The effects of carrier gas and substrate temperature on ZnO films prepared by ultrasonic spray pyrolysis

ZnO films were deposited on glass substrates in the temperature range of 350–470 °C under an atmosphere of compressed air or nitrogen (N₂) by using ultrasonic spray pyrolysis technique. Structural, electrical and optical properties of the ZnO films were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), electrical two-probe and optical transmittance measurements. The ZnO films deposited in the range of 350–430 °C were polycrystalline with the wurtzite hexagonal structure having preferred orientation depending on the substrate temperature. The ZnO films deposited below 400 °C had a preferred (100) orientation while those deposited above 400 °C mostly had a preferred (002) orientation. The resistivity values of ZnO films depended on the types of carrier gas. The ZnO thin films deposited under N₂ atmosphere in the range of 370–410 °C showed dense surface morphologies and resistivity values of 0.6–1.1 Ω-cm, a few orders of magnitude lower than those deposited under compressed air. Hydrogen substition in ZnO possibly contributed to decreasing resistivity in ZnO thin films deposited under N₂ gas. The Hall measurements showed that the behavior of ZnO films deposited at 410 °C under the N₂ atmosphere was n-type with a carrier density of 8.9–9.2×10¹⁶ cm^-3 and mobility of ～70 cm²/Vs. ZnO thin films showed transmission values at 550 nm wavelength in a range of 70–80%. The values of band gaps extrapolated from the transmission results showed bandgap shrinkage in an order of milli electron volts in ZnO films deposited under N₂ compared to those deposited under compressed air. The calculation showed that the bandgap reduction was possibly a result of carrier–carrier interactions.     

Si-implantation activation annealing of GaN up to 1400°C

Implant activation annealing of Si-implanted GaN is reported for temperatures from 1100 to 1400°C. Free electron concentrations up to 3.5×10²⁰ cm⁻³ are estimated at the peak of the implanted profile with Hall mobilities of ∼60 cm²/Vs for annealing at 1300°C for 30 s with an AIN encapsulant layer. This mobility is comparable to epitaxial GaN doped at a similarly high level. For annealing at ≥1300°C, the sample must be encapsulated with AIN to prevent decomposition of the GaN layer. Channeling Rutherford backscattering demonstrates the partial removal of the implant damage after a 1400°C anneal with a minimum channeling yield of 12.6% compared to 38.6% for the as-implanted spectrum. Scanning electron microscope images show evidence of decomposition of unencapsulated GaN after a 1300°C anneal and complete sublimation after 1400°C. The use of AIN encapsulation and annealing at temperatures of ∼1300°C will allow the formation of selective areas of highly doped GaN to reduce the contact and access resistance in GaN-based transistors and thyristors.     

Pulsed laser deposition and processing of wide band gap semiconductors and related materials

The present work describes the novel, relatively simple, and efficient technique of pulsed laser deposition for rapid prototyping of thin films and multi-layer heterostructures of wide band gap semiconductors and related materials. In this method, a KrF pulsed excimer laser is used for ablation of polycrystalline, stoichiometric targets of wide band gap materials. Upon laser absorption by the target surface, a strong plasm a plume is produced which then condenses onto the substrate, kept at a suitable distance from the target surface. We have optimized the processing parameters such as laser fluence, substrate temperature, background gas pressure, target to substrate distance, and pulse repetition rate for the growth of high quality crstalline thin films and heterostructures. The films have been characterized by x-ray diffraction, Rutherford backscattering and ion channeling spectrometry, high resolution transmission electron microscopy, atomic force microscopy, ultraviolet (UV)-visible spectroscopy, cathodoluminescence, and electrical transport measurements. We show that high quality AlN and GaN thin films can be grown by pulsed laser deposition at relatively lower substrate temperatures (750–800°C) than those employed in metal organic chemical vapor deposition (MOCVD), (1000–1100°C), an alternative growth method. The pulsed laser deposited GaN films (∼0.5 μm thick), grown on AlN buffered sapphire (0001), shows an x-ray diffraction rocking curve full width at half maximum (FWHM) of 5–7 arc-min. The ion channeling minimum yield in the surface region for AlN and GaN is ∼3%, indicating a high degree of crystallinity. The optical band gap for AlN and GaN is found to be 6.2 and 3.4 eV, respectively. These epitaxial films are shiny, and the surface root mean square roughness is ∼5–15 nm. The electrical resistivity of the GaN films is in the range of 10⁻²–10² Θ-cm with a mobility in excess of 80 cm²V⁻¹s⁻¹ and a carrier concentration of 10¹⁷–10¹⁹ cm⁻³, depending upon the buffer layers and growth conditions. We have also demonstrated the application of the pulsed laser deposition technique for integration of technologically important materials with the III–V nitrides. The examples include pulsed laser deposition of ZnO/GaN heterostructures for UV-blue lasers and epitaxial growth of TiN on GaN and SiC for low resistance ohmic contact metallization. Employing the pulsed laser, we also demonstrate a dry etching process for GaN and AlN films.     

ZnO spintronics and nanowire devices

ZnO is a very promising material for spintronics applications, with many groups reporting room-temperature ferromagnetism in films doped with transition metals during growth or by ion implantation. In films doped with Mn during pulsed laser deposition (PLD), we find an inverse correlation between magnetization and electron density as controlled by Sn-doping. The saturation magnetization and coercivity of the implanted single-phase films were both strong functions of the initial anneal temperature, suggesting that carrier concentration alone cannot account for the magnetic properties of ZnO:Mn and factors such as crystalline quality and residual defects play a role. Plausible mechanisms for ferromagnetism include the bound magnetic polaron model or exchange that is mediated by carriers in a spin-split impurity band derived from extended donor orbitals. The progress in ZnO nanowires is also reviewed. The large surface area of nanorods makes them attractive for gas and chemical sensing, and the ability to control their nucleation sites makes them candidates for microlasers or memory arrays. Single ZnO nanowire depletion-mode metal-oxide semiconductor field effect transistors exhibit good saturation behavior, threshold voltage of ∼−3 V, and a maximum transconductance of 0.3 mS/mm. Under ultraviolet (UV) illumination, the drain-source current increased by approximately a factor of 5 and the maximum transconductance was ∼5 mS/mm. The channel mobility is estimated to be ∼3 cm²/Vss, comparable to that for thin film ZnO enhancement mode metal-oxide semiconductor field effect transistors (MOSFETs), and the on/off ratio was ∼25 in the dark and ∼125 under UV illumination. The Pt Schottky diodes exhibit excellent ideality factors of 1.1 at 25°C, very low reverse currents, and a strong photoresponse, with only a minor component with long decay times thought to originate from surface states. In the temperature range from 25°C to 150°C, the resistivity of nanorods treated in H₂ at 400°C prior to measurement showed an activation energy of 0.089 eV and was insensitive to ambient used. By contrast, the conductivity of nanorods not treated in H₂ was sensitive to trace concentrations of gases in the measurement ambient even at room temperature, demonstrating their potential as gas sensors. Sensitive pH sensors using single ZnO nanowires have also been fabricated.     

Tailoring the Structural and Optoelectronic Properties of Al-Doped Nanocrystalline ZnO Thin Films

This paper describes the effect of Al doping (0 at.% to 6 at.%) on the structural and optoelectronic properties of nanocrystalline ZnO thin films deposited by thermal evaporation. X-ray diffraction patterns confirm that an increase in Al concentration (from 0% to 6%) in ZnO lowers the crystallinity of the films and reduces grain size. Al doping is also found to influence the optical properties of the ZnO thin films. Visible transmittance above 85% was obtained by increasing the Al doping to 6%. The optical bandgap was found to vary from 3.20 eV to 3.97 eV with changing Al content from 0% to 6%, which is in accordance with the Burstein–Moss shift. The mobility of ZnO thin films can be varied from 5.60 cm²/Vs to 24.25 cm²/Vs, the carrier concentration from 5.93 × 10¹⁸/cm³ to 9.11 × 10²⁰/cm³, and the resistivity from 4.62 × 10⁻⁴ Ω cm to 4.34 × 10⁻² Ω cm, depending on the Al doping concentration (0% to 6%). This study suggests that ZnO:Al films can be tailor-made to meet the requirements for various optoelectronic applications such as flexible photocells or ultraviolet (UV) photodetectors covering a wide range of short wavelengths.     

P-type doping of GaAs by carbon implantation

The electrical properties of C-implanted <100> GaAs have been studied following rapid thermal annealing at temperatures in the range from 750 to 950°C. This includes dopant profiling using differential Hall measurements. The maximum p-type activation efficiency was found to be a function of C-dose and annealing temperature, with the optimum annealing temperature varying from 900°C for C doses of 5 × 10¹³ cm⁻² to 800°C for doses ≥5 × 10¹⁴cm⁻². For low dose implants, the net p-type activation efficiency was as high as 75%; while for the highest dose implants, it dropped to as low as 0.5%. Moreover, for these high-dose samples, 5 × 10¹⁵ cm⁻², the activation efficiency was found to decrease with increasing annealing temperature, for temperatures above ∼800°C, and the net hole concentration fell below that of samples implanted to lower doses. This issue is discussed in terms of the amphoteric doping behavior of C in GaAs. Hole mobilities showed little dependence on annealing temperature but decreased with increasing implant dose, ranging from ∼100 cm²/V·s for low dose implants, to ∼65 cm²/V·s for high dose samples. These mobility values are the same or higher than those for Be-, Zn-, or Cd-implanted GaAs.     

Fabrication of p-Type ZnO Thin Films via DC Reactive Magnetron Sputtering by Using Na as the Dopant Source

The Na-doped p-type ZnO thin films were prepared by DC reactive magnetron sputtering. Two types of substrates were used for separate testing purposes: silicon wafers for crystallinity measurements and glass slides for electrical and optical transmittance measurements. The lowest room-temperature resistivity under the optimal condition was 59.9 Ω cm, with a Hall mobility of 0.406 cm² V⁻¹s⁻¹ and a carrier concentration of 2.57 × 10¹⁷ cm⁻³. The Na-doped ZnO thin films possessed a good crystallinity with c-axis orientation and a high transmittance (∼85%) in the visible region. The effects of the substrate temperature on the crystallinity and the electrical properties were discussed.     

Zinc Oxide Thin-Film Transistors Fabricated at Low Temperature by Chemical Spray Pyrolysis

We report the electrical behavior of undoped zinc oxide thin-film transistors (TFTs) fabricated by low-temperature chemical spray pyrolysis. An aerosol system utilizing aerodynamic focusing was used to deposit the ZnO. Polycrystalline films were subsequently formed by annealing at the relatively low temperature of 140°C. The saturation mobility of the TFTs was 2 cm²/Vs, which is the highest reported for undoped ZnO TFTs manufactured below 150°C. The devices also had an on/off ratio of 10⁴ and a threshold voltage of ?3.5 V. These values were found to depend reversibly on measurement conditions.     

Low-Temperature Preparation of Undoped ZnO Films with High Transparency and Conductivity by Ion Beam Deposition

Low-temperature growth of undoped ZnO films with high transparency and low electrical resistance was performed by ion beam sputtering. After systematic testing, resistivity as low as 2.95 × 10⁻³ Ω cm was obtained at a substrate temperature of 150°C, ion source voltage of 850 V, and ion beam current of 30 mA. The transmittance of the ZnO films was in the range of 85% to 90%. Hall measurements showed that a high mobility of 21.41 cm²/Vs was obtained for films less than 200 nm thick. The related microstructures and physical properties were measured and are discussed.     

Enhanced infrared transmission of GZO film by rapid thermal annealing for Si thin film solar cells

Ga doped ZnO (GZO) films prepared by sputtering at room temperature were rapid thermal annealed (RTA) at elevated temperatures. With increasing annealing temperature up to 570°C, film transmission enhanced significantly over wide spectral range especially in infrared region. Hall effect measurements revealed that carrier density decreased from ∼8 × 10²⁰ to ∼ 3 × 10²⁰ cm⁻³ while carrier mobility increased from ∼15 to ∼28 cm²/Vs after the annealing, and consequently low film resistivity was preserved. Hydrogenated microcrystalline Si (µc‐Si:H) and microcrystalline Si_1‐xGe_x (µc‐Si_1‐xGe_x:H, x = 0.1) thin film solar cells fabricated on textured RTA‐treated GZO substrates demonstrated strong enhancement in short‐circuit current density due to improved spectral response, exhibiting quite high conversion efficiencies of 9.5% and 8.2% for µc‐Si:H and µc‐Si_0.9Ge_0.1:H solar cells, respectively. Copyright © 2011 John Wiley & Sons, Ltd.     

Selenium implantation in GaAs

The dependence of carrier concentration and mobility profiles on the dose of 400 keV Se ions implanted into Cr-doped semi-insulating GaAs, and on the annealing temperature has been studied for doses ranging from 3 × 10¹²/cm² to 2 × 10¹⁵/cm² and for annealing temperatures between 800 and 1000°C. Sputtered aluminum oxy-nitride and silicon nitride films were used as encapsulants for protection of the implanted surface during annealing treatments. The carrier profiles exhibited deep tails for implantations along both random and {110} planar directions. It was found that annealing temperatures of 900°C or above were necessary to obtain high carrier density and mobility values for implantation doses above 1 × 10¹⁴/cm². Samples encapsulated with aluminum oxy-nitride films exhibited 3 to 4 times higher carrier concentration values and also slightly higher mobility values than those encapsulated with silicon nitride films. The maximum carrier concentration obtained was about 4 × 10¹⁸/cm³ with aluminum oxy-nitride films as the encapsulant.     

Investigation of optical and electronic properties in Al–Sn co-doped ZnO thin films

Al-Sn co-doped ZnO thin films were deposited onto quartz substrates by sol-gel processing. The surface morphology and electrical and optical properties were investigated at different annealing temperatures. The surface morphology showed a closely packed arrangement of crystallites in all the doped films. As prepared co-doped films show a preferred orientation along an (0 0 2) plane. This preferred orientation was enhanced by increasing the annealing temperature to between 400 °C and 500 °C, but there was a shift to the (1 0 1) plane when the annealing temperature rose above 500 °C. These samples show, on average, 91.2% optical transmittance in the visible range. In this study, the optical band gap of all the doped films was broadened compared with pure ZnO, regardless of the different annealing temperature. The carrier concentration and carrier mobility of the thin films were also investigated.     

Ultraviolet-assisted annealing for low-temperature solution-processed p-type gallium tin oxide (GTO) transparent semiconductor thin films

Solution-processed p-type gallium tin oxide (GTO) transparent semiconductor thin films were prepared at a low temperature of 300 °C using ultraviolet (UV)-assisted annealing instead of conventional high-temperature annealing (> 500 °C). We report the effects of UV irradiation time on the structural, optical, and electrical properties of sol-gel derived GTO thin films and a comparison study of the physical properties of UV-assisted annealed (UVA) and conventional thermally annealed (CTA) GTO thin films. The Ga doping content was fixed at 15 at% in the precursor solution ([Ga]/[Sn]+[Ga] = 15%). After a spin-coating and preheating procedure was performed two times, the dried sol-gel films were heated on a hotplate at 300 °C under UV light irradiation for 1–4 h. Each UVA GTO thin film had a dense microstructure and flat free surface and exhibited an average optical transmittance approaching 85.0%. The level of crystallinity, crystallite size, and hole concentration density of the GTO thin films increased with increasing UV irradiation time. In this study, the UVA 4 h thin film samples exhibited the highest hole concentration (9.87 × 10¹⁷ cm⁻³) and the lowest resistivity (1.8 Ω cm) and had a hole mobility of 5.1 cm²/Vs.     

Investigation into Texture,Preferential Orientation,and Optical Properties of Zinc Oxide Nanopolycrystalline Thin Films Deposited by the Sol–Gel Technique on Different Substrates

ZnO nanopolycrystalline thin films were deposited by the sol–gel technique on glass and silicon, and compared systematically via atomic force microscopy, scanning electron microscopy, x-ray diffraction, UV–Vis spectrophotometry, and fluorescence spectrophotometry. The thickness of the ZnO films was measured by ellipsometric microscopy. A higher preheating temperature was needed to obtain films with a strong preferential orientation. The optimal annealing temperatures for c-axis films on glass and silicon substrates were 525°C and 750°C, respectively. The relative intensity of the blue–green emission peak tends to increase with the annealing temperature. When the film is annealed in N₂, the transmittance of the film reduces while the intensity of the blue–green emission increases.     

Room-temperature ferromagnetic ordering in Mn-doped ZnO thin films grown by pulsed laser deposition

The ferromagnetic ordering in Mn-doped ZnO thin films grown by pulsed laser deposition (PLD) as a function of oxygen pressure and substrate temperature has been investigated. Room-temperature ferromagnetic behaviors in the Mn-doped ZnO films grown at 700°C and 800°C under 10⁻¹ torr in oxygen pressure were found, whereas ferromagnetic ordering in the films grown under 10⁻³ torr disappeared at 300 K. The large positive magnetoresistance (MR), ∼10%, was observed at 5 K at low fields and small negative MR was observed at high fields, irrespective of oxygen pressure. In particular, anomalous Hall effect (AHE) in the Mn-doped ZnO film grown at 700°C under 10⁻¹ Torr has been observed up to 210 K. In this work, the observed AHE is believed to be further direct evidence demonstrating that the Mn-doped ZnO thin films are ferromagnetic.     

Properties of antimony doped ZnO thin films deposited by spray pyrolysis technique

Antimony (Sb) doped zinc oxide (ZnO) thin films were deposited on the glass substrate at 450°C using spray pyrolysis technique. Effect of Sb doping on surface morphology structural, optical and electrical properties were studied. X-ray diffraction (XRD) analysis showed that both the undoped and doped ZnO thin films are polycrystalline in nature with (101) preferred orientation. SEM analysis showed a change in surface morphology of Sb doped ZnO thin films. Doping results in a marked increase in conductivity without affecting the transmittance of the films. ZnO films prepared with 3 at % Sb shows the lowest resistivity of 0.185 Ohm cm with a Hall mobility of 54.05 cm² V^–1 s^–1, and a hole concentration of 6.25 × 10¹⁷ cm^–3.     

Correlation of arsenic incorporation and its electrical activation in MBE HgCdTe

The behavior of arsenic for p-type doping of MBE HgCdTe layers has been studied for various annealing temperatures and arsenic doping concentrations. We have demonstrated that arsenic is in-situ incorporated into HgCdTe layers during MBE growth. The carrier concentration has been measured by the Van der Pauw technique, and the total arsenic concentration has been determined by secondary ion mass spectroscopy. After annealing at 250°C under an Hg over pressure, As-doped HgCdTe layers show highly compensated n-type properties and the carrier concentration is approximately constant (∼mid 10¹⁵ cm⁻³) until the total arsenic concentration in the HgCdTe layers approach mid 10¹⁷ cm⁻³. The source of n-type behavior does not appear to be associated with arsenic dopants, such as arsenic atoms occupying Hg vacancy sites, but rather unidentified structural defects acting as donors. When the total arsenic concentration is above mid 10¹⁷ cm⁻³, the carrier concentration shows a dependence on the arsenic concentration while remaining n-type. We conjecture that the increase in n-type behavior may be due to donor arsenic tetramers or donor tetramer clusters. Above a total arsenic concentration of 1∼2×10¹⁸ cm⁻³, after annealing at 300°C, the arsenic acceptor activation ratio rapidly decreases below 100% with increasing arsenic concentration and is smaller than that after annealing at 450°C. The electrically inactive arsenic is inferred to be in the form of neutral arsenic tetramer clusters incorporated during the MBE growth. Annealing at 450°C appears to supply enough thermal energy to break some of the bonds of neutral arsenic tetramer clusters so that the separated arsenic atoms could occupy Te sites and behave as acceptors. However, the number of arsenic atoms on Te sites is saturated at ∼2×10¹⁸ cm⁻³, possibly due to a limitation of its solid solubility in HgCdTe.     

Effects of Rapid Thermal Annealing on Electrical Transport in Heavily Doped ZnO Thin Films Deposited at Different Substrate Temperatures

In this work, heavily doped ZnO thin films with carrier concentrations of 1.7 × 10²⁰–1.1 × 10²¹ cm^?3 were prepared on glass substrates using direct current magnetron sputtering combined with rapid thermal annealing (RTA). The effects of RTA on the electrical transport properties of the thin films were investigated. Results showed that the resistivities of the thin films deposited at low temperatures were markedly improved due to the increased mobilities and/or carrier concentrations. Temperature-dependent Hall measurements and theoretical calculations suggested that the influence of grain boundary scattering was negligible for all the samples and the mobility was mainly determined by ionized impurity scattering. The influence of crystallographic defects on the mobility could be effectively reduced via RTA when the carrier concentration was above 4.0 × 10²⁰ cm^?3, resulting in a mobility and resistivity close to the ionized impurity scattering theoretical estimation. The highest mobility of 46 cm² V^?1 s^?1 at the resistivity of 2.8 × 10^?4 Ω cm and the lowest resistivity of 2.6 × 10^?4 Ω cm were achieved for the RTA-treated 1 wt.% Al-doped ZnO and 5 wt.% Ga-doped ZnO thin films, respectively.     

Time relaxation of point defects in p- and n-(HgCd)Te after ion milling

Time relaxation of the electrical conductivity σ(77 K) and Hall coefficient R_H(77 K) of the n-type layer created by ion milling is investigated in Hg vacancy-doped, As-doped, and In-predoped p-type, and In-doped n-type Hg_1−xCd_xTe (0.2 < x < 0.22) samples. We show that the n-type layer is formed, and the temperature-activated relaxation occurs in all cases. The annealing at 75°C results in a gradual degradation of the converted n-type layer and a back n-to-p conversion within 8 days. The existence of a high-conducting, surface-damaged region with a high-electron density (∼10¹⁸ cm⁻³) and a low mobility (∼10³ cm²/Vs) is confirmed, and its influence on the relaxation is studied.     

Spontaneous growth by sol-gel process of low temperature ZnO as cathode buffer layer in flexible inverted organic solar cells

In this study, the sol–gel method was employed to prepare zinc oxide (ZnO) thin films as cathode buffer layers for inverted organic solar cells (IOSCs). We used a low temperature sol-gel process for the synthesis of ZnO thin films, in which the molar ratio of zinc acetate dihydrate (ZAD) to ethanolamine (MEA) was varied; subsequently, using the thin films, we successfully fabricated inverted solar cells on flexible plastic substrates. A ZnO sol–gel was first prepared by dissolving ZAD and MEA in ethylene glycol monomethyl ether (EGME). The molar ratios of ZAD to MEA were set as 1:1.2, 1:1, and 1:0.8, and we investigated the characteristics of the resulting ZnO thin films. We investigated the optical transmittance, surface roughness, and surface morphology of the films. Then, we discussed the reasons about the improvement of the device efficiency. The devices were fabricated using the ZnO thin films as cathode buffer layers. The results indicated that the morphology of the thin films prepared using the ZAD to MEA ratios of 1:1 and 1:0.8 changed to a rippled nanostructure after two-step annealing. The PCE was enhanced because of the higher light absorption in the active layer caused by the nanostructure. The structure of the inverted device was ITO/ZnO/P3HT:PC₆₁BM/MoO₃/Ag. The short-circuit current densities (8.59 mA/cm² and 8.34 mA/cm²) of the devices with films prepared using the ZAD to MEA ratios of 1:1 and 1:0.8 ratios, respectively, and annealed at 125 °C were higher than that of the device containing the ZnO thin film that was annealed at 150 °C. Inverted solar cells with ZnO films that were prepared using the ZAD to MEA ratios of 1:1 and 1:0.8 and annealed at 125 °C exhibited PCEs of 3.38% and 3.30%, respectively. More than that, PCEs of the flexible device can reach up to 1.53%.