Hybrid lead-halide perovskites as novel materials for thin film direct and flexible ionizing radiation detectors

Ionizing radiations are important tools employed every day in the modern society. For example, in medicine they are routinely used for diagnostic and therapy. The large variety of applications leads to the need of novel, more efficient, low-cost ionizing radiation detectors with new functionalities. Personal dosimetry would benefit from wearable detectors able to conform to the body surfaces. Traditional semiconductors used for ionizing radiation direct detectors offer high performance but they are intrinsically stiff, brittle and require high voltages to operate. Hybrid lead-halide perovskites emerged recently as a novel class of materials for ionizing radiation detection. They combine high absorption coefficient, solution processability and high charge transport capability, enabling efficient and low-cost detection. The deposition from solution allows the fabrication of thin-film flexible devices. In this thesis, I studied the detection properties of different types of hybrid perovskites, deposited from solution in thin-film form, and tested under X-rays, gamma-rays and protons beams. I developed the first ultraflexible X-ray detector with exceptional conformability. The effect of coupling organic layers with perovskites was studied at the nanoscale giving a direct demonstration of trap passivation effect at the grain boundaries. Different perovskite formulations were deposited and tested to improve the film stability. I report about the longest aging studies on perovskite X-ray detectors showing that the addition of starch in the precursors’ solution can improve the stability in time with only a 7% decrease in sensitivity after 630 days of storage in ambient conditions. 2D perovskites were also explored as direct detector for X-rays and gamma-rays. Detection of 511 keV photons by a thin-film device is here demonstrated and was validated for monitoring a radiotracer injection. At last, a new approach has been used: a 2D/3Dmixed perovskite thin-film demonstrated to reliably detect 5 MeV protons, envisioning wearable dose monitoring during proton/hadron therapy treatments.

A CMOS/SOI single-input PWM discriminator for low-voltage body-implanted applications

A CMOS/SOI circuit to decode Pulse-Width Modulation (PWM) signals is presented as part of a body-implanted neurostimulator for visual prosthesis. Since encoded data is the sole input to the circuit, the decoding technique is based on a novel double-integration concept and does not require low-pass filtering. Non-overlapping control phases are internally derived from the incoming pulses and a fast-settling comparator ensures good discrimination accuracy in the megahertz range. The circuit was integrated on a 2 mum single-metal thin-film CMOS/SOI fabrication process and has an effective area of 2 mm(2). Measured resolution of encoding parameter a is better than 10% at 6 MHz and V-DD = 3.3 V. Idle-mode consumption is 340 LW. Pulses of frequencies up to 15 MHz and alpha = 10% can be discriminated for 2.3 V less than or equal to V-DD less than or equal to 3.3 V. Such an excellent immunity to V-DD deviations meets a design specification with respect to inherent coupling losses on transmitting data and power by means of a transcutaneous link.

AlN-based BAW resonators with CNT electrodes for gravimetric biosensing

Solidly mounted resonators (SMRs) with a top carbon nanotubes (CNTs) surface coating that doubles as an electrode and as a sensing layer have been fabricated. The influence of the CNTs on the frequency response of the resonators was studied by direct comparison to identical devices with a top metallic electrode. It was found that the CNTs introduced significantly less mass load on the resonators and these devices exhibited a greater quality factor, Q (>2000, compared to ∼1000 for devices with metal electrodes), which increases the gravimetric sensitivity of the devices by allowing the tracking of smaller frequency shifts. Protein solutions with different concentrations were loaded on the top of the resonators and their responses to mass-load from physically adsorbed coatings were investigated. Results show that resonators using CNTs as the top electrode exhibited a higher frequency change for a given load (∼0.25 MHz cm2 ng−1) compared to that of a metal thin film electrode (∼0.14 MHz cm2 ng−1), due to the lower mass of the CNTelectrodes and their higher active surface area compared to that of a thin film metal electrode. It is therefore concluded that the use of CNTelectrodes on resonators for their use as gravimetric biosensors is a significant improvement over metallic electrodes that are normally employed.

Solidly Mounted Resonators with Carbon Nanotube Electrodes for Biosensing Applications

The work reported here shows a direct experimental comparison of the sensitivities of AlN solidly mounted resonators (SMR)-based biosensors fabricated with standard metal electrodes and with carbon nanotube electrodes. SMRs resonating at frequencies around 1.75 GHz have been fabricated, some devices using a thin film of multi-wall carbon nanotubes (CNTs) as the top electrode material and some identical devices using a chromium/gold electrode. Protein solutions with different concentrations were loaded on the top of the resonators and their responses to mass-load from physically adsorbed coatings were investigated. Results show that resonators using CNTs as the top electrode material exhibited higher frequency change for a given load due to the higher active surface area of a thin film of interconnecting CNTs compared to that of a metal thin film electrode and hence exhibited greater mass loading sensitivity. It is therefore concluded that the use of CNT electrodes on resonators for their use as gravimetric biosensors is viable and worthwhile.

A comparison between neutron-fluence measurements using metal-activation monitors and standard glasses calibrated via thin uranium-fission monitors and via ηq method

The two fundamental approaches to fission-track dating involve either an explicit determination of the thermal neutron fluence (φ-method) or a calibration against age standards (ζ-method). The neutron fluence measurements are carried out with metal-activation monitors or with uranium-fission monitors, co-irradiated with the samples. Uranium-fission monitors consist of either a thin mono-atomic) film, or a thick fission source (standard uranium glass) irradiated against a muscovite external track detector. In this work, different techniques for performing neutron-fluence measurements were compared: based on thin-film calibration, based on thick-source calibration, and based on gamma spectrometry of co-irradiated metal monitors (Au, Co). The results suggest that more experiments are needed to make all calibrations consistent, including new measurements of the length of etched induced tracks in mica. Also the standard glass calibration carried out with thin films should be confirmed with a greater number of calibrating irradiations. © 2013 Elsevier Ltd. All rights reserved.

Ion beam modification and analysis of metal/polymer bi-layer thin films

A set of varying-thickness Au-films were thermally evaporated onto poly(styrene-co-acrylonitrile) thin film surfaces. The Au/PSA bi-layer targets were then implanted with 50 keV N+ ions to a fluence of 1 × 1016 ions/cm2 to promote metal-to-polymer adhesion and to enhance their mechanical and electrical performance. Electrical conductivity measurements of the implanted Au/PSA thin films showed a sharp percolation behavior versus the pre-implant Au-film thickness with a percolation threshold near the nominal thickness of 44 Å. The electrical conductivity results are discussed along with the film microstructure and the elemental diffusion/mixing within the Au/PSA interface obtained by scanning electron microscopy (SEM) and ion beam analysis techniques (RBS and ERD).

Influence of the metal center on the morphology of coordination compounds thin films

Thin film morphology of tris-(8-hydroxyquinolate) aluminium (III) (Alq3) and bis-(8-hydroxyquinolate) oxovanadium (IV) (VOq2) are compared. Alq3 films deposited onto mica at 300K look almost featureless, but dendrimers or randomly distributed needle-shaped crystallites appear as a consequence of crystallization in time. We show that a possible origin of this process is exposure to solvent vapors. On the other hand, VOq2 films retain their textured morphology as thickness increases because of stabilizing intermolecular interactions between vanadyl groups.

Influence of the metal center on the morphology of coordination compounds thin films

Thin film morphology of tris-(8-hydroxyquinolate) aluminium (III) (Alq3) and bis-(8-hydroxyquinolate) oxovanadium (IV) (VOq2) are compared. Alq3 films deposited onto mica at 300K look almost featureless, but dendrimers or randomly distributed needle-shaped crystallites appear as a consequence of crystallization in time. We show that a possible origin of this process is exposure to solvent vapors. On the other hand, VOq2 films retain their textured morphology as thickness increases because of stabilizing intermolecular interactions between vanadyl groups.

Development and characterisation of solution processed vanadium oxide and transparent metal oxide thin films

Metal oxide thin films are important for modern electronic devices ranging from thin film transistors to photovoltaics and functional optical coatings. Solution processed techniques allow for thin films to be rapidly deposited over a range of surfaces without the extensive processing of comparative vapour or physical deposition methods. The production of thin films of vanadium oxide prepared through dip-coating was developed enabling a greater understanding of the thin film formation. Mechanisms of depositing improved large area uniform coverage on a number of technologically relevant substrates were examined. The fundamental mechanism for polymer-assisted deposition in improving thin film surface smoothness and long range order has been delivered. Different methods were employed for adapting the alkoxide based dip-coating technique to produce a variety of amorphous and crystalline vanadium oxide based thin films. Using a wide range of material, spectroscopic and optical measurement techniques the morphology, structure and optoelectronic properties of the thin films were studied. The formation of pinholes on the surface of the thin films, due to dewetting and spinodal effects, was inhibited using the polymer assisted deposition technique. Uniform thin films with sub 50 nm thicknesses were deposited on a variety of substrates controlled through alterations to the solvent-alkoxide dilution ratios and employing polymer assisted deposition techniques. The effects of polymer assisted deposition altered the crystallized VO thin films from a granular surface structure to a polycrystalline structure composed of high density small in-plane grains. The formation of transparent VO based thin film through Si and Na substrate mediated diffusion highlighted new methods for material formation and doping.

Patterning optically clear films: co-planar transparent and color-contrasted thin films from interdiffused electrodeposited and solution-processed metal oxides

Transparent thin films can now be site-selectively patterned and positioned on surface using mask-defined electrodeposition of one oxide and overcoating with a different solution-processed oxide, followed by thermal annealing. Annealing allows an interdiffusion process to create a new oxide that is entirely transparent. A primary electrodeposited oxide can be patterned and the secondary oxide coated over the entire substrate to form high color contrast coplanar thin film tertiary oxide. The authors also detail the phase formation and chemical state of the oxide and how the nature of the electrodeposited layer and the overlayer influence the optical clearing of the patterned oxide film.

Laser-assisted deposition of thin films from photoexcited vapour phases

Laser-assisted chemical vapour deposition (LCVD) has been extensively studied in the last two decades. A vast range of applications encompass various areas such as microelectronics, micromechanics, microelectromechanics and integrated optics, and a variety of metals, semiconductors and insulators have been grown by LCVD. In this article, we review briefly the LCVD process and present two case studies of thin film deposition related to laser thermal excitation (e.g., boron carbide) and non-thermal excitation (e.g., CrO(2)) of the gas phase.

InOx thin films deposited by plasma assisted evaporation: application in light shutters

An integration of undoped InOx and commercial ITO thin films into laboratory assembled light shutter devices is made. Accordingly, undoped transparent conductive InOx thin films, about 100 nm thick, are deposited by radiofrequency plasma enhanced reactive thermal evaporation (rf-PERTE) of indium teardrops with no intentional heating of the glass substrates. The process of deposition occurs at very low deposition rates (0.1-0.3 nm/s) to establish an optimized reaction between the oxygen plasma and the metal vapor. These films show the following main characteristics: transparency of 87% (wavelength, lambda = 632.8 nm) and sheet resistance of 52 Omega/sq; while on commercial ITO films the transparency was of 92% and sheet resistance of 83 Omega/sq. The InOx thin film surface characterized by AFM shows a uniform grain texture with a root mean square surface roughness of Rq similar to 2.276 nm. In contrast, commercial ITO topography is characterized by two regions: one smoother with Rq similar to 0.973 nm and one with big grains (Rq similar to 3.617 nm). For the shutters assembled using commercial ITO, the light transmission coefficient (Tr) reaches the highest value (Tr-max) of 89% and the lowest (Tr-min) of 1.3% [13], while for the InOx shutters these values are 80.1% and 3.2%, respectively. Regarding the electric field required to achieve 90% of the maximum transmission in the ON state (E-on), the one presented by the devices assembled with commercial ITO coated glasses is 2.41 V/mu m while the one presented by the devices assembled with InOx coated glasses is smaller, 1.77 V/mu m. These results corroborate the device quality that depends on the base materials and fabrication process used. (C) 2014 Elsevier Ltd. All rights reserved.

Magnetotransport properties of metal/LaAlO3/SrTiO3 heterostructures

The quasi two-dimensional electron gas (q2DEG) hosted in the interface of an epitaxially grown lanthanum aluminate (LaAlO3) thin film with a TiO2-termi-nated strontium titanate (SrTiO3) substrate (001) has been massively studied in the last few years. The confinement of mobile electrons to within a few nanome-ters from the interface, superconductive behavior at low temperatures and elec-tron mobility exceeding 1000 cm2/(V.s) make this system an interesting candi-date to explore the physics of spin injection and transport. However, due to the critical thickness for conduction of 4 unit cells (uc) of LaAlO3, a high tunneling resistance hampers electrical access to the q2DEG, preventing proper injection of spin polarized current. Recently, our group found that depositing a thin overlayer of Co on LaAlO3 reduces the critical thickness, enabling conduction with only 1 uc of LaAlO3. Two scenarios arise to explain this phenomenon: a pinning of the Fermi level in the metal, inducing charge transfer in the SrTiO3; the creation of oxygen vacancies at the interface between LaAlO3 and the metal, leading to an n-type doping of the SrTiO3. In this dissertation, we will report on magnetotransport of metal/LaAlO3/SrTiO3 (metal: Ti, Ta, Co, Py, Au, Pt, Pd) heterostructures with 2 uc of LaAlO3 studied at low temperatures (2 K) and high magnetic fields (9 T). We have analyzed the transport properties of the gas, namely, the carrier concen-tration, mobility and magnetotransport regime and we will discuss the results in the light of the two scenarios mentioned above.

Electrical and optical properties of Zn-In-Sn-O transparent conducting thin films

Indium tin oxide (ITO) is one of the widely used transparent conductive oxides (TCO) for application as transparent electrode in thin film silicon solar cells or thin film transistors owing to its low resistivity and high transparency. Nevertheless, indium is a scarce and expensive element and ITO films require high deposition temperature to achieve good electrical and optical properties. On the other hand, although not competing as ITO, doped Zinc Oxide (ZnO) is a promising and cheaper alternative. Therefore, our strategy has been to deposit ITO and ZnO multicomponent thin films at room temperature by radiofrequency (RF) magnetron co-sputtering in order to achieve TCOs with reduced indium content. Thin films of the quaternary system Zn-In-Sn-O (ZITO) with improved electrical and optical properties have been achieved. The samples were deposited by applying different RF powers to ZnO target while keeping a constant RF power to ITO target. This led to ZITO films with zinc content ratio varying between 0 and 67%. The optical, electrical and morphological properties have been thoroughly studied. The film composition was analysed by X-ray Photoelectron Spectroscopy. The films with 17% zinc content ratio showed the lowest resistivity (6.6 × 10 - 4 Ω cm) and the highest transmittance (above 80% in the visible range). Though X-ray Diffraction studies showed amorphous nature for the films, using High Resolution Transmission Electron Microscopy we found that the microstructure of the films consisted of nanometric crystals embedded in a compact amorphous matrix. The effect of post deposition annealing on the films in both reducing and oxidizing atmospheres were studied. The changes were found to strongly depend on the zinc content ratio in the films.

Degradation of thin tungsten filaments at high temperature in HWCVD

The degradation of the filaments is usually studied by checking the silicidation or carbonization status of the refractory metal used as catalysts, and their effects on the structural stability of the filaments. In this paper, it will be shown that the catalytic stability of a filament heated at high temperature is much shorter than its structural lifetime. The electrical resistance of a thin tungsten filament and the deposition rate of the deposited thin film have been monitored during the filament aging. It has been found that the deposition rate drops drastically once the quantity of dissolved silicon in the tungsten reaches the solubility limit and the silicides start precipitating. This manuscript concludes that the catalytic stability is only guaranteed for a short time and that for sufficiently thick filaments it does not depend on the filament radius.