Rodrigo Martins

Zinc oxide (ZnO) has attracted recent interest for a range of applications, including use as a transparent conductive oxide (TCO) and in gas sensor devices. This paper compares ZnO films grown using two methods designed for the production of thin films, namely sol-gel and aerosol assisted chemical vapour deposition (AACVD) for potential use in sensor and TCO applications. Materials produced by the sol-gel route were observed to be amorphous when annealed at 350 °C, but were crystalline when annealed at higher temperatures and had a relatively open grain structure when compared to the AACVD films. Electrical characterization showed that materials were highly resistive, but that their properties varied considerably when the measurements were performed in vacuum or in air. This behaviour was rapidly reversible and reproducible for room temperature measurement. In contrast materials grown by aerosol-assisted CVD were non-porous, polycrystalline and conductive. Measured electrical properties did not vary with changing measurement atmosphere. These differences are discussed in terms of the structural characterisation of the films and some comments are made regarding the suitability of both approaches for the growth of ZnO thin film sensor materials. © 2009 Elsevier B.V. All rights reserved.

Copper oxide thin films were obtained by annealing (temperature ranging between 100 and 450 °C) the metallic Cu films deposited on glass substrates by e-beam evaporation. XRD studies confirmed that the cubic Cu phase of the asdeposited films changes into single cubic Cu 2Ophase and single monoclinic CuO phase, depending on the annealing conditions. The crystallite size is varied betweeñ12 and 31 nm. The lattice parameters of cubic Cu and Cu 2Ophases are estimated tõ3.60 and ̃4.26 Å , respectively. The films with Cu 2O phase showed p-type characteristics. The conductivity is decreased linearly with the decreasing temperature (1/T), which has confirmed the semiconductor nature of the deposited films. The calculated activation energy is varied between 0.10 and 0.16 eV. The surface microstructure is changed depending on the variation in the annealing temperature. The poor transmittance of the asdeposited films (<1%) is increased to a maximum of ̃80% (800 nm) on annealing at 200 °C. The estimated direct allowed band gap is varied between 1.73 and 2.89 eV. © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In this paper ageing effects of the solution used to prepare fluorine-doped ZnO films by the spray pyrolysis technique were investigated, concerning its role on the structure, the electrical and optical properties of films produced. The data reveal that the sheet resistance of the ZnO:F thin film decreases with the age of the solution used, reaching a minimum of 24 Ω/□, after 15 days. On the other hand the optical transmittance increases for films deposited using 6 days aging solution, decreasing afterwards as the aging time increases, being the optical transmittance in the visible range below 55%, for films deposited from solutions 36 days in age. The X-ray diffraction spectra show that the aged films are polycrystalline in nature with a [100] predominant orientation. The data also show that the intensity of (100) peak increases as the time of solution age increases, which is related to an improvement of the film crystallinity. © 2009 Elsevier B.V. All rights reserved.

The special Professor Walter E. Spear commemoration issue of the Philosophical Magazine, published in October 2009, contains papers which cover the numerous relevant issues, driven by commercial applications, primarily solar energy and displays. Kocka reviews the complex microstructure of crystallites embedded in the amorphous silicon tissue, the transport mechanism is determined by the conductive grains and influenced by the passivation through H at the grain boundaries. Hugger and co-researchers report on transient photocapacitance spectroscopy and drive-level capacitance profiling as a way of elucidating the fundamental electronic properties of hydrogenated ncSi. Tawada recounts the history of a-Si:H pin heterojunction solar cells, emphasizing the role of the p-type silicon carbide layer in the improvement of the device. Schubert and colleagues focus their work on the production of flexible PV modules with many applications in the architectural arena or integrated into clothing.

A quantitative study of the dynamics of threshold-voltage shifts with time in gallium-indium zinc oxide amorphous thin-film transistors is presented using standard analysis based on the stretched exponential relaxation. For devices using thermal silicon oxide as gate dielectric, the relaxation time is 3× 105 s at room temperature with activation energy of 0.68 eV. These transistors approach the stability of the amorphous silicon transistors. The threshold voltage shift is faster after water vapor exposure suggesting that the origin of this instability is charge trapping at residual-water-related trap sites. © 2009 American Institute of Physics.

The effect of oxygen partial pressure on the properties of In2 O3 - Ga2 O3 thin films produced by sputtering at room temperature aimed at thin film transistor (TFT) application is reported in this work. When produced in the absence of oxygen, the films are polycrystalline, while in the presence of oxygen, the films are amorphous. The films' resistivity is tuned between 10-3 and 104 γ cm. Moreover, the films present a high transmittance (> 80%) and a smooth surface (rrms =1.2 nm). The high performance as-produced transistors present high saturation mobility (μsat ≈43 cm2 /V s) and a subthreshold gate-voltage swing of 0.51 V/dec, which is reduced to 0.27 V/dec after 150°C annealing. © 2009 The Electrochemical Society.

Molybdenum (0-1 at. %) doped indium oxide thin films with high near-infrared (NIR) transparency and high carrier mobility were deposited on Corning-1737 glass substrates at 400 °C by a spray pyrolysis experimental technique. X-ray diffraction (XRD) analysis confirmed the cubic bixbyite structure of indium oxide. The preferred growth orientation along the (222) plane for the low Mo doping level (0.5 at. %) shifts to (400) for higher Mo doping levels (<0.6 at. %). The crystallite size extracted from the XRD data corroborates the changes in full width at half maximum due to the variation in Mo doping. A scanning electron microscopy study illustrated the evolution in the surface microstructure as a function of Mo doping. The negative sign of the Hall coefficient confirmed the n -type conductivity. A high carrier mobility of ∼122.4 cm2 /V s, a carrier concentration of ∼9.5× 1019 cm-3, a resistivity of ∼5.3× 10-4cm, and a high figure of merit of ∼4.2× 10-2 -1 are observed for the films deposited with 0.5 at. % Mo. The obtained high average transparency of ∼83% in the wavelengths ranging from 400 to 2500 nm confirmed the extension of transmittance well into the NIR region. © 2009 American Institute of Physics.

Molybdenum-doped indium oxide (IMO) thin films were deposited at 450 °C for varying molybdenum concentrations in the range of 0.5-2 at% by the spray pyrolysis technique. These films confirmed the cubic bixbyite structure of polycrystalline In2O3. The preferred growth orientation along the (2 2 2) plane shifts to (4 0 0) on higher Mo doping levels. The films doped with 0.5 at% Mo showed high mobility of 76.9 cm2/(V s). The high visible transmittance extends well into the near-infrared region. A possibility of using the produced IMO films in nanocrystalline (nc) silicon solar cell applications is discussed in this article. The morphological studies showed a change in the microstructure, which is consistent with the change in crystallographic orientation. © 2008 Elsevier B.V. All rights reserved.

In this paper we present a study of boron-doped nc-Si:H films prepared by PECVD at high deposition pressure (≥4 mbar), high plasma power and low substrate temperature (≤200 °C) using trimethylboron (TMB) as a dopant gas. The influence of deposition parameters on electrical, structural and optical properties is investigated. We determine the deposition conditions that lead to the formation of p-type nanocrystalline silicon thin films with very high crystallinity, high value of dark conductivity (>7 (Ω cm)-1) and high optical band gap (≥1.7 eV). Modeling of ellipsometry spectra reveals that the film growth mechanism should proceed through a sub-surface layer mechanism that leads to silicon crystallization. The obtained films are very good candidates for application in amorphous and nanocrystalline silicon solar cells as a p-type window layer. © 2009 Elsevier Ltd. All rights reserved.

Indium molybdenum oxide thin films were deposited using different radio-frequency sputtering units on glass substrates at room temperature from an In 2O 3 (95 wt.%): Mo (5 wt.%) target. The film thickness ranges between 160 and 275 nm. The chamber volume of Unit-1 was ̃2.4 times larger than that of Unit-2. Apart from the chamber volume, a significant difference between the two units was the sputtering pressure. The films were characterized by their structural, morphological, optical, and electrical properties. A strong reflection from (222) plane was obtained for the ̃275 nm thick films deposited in Unit-1. The films deposited with <275 nm thickness and those deposited in Unit-2 are close to amorphous with a small crystalline fraction. The surface of the films deposited in Unit-1 is comprised of randomly arranged crystallites, which is restructured with the increasing film thickness to become a well defined "rice field" like structure (275 nm thick). The films deposited in Unit-2 are comprised of many holes on the surface that is presumably due to back sputtering. The average visible transmittance calculated in the wavelength between 400 and 800 nm ranges from 70 to 82%. The optical band gap is found to vary between 3.80 and 3.86 eV. The lowest bulk resistivity of the films deposited in Unit-1 was increased from ̃4.06×10 -3 to 4.07×10 -1ωcm when deposited in Unit-2. The carrier concentration was decreased from 1.31×10 20 to 1.03×10 18 cm -3 but the Hall mobility increased from 11.7 to 15.0 cm2 V -1 s -1. © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

ZnO films were deposited on c-plane sapphire substrates in Ar atmosphere by ii magnetron sputtering and were post-annealed at 400°C in green gas (95% N2 + 5% H2). The properties of the as-grown and annealed films have been characterized by X-ray diffraction (XRD), Rutherford backscattering (RBS), elastic recoil detection analysis (ERDA), Hall measurement and photoluminescence spectra. XRD studies confirmed the variation in strain and an improvement in crystallinity. From RBS and ERDA analysis, the presence of H atoms on the surface of the as-grown ZnO films was evidenced. Annealing in green gas increased the amount of H in the film. Compared with the as-grown films, the ultra exciting intensity obviously decreases in the annealed films and new optical active centres in the blue/violet ( 3.0 eV) and red ( 1.9) regions are emerged in the PL spectrum. The positive sign of Hall coefficient confirmed the low (-type conductivity in the as grown films, which was improved after annealing. However, the (-type conductivity was not stable, especially for the annealed sample it changes from ( type to n type after 9 days. Copyright © 2009 American Scientific Publishers All rights reserved.

This paper reports the performance of small area solar cells, 128 linear integrated position sensitive detector arrays and thin film transistors based on nanostructured silicon thin films produced by plasma-enhanced chemical vapour deposition technique, close to the onset of dusty plasma conditions, within the transition region from amorphous to microcrystalline. The small area solar cells, produced in a modified single chamber reactor, exhibited very good electrical characteristics with a conversion efficiency exceeding 9%. The 128 integrated position sensitive detector arrays, based on a similar pin structure, allow real-time 3D object imaging with a resolution higher than 90 l p/mm. The thin film transistors produced exhibited field effect mobility of 2.47 cm 2/V/s, threshold voltage of 2 V, on/off ratio larger than 10 7 and sub-threshold slopes of 0.32 V/decade, which are amongst the best results reported for this type of device. © 2009 Taylor & Francis.

The effect is considered of order and disorder on the electrical and optical performance of ionic oxide semiconductors used to produce optoelectronic devices such as p-n heterojunction solar cells and thin-film transistors (TFTs). The results obtained show that p-type c-Si/a-IZO/poly-ZGO solar cells exhibit efficiencies above 14% in device areas of about 2.34 cm2, whereas amorphous oxide TFTs based on the Ga-Zn-Sn-O system demonstrate superior performance to the polycrystalline ZnO TFTs, with ION/I OFF ratio exceeding 107, turn-on voltage below 1-2 V and saturation mobility above 25 cm2 V-1 s-1. In addition, preliminary data on a p-type oxide TFT based on the Zn-Cu-O system are presented. © 2009 Taylor & Francis.

The aim of this research is to study the role of concentration variations on precursor solution of nitrogen doped ZnO (ZnO:N) thin films which has been prepared by spray pyrolysis technique. SEM micrographs show that ZnO:N films in 0.1 ML concentration have a mono-disperse surface with nano-spheres of 50 nm in diameter. In higher molarities the nano-spheres agglomerate leading to particle formation. For 0.4 ML concentrations this change is observed, where plume like particles are seen over the surface of ZnO:N thin film. This change corresponds also to changes observed in the XRD spectra, where crystal orientation of ZnO:N thin films changes from (002) to (100). All of the ZnO:N thin films have kept their sharp ultra violet absorption edge, but the transparency in visible spectra region decreases as the molarities in precursor solution increase. Photoluminescence spectra at room temperature revealed emissions at 2.33 eV, 2.54 eV and 3.16 eV that can be attributed to the presence of nitrogen in ZnO structure. We also observe that all samples analyzed show a p-type Hall effect behavior, and that as the molarities in the precursor solution increase, the electrical resistivity of the films decreases, due to an enhancement of free carriers, while the mobility decreases. These data prove the capability of spray pyrolysis as a viable technique in preparing p-type TCO materials and so, fully transparent CMOS-like devices. © 2009 Elsevier B.V. All rights reserved.

In this paper we report the use of a sheet of cellulose fiber-based paper as the dielectric layer used in oxide based semiconductor thin film field-effect transistors (FETs). In this new approach we are using the cellulose fiber-based paper in an "interstate" structure since the device is build on both sides of the cellulose sheet. Such hybrid FETs present excellent operating characteristics such as high channel saturation mobility (>30 cm 2/Vs), drain-source current on/off modulation ratio of approximately 104, near-zero threshold voltage, enhancement n-type operation and sub-threshold gate voltage swing of 0.8 V/decade. The cellulose fiber-based paper FETs characteristics have been measured in air ambient conditions and present good stability. The obtained results outpace those of amorphous Si TFTs and rival with the same oxide based TFTs produced on either glass or crystalline silicon substrates. The compatibility of these devices with large-scale/large-area deposition techniques and low cost substrates as well as their very low operating bias delineates this as a promising approach to attain high-performance disposable electronics like paper displays, smart labels, smart packaging, RFID and point-of-care systems for self analysis in bio-applications, among others. © 2009 SPIE.

High performance transparent thin-film transistors deposited on glass substrates and entirely processed at a low temperature not exceeding 150°C are presented and analyzed in this paper. Besides being based on an amorphous oxide semiconductor, the main innovation of this work relies on the use of sputtered multicomponent oxides as dielectric materials based on mixtures of Ta2O5 with SiO2 or Al2O3. These multicomponent dielectrics allow to obtain amorphous structures and low leakage currents while preserving a high dielectric constant. This results in transistors with remarkable electrical properties, such as field-effect mobility exceeding 35 cm2 V-1 s-1, close to 0 V turn-on voltage, on/off ratio higher than 106, and a subthreshold slope of 0.24 V decade-1, obtained with a Ta2O5: SiO2 dielectric. When subjected to severe current stress tests, optimized devices show little and reversible variation in their electrical characteristics. The devices presented here have properties comparable to the ones using plasma-enhanced chemical vapor deposited SiO2 at 400°C, reinforcing the success of this amorphous multicomponent dielectric approach for low temperature, high performance, and transparent electronic circuits. © 2009 The Electrochemical Society.

The authors report on the performance of polymer-based light-emitting diodes, LEDs, using amorphous zinc oxide-doped indium oxide, IZO, as anode. In particular, LEDs with poly[(2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene] as electroluminescent layer and aluminium cathodes, show higher efficiency with this IZO anode (0.015 cd/A) than with indium-tin oxide (ITO) (0.010 cd/A). Inspite of the higher resistance of this IZO electrode, compared with ITO, the fact that it can be processed at lower temperatures and allows similar or even higher efficiency values for polymer LEDs make this material a good candidate for display and other optoelectronic applications. © 2009 Elsevier B.V. All rights reserved.

Indium molybdenum oxide (IMO) thin films were deposited by RF magnetron sputtering on glass substrates at room temperature. The deposition and argon partial pressures were maintained at 6.0 × 10-1 Pa and 3.0 × 10-1 Pa, respectively. The oxygen partial pressure (OPP) was varied in the range 1.0-6.0 × 10-3 Pa. The films were sputtered at 40 W for 30 min using the target consisted In2O3 (98 wt%): Mo (2 wt%). The films are polycrystalline with a slight preferential orientation along (2 2 2) plane. The crystallinity is increased with the increasing OPP. The negative sign of Hall coefficient confirmed the n-type conductivity. A maximum mobility ∼19 cm2 V-1 s-1 is obtained for the films deposited with OPP of 3.6 × 10-3 Pa. The average visible transmittance calculated in the wavelength ranging 500-800 nm is ranging between 2% and 77%. The optical band gap calculated from the absorption data is varied between 3.69 and 3.91 eV. A striking feature is that the work function of the films is wide ranging 4.61-4.93 eV. A possibility of using the produced IMO films as transparent conducting oxide in photovoltaic applications such as organic solar cells is discussed in this article. © 2008 Elsevier Ltd. All rights reserved.

Hafnium oxide-aluminum oxide (HfAlO) dielectric films were cosputtered using HfO2 and Al2 O3 targets, and their properties are studied in comparison with pure HfO2 films. The X-ray diffraction studies confirmed that the HfO2 films are nanocrystalline with a monoclinic phase. The as-deposited HfAlO films with a chemical composition of (HfO2) 0.86 (Al2 O3) 0.14 are amorphous even after annealing at 500°C. Further, the cosputtered films show a slight reduction in leakage current. The leakage current density may be significantly reduced below 3× 10-10 A cm-2 at an electric field of 0.25 MV/cm when applying the proper radio-frequency bias to the substrate. © 2009 The Electrochemical Society.

Here we report the performance of a selective floating gate (V GS) n-type non-volatile memory paper field-effect transistor. The paper dielectric exhibits a spontaneous polarization of about 1 mCm-2 and GIZO and IZO amorphous oxides are used respectively as the channel and the gate layers. The drain and source regions are based in continuous conductive thin films that promote the integration of fibres coated with the active semiconductor. The floating memory transistor writes, reads and erases the stored information with retention times above 14500 h, and is selective (for VGS > 5 ± 0.1 V). That is, to erase stored information a symmetric pulse to the one used to write must be utilized, allowing to store in the same space different information. © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molybdenum doped (0-1 at. %) indium oxide thin films with high near infrared (NIR) transparency and carrier mobility were deposited on Corning-1737 glass substrates at 400 °C by spray pyrolysis experimental technique. Films with mobility as high as ∼149 cm2 /V s were obtained when annealed in vacuum at 550 °C, which also possess carrier concentration of ∼1× 1020 cm-3 and resistivity as low as ∼4.0× 10-4 cm. Further, both the average visible transmittance (500-800 nm) and the average NIR transmittance are >83%. This clearly shows that the transmittance is extended well into the NIR region. © 2009 American Institute of Physics.

In this work, we present the structural and electrical properties of HfO 2, HfO 2 +SiO 2, and HfO 2 +Al 2O 3 dielectric composite layers deposited by sputtering without any intentional substrate heating. The films were deposited on glass and 〈100〉 crystalline silicon (c-Si) substrates from ceramic targets by using argon (Ar) and oxygen (O 2) as sputtering and reactive gases, respectively. The incorporation of SiO 2 and Al 2O 3 into hafnia was obtained by co-sputtering and itwas controlled by adjusting the ratio of r.f. power applied between the targets. The HfO 2 films present a microcrystalline structure, when deposited at room temperature (RT). The lowest leakage current in c-Si MIS (Metal-Insulator- Semiconductor) structures (below 10 9A/cm 2 at 10V on films with a thickness around 180 nm) was obtained for an Ar/O 2 ratio of 14:1 sccm, and further increase in O 2 flow does not enhance the electrical characteristics. The codeposition of SiO 2 or Al 2O 3 with hafnia has a strong influence on the structure of the resulting films since they become amorphous. The leakage current in MISstructures incorporating these multi-component dielectrics is reduced at least by a factor of 2, which is accompanied by an increase on the band gap. The dielectric constant is decreased due to the lower values for SiO 2 and Al 2O 3. © 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Zinc oxide is getting an enormous attention due to its potential applications in a variety of fields such as optoelectronics, spintronics and sensors. The renewed interest in this wide band gap oxide semiconductor relies on its direct high energy gap (Eg ∼ 3.437 eV at low temperatures) and large exciton binding energy. However to reach the stage of device production the difficulty to produce in a reproducible way p-type doping must be overcome. In this study we discuss the structural and optical properties of ZnO films doped with nitrogen, a potential p-type dopant. The films were deposited by magnetron sputtering using different conditions and substrates. The composition and structural properties of the films were studied combining X-ray diffraction (XRD), Rutherford backscattering (RBS), and heavy ion elastic recoil detection analysis (HI-ERDA). The results show an improvement of the quality of the films deposited on sapphire with increasing radio-frequency (RF) power with a preferentially growth along the c-axis. The ERDA analysis reveals the presence of H in the films and a homogeneous composition over the entire thickness. The photoluminescence of annealed samples evidences an improvement on the optical quality as identified by the well structured near band edge recombination. © 2009 Elsevier Ltd. All rights reserved.

This work analyzes the role of processing parameters on the electrical performance of GIZO (Ga2 O3: In2 O3:ZnO) films and thin-film transistors (TFTs). Parameters such as oxygen partial pressure, deposition pressure, target composition, thickness, and annealing temperature are studied. Generally, better devices are obtained when low oxygen partial pressure is used. This is related to the damage induced by oxygen ion bombardment and very high film's resistivity when higher oxygen partial pressures are used. Low deposition pressures and targets with richer indium compositions led to films with high carrier concentration, resulting in transistors with field-effect mobility as high as ∼80 cm2 Vs but poor channel conductivity modulation, becoming ineffective as switching devices. Nevertheless, it is demonstrated that reducing the GIZO thickness from 40 to 10 nm greatly enhances the switching behavior of those devices, due to the lower absolute number of free carriers and hence to their easier depletion. Annealing also proves to be crucial to control device performance, significantly modifying GIZO electrical resistivity and promoting local atomic rearrangement, being the optimal temperature determined by the as-produced films' properties. For the best-performing transistors, even with a low annealing temperature (150°C), remarkable properties such as μFE =73.9 cm2 Vs, onoff ratio≈7× 107, VT ≈0.2 V, and S=0.29 Vdec are achieved. © 2008 The Electrochemical Society.