Electrolithography- A New and Versatile Process for Nano Patterning

We report a new lithography technique based on electromigration driven material transport for drawing patterns at nanometer scales in ambient conditions. We use a thin metal film as a masking layer and a polymer layer beneath it as a pattern transfer layer. The desired pattern is drawn in the metal layer by etching the metal with a conducting scanning probe assisted by liquid electromigration. The pattern drawn on the metal layer is transferred to the polymer layer by etching the polymer with an appropriate solvent. Subsequently, the pattern is transferred to the desired material layer using a film deposition technique followed by conventional lift-off process. Using this simple technique, we have achieved pattern resolutions of 9 nm on the polymer and 40 nm on transferring the pattern to another material. Based on the ease of use and process costs, this technique promises to be competitive to e-beam lithography that employs high energy and ultra-high vacuum, or the industrial standard ultra-violet light photolithography that employs extremely expensive implements to reach nano-scale resolutions. We also demonstrate direct mask writing using this technique and explain the fundamentals behind the workings of the developed method.

Development of an automated ultrasonic spray pyrolysis system and the growth of Cu2ZnSnS4 thin films

An automated ultrasonic spray pyrolysis system is fabricated for the growth of thin films. The system is equipped with x-y movement and enables film deposition in different patterns and spray rates. Cu-2(Zn,Sn)S-4 (CZTS) films are deposited using this setup. The substrate temperature (T-s) is varied from 240 to 490 degrees C. Kesterite CZTS phase is observed in all the films together with binary phases. The films prepared at T-s <340 degrees C showed SnxSy phase and those at T-s >340 degrees C showed Cu2S phase. Sulfur incorporation is maximum (40%) at 440 degrees C and the films showed better morphology. The Cu and S concentrations are varied to remove binary phases. Depth wise elemental analysis confirmed the existence of single phase CZTS. p-Type CZTS films of resistivity in the range of 10(2)-10(3) Omega cm are obtained. (C) 2015 Elsevier B.V. All rights reserved.

Growth of ultrahigh density vertically aligned carbon nanotube forests for interconnects.

We present a general catalyst design to synthesize ultrahigh density, aligned forests of carbon nanotubes by cyclic deposition and annealing of catalyst thin films. This leads to nanotube forests with an area density of at least 10(13) cm(-2), over 1 order of magnitude higher than existing values, and close to the limit of a fully dense forest. The technique consists of cycles of ultrathin metal film deposition, annealing, and immobilization. These ultradense forests are needed to use carbon nanotubes as vias and interconnects in integrated circuits and thermal interface materials. Further density increase to 10(14) cm(-2) by reducing nanotube diameter is possible, and it is also applicable to nanowires.

Rational design of zinc phosphide heterojunction photovoltaics

The prospect of terawatt-scale electricity generation using a photovoltaic (PV) device places strict requirements on the active semiconductor optoelectronic properties and elemental abundance. After reviewing the constraints placed on an "earth-abundant" solar absorber, we find zinc phosphide (α-Zn₃P₂) to be an ideal candidate. In addition to its near-optimal direct band gap of 1.5 eV, high visible-light absorption coefficient (>10⁴ cm^-1), and long minority-carrier diffusion length (>5 μm), Zn₃P₂ is composed of abundant Zn and P elements and has excellent physical properties for scalable thin-film deposition. However, to date, a Zn₃P₂ device of sufficient efficiency for commercial applications has not been demonstrated. Record efficiencies of 6.0% for multicrystalline and 4.3% for thin-film cells have been reported, respectively. Performance has been limited by the intrinsic p-type conductivity of Zn₃P₂ which restricts us to Schottky and heterojunction device designs. Due to our poor understanding of Zn₃P₂ interfaces, an ideal heterojunction partner has not yet been found.

The goal of this thesis is to explore the upper limit of solar conversion efficiency achievable with a Zn₃P₂ absorber through the design of an optimal heterojunction PV device. To do so, we investigate three key aspects of material growth, interface energetics, and device design. First, the growth of Zn₃P₂ on GaAs(001) is studied using compound-source molecular-beam epitaxy (MBE). We successfully demonstrate the pseudomorphic growth of Zn₃P₂ epilayers of controlled orientation and optoelectronic properties. Next, the energy-band alignments of epitaxial Zn₃P₂ and II-VI and III-V semiconductor interfaces are measured via high-resolution x-ray photoelectron spectroscopy in order to determine the most appropriate heterojunction partner. From this work, we identify ZnSe as a nearly ideal n-type emitter for a Zn₃P₂ PV device. Finally, various II-VI/Zn₃P₂ heterojunction solar cells designs are fabricated, including substrate and superstrate architectures, and evaluated based on their solar conversion efficiency.

Investigations of the conductor-semiconductor interface

I. Schottky barriers produced by polymeric sulfur nitride, (SN)_x, on nine common III-V and II-VI compound semiconductors are compared to barriers formed by Au. The conductor (SN)_x produces significantly higher barriers to n-type semiconductors and lower barriers to p-type semiconductors than Au, the most electronegative elemental metal. The barrier height improvement, defined as ɸ(SN)_x - ɸ(Au), is smaller on covalent semiconductors than on ionic semiconductors; (SN)x barriers follow the ionic-covalent transition. Details of (SN)_x film deposition, samples preparation, and barrier height measurements are described.

II. The rate of dissolution of amorphous Si into solid Al is measured. The rate of movement of the amorphous Si/Al interface is found to be much faster than predicted by a simple model of the transport of Si through Al. This result is related to defects in the growth of epitaxial Si using the solid phase epitaxy process.

Nanostructuring of materials for device and sensor applications

The recent developments in nanotechnology are reviewed, with particular emphasis on its application in microsystem technology where increased reliability is achieved by integrating the sensor and the readout electronics on the same substrate. New applications may be possible using integrated micromechanical clips to connect optic fibers and components in integrated silicon systems. Some of the key developments in enabling technologies are also described, including the control of thin film deposition, nanostructuring to tailor the properties of thin film, silicon micromachining to make sensors, and microclips for the low-cost assembly of integrated optical microsystems.

Effect of surface treatment of GaN based light emitting diode wafers on the leakage current of light emitting diode devices

To form low-resistance Ohmic contact to p-type GaN, InGaN/GaN multiple quantum well light emitting diode wafers are treated with boiled aqua regia prior to Ni/Au (5 nm/5 nm) film deposition. The surface morphology of wafers and the current-voltage characteristics of fabricated light emitting diode devices are investigated. It is shown that surface treatment with boiled aqua regia could effectively remove oxide from the surface of the p-GaN layer, and reveal defect-pits whose density is almost the same as the screw dislocation density estimated by x-ray rocking curve measurement. It suggests that the metal atoms of the Ni/Au transparent electrode of light emitting diode devices may diffuse into the p-GaN layer along threading dislocation lines and form additional leakage current channels. Therefore, the surface treatment time with boiled aqua regia should not be too long so as to avoid the increase of threading dislocation-induced leakage current and the degradation of electrical properties of light emitting diodes

Enhancement of electroluminescence in p-i-n structures with nano-crystalline Si/SiO2 multilayers

Nano-crystalline Si/SiO2 multilayers were prepared by alternately changing the ultra-thin amorphous Si film deposition and the in situ plasma oxidation process followed by the post-annealing treatments. Well-defined periodic structures can be achieved with 2.5 nm thick SiO2 sublayers. It is shown that the size of formed nano-crystalline Si is about 3 nm. Room temperature electroluminescence can be observed and the spectrum contains two luminescence bands located at 650 nm and 520 nm. In order to improve the hole injection probability, p-i-n structures containing a nanocrystalline Si/SiO2 luminescent layer were designed and fabricated on different p-type substrates. It is found that the turn-on voltage of p-i-n structures is obviously reduced and the luminescence intensity increases by 50 times. It is demonstrated that the use of a heavy-doped p-type substrate can increase the luminescence intensity more efficiently compared with the light-doped p-type substrate due to the enhanced hole injection.

CONSTRUCTION AND APPLICATIONS OF A DUAL MASS-SELECTED LOW-ENERGY ION-BEAM SYSTEM

A direct ion beam deposition system designed for heteroepitaxy at a low substrate temperature and for the growth of metastable compounds has been constructed and tested. The system consists of two mass-resolved low-energy ion beams which merge at the target with an incident energy range 50-25 000 eV. Each ion beam uses a Freeman ion source for ion production and a magnetic sector for mass filtering. While a magnetic quadrupole lens is used in one beam for ion optics, an electrostatic quadrupole lens focuses the other beam. Both focusing approaches provide a current density more than 100-mu-A/cm2, although the magnetic quadrupole gives a better performance for ion energies below 200 eV. The typical current of each beam reaches more than 0.3 mA at 100 eV, with a ribbon beam of about 0.3-0.5 x 2 cm2. The target is housed in an ultrahigh vacuum chamber with a base pressure of 1 x 10(-7) Pa and a typical pressure of 5 x 10(-6) Pa when a noncondensable beam like argon is brought into the chamber. During deposition, the target can be heated to 800-degrees-C and scanned mechanically with an electronic scanning control unit. The dual beam system has been used to grow GaN using a Ga+ and a N+ beam, and to study the oxygen and hydrogen ion beam bombardment effects during carbon ion beam deposition. The results showed that the simultaneous arrival of two beams at the target is particularly useful in compound formation and in elucidation of growth mechanisms.

Improving performance of polymer photovoltaic devices using an annealing-free approach via construction of ordered aggregates in solution

Low crystalline order has been proved to be one of the main hindrances for achieving high performance devices based on thin films composed of crystallizable polymer. In this work, we use a facile method to substantially improve crystallinity of poly(3-hexylthiophene) (P3HT) in its pure or composite film via the construction of ordered precursors in the solution used for thin film deposition. These improvements have been confirmed by bright-field transmission electron micrography, electron diffraction, UV-Vis absorption and wide-angle X-ray diffraction.

Novel < 110 >-oriented organic-inorganic perovskite compound stabilized by N-(3-aminopropyl) imidazole with improved optical properties

In the organic-inorganic perovskites family, the < 100 >-oriented type has been extensively investigated as a result of its unique magnetic, optical, and electrical properties, and only one type of < 110 >-oriented hybrid perovskite stabilized by methylammonium and iodoformamidinium cations or the latter themselves has been known so far. In this paper, another novel < 110 >-oriented organic-inorganic perovskite (C6H13N3)-PbBr4 (compound 1) has been prepared by reacting N-(3-aminopropyl)imidazole (API) with PbBr2 in hydrobromic acid. The crystal structure is determined, which indicates that the perovskite is stabilized by API. The introduction of the optically active organic ligand API into the hybrid perovskite results in a red shift and a great enhancement of photoluminescence in the perovskite with respect to organic ligand API itself. These results have been explained according to calculation based on density-functional theory. Moreover, the excellent film processing ability for the perovskite (C6H13N3)PbBr4 together with the improved optical properties makes it have potential application in optoelectronic devices.

Study of multiferroic materials

The present PhD work aims the research and development of materials that exhibit multiferroic properties, in particular having a significant interaction between ferromagnetism and ferroelectricity; either directly within an intrinsic single phase or by combining extrinsic materials, achieving the coupling of properties through mechanic phenomena of the respective magnetostriction and piezoelectricity. These hybrid properties will allow the cross modification of magnetic and electric polarization states by the application of cross external magnetic and/or electric fields, giving way to a vast area for scientific investigation and potential technological applications in a new generation of electronic devices, such as computer memories, signal processing, transducers, sensors, etc. Initial experimental work consisted in chemical synthesis of nano powders oxides by urea pyrolysis method: A series of ceramic bulk composites with potential multiferroic properties comprised: of LuMnO3 with La0.7Sr0.3MnO3 and BaTiO3 with La0.7Ba0.3MnO3; and a series based on the intrinsic multiferroic LuMn1-zO3 phase modified with of Manganese vacancies. The acquisition of a new magnetron RF sputtering deposition system, in the Physics Department of Aveiro University, contributed to the proposal of an analogous experimental study in multiferroic thin films and multilayer samples. Besides the operational debut of this equipment several technical upgrades were completed like: the design and construction of the heater electrical contacts; specific shutters and supports for the magnetrons and for the substrate holder and; the addition of mass flow controllers, which allowed the introduction of N2 or O2 active atmosphere in the chamber; and the addition of a second RF generator, enabling co-deposition of different targets. Base study of the deposition conditions and resulting thin films characteristics in different substrates was made from an extensive list of targets. Particular attention was given to thin film deposition of magnetic phases La1-xSrxMnO3, La1-xBaxMnO3 and Ni2+x-yMn1-xGa1+y alloy, from the respective targets: La0.7Sr0.3MnO3, La0.7Ba0.3MnO3; and NiGa with NiMn. Main structural characterization of samples was performed by conventional and high resolution X-Ray Diffraction (XRD); chemical composition was determined by Electron Dispersion Spectroscopy (EDS); magnetization measurements recur to a Vibrating Sample Magnetometer (VSM) prototype; and surface probing (SPM) using Magnetic-Force (MFM) and Piezo-Response (PFM) Microscopy. Results clearly show that the composite bulk samples (LuM+LSM and BTO+LBM) feat the intended quality objectives in terms of phase composition and purity, having spurious contents below 0.5 %. SEM images confirm compact grain packaging and size distribution around the 50 nm scale. Electric conductivity, magnetization intensity and magneto impedance spreading response are coherent with the relative amount of magnetic phase in the sample. The existence of coupling between the functional phases is confirmed by the Magnetoelectric effect measurements of the sample “78%LuM+22%LSM” reaching 300% of electric response for 1 T at 100 kHz; while in the “78%BTO+22%LBM” sample the structural transitions of the magnetic phase at ~350 K result in a inversion of ME coefficient the behavior. A functional Magneto-Resistance measurement system was assembled from the concept stage until the, development and operational status; it enabled to test samples from 77 to 350 K, under an applied magnetic field up to 1 Tesla with 360º horizontal rotation; this system was also designed to measure Hall effect and has the potential to be further upgraded. Under collaboration protocols established with national and international institutions, complementary courses and sample characterization studies were performed using Magneto-Resistance (MR), Magneto-Impedance (MZ) and Magneto-Electric (ME) measurements; Raman and X-ray Photoelectron Spectroscopy (XPS); SQUID and VSM magnetization; Scanning Electron Microscopy (SEM) and Rutherford Back Scattering (RBS); Scan Probe Microscopy (SPM) with Band Excitation Probe Spectroscopy (BEPS); Neutron Powder Diffraction (NPD) and Perturbed Angular Correlations (PAC). Additional collaboration in research projects outside the scope of multiferroic materials provided further experience in sample preparation and characterization techniques, namely VSM and XPS measurements were performed in cubane molecular complex compounds and enable to identify the oxidation state of the integrating cluster of Ru ions; also, XRD and EDS/SEM analysis of the acquired targets and substrates implied the devolution of some items not in conformity with the specifications. Direct cooperation with parallel research projects regarding multiferroic materials, enable the assess to supplementary samples, namely a preliminary series of nanopowder Y1-x-yCaxØyMn1O3 and of Eu0.8Y0.2MnO3, a series of micropowder composites of LuMnO3 with La0.625Sr0.375MnO3 and of BaTiO3 with hexagonal ferrites; mono and polycrystalline samples of Pr1-xCaxMnO3, La1-xSrxMnO3 and La1-xCaxMnO3.

Spray Pyrolysed Zinc Oxide Thin Films : Effects of Doping and Ion Beam Irradiation

In recent years scientists have made rapid and significant advances in the field of semiconductor physics. One of the most important fields of current interest in materials science is the fundamental aspects and applications of conducting transparent oxide thin films (TCO). The characteristic properties of such coatings are low electrical resistivity and high transparency in the visible region. The first semitransparent and electrically conducting CdO film was reported as early as in 1907 [1]. Though early work on these films was performed out of purely scientific interest, substantial technological advances in such films were made after 1940. The technological interest in the study of transparent semiconducting films was generated mainly due to the potential applications of these materials both in industry and research. Such films demonstrated their utility as transparent electrical heaters for windscreens in the aircraft industry. However, during the last decade, these conducting transparent films have been widely used in a variety of other applications such as gas sensors [2], solar cells [3], heat reflectors [4], light emitting devices [5] and laser damage resistant coatings in high power laser technology [6]. Just a few materials dominate the current TCO industry and the two dominant markets for TCO’s are in architectural applications and flat panel displays. The architectural use of TCO is for energy efficient windows. Fluorine doped tin oxide (FTO), deposited using a pyrolysis process is the TCO usually finds maximum application. SnO2 also finds application ad coatings for windows, which are efficient in preventing radiative heat loss, due to low emissivity (0.16). Pyrolitic tin oxide is used in PV modules, touch screens and plasma displays. However indium tin oxide (ITO) is mostly used in the majority of flat panel display (FPD) applications. In FPDs, the basic function of ITO is as transparent electrodes. The volume of FPD’s produced, and hence the volume of ITO coatings produced, continues to grow rapidly. But the current increase in the cost of indium and the scarcity of this material created the difficulty in obtaining low cost TCOs. Hence search for alternative TCO materials has been a topic of active research for the last few decades. This resulted in the development of binary materials like ZnO, SnO2, CdO and ternary materials like II Zn2SnO4, CdSb2O6:Y, ZnSO3, GaInO3 etc. The use of multicomponent oxide materials makes it possible to have TCO films suitable for specialized applications because by altering their chemical compositions, one can control the electrical, optical, chemical and physical properties. But the advantages of using binary materials are the easiness to control the chemical compositions and depositions conditions. Recently, there were reports claiming the deposition of CdO:In films with a resistivity of the order of 10-5 ohm cm for flat panel displays and solar cells. However they find limited use because of Cd-Toxicity. In this regard, ZnO films developed in 1980s, are very useful as these use Zn, an abundant, inexpensive and nontoxic material. Resistivity of this material is still not very low, but can be reduced through doping with group-III elements like In, Al or Ga or with F [6]. Hence there is a great interest in ZnO as an alternative of ITO. In the present study, we prepared and characterized transparent and conducting ZnO thin films, using a cost effective technique viz Chemical Spray Pyrolysis (CSP). This technique is also suitable for large area film deposition. It involves spraying a solution, (usually aqueous) containing soluble salts of the constituents of the desired compound, onto a heated substrate.

Growth and characterization of perovskite oxide ferroelectric thin films and its applications

Department of Physics, Cochin University of Science and Technology

An investigation on the preparation and properties of certian semiconducting sulphide thin films

In this thesis the preparation and properties of thin films of certain semiconducting sulphides (sulphides of tin, copper and indium) are reported. As single source evaporation does not yield satisfactory films of these compounds for a variety of reasons, reactive evaporation of the metal in a sulphur atmosphere has been used for film preparation. It was found that for each metal sulphide a stoichimetric interval of fluxes and substrate temperature exists for the formation of the compound in accordance with the analysis of Guenther. The first chapter of the thesis gives a resume of the basic principles of semiconductor physics relevant to the work reported here. In the second chapter is discussed in detail the reactive evaporation techniques like ordinary reactive evaporation, activated reactive evaporation and reactive ion plating. Third chapter deals with the experimental techniques used in this study for film preparation and characterization. In the next seven chapters is discussed the preparation and properties of the compound films studied. The last chapter gives a general theory of the formation of compound films in various deposition techniques in terms of the kinetic energy of the film forming particles. It must be mentioned here that this is of fundamental importance to thin film deposition and is virtually untouched in the literature