Rodrigo Martins

ZnO films with and without a self-buffer layer were grown on c-plane sapphire substrates by atmospheric metal organic chemical vapor deposition. The influence of the buffer layer thickness, annealing temperature and annealing time on ZnO films has been investigated. The full width at half maximum of the ω-rocking curve of the optimized self-buffer layer sample is only 395 arc sec. Its surface is composed of regular columnar hexagons. After the buffer layer was introduced, the A1 longitudinal mode peak at 576 cm- 1, related to the defects, disappears in Raman spectra. For the photoluminescence, besides the strong donor binding exciton peak at 3.3564 eV, an ionized donor binding exciton and a free exciton peak is respectively observed at 3.3673 and 3.3756 eV at the high-energy side in the spectrum of the sample with the buffer layer. © 2006 Elsevier B.V. All rights reserved.

N, (N+Ga) and (N+Al) doped ZnO films were deposited on c-plane sapphire substrates by RF magnetron sputtering at room temperature. The samples were characterized by their structural, surface morphological, compositional and optical properties. The x-ray diffraction studies confirmed the co-doping of (N+Ga) and (N+Al) besides showing improvement in the crystallinity when compared with the single Ndoping. The surface of the films becomes rougher after co-doping. The x-ray photoelectron spectroscopy and Rutherford back-scattering analysis indicate that the co-doping changes the chemical states and varies the amount of nitrogen (N) in ZnO. The amount of 'N' has been greatly increased for (N+Ga) co-doping, indicating that it is the best co-doping pair for p-type ZnO. Additionally, co-doping has increased the average visible transmittance (40-650nm) and the optical band gap is shifted towards shorter wavelength. In the case of (N+Al) co-doping, the band gap becomes wider than that of undoped ZnO. © IOP Publishing Ltd.

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.

In order to study the properties of P-doped ZnO films deposited at low temperature substrates, P-doped ZnO films were RF-sputtered on sapphire substrates in the range from RT to 350°C. XRD spectra indicated the growth of the crystallites along the strongest <001> orientation. Further ZnO (002) peak became the weakest when the film was sputtered at 250°C. AFM pictures showed that the surface morphology varied with the deposition temperature. The sample RMS increased with the increase of substrate temperature. XPS spectra showed a clear broad P 2p peak at about 134 eV. Further the film composition varied with the substrate temperature. The average visible transmittance calculated in the wavelength ranging 400-600 nm was more than 60%. The optical band gap calculated from the absorption coefficient was about 3.2 eV. The Hall measurements confirm the n-type conductivity of the films. The carrier concentration in the films decreases with the increase of substrate temperature. The study is helpful for understanding the properties of P-doped ZnO films sputtered at lower substrate temperature and achieving p type ZnO films at lower temperature.

Two self-buffer layers were grown on c-plane sapphire substrates by atmospheric MOCVD method using DEZn, tert-butanol as precursors and H 2 as carrier gas. Then, they were respectively annealed in growth process and oxygen environment. After that, ZnO films were respectively grown on them. XRD spectra show that all the films were grown in [002] orientation. Furthermore, the film with a buffer layer annealed in oxygen exhibits much higher crystal quality. Its FWHM of the rocking curve is only 567arcsec. Furthermore, its Raman scattering spectrum appears a much stronger E2 mode peak at 436cm-1 and its PL spectrum appears a shoulder at 3.367eV on the higher energy side. © 2006 WILEY-VCH Verlag GmbH & Co. KGaA,.

Nitrogen (N)-doped ZnO thin films were RF sputtered with different N2 volume (ranging from 10% to 100%) on sapphire (001) substrates. The influence of N2 vol.% on the properties of ZnO films was analyzed by various characterization techniques. The X-ray diffraction studies showed that the films grow along the preferential (002) crystallographic plane and the crystallinity varied with varying N2 vol.%. The films sputtered with 25 vol.% N2 showed better crystallinity. The transmittance was decreased with increasing N2 volume until 25% and was almost constant above 25%. A maximum optical band gap (2.08 eV) obtained for 10 vol.% N2 decreased with increasing N2 volume to reach a minimum of 1.53 eV at 100%. The compositional analysis confirmed the incorporation of N into ZnO films, and its concentration increased with increasing N2 volume to reach a maximum of ∼ 3.7 × 1021 atom/cm3 at 75% but then decreased slightly to 3.42 × 1021 atoms/cm3. The sign of Hall coefficient confirmed that the films sputtered with ≤ 25 vol.% N2 possess p-type conductivity which changes to n-type for > 25 vol.% N2. © 2007 Elsevier B.V. All rights reserved.

N-doped ZnO films were deposited by RF magnetron sputtering in N2/Ar gas mixture and were post-annealed at different temperatures (Ta) ranging from 400 to 800 °C in O2 gas at atmospheric pressure. The as-deposited and post-annealed films were characterized by their structural (XRD), compositional (SIMS, XPS), optical (UV-vis-NIR spectrometry), electrical (Hall measurements), and optoelectronic properties (PL spectra). The XRD results authenticate the improvement of crystallinity following post-annealing. The weak intensity of the (0 0 2) reflection obtained for the as-deposited N-doped ZnO films was increased with the increasing Ta to become the preferred orientation at higher Ta (800 °C). The amount of N-concentration and the chemical states of N element in ZnO films were changed with the Ta, especially above 400 °C. The average visible transmittance (400-800 nm) of the as-deposited films (26%) was increased with the increasing Ta to reach a maximum of 75% at 600 °C but then decreased. In the PL spectra, A0X emission at 3.321 eV was observed for Ta = 400 °C besides the main D0X emission. The intensity of the A0X emission was decreased with the increasing Ta whereas D0X emission became sharper and more optical emission centers were observed when Ta is increased above 400 °C. © 2008 Elsevier B.V. All rights reserved.

N-doped ZnO films were radio frequency (RF) sputtered on glass substrates and studied as a function of oxygen partial pressure (OPP) ranging from 3.0×10-4 to 9.5×10-3 Pa. X-ray diffraction patters confirmed the polycrystalline nature of the deposited films. The crystalline structure is influenced by the variation of OPP. Atomic force microscopy analysis confirmed the agglomeration of the neighboring spherical grains with a sharp increase of root mean square (RMS) roughness when the OPP is increased above 1.4×10-3 Pa. X-ray photoelectron spectroscopy analysis revealed that the incorporation of N content into the film is decreased with the increase of OPP, noticeably N 1s XPS peaks are hardly identified at 9.5×10-3 Pa. The average visible transmittance (380-700 nm) is increased with the increase of OPP (from ∼17 to 70), and the optical absorption edge shifts towards the shorter wavelength. The films deposited with low OPP (≤ 3.0×10-4 Pa) show n-type conductivity and those deposited with high OPP (≥ 9.0×10-4 Pa) are highly resistive (>105 ·cm) © 2010 The Nonferrous Metals Society of China.

Nitrogen and Phosphorus co-doped (N+P)- zinc oxide (ZnO) films were RF sputtered on corning glass substrates at 350 °C and comparatively studied with undoped, N-, and P- doped ZnO. X-ray diffraction spectra confirmed that the ZnO structure with a preferred orientation along <002> direction. Scanning electron microscope analysis showed different microstructure for the N+P co-doping, and thus probably confirming the co-existence of both the dopants. X-ray photoelectron spectroscopy spectra revealed that the chemical composition in N+P co-doped ZnO are different from that found in undoped, N-, and P- doped ZnO. The atomic ratio of N and P in N+P co-doped ZnO is higher than that in single N or P doped ZnO. One broad ZnO emission peak around 420 nm is observed in photoluminescence spectra. The relative intensity of the strongest peak obtained from co-doped ZnO films is about twice than the P- doped and thrice than the pure and N- doped films. © (2013) Trans Tech Publications, Switzerland.

Nitrogen-doped ZnO films were deposited by RF magnetron sputtering in 75% of N2 / (Ar + N2) gas atmosphere. The influence of substrate temperature ranging from room temperature (RT) to 300 °C was analyzed by X-ray diffractometry (XRD), spectrophotometry, X-ray photoelectron spectroscopy (XPS), secondary-ion mass spectrometry (SIMS) and Hall measurements setup. The XRD studies confirmed the hexagonal ZnO structure and showed that the crystallinity of these films increased with increasing substrate temperature (Ts). The optical studies indicate the average visible transmittance in the wavelength ranging 500-800 nm increases with increasing Ts. A minimum transmittance (9.84%) obtained for the films deposited at RT increased with increasing Ts to a maximum of 88.59% at 300 °C (500-800 nm). Furthermore, it was understood that the band gap widens with increasing Ts from 1.99 eV (RT) to 3.30 eV (250 °C). Compositional analyses (XPS and SIMS) confirmed the nitrogen (N) incorporation into the ZnO films and its decreasing concentration with increasing Ts. The negative sign of Hall coefficients confirmed the n-type conducting. © 2007 Elsevier B.V. All rights reserved.

ZnO films were grown on sapphire (001) substrate by atmospheric MOCVD using diethyl zinc and tertiary butanol precursors. The influence of different carrier gases (H2 and He) on the properties was analyzed by their structural (XRD), microstructural (SEM) and compositional (SIMS) characterization. The intensity of the strongest diffraction peak from ZnO (002) plane was increased by about 2 orders of magnitude when He is used as carrier gas, indicating the significant enhancement in crystallinity. The surface of the samples grown using H2 and He carrier gases was composed of leaf-like and spherical grains respectively. Hydrogen [H] content in the film grown using H2 is higher than that using He, indicating that the [H] was influenced by the H2 carrier gas. Ultraviolet emission dominates the low temperature PL spectra. The emission from ZnO films grown using He show higher optical quality and more emission centers.

N-doped ZnO films were deposited on glass substrates by RF magnetron sputtering with different deposition pressures. The samples were characterized by X-ray diffraction (XRD), atomic force morphology (AFM), X-ray photoelectron spectroscopy (XPS), Hall measurements and optical spectrophotometer. The XRD patterns confirmed that the films are polycrystalline and the influence of deposition pressure on the structural properties. AFM microstructures also authenticated the change in the size and shape of the grains as a function of deposition pressure; the root mean square (RMS) roughness has reached a maximum (10.65 nm) at 1.5 x 10 -2 mbar. XPS spectra revealed the change in the chemical composition. The amount of adsorbed oxygen and nitrogen at oxide sites has reached the maximum at 9.0 x 10 -3 mbar, where the film showed p-type conductivity. The optical transmittance spectra have indicated that the absorption edge is shifted towards the shorter wavelength at higher deposition pressure. Correspondingly, the optical band gap is increased from 2.17 to 2.80 eV. The average visible transmittance in the wavelength ranging 500-800 nm has been increased from 49% to 82%. Copyright © 2010 American Scientific Publishers All rights reserved.

P- and n-type weakly absorbing highly conductive (σ>0·1Ω-1 cm-1) SiC thin films with similar structural and optoelectronic properties have been prepared in a two-consecutive-decomposition-deposition-chamber reactor. These films are composed of Si microcrystals (δ = 50-100 Å) embedded in an amorphous Si:0:C:H matrix, with concentrations up to 25at.%O and 20at.%C. From diffraction studies there is no evidence for the presence of SiC crystallites. Electrical conduction appears to be in extended states via percolation channels through Si crystallites of sufficient volume fraction. © 1991 Taylor & Francis Ltd.

Diffraction and other structural measurements on n-type SiC thin films prepared in a TCDDC (two consecutive decomposition and deposition chamber) system indicate the presence of Si microcrystals (without evidence for SiC crystallites). Weakly absorbing, highly conductive layers (σ ≥ 10-1 (Ω-cm)-1) contain up to 20 at.% C and 25 at.% O. The optoelectronic properties of these films can be explained in terms of a sufficient volume fraction (above the percolation threshold) of Si microcrystals surrounded by an a-Si:C:O:H matrix.

This paper focuses on the engineering procedures governing the synthesis of tungsten oxide nanocrystals and the formulation of printable dispersions for electrochromic applications. By that means, we aim to stress the relevancy of a proper design strategy that results in improved physicochemical properties of nanoparticle loaded inks. In the present study inkjet printable nanostructured tungsten oxide particles were successfully synthesized via hydrothermal processes using pure or acidified aqueous sol-gel precursors. Based on the proposed scheme, the structure and morphology of the nanoparticles were tailored to ensure the desired printability and electrochromic performance. The developed nanomaterials with specified structures effectively improved the electrochemical response of printed films, resulting in 2.5 times higher optical modulation and 2 times faster coloration time when compared with pure amorphous films. © The Royal Society of Chemistry 2015.

The microstructural aspects related to crystalline or amorphous structure of as-deposited and annealed films of sol-gel-derived WO 3 are shown in the literature to be critical for electrochromic (EC) performance. In consideration of ion insertion materials, there is a need for developing light and at the same time nanocrystalline structures to improve both coloration efficiency and switching kinetics. By controlling microstructure and morphology, one could design a material with optimal EC performance. This report compares the microstructural and morphological characteristics of standard WO 3 wet deposition techniques versus inkjet printing technology (IPT), correlating these features with their optical and electrochemical performances, emphasizing the importance of the dual-phase a-WO 3/TiO 2/WO X film composition proposed in this work for high-performance EC applications. The effect of the type and content of metal oxide nanoparticles in the precursor sols formulated in various peroxopolytungstic acid (PTA) and oxalic acid (OAD) proportions on film properties is comprehensively studied using multi-factorial design of experiment (DOE). To the authors' knowledge, no other report on sol-gel deposition of inorganic EC materials via the inkjet printing technique exists, in which furthermore the film crystallinity can be controlled under low-temperature process conditions. The proposed method enables development of EC films which irrespective of their composition (a-WO 3, a-WO 3/TiO 2 or a-WO 3/TiO 2/WO X) outperform their amorphous or nanocrystalline analogues presented as the state-of-the-art due to their superior chemical and physical properties. © 2012 The Royal Society of Chemistry.

Engineering procedures governing the selection or development of printable nanostructured metal oxide nanoparticles for chromic, photovoltaic, photocatalytic, sensing, electrolyte-gated TFTs, and power storage applications are established in this chapter. The main focus is given on how to perform the material selection and formulation of printable dispersion in order to develop functional films for electrochemical applications. This chapter is divided into four main parts. Firstly, a brief introduction on electrochemically active nanocrystalline metal oxide films developed via printing techniques is given. This is followed by the description of the film morphology, structure, and required functionality. A theoretical approach to understand the impact of size and shape of nanoparticles on an ink formulation and electrochemical performance being the subject of the third section provides a greater control over the material selection. We attempt to describe these properties and show that for a given material, geometry and size of the nanoparticles have a major influence on the electrochemical reactivity and response time. This gives the ability to tune the performance of the film simply by varying the morphology of incorporated nanostructures. This section is completed by the recommendations on each major step of an ink formulation, together with imposed critical constraints concerning the fluid control. Finally, the performance of the ink-jetprinted dual-phase electrochromic films is discussed as a case study. By providing such a rather systematic survey, we aim to stress the importance of proper design strategy that would result in both improved physicochemical properties of nanoparticle-loaded inks and enhanced electrochemical performance of printed functional films. © Springer International Publishing Switzerland 2016.