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Structural and Optical Properties of Eu Doped ZnO Nanorods prepared by Pulsed Laser DepositionAlarawi, Abeer 23 June 2014 (has links)
Nano structured wide band gap semiconductors have attracted attention of many researchers due to their potential electronic and optoelectronic applications. In this thesis, we report successful synthesis of well aligned Eu doped ZnO nano-rods prepared, for the first time to our knowledge, by pulsed laser deposition (PLD) without any catalyst. X-ray diffraction (XRD) patterns shows that these Eu doped ZnO nanorods are grown along the c-axis of ZnO wurtzite structure. We have studied the effect of the PLD growth conditions on forming vertically aligned Eu doped ZnO nanorods. The structural properties of the material are investigated using a -scanning electron microscope (SEM). The PLD parameters must be carefully controlled in order to obtain c-axis oriented ZnO nanorods on sapphire substrates, without the use of any catalyst. The experiments conducted in order to identify the optimal growth conditions confirmed that, by adjusting the target-substrate distance, substrate temperature, laser energy and deposition duration, the nanorod size could be successfully controlled. Most importantly, the results indicated that the photoluminescence (PL) properties reflect the quality of the ZnO nanorods. These parameters can change the material’s structure from one-dimensional to two-dimensional however the laser energy and frequency affect the size and the height of the nanorods; the xygen pressure changes the density of the nanorods.
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Nanostructured Thermoelectric Oxides for Energy Harvesting ApplicationsAbutaha, Anas I. 24 November 2015 (has links)
As the world strives to adapt to the increasing demand for electrical power, sustainable energy sources are attracting significant interest. Around 60% of energy utilized in the world is wasted as heat. Different industrial processes, home heating, and exhausts in cars, all generate a huge amount of unused waste heat. With such a huge potential, there is also significant interest in discovering inexpensive technologies for power generation from waste heat. As a result, thermoelectric materials have become important for many renewable energy research programs. While significant advancements have been done in improving the thermoelectric properties of the conventional heavy-element based materials (such as Bi2Te3 and PbTe), high-temperature applications of thermoelectrics are still limited to one materials system, namely SiGe, since the traditional thermoelectric materials degrade and oxidize at high temperature. Therefore, oxide thermoelectrics emerge as a promising class of materials since they can operate athigher temperatures and in harsher environments compared to non-oxide thermoelectrics. Furthermore, oxides are abundant and friendly to the environment. Among oxides, crystalline SrTiO3 and ZnO are promising thermoelectric materials.
The main objective of this work is therefore to pursue focused investigations of SrTiO3 and ZnO thin films and superlattices grown by pulsed laser deposition (PLD), with the goal of optimizing their thermoelectric properties by following different strategies. First, the effect of laser fluence on the thermoelectric properties of La doped epitaxial SrTiO3 films is discussed. Films grown at higher laser fluences exhibit better thermoelectric performance. Second, the role of crystal orientation in determining the thermoelectric properties of epitaxial Al doped ZnO (AZO) films is explained. Vertically aligned (c-axis) AZO films have superior thermoelectric properties compared to other films with different crystal orientations. Third, additional B-site doping of A-site doped SrTiO3 films leads to a prominent reduction in the lattice thermal conductivity without limiting the electrical transport, and hence an improvement in the figure of merit is noticed. Fourth and last, the enhancement of thermoelectric properties of thermally robust, high quality SrTiO3-based superlattices is discussed. Beside the randomly distributed oxygen vacancies and extrinsic dopants, the structure of SrTiO3-based superlattices increases the scattering of phonons at the interfaces between the alternative layers, and hence reducing the thermal conductivity, which leads to a notable enhancement in the figure of merit.
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Desenvolvimento de um detector de nêutrons por meio da deposição de filme fino de boro via laser / Development of a thermal neutron detector by boron film deposition using laserCosta, Priscila 26 April 2019 (has links)
O protótipo de um detector de nêutrons térmicos portátil foi desenvolvido no Instituto de Pesquisa Energéticas e Nucleares (IPEN-CNEN/SP), utilizando um fotodiodo de Si do tipo PIN associado a um filme de boro enriquecido. O filme de boro foi fabricado por meio da técnica de Deposição a Laser Pulsado, considerando duas possibilidades para depositar o boro: deposição direta do boro na face do fotodiodo e deposição na lâmina de vidro. Foram desenvolvidos dois protótipos, no primeiro foi possível ler apenas o sinal elétrico do sistema fotodiodo-boro no qual o filme está depositado na lâmina de vidro. Para aprimorar a resposta do sistema de detecção, outro circuito foi desenvolvido e permitiu contar nêutrons em ambas as situações tanto do filme na lamínula quanto do filme direto no fotodiodo. A caracterização dos protótipos foi feita via irradiação de feixes de nêutrons predominantemente térmicos e frios, por meio de quatro experimentos principais: reposta do sistema ao fluxo de nêutrons, teste de linearidade, resposta angular e o teste de reprodutibilidade. Os protótipos apresentaram uma resposta linear à variação do fluxo, reprodutibilidade, e a resposta angular não foi isotrópica. A eficiência intrínseca em porcentagem do protótipo 1 para um espectro de nêutrons predominantemente térmicos e frios foi (1,17 ± 0,01) % e (1,37 ± 0,01) %, respectivamente. No protótipo 2 foram feitas medições de nêutrons com os dois sistemas fotodiodo-boro (lâmina de vidro, direto no fotodiodo), porém nas medidas com o boro direto no sensor houve um aumento significativo no ruído eletrônico. A eficiência intrínseca do protótipo 2 para os nêutrons frios foi de (5,2 ± 0,4) %. / A portable thermal neutron detector prototype, using a silicon photodiode type PIN coupled to a boron converter, was developed at Nuclear and Energy Research Institute (IPEN-CNEN/SP). The boron layers were made by Pulsed Laser Deposition method using two configurations: directly deposited on the surface of photodiode and at a glass surface. Two prototypes were made in this study using two different associated electronics, in the first prototype is only possible reads signs from the photodiode coupled to boron film and in the second one reads both types of configurations (directly on the photodiode, boron glass). The prototypes were characterized using thermal and cold neutron beam. Four experiments were performed: response of the detection system at neutron beam, linearity test, angular response and repetitive test. The prototypes present a linear behavior, were reproducible and the angular response of the prototypes was not isotropic. The values of intrinsic efficiency from the prototype 1 for thermal and cold neutron were respectively: (1.17 ± 0.01) % e (1.37 ± 0.01) %. In the prototype 2 it was performed an experiment for compare the read out in the detection system for the two possible configuration of system photodiode-boron, in the situation that the boron is part integrant of the system there was an significant increase in the electronic noise, therefore the characterization of this prototype were made using the boron film coupled to the photodiode, and intrinsic efficiency for cold neutron beam was (5.2 ± 0.4) %.
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Study Of Pulsed Laser Ablated Barium Strontium Titanate Thin Flims For Dynamic Random Access Memory ApplicationsSaha, Sanjib 08 1900 (has links)
The present study describes the growth and characterization of pulsed laser ablated Bao.sSro.sTiOs (BST) thin films. Emphasis has been laid on the study of a plausible correlation between structure and property in order to optimize the processing parameters suitably for required application. An attempt has been made to understand the basic properties such as, origin of dielectric response, charge transfer under low and high-applied electric fields across the BST capacitor and finally the dielectric breakdown process.
Chapter 1 gives a brief introduction on the application of ferroelectric thin films in microelectronic industry and its growth techniques. It also addresses the present issues involved in the introduction of BST as a capacitor material for high-density dynamic random access memories. Chapter 2 outlines the motivation for the present study and briefly outlines the research work involved.
Chapter 3 describes the experimental procedure involved in the growth and characterization of BST thin films using pulsed laser ablation technique. Details include the setup design for PLD growth, material synthesis for the ceramic targets, deposition conditions used for thin film growth and basic characterizations methods used for study of the grown films.
Chapter 4 describes the effect of systematic variation of deposition parameters on the physical and electrical properties of the grown BST films. The variation in processing conditions has been found to directly affect the film crystallinity, structure and morphology. The change observed in these physical properties may also be correlated to the observed electrical properties. This chapter summarizes the optimal deposition conditions required for growing BST thin films using a pulsed laser ablation technique.
Microstructure of BST films has been categorized into two types: (a) Type I structure, with multi-grains through the film thickness, for amorphous as-grown films after high temperature annealing (exsitu crystallized), and (b) columnar structure (Type II) films, which were as-grown well-crystallized films, deposited at high temperatures.
The ac electrical properties have been reviewed in detail in Chapter 5. Type I films showed a relatively lower value of dielectric constant (e ~ 426) than Type II films with dielectric constant around 567. The dissipation factors were around 0.02 and 0.01 for Type I and Type II films respectively. The dispersion in the frequency domain characteristics has been quantitatively explained using Jonscher's theory. Complex impedance spectroscopy employed showed significant grain boundary response in the case of multi-grained Type I films while negligible contribution from grain boundaries has been obtained in the case of columnar grained Type II BST films. The average relaxation time r obtained from the complex impedance plane plots show almost three orders higher values for Type I films. The obtained results suggest that in multi-grained samples, grain boundary play a major role in electrical properties. This has been explained in accordance to a model proposed on the basis of depleted grains in the case of Type I films where the grain sizes are smaller than the grain boundary depletion width.
Chapter 6 describes the dc leakage properties of the grown BST thin films and the influence of microstructure on the leakage properties. It was evident from the analysis of the graph of leakage current against measurement temperature, that, the observed leakage behavior in BST films, can not be attributed to a single charge transport mechanism. For Type I films, the Arrhenius plot of the leakage current density with 1000/T exhibits different regions with activation energy values in the range of 0.5 and 2.73 for low fields (2.5kV/cm). The activation energy changes over to 1.28 eV at high fields (170 kV/cm). The obtained values agree well with that obtained from the ac measurements, thus implying a similarity in the origin of the transport process. The activation energy value in the range of 0.5 eV is attributed to the electrode/film Schottky barrier, while the value in the range of 2.73 eV is due to deep trap levels originating from Ti+3 centers. The value in the range of 1.28 eV has been attributed to oxygen vacancy motion. Similar results have been obtained from the Arrhenius plot of the leakage current for Type II films. In this case, only two different activation energy values can be identified in the measured temperature and applied electric field range. At low fields the activation energy value was around 0.38 eV while at high fields the value was around 1.06 eV. These values have been identified to be originating from the electrode/film Schottky barrier and oxygen vacancy motion respectively. Thus a complete picture of the charge transport process in the case of BST thin film may be summarized as comprising of both electronic motion as well as contribution from oxygen vacancy motion.
The effect of electrical stress on the capacitance-voltage (C-V) and the leakage current has been analyzed in Chapter 7. From the change in the zero bias capacitance after repeated electron injection through the films the values of the electronic capture cross-section and the total trap density for Type I and II films have been estimated. The results showed higher values for Type I film in comparison to Type II films. The difference has been attributed to the presence of grain boundaries and a different interface in the case of Type I films when compared to Type II films where the absence of grain boundaries is reflected in the columnar microstructure. A study of the time-dependent-dielectric-breakdown (TDDB) characteristics under high fields for Type I and Type II films showed higher endurance for Type I film. On the other hand space-charge-transient characteristics have been observed in the case of Type II films at elevated temperature of measurement. Mobility and activation energy values extracted from the transient characteristics are found to be in the range of 1 x 10~12 cm2 /V-sec and 0.73 eV respectively, suggesting a very slow charge transport process, which has been attributed to the motion of oxygen vacancies. An overall effect of electrical stress suggested that oxygen vacancy motion can be related to the observed resistance degradation and TDDB, which has been further enhanced by the combination of high temperature and high electric fields.
Chapter 8 deals with the effect of intentional doping in the BST films. The doping includes Al at the Ti-site, Nb in the Ti-site and La at the Ba/Sr-site. The effect of doping was observed both on the structure and electrical properties of the BST films. Acceptor doping of 0.1 atomic 7c Al was found to decrease the dielectric constant as well as the leakage current. For higher concentration of acceptor-dopant, the leakage current was found to increase while showing space-charge-transient in the TDDB characteristics, again suggesting the effect of increased concentration of oxygen vacancies. Donor doping using 2 atomic % La and Xb significantly improved the leakage as well as the TDDB characteristics by reducing the concentration of oxygen vacancies. A further procedure using graded donor doping in the BST films exhibits even better leakage and TDDB properties. An unconventional, graded doping of donor cations has been carried out to observe the impact on leakage behavior, in particular. The leakage current measured for a graded La-doped BST film show almost six orders of lower leakage current in comparison to undoped BST films, while endurance towards breakdown has been observed to increase many-fold.
Chapter 9 highlights the main findings of the work reported in this thesis and lists suggestions for future work, to explore new vistas ahead.
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Multiferroic hexagonal HoMnO3 filmsKim, Jong-Woo 18 January 2010 (has links) (PDF)
The fundamental properties of hexagonal multiferric HoMnO3 films have been thoroughly investigated. The films are grown by pulsed laser deposition on Y:ZrO2(111) substrates. High quality epitaxial HoMnO3 films of 25 { 1000 nm thickness were successfully prepared. The film properties are compared to those of single-crystals.
The magnetization measurements revealed that the films show a deviating magnetic behavior from the single-crystals in several ways. For instance, the films have a weakened antiferromagnetic Ho3+ order confirmed from magnetic susceptibility. The difierences are likely to be related to the modified (mostly larger) lattice parameters of films. An approximate phase diagram in comparison with the single-crystal's one is constructed. For multiferroicity investigations, Second Harmonic Generation
(SHG; in collaboration with the group of M. Fiebig) has been employed. By SHG, the ferroelectric polar order of the films is obviously confirmed. The ferroelectric switching at room temperature could be clearly demonstrated, whereas leakage of films requires generally a more sophisticated approach. / Die fundamentalen Eigenschaften von hexagonalen multiferroischen HoMnO3 Schichten
werden eingehend untersucht. Die dünnen Schichten wurden mittels gepulster
Laserdeposition auf Y:ZrO2(111)-Substraten gewachsen. Hochwertige epitaktische
HoMnO3-Dünnschichten von 25 { 1000 nm Dicke wurden erfolgreich hergestellt. Die
Dünnschichteigenschaften werden mit denen von Einkristallen verglichen. Die Magnitisierungsmessungen
ergeben, dass die dünnen Schichten ein von den Einkristallen
in verschiedener Weise abweichendes magnetischen Verhalten zeigen. Zum Beispiel
haben die dünnen Schichten eine abgeschwächte antiferromagntetische Ho3+ Ordnung,
die durch die magnetische Suszeptibilität bestätigt wird. Die Unterschiede
sind wahrscheinlich auf die veränderten (meistens grösseren) Gitterparameter der
dünnen Schichten zurückzuführen. Ein Phasendiagramm wird zum Vergleich mit
Einkristallen konstruiert. Durch Second Harmonic Generation (SHG; in Zusammenarbeit
mit der Gruppe von M. Fiebig) wird die ferroelektrische Ordnung der dünnen
Schichten eindeutig bestätigt. Das ferroelektrische Umschalten bei Raumtemperatur
kann eindeutig nachgewiesen werden, wobei durch den Leckstrom der dünnen Schichten
allgemein eine detailliertere Vorgehensweise benötigt wird.
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Films minces intelligents à propriétés commandables pour des applications électriques et optiques avancées : dopage du dioxyde de vanadium / Smart thin films with controllable properties for advanced electronic and optical applications : doping of vanadium dioxideZaabi, Rafika 02 December 2015 (has links)
Cette thèse concerne l’étude de l’effet du dopage au chrome sur les propriétés structurales, électriques et optiques des films de dioxyde de vanadium. Ces films V(1-x)CrxO2 (x allant de 0 à 25%) de 110 nm d’épaisseur ont été déposés par dépôt par ablation laser (PLD) multicibles sur substrat saphir c. Ils ont été caractérisés grâce à des techniques d’analyse morphologique, structurale, électrique et optique. Les différentes phases présentes dans les films V(1-x)CrxO2 ont été identifiées par DRX, spectroscopie Raman et comparées au diagramme de phase du matériau massif. Les phases M1, M2 et M3, un mélange M2 + M3 et la phase R ont été identifiées. En revanche la phase M4 n’a pas été détectée pour des dopages supérieurs à 8%, montrant une réelle différence entre diagrammes de phase du matériau massif et des films. Le dopage au chrome a permis d’augmenter la température de transition isolant-métal de 68 à 102°C. En revanche, la dynamique de cette transition, déterminée par mesure de transmission optique ou par mesure de résistivité électrique, est souvent diminuée. Enfin, des dispositifs à deux terminaux à base de films V(1-x)CrxO2 ont été réalisés. Leurs caractérisations courant-tension montrent que le dopage au chrome influence fortement le seuil d’activation de la transition entre les états isolant et métallique. / This thesis presents a study of the effect of chromium doping on structural, electrical and optical properties of thin films of vanadium dioxide. These V(1-x)CrxO2 thin films (x from 0 to 25%) of 110 nm thick have been deposited on c sapphire substrate by multi target Pulsed Laser Deposition method. Their morphological, structural, electrical and optical properties have been studied. Different phases for V(1-x)CrxO2 have been identified by XRD and Raman analysis and compared to those of bulk material. M1, M2, M3, a mixture M2 + M3 and R phases are present. The M4 phase has not been detected for doping above 8%, showing a real difference between phase diagram of bulk and thin films. Chromium doping also increases the metal-insulator transition temperature from 68°C to 102°C. Moreover, the transition dynamics, determined using optical transmission and electrical resistivity measurements, decreases. Finally, two terminal switches based on V(1-x)CrxO2 thin films have been fabricated. Their current-voltage characterization showed that chromium doping affects the activation threshold voltage of the metal to insulator transition.
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Optimisation de films minces électrochromes à base d’oxyde de nickel / Optimization of nickel oxide-based electrochromic thin filmsPark, Dae Hoon 08 June 2010 (has links)
Dans la perspective du développement de vitrages électrochromes « en milieu protonique », des films minces électrochromes à coloration anodique, à base d’oxyde de nickel, ont été synthétisés et caractérisés. Afin d’améliorer la durabilité des films minces à base de NiO, trois approches ont été envisagées. (i)Des films d’oxyde de nickel et d’oxyde mixte nickel/lithium, déposés par PLD (Pulsed Laser Deposition). Nous avons étudié l’influence du lithium sur les propriétés physico-chimiques (‘amorphisation..), et les caractéristiques électrochromes (électrochimique-optique) en milieu aqueux KOH 1M. (ii) Des films composites, préparés par voie chimique (solution), constitués d’une phase amorphe (en diffraction des Rayons X), de composition Ti1-xZnxO2-x?x, englobant des cristallites de NiO de ~ 5 nm de diamètre. Les courbes voltampérométriques révèlent que seule la phase NiO est électrochimiquement active, mais la phase amorphe, grâce aux lacunes anioniques neutres, ?x, renforce la tenue mécanique des films déposés sur les substrats FTO/verre. Il s’ensuit que ces films composites sont plus stables au cyclage, en milieu aqueux KOH 1M, que leurs homologues TiO2/NiO. (iii) Des films minces d’oxyde de nickel dopés par du carbone, préparés par une voie sol-gel originale, présentant une remarquable tenue en cyclage (> 25000 cycles en milieu aqueux KOH 1M), jamais observée jusqu’ici pour NiO. / Aiming at enhancing the electrochromic properties of NiO thin films, deposited on FTO substrates, we have employed three different approaches. They deal with: 1) lithium doping of NiO, the corresponding thin film-deposition method is PLD (Pulsed Laser Deposition); 2) NiO nanoparticles embedded into zinc doped amorphous titanium oxide matrix, a solution method is used to deposit the corresponding thin films ; 3) Carbon-doped NiO thin films deposited using, a specific sol-gel method. Owing to lithium doping of NiO, we could induce film amorphization, thereby enhancing the film electrochemical-capacity. Most importantly, the adhesion between the film and the FTO substrate was improved leading to enhanced electrochemical cyclability in aqueous KOH electrolyte. We could enhance the electrochromic performances of TiO2/NiO composite thin films by doping TiO2 with Zn2+, forming to a new composite thin film Ti1-xZnxO2-x?x-NiO. Finally we have successfully stabilized the electrochromic properties (durability and optical property) of NiO thin films in aqueous KOH electrolyte, owing to the development of a specific sol-gel method leading to carbon-doped NiO nanoparticles. For the first time 25000 cycles were successfully achieved without significant decrease of the electrochromic performances.
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Studies On Superconucting, Metallic And Ferroelectric Oxide Thin Films And Their Heterostructures Grown By Pulsed Laser DepositionSatyalakshmi, K M 05 1900 (has links) (PDF)
No description available.
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Multiferroic hexagonal HoMnO3 filmsKim, Jong-Woo 22 December 2009 (has links)
The fundamental properties of hexagonal multiferric HoMnO3 films have been thoroughly investigated. The films are grown by pulsed laser deposition on Y:ZrO2(111) substrates. High quality epitaxial HoMnO3 films of 25 { 1000 nm thickness were successfully prepared. The film properties are compared to those of single-crystals.
The magnetization measurements revealed that the films show a deviating magnetic behavior from the single-crystals in several ways. For instance, the films have a weakened antiferromagnetic Ho3+ order confirmed from magnetic susceptibility. The difierences are likely to be related to the modified (mostly larger) lattice parameters of films. An approximate phase diagram in comparison with the single-crystal's one is constructed. For multiferroicity investigations, Second Harmonic Generation
(SHG; in collaboration with the group of M. Fiebig) has been employed. By SHG, the ferroelectric polar order of the films is obviously confirmed. The ferroelectric switching at room temperature could be clearly demonstrated, whereas leakage of films requires generally a more sophisticated approach. / Die fundamentalen Eigenschaften von hexagonalen multiferroischen HoMnO3 Schichten
werden eingehend untersucht. Die dünnen Schichten wurden mittels gepulster
Laserdeposition auf Y:ZrO2(111)-Substraten gewachsen. Hochwertige epitaktische
HoMnO3-Dünnschichten von 25 { 1000 nm Dicke wurden erfolgreich hergestellt. Die
Dünnschichteigenschaften werden mit denen von Einkristallen verglichen. Die Magnitisierungsmessungen
ergeben, dass die dünnen Schichten ein von den Einkristallen
in verschiedener Weise abweichendes magnetischen Verhalten zeigen. Zum Beispiel
haben die dünnen Schichten eine abgeschwächte antiferromagntetische Ho3+ Ordnung,
die durch die magnetische Suszeptibilität bestätigt wird. Die Unterschiede
sind wahrscheinlich auf die veränderten (meistens grösseren) Gitterparameter der
dünnen Schichten zurückzuführen. Ein Phasendiagramm wird zum Vergleich mit
Einkristallen konstruiert. Durch Second Harmonic Generation (SHG; in Zusammenarbeit
mit der Gruppe von M. Fiebig) wird die ferroelektrische Ordnung der dünnen
Schichten eindeutig bestätigt. Das ferroelektrische Umschalten bei Raumtemperatur
kann eindeutig nachgewiesen werden, wobei durch den Leckstrom der dünnen Schichten
allgemein eine detailliertere Vorgehensweise benötigt wird.
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Pulsed Laser Ablated Dilute Magnetic Semiconductors and Metalic Spin ValvesGhoshal, Sayak January 2013 (has links) (PDF)
Spintronics (spin based electronics) is a relatively new topic of research which is important both from the fundamental and technological point of view. In conventional electronics charge of the electron is manipulated and controlled to realize electronic devices. Spintronics uses charge as well as the spin degree of freedom of electrons, which is completely ignored in the charge based devices. This new device concept brings in a whole new set of device possibilities with potential advantages like higher speed, greater efficiency, non-volatility, reduced power consumption etc. The first realization of the spintronic device happened in 1989, owing to the discovery of the Giant Magneto-resistive (GMR) structure showing a large resistance change by the application of an external magnetic field. Nobel Prize in Physics is awarded for this discovery in 2007. In less than ten years, such devices moved from the lab to commercial devices, as read head sensors in hard disc drives. This new sensor led to an unprecedented yearly growth in the area l density of bits in a magnetic disc drive. Since 2005, another spintronic device known as Magnetic Tunnel Junction (MTJ) which shows a better performance replaced the existing GMR structures in the read heads. Another device which can potentially replace Si based Dynamic Random Access Memory (DRAM) is Magneto-resistive Random Access Memory (MRAM). Being magnetic it is non-volatile, which means not only it retains its memory with the power turned off but also there is no constant power required for frequent refreshing. This can save a lot of power(~ 10-15 Watts in a DRAM), which is quite significant amount for any portable device which runs under battery. Prototype of a commercial MRAM is also made during 2004-2005 by Infineon and Freescale Semiconductors. Recent development has shown switching of magnetic moment by spin-polarised currents (known as spin transfer torque), electric fields, and photonic fields. Instead of Oersted field switching in the conventional MRAM devices, spin torque effect can also be used to switch a magnetic element more efficiently. Recently Spin-Torque MRAM has gained lot of interest due to it’s less power consumption during the writing process. A continuous research effort is going on in realizing other proposed spintronic devices, such as Spin Torque Oscillator, Spin Field Effect Transistor , Race Track Memory etc. which are yet to get realized or yet to make their entry in the commercial devices.
Spintronics can be divided in to two broad subfields viz.(1) Semiconductor Spintronics and (2) Metallic Spintronics. Most of the devices belong to the second class whereas the former one is rich in fundamental science and not yet cleared its path towards the world of application. Any spintronic device requires ferromagnetic material which is generally the source of spin polarized electrons. For semiconductor spintronic devices, the main obstacle is the non-existence of the ferromagnetic semiconductor above room temperature (RT). So the development in this direction is very much dependent on the material science research and discovery of novel material systems. Almost a decade back, Dilute Magnetic Semiconductors (DMS) are proposed to behaving RT ferromagnetism. As a result an intense theoretical and experimental research is being carried out since then on these materials. Still a general consensus is lacking both in terms of theory as well as experiment.
There are many methodologies and thin film deposition protocols have been followed by different research groups to realize spintronic device concepts. The deposition techniques such as magnetron sputtering, molecular beam epitaxy have been found very efficient for growing metallic spintronic devices. For semiconductor spintronics especially in the area of Dilute Magnetic Semiconductors (DMS) pulsed laser ablation is also considered to be a viable technique. Even though pulsed laser ablation is a very powerful technique to prepare stoichiometric multi-component oxide films, it’s viability for the growth of metallic films and multilayer is considered to be limited. In this regard, we have used pulsed laser ablation to prepare pure and Co doped ZnO films, to examine the magnetic and magneto-transport behavior of these oxides. In addition extensive work has been carried out to optimize and reproducibly prepare metallic multilayer by Pulsed Laser Deposition to realize Spin Valve (SV) effect, which proves the viability of this technique for making metallic multilayer. This thesis deals with the study of Pulsed Laser Deposition(PLD) deposited DMSs and metallic SVs. The thesis is organized into seven chapters as described below:
• Chapter:1
This chapter gives an introduction to Spintronics and the different device structures. It is followed by a brief description of the motivation of the present work. Since magnetism is at the heart of the spintronics, next we attempt to introduce some of the basic concepts in magnetism, which are related to the topics discussed in the following chapters. We discuss about various exchange interactions responsible for the long range ferromagnetic ordering below Curie temperature in different compounds. Other magnetic properties are also discussed. Then another important phenomenon called magnetic anisotropy is brought in. We discuss the origin of different types of anisotropy in materials. These anisotropies are also responsible for magnetic domain formation. Then a description of the different types of domain walls are introduced. Unlike conventional electronics, spintronics deals with spin polarized current. A short description of spin polarization from the band picture and concept of half-metal is introduced.
The next part (Section-I) of this chapter gives an overview of the challenges in semiconductor spintronics. The spin injection efficiency from a ferromagnetic metal to a semiconductor is found to be poor. This problem is attributed to the conductivity mismatch at the interface. DMS materials can be potential candidates in order to solve this problem. Ferromagnetism in these proposed materials cannot be explained in terms of the standard exchange mechanisms. A model was first proposed for the hole doped system based on Zener model. A more apt model for the n-doped high dielectric materials is then proposed based on Bound Magnetic Polarons (BMP). These models for the unusual ferromagnetism are briefly discussed. Although ferromagnetism is observed by different groups, often questions are raised about the intrinsic origin of this behavior and the topic is still under debate. In this study we have tried to correlate the magnetic property with the transport property as the transport properties are generally not affected much by the presence of external impurities and probes the intrinsic property of the material. Transport and the magneto-transport in disordered materials in general are discussed. A specific model proposed for degenerate semiconductors, which is used for fitting our experimental data is explained. As the ferromagnetism in these materials are generally found to be related to the defects, different types of possible defects are described.
Section-II deals with the metallic SV devices. In the history of spintronics, this is one of the most basic and most studied structures, but still having a lot of interest both fundamentally and technologically. A brief history of this discovery and a chronological progress in the device structure is discussed. Our work focuses on the metallic spin valve (SV) structures. Different types of SVs and their properties are explained. In a SV structure one of the ferromagnets (FM) is pinned using an adjuscent antiferromagnetic layer by an effect called exchange bias. A brief description of exchange bias and the effects of different parameters is given. This is followed by a discussion about the theory of GMR which deals with the spin dependent scattering at the bulk and at the interfaces, their relative contributions, effect of the band matching etc. A simple resistor model is used to explain the qualitative behavior of these SVs. The chapter is concluded with a brief summery and applications.
• Chapter:2
This chapter provides a brief description of some of the experimental apparatus that are used to perform various experiments. The chapter is organized according to the general functionality of the techniques. This includes different thin film deposition techniques which are used depending on the requirements and also for comparing the properties of the samples, grown by different techniques. Structural, spectroscopic, magnetic and different microscopy techniques which are extensively used throughout, are discussed and their working principles are explained. This work also involves nano/microstructuring of devices. Mainly two structuring techniques are used viz. e-beam lithography and optical lithography by laser writer. In this section we will be discussing about these two techniques and other associated techniques like lift-off, etching etc. Effect of different parameters on the device structures are highlighted.
• Chapter:3
Chapter-3 deals with the synthesis and characterization of the pure and 5% Co doped ZnO bulk samples. First a brief introduction about the ZnO crystal structure, band structure and other properties are given followed by the synthesis technique followed in our study. Synthesis is done by low temeperature in organic co-precipitation method. This liquid phase synthesis gives better homogeniety. As-grown sample is also sintered at a higher temperature. Structural study confirms the proper synthesis of the intended compound. Spectroscopic as well as magnetic study of the bulk doped sample indicates the presence of Co nano clusters in the low temperature synthesized sample, whereas after sintering indication of Co2+ is observed which reflects in the magnetic property as well. These samples are used as target material for laser ablation.
• Chapter:4
Chapter-4 presents the results of the pure and Co doped ZnO thin film samples. Thin films are grown by PLD method on r-plane Sapphire substrates. Details of the growth technique and the deposition parameters are explained. Our result shows that 5% Co doped ZnO thin film is ferromagnetic in nature as expected in a DMS material, although the film is grown using a paramagnetic target. We also report that pure ZnO grown in an oxygen deficient condition giving ferromagnetic behavior. Not only that, the obtained saturation moment is much higher compared to the Co doped sample. We have demonstrated that the FM can be tuned by tuning the oxygen content and FM disappears when the film is annealed in an oxygen environment .But for the Co doped sample magnetic property could not be tuned much as Co doping stabilizes the surface states. To exclude the possibilities of the extrinsic origin we have done a detailed magneto-transport study for both doped and undoped films. For ZnO, we have shown a one to one correlation of the magnetic and magneto-transport data which further supports the fact that the obtained magnetic behavior is intrinsic. Fitting of the magnetorsistance (MR) data for the pure and Co doped ZnO samples is done using a semi-empirical formula, consisting of both positive and negative MR terms originally proposed for degenerate semiconductors .Excellent agreement of the experimental data is found with the formula. For pure ZnO sample we have extracted the mobility, carrier concentration etc .by Hall measurement. The fabrication steps of Hall bar sample which involves optical lithography and ion beam etching are discussed. 3D e-e interaction induced transport mechanism is found to be dominant in case of oxygen deficient pure ZnO.
• Chapter:5
Chapter-5 demonstrates the tuning of band gap of ZnO by alloying with MgO. By changing the ZnO:MgO ratio in PLD grown films, we could tune the band gap over a wide range. Composition alanalysis is done by Rutherford Back-Scattering. Structural and spectroscopic studies are carried out, which shows tuning of band gap upon alloying with MgO. We could tune ZnO band gap from 3.3eV to 3.92eV by30% MgO alloying, while retaining the Wurtzite crystal structure.
• Chapter:6
Chapter-6 demonstrates the metallic Pseudo Spin Valve (PSV) structures grown by sputtering and by PLD. Main focus of this chapter is to show that, PLD can be aviable technique for making metallic PSV and Spin Valve (SV) structures. This is almost an unexplored technique for growing metallic thin film SVs, as it is evident in the literature. NiFe and Co are used as the soft and hard FM layers respectively, Au and Cu are used as the spacer layer. FeMn is used for pinning the Co layer in case of the SV structures. The first section describes the properties of these materials and then substrate preparation, deposition parameters etc. are explained in details. Properties of sputter deposited PSV structures are also described. Thickness variation of different layers, double PSV structure and angular variation of the MR properties are presented. Generally two measurement geometries are followed for the SV measurements viz.(1) Current In Plane (CIP) and (2) Current Perpendicular to Plane(CPP). We have carried out MR studies in both the measurement geometries. Measurement in CPP geometry is much more involved than CIP and need structuring with multiple lithography steps. CPP measurement geometry scheme and the process steps are discussed. For this measurement a special ac bridge technique is followed which is also discussed.
In the next part we have demonstrated PSV and SV structures, grown, using PLD in an Ultra High Vacuum (UHV) system. Not only that, we have obtained a CIPMR as high as 3.3%. PLD is generally thought to be a technique for oxide deposition and metallic multilayers are not deposited due to particulate formation, high enegy of the adatom species which can lead to inter-mixing at the interface etc. But in this study we have shown that by properly tuning the deposition parameters, it is possible to grow SVs using PLD. We have found the roughness of the PLD grown films are much lower compared to the sputtered films. For top SV structures we have obtained exchange bias even in the absence of applied field during deposition. This effect is observed by performing magnetic and magneto-resistance measurements. Effect of different layer thicknesses, field annealing etc. are discussed. Two different spacer layers are used and their properties are compared. We have found that the interface engineered structures are giving highest MR among the different samples. Then a conclusion of our study is presented followed by a discussion on the difficulties and challenges faced for optimizing the PLD grown SVs.
• Chapter:7
Finally, in Chapter-7, various results are summarized and a broad outlook is given. Perspectives for the continuation of the present work is also given.
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