 4.71 and 5.2 to 7.0 cd A(-1). The performance tolerance to the layer thickness of Li(acac) is also better than that of the device with LiF. LiF can only be used when deposited as an ultra- thin layer because of its highly insulating nature, while the Li(acac) can be as thick as 5 nm without significantly affecting the EL performance. We suppose that the free lithium released from Li(acac) improves the electron injection when Li(acac) is covered with an Al cathode.

NaCl/Ca/Al as an efficient cathode in organic light-emitting devices

An efficient cathode NaCl/Ca/Al used to improve the performance of organic light-emitting devices (OLEDs) was reported. Standard NM-bis(1-naphthyl)-NAP-diphenyl-1,1' biphenyl 4,4'-dimaine (NPB)/tris-(8-hydroxyquinoline) aluminum (Alq(3)) devices with NaCl/Ca/Al cathode showed dramatically enhanced electroluminescent (EL) efficiency. A power efficiency of 4.6 lm/W was obtained for OLEDs with 2 nm of NaCl and 10 nm of Ca, which is much higher than 2.0 lm/W, 3.1 lm/W, 2.1 lm/ W and 3.6 lm/W in devices using, respectively, the LiF (1 nm)/Al, LiF (1 nm)/Ca (10 nm)/Al, Ca (10 nm)/Al and NaCl (2 nm)/ Al cathodes. The investigation of the electron injection in electron-only devices indicates that the utilization of the NaCl/Ca/Al cathode substantially enhances the electron injection current, which in case of OLEDs leads to the improvement of the brightness and efficiency.

High-efficiency photovoltaics through mechanically stacked integration of solar cells based on the InP lattice constant

Solar Energy is a clean and abundant energy source that can help reduce reliance on fossil fuels around which questions still persist about their contribution to climate and long-term availability. Monolithic triple-junction solar cells are currently the state of the art photovoltaic devices with champion cell efficiencies exceeding 40%, but their ultimate efficiency is restricted by the current-matching constraint of series-connected cells. The objective of this thesis was to investigate the use of solar cells with lattice constants equal to InP in order to reduce the constraint of current matching in multi-junction solar cells. This was addressed by two approaches: Firstly, the formation of mechanically stacked solar cells (MSSC) was investigated through the addition of separate connections to individual cells that make up a multi-junction device. An electrical and optical modelling approach identified separately connected InGaAs bottom cells stacked under dual-junction GaAs based top cells as a route to high efficiency. An InGaAs solar cell was fabricated on an InP substrate with a measured 1-Sun conversion efficiency of 9.3%. A comparative study of adhesives found benzocyclobutene to be the most suitable for bonding component cells in a mechanically stacked configuration owing to its higher thermal conductivity and refractive index when compared to other candidate adhesives. A flip-chip process was developed to bond single-junction GaAs and InGaAs cells with a measured 4-terminal MSSC efficiency of 25.2% under 1-Sun conditions. Additionally, a novel InAlAs solar cell was identified, which can be used to provide an alternative to the well established GaAs solar cell. As wide bandgap InAlAs solar cells have not been extensively investigated for use in photovoltaics, single-junction cells were fabricated and their properties relevant to PV operation analysed. Minority carrier diffusion lengths in the micrometre range were extracted, confirming InAlAs as a suitable material for use in III-V solar cells, and a 1-Sun conversion efficiency of 6.6% measured for cells with 800 nm thick absorber layers. Given the cost and small diameter of commercially available InP wafers, InGaAs and InAlAs solar cells were fabricated on alternative substrates, namely GaAs. As a first demonstration the lattice constant of a GaAs substrate was graded to InP using an InxGa1-xAs metamorphic buffer layer onto which cells were grown. This was the first demonstration of an InAlAs solar cell on an alternative substrate and an initial step towards fabricating these cells on Si. The results presented offer a route to developing multi-junction solar cell devices based on the InP lattice parameter, thus extending the range of available bandgaps for high efficiency cells.

Dynamic in situ optical and magneto-optical monitoring of the growth of Co-Pd multilayers

In situ ellipsometry and Kerr polarimetry have been used to follow the continuous evolution of the optical and magneto- optical properties of multiple layers of Co and Pd during their growth. Films were sputter deposited onto a Pd buffer layer on glass substrates up to a maximum of N = 10 bi-layer periods according to the scheme glass/Pd(10)Ar x (0.3Co/3Pd) (nm). Magnetic hysteresis measurements taken during the deposition consistently showed strong perpendicular anisotropy at all stages of film growth following the deposition of a single monolayer of Co. Magneto-optic signals associated with the normal-incidence polar Kerr effect indicated strong polarization of Pd atoms at both Co-Pd and Pd-Co interfaces and that the magnitude of the complex magneto-optic Voigt parameter and the magnetic moment of the Pd decrease exponentially with distance from the interface with a decay constant of 1.1 nm(- 1). Theoretical simulations have provided an understanding of the observations and allow the determination of the ultrathin- film values of the elements of the skew-symmetric permittivity tensor that describe the optical and magneto-optical properties for both CO and Pd. Detailed structure in the observed Kerr ellipticity shows distinct Pd-thickness-dependent oscillations with a spatial period of about 1.6 nm that are believed to be associated with quantum well levels in the growing Pd layer.

Phase transitions in epitaxial Ba0.5Sr0.5TiO3 thin films

Ba0.5Sr0.5TiO3 (BST) thin-film capacitor structures with various thicknesses, (50-1200 nm) and different strain conditions (on lanthanum strontium cobalt oxide La0.5Sr0.5CoO3 and strontium ruthenate SrRuO3 buffer layers) were made using pulsed laser deposition, and characterized by x-ray diffraction. The out-of-plane lattice parameter was followed as a function of temperature within the 100-300 K temperature interval. The phase sequence (cubic-tetragonal-orthorhombic-rhombohedral) known to exist in the bulk analog is shown to be strongly affected by both the stress conditions imposed by the buffer layer and the thickness of the BST film itself. Thus, no phase transition was found for the in-plane compressed BST films. On the stress-free BST films, on the contrary, more phase transitions were observed. It appeared that the complexity of structural phase transitions increased as the film thickness in this system was reduced.

Epitaxial growth of non-c-oriented ferroelectric SrBi2Ta2O9 thin films on Si(100) substrates

Epitaxial SrBi2Ta2O9 (SBT) thin films with well-defined (116) orientation have been grown by pulsed laser deposition on Si(100) substrates covered with an yttria-stabilized ZrO2 (YSZ) buffer layer and an epitaxial layer of electrically conductive SrRuO3. Studies on the in-plane crystallographic relations between SrRuO3 and YSZ revealed a rectangle-on-cube epitaxy with respect to the substrate. X-ray diffraction pole figure measurements revealed well defined orientation relations, viz. SBT(116)\\ SrRuO3(110)\\ YSZ(100)\\ Si(100), SBT[110]\\ SrRuO3[001], and SrRuO3[111]\\ YSZ[110]\\ Si[110].

Caracterização e modificação de heteroestruturas de nitretos do grupo III

Os nitretos binários semicondutores do grupo III, e respetivos compostos, são vastamente estudados devido à sua possível aplicabilidade em dispositivos optoeletrónicos, tais como díodos emissores de luz (LEDs) e LASERs, assim como dispositivos para a eletrónica de elevadas temperatura, potência e frequência. Enquanto se concretizou a comercialização na última década de LEDs e LASERs recorrendo ao ternário In1-yGayN, estudos das propriedades fundamentais estruturais e óticas, assim como de técnicas de processamento no desenvolvimento de novas aplicações de outros ternários do grupo III-N encontram-se na sua fase inicial. Esta tese apresenta a investigação experimental de filmes finos epitaxiais de Al1-xInxN crescidos sobre camadas tampão de GaN e de Al1-yGayN e o estudo do recozimento e implantação de super-redes (SL) compostas por pontos quânticos de GaN (QD) envolvidos por camadas de AlN. Apesar do hiato energético do Al1-xInxN poder variar entre os 0,7 eV e os 6,2 eV e, por isso, numa gama, consideravelmente superior à dos ternários Al1-yGayN e InyGa1-yN, o primeiro é o menos estudado devido a dificuldades no crescimento de filmes com elevada qualidade cristalina. É efetuada, nesta tese, uma caracterização estrutural e composicional de filmes finos de Al1-xInxN crescidos sobre camadas tampão de GaN e de Al1-yGayN usando técnicas de raios-X, feixe de iões e de microscopia. Mostra-se que o Al1-xInxN pode ser crescido com elevada qualidade cristalina quando a epitaxia do crescimento se aproxima da condição de rede combinada do Al1-xInxN e da camada tampão (GaN ou Al1-yGayN), isto é, com conteúdo de InN de ~18%, quando crescido sobre uma camada de GaN. Quando o conteúdo de InN é inferior/superior à condição de rede combinada, fenómenos de relaxação de tensão e deterioração do cristal tais como o aumento da rugosidade de superfície prejudicam a qualidade cristalina do filme de Al1-xInxN. Observou-se que a qualidade dos filmes de Al1-xInxN depende fortemente da qualidade cristalina da camada tampão e, em particular, da sua morfologia e densidade de deslocações. Verificou-se que, dentro da exatidão experimental, os parâmetros de rede do ternário seguem a lei empírica de Vegard, ou seja, variam linearmente com o conteúdo de InN. Contudo, em algumas amostras, a composição determinada via espetrometria de retrodispersão de Rutherford e difração e raios-X mostra valores discrepantes. Esta discrepância pode ser atribuída a defeitos ou impurezas capazes de alterar os parâmetros de rede do ternário. No que diz respeito às SL dos QD e camadas de AlN, estudos de recozimento mostraram elevada estabilidade térmica dos QD de GaN quando estes se encontram inseridos numa matriz de AlN. Por implantação iónica, incorporou-se európio nestas estruturas e, promoveu-se a ativação ótica dos iões de Eu3+ através de tratamentos térmicos. Foram investigados os efeitos da intermistura e da relaxação da tensão ocorridos durante o recozimento e implantação nas propriedades estruturais e óticas. Verificou-se que para fluências elevadas os defeitos gerados por implantação são de difícil remoção. Contudo, a implantação com baixa fluência de Eu, seguida de tratamento térmico, promove uma elevada eficiência e estabilidade térmica da emissão vermelha do ião lantanídeo incorporado nos QD de GaN. Estes resultados são, particularmente relevantes, pois, na região espetral indicada, a eficiência quântica dos LEDs convencionais de InGaN é baixa.

Extension of electrochemically active sites in SOFCs and SOECs

Solid oxide fuel (SOFCs) and electrolyzer (SOECs) cells have been promoted as promising technologies for the stabilization of fuel supply and usage in future green energy systems. SOFCs are devices that produce electricity by the oxidation of hydrogen or hydrocarbon fuels with high efficiency. Conversely, SOECs can offer the reverse reaction, where synthetic fuels can be generated by the input of renewable electricity. Due to this similar but inverse nature of SOFCs and SOECs, these devices have traditionally been constructed from comparable materials. Nonetheless, several limitations have hindered the entry of SOFCs and SOECs into the marketplace. One of the most debilitating is associated with chemical interreactions between cell components that can lead to poor longevities at high working temperatures and/or depleted electrochemcial performance. Normally such interreactions are countered by the introduction of thin, purely ionic conducting, buffer layers between the electrode and electrolyte interface. The objective of this thesis is to assess if possible improvements in electrode kinetics can also be obtained by modifying the transport properties of these buffer layers by the introduction of multivalent cations. The introduction of minor electronic conductivity in the surface of the electrolyte material has previously been shown to radically enhance the electrochemically active area for oxygen exchange, reducing polarization resistance losses. Hence, the current thesis aims to extend this knowledge to tailor a bi-functional buffer layer that can prevent chemical interreaction while also enhancing electrode kinetics.The thesis selects a typical scenario of an yttria stabilized zirconia electrolyte combined with a lanthanide containing oxygen electrode. Gadolinium, terbium and praseodymium doped cerium oxide materials have been investigated as potential buffer layers. The mixed ionic electronic conducting (MIEC) properties of the doped-cerium materials have been analyzed and collated. A detailed analysis is further presented of the impact of the buffer layers on the kinetics of the oxygen electrode in SOFC and SOEC devices. Special focus is made to assess for potential links between the transport properties of the buffer layer and subsequent electrode performance. The work also evaluates the electrochemical performance of different K2NiF4 structure cathodes deposited onto a peak performing Pr doped-cerium buffer layer, the influence of buffer layer thickness and the Pr content of the ceria buffer layer. It is shown that dramatic increases in electrode performance can be obtained by the introduction of MIEC buffer layers, where the best performances are shown to be offered by buffer layers of highest ambipolar conductivity. These buffer layers are also shown to continue to offer the bifunctional role to protect from unwanted chemical interactions at the electrode/electrolyte interface.

Preparation and characterisation of certain II-VI, I-III-VI2 semiconductor thin films and transparent conducting oxides

There is an increasing demand for renewable energies due to the limited availability of fossil and nuclear fuels and due to growing environmental problems. Photovoltaic (PV) energy conversion has the potential to contribute significantly to the electrical energy generation in the future. Currently, the cost for photovoltaic systems is one of the main obstacles preventing production and application on a large scale. The photovoltaic research is now focused on the development of materials that will allow mass production without compromising on the conversion efficiencies. Among important selection criteria of PV material and in particular for thin films, are a suitable band gap, high absorption coefficient and reproducible deposition processes capable of large-volume and low cost production. The chalcopyrite semiconductor thin films such as Copper indium selenide and Copper indium sulphide are the materials that are being intensively investigated for lowering the cost of solar cells. Conversion efficiencies of 19 % have been reported for laboratory scale solar cell based on CuInSe2 and its alloys. The main objective of this thesis work is to optimise the growth conditions of materials suitable for the fabrication of solar cell, employing cost effective techniques. A typical heterojunction thin film solar cell consists of an absorber layer, buffer layer and transparent conducting contacts. The most appropriate techniques have been used for depositing these different layers, viz; chemical bath deposition for the window layer, flash evaporation and two-stage process for the absorber layer, and RF magnetron sputtering for the transparent conducting layer. Low cost experimental setups were fabricated for selenisation and sulphurisation experiments, and the magnetron gun for the RF sputtering was indigenously fabricated. The films thus grown were characterised using different tools. A powder X-ray diffractometer was used to analyse the crystalline nature of the films. The energy dispersive X-ray analysis (EDX) and scanning electron microscopy i (SEM) were used for evaluating the composition and morphology of the films. Optical properties were investigated using the UV-Vis-NIR spectrophotometer by recording the transmission/absorption spectra. The electrical properties were studied using the two probe and four probe electrical measurements. Nature of conductivity of the films was determined by thermoprobe and thermopower measurements. The deposition conditions and the process parameters were optimised based on these characterisations.

Engineering the Properties of Indium Sulfide for Thin Film Solar Cells by Doping

In the present work, structural, optical and electrical properties of indium sulfide are tuned by specific and controlled doping. Silver, tin, copper and chlorine were used as the doping elements. In2S3 thin films for the present study were prepared using a simple and low cost “Chemical Spray Pyrolysis (CSP)” technique. This technique is adaptable for large-area deposition of thin films in any required shape and facilitates easiness of doping and/or variation of atomic ratio. It involves spraying a solution, usually aqueous, containing soluble salts of the constituents of the desired compound onto a heated substrate. Doping process was optimized for different doping concentrations. On optimizing doping conditions, we tuned the structural, optical and electrical properties of indium sulfide thin films making them perform as an ideal buffer layer.

Automation of Chemical Spray Pyrolysis Unit and Fabrication of Sprayed CuInS2/In2S3 Solar Cell

Aim of the present work was to automate CSP process, to deposit and characterize CuInS2/In2S3 layers using this system and to fabricate devices using these films.An automated spray system for the deposition of compound semiconductor thin films was designed and developed so as to eliminate the manual labour involved in spraying and facilitate standardization of the method. The system was designed such that parameters like spray rate, movement of spray head, duration of spray, temperature of substrate, pressure of carrier gas and height of the spray head from the substrate could be varied. Using this system, binary, ternary as well as quaternary films could be successfully deposited.The second part of the work deal with deposition and characterization of CuInS2 and In2S3 layers respectively.In the case of CuInS2 absorbers, the effects of different preparation conditions and post deposition treatments on the optoelectronic, morphological and structural properties were investigated. It was observed that preparation conditions and post deposition treatments played crucial role in controlling the properties of the films. The studies in this direction were useful in understanding how the variation in spray parameters tailored the properties of the absorber layer. These results were subsequently made use of in device fabrication process.Effects of copper incorporation in In2S3 films were investigated to find how the diffusion of Cu from CuInS2 to In2S3 will affect the properties at the junction. It was noticed that there was a regular variation in the opto-electronic properties with increase in copper concentration.Devices were fabricated on ITO coated glass using CuInS2 as absorber and In2S3 as buffer layer with silver as the top electrode. Stable devices could be deposited over an area of 0.25 cm2, even though the efficiency obtained was not high. Using manual spray system, we could achieve devices of area 0.01 cm2 only. Thus automation helped in obtaining repeatable results over larger areas than those obtained while using the manual unit. Silver diffusion on the cells before coating the electrodes resulted in better collection of carriers.From this work it was seen CuInS2/In2S3 junction deposited through automated spray process has potential to achieve high efficiencies.

Photothermal beam deflection for non-destructive evaluation of semiconductor thin films

Non-destructive testing (NDT) is the use of non-invasive techniques to determine the integrity of a material, component, or structure. Engineers and scientists use NDT in a variety of applications, including medical imaging, materials analysis, and process control.Photothermal beam deflection technique is one of the most promising NDT technologies. Tremendous R&D effort has been made for improving the efficiency and simplicity of this technique. It is a popular technique because it can probe surfaces irrespective of the size of the sample and its surroundings. This technique has been used to characterize several semiconductor materials, because of its non-destructive and non-contact evaluation strategy. Its application further extends to analysis of wide variety of materials. Instrumentation of a NDT technique is very crucial for any material analysis. Chapter two explores the various excitation sources, source modulation techniques, detection and signal processing schemes currently practised. The features of the experimental arrangement including the steps for alignment, automation, data acquisition and data analysis are explained giving due importance to details.Theoretical studies form the backbone of photothermal techniques. The outcome of a theoretical work is the foundation of an application.The reliability of the theoretical model developed and used is proven from the studies done on crystalline.The technique is applied for analysis of transport properties such as thermal diffusivity, mobility, surface recombination velocity and minority carrier life time of the material and thermal imaging of solar cell absorber layer materials like CuInS2, CuInSe2 and SnS thin films.analysis of In2S3 thin films, which are used as buffer layer material in solar cells. The various influences of film composition, chlorine and silver incorporation in this material is brought out from the measurement of transport properties and analysis of sub band gap levels.The application of photothermal deflection technique for characterization of solar cells is a relatively new area that requires considerable attention.The application of photothermal deflection technique for characterization of solar cells is a relatively new area that requires considerable attention. Chapter six thus elucidates the theoretical aspects of application of photothermal techniques for solar cell analysis. The experimental design and method for determination of solar cell efficiency, optimum load resistance and series resistance with results from the analysis of CuInS2/In2S3 based solar cell forms the skeleton of this chapter.

Spray Pyrolysed CuInS2/In2S3 Solar Cell: Material Characterization and Device Fabrication

As emphasis towards sustainable and Renewable energy resources grows world-wide,interest in the capture and use of solar energy is increasing dramatically.Solar cells have been known and used for many years,but depletion of conventional energy resources resulted in the intensification of research on solar cells leading to new design and technique of fabrication.The current emphasis is directed towards high effiency inexpensive solar cells.This thesis includes deposition and characterization of CuInS2 and In2S3 thin films using chemical Spray Pyrolysis(CSP) technique.The optimum condition for these films to be used as absorber and buffer layer respectively in solar cells were thus found out.Solar cell with the stucture,ITO/CuInS2/In2S3/metal electrode was fabricated using these well-characterized films,which yielded an efficiency of 9.5%.

Preparation of sub-micrometre thick CulnSe2 films using sequential evaporation technique for device fabrication

In this work. Sub-micrometre thick CulnSe2 films were prepared using different techniques viz, selenization through chemically deposited Selenium and Sequential Elemental Evaporation. These methods are simpler than co-evaporation technique, which is known to be the most suitable one for CulnSe2 preparation. The films were optimized by varying the composition over a wide range to find optimum properties for device fabrication. Typical absorber layer thickness of today's solar cell ranges from 2-3m. Thinning of the absorber layer is one of the challenges to reduce the processing time and material usage, particularly of Indium. Here we made an attempt to fabricate solar cell with absorber layer of thickness buffer layer, replacing toxic CdS.