Effects of oxygen concentration on the properties of Al-doped ZnO transparent conductive films deposited by pulsed DC magnetron sputtering

The effect of oxygen concentration on the properties of Al-doped ZnO (AZO) transparent conductive films has been investigated on the films deposited by pulsed DC magnetron sputtering using a cylindrical ZnO target containing 2 wt% Al. AZO films were deposited at 230 °C to the thickness of about 1000 nm and the oxygen concentration was controlled by varying the O₂/Ar supply ratio from 0 to 0.167. With the increasing O₂/Ar ratio, crystallinity of the AZO films deteriorated while the film surface became smooth. Accompanying this, electrical properties also deteriorated significantly. When the O₂/Ar ratios were 0 and 0.033, the AZO films showed metallic conduction behavior with the electrical resistivity in the mid 10^?4 Ω cm range. However, when the ratios were 0.100 and 0.167, the films showed poor electrical conduction behavior similar to semiconductors as deduced from the transmittance behavior. Spectroscopic analysis showed that such deteriorating properties are due to the formation of condensed oxide group through the reaction between excess oxygen and dopant aluminum.     

Memory characteristics of Al2O3/La2O3/Al2O3 multi-layer films with various blocking and tunnel oxide thicknesses

In order to investigate charge trap characteristics with various thicknesses of blocking and tunnel oxide for application to non-volatile memory devices, we fabricated 5 and 15 nm Al₂O₃/5 nm La₂O₃/5 nm Al₂O₃ and 15 nm Al₂O₃/5 nm La₂O₃/5, 7.5, and 10 nm Al₂O₃ multi-stack films, respectively. The optimized structure was 15 nm Al₂O₃ blocking oxide/5 nm La₂O₃ trap layer/5 nm Al₂O₃ tunnel oxide film. The maximum memory window of this film of about 1.12 V was observed at 11 V for 10 ms in program mode and at ?13 V for 100 ms in erase mode. At these program/erase conditions, the threshold voltage of the 15 nm Al₂O₃/5 nm La₂O₃/5 nm Al₂O₃ film did not change for up to about 10⁴ cycles. Although the value of the memory window in this structure was not large, it is thought that a memory window of 1.12 V is acceptable in the flash memory devices due to a recently improved sense amplifier.     

Effect of AlN buffer layer thickness on the properties of GaN films grown by pulsed laser deposition

The GaN films are grown by pulsed laser deposition (PLD) on sapphire, AlN(30 nm)/Al₂O₃ and AlN(150 nm)/Al₂O₃, respectively. The effect of AlN buffer layer thickness on the properties of GaN films grown by PLD is investigated systematically. The characterizations reveal that as AlN buffer layer thickness increases, the surface root-mean-square (RMS) roughness of GaN film decreases from 11.5 nm to 2.3 nm, while the FWHM value of GaN film rises up from 20.28 arcmin to 84.6 arcmin and then drops to 31.8 arcmin. These results are different from the GaN films deposited by metal organic chemical vapor deposition (MOCVD) with AlN buffer layers, which shows the improvement of crystalline qualities and surface morphologies with the thickening of AlN buffer layer. The mechanism of the effect of AlN buffer layer on the growth of GaN films by PLD is hence proposed.     

Thickness dependent barrier performance of permeation barriers made from atomic layer deposited alumina for organic devices

Organic devices like organic light emitting diodes (OLEDs) or organic solar cells degrade fast when exposed to ambient air. Hence, thin-films acting as permeation barriers are needed for their protection. Atomic layer deposition (ALD) is known to be one of the best technologies to reach barriers with a low defect density at gentle process conditions. As well, ALD is reported to be one of the thinnest barrier layers, with a critical thickness – defining a continuous barrier film – as low as 5–10 nm for ALD processed Al₂O₃. In this work, we investigate the barrier performance of Al₂O₃ films processed by ALD at 80 °C with trimethylaluminum and ozone as precursors. The coverage of defects in such films is investigated on a 5 nm thick Al₂O₃ film, i.e. below the critical thickness, on calcium using atomic force microscopy (AFM). We find for this sub-critical thickness regime that all spots giving raise to water ingress on the 20 × 20 μm² scan range are positioned on nearly flat surface sites without the presence of particles or large substrate features. Hence below the critical thickness, ALD leaves open or at least weakly covered spots even on feature-free surface sites. The thickness dependent performance of these barrier films is investigated for thicknesses ranging from 15 to 100 nm, i.e. above the assumed critical film thickness of this system. To measure the barrier performance, electrical calcium corrosion tests are used in order to measure the water vapor transmission rate (WVTR), electrodeposition is used in order to decorate and count defects, and dark spot growth on OLEDs is used in order to confirm the results for real devices. For 15–25 nm barrier thickness, we observe an exponential decrease in defect density with barrier thickness which explains the likewise observed exponential decrease in WVTR and OLED degradation rate. Above 25 nm, a further increase in barrier thickness leads to a further exponential decrease in defect density, but an only sub-exponential decrease in WVTR and OLED degradation rate. In conclusion, the performance of the thin Al₂O₃ permeation barrier is dominated by its defect density. This defect density is reduced exponentially with increasing barrier thickness for alumina thicknesses of up to at least 25 nm.     

Influence of processing and annealing steps on electrical properties of InAlN/GaN high electron mobility transistor with Al2O3 gate insulation and passivation

We report on preparation and electrical characterization of InAlN/AlN/GaN metal–oxide–semiconductor high electron mobility transistors (MOS HEMTs) with Al₂O₃ gate insulation and surface passivation. About 12 nm thin high-κ dielectric film was deposited by MOCVD. Before and after the dielectric deposition, the samples were treated by different processing steps. We monitored and analyzed the steps by sequential device testing. It was found that both intentional (ex situ) and unintentional (in situ before Al₂O₃ growth) InAlN surface oxidation increases the channel sheet resistance and causes a current collapse. Post deposition annealing decreases the sheet resistance of the MOS HEMT devices and effectively suppresses the current collapse. Transistors dimensions were source-to-drain distance 8 μm and gate width 2 μm. A maximum transconductance of 110 mS/mm, a drain current of ～0.6 A/mm (V_GS = 1 V) and a gate leakage current reduction from 4 to 6 orders of magnitude compared to Schottky barrier (SB) HEMTs was achieved for MOS HEMT with 1 h annealing at 700 °C in forming gas ambient. Moreover, InAlN/GaN MOS HEMTs with deposited Al₂O₃ dielectric film were found highly thermally stable by resisting 5 h 700 °C annealing.     

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.     

Influence of cathode roughness on the performance of F8BT based organic–inorganic light emitting diodes

Hybrid light emitting diodes (HyLED) with a structure of FTO/ZnO/F8BT/MoO₃/Au/Ag is fabricated and the influence of surface roughness of cathode (FTO/ZnO) is investigated. The roughness of FTO could be decreased from 9.2 nm to 2.2 nm using a mild polishing process. The ZnO film, deposited by spray pyrolysis, functions as an electron injection layer. The roughness of the FTO/ZnO surface is found also highly dependent on the ZnO thickness. For thin ZnO films (20 nm), polishing results in better efficacy and power efficiency of LED devices, with nearly a two times improvement. For thick ZnO films (210 nm), the overall FTO/ZnO roughness is almost independent of the FTO roughness, hence both polished and unpolished substrates exhibit identical performance. Increasing ZnO thickness generally improves the electron injection condition, leading to lower turn on voltage and higher current and power efficiencies. However, for too large ZnO thickness (210 nm) the ohmic loss across the film dominates and deteriorates the performance. While the polished substrates show less device sensitivity to ZnO thickness and better performance at thin ZnO layer, best performance is obtained for unpolished substrates with 110 nm ZnO thickness. Larger interface area of ZnO/F8BT and enhanced electric filed at sharp peaks/valleys could be the reason for better performance of devices with unpolished substrates.     

Interface studies of ALD-grown metal oxide insulators on Ge and III–V semiconductors (Invited Paper)

Atomic layer deposited (ALD) HfO₂/GeO_xN_y/Ge(1 0 0) and Al₂O₃/In_0.53Ga_0.47As(1 0 0) ? 4 × 2 gate stacks were analyzed both by MOS capacitor electrical characterization and by advanced physical characterization to correlate the presence of electrically-active defects with chemical bonding across the insulator/channel interface. By controlled in situ plasma nitridation of Ge and post-ALD annealing, the capacitance-derived equivalent oxide thickness was reduced to 1.3 nm for 5 nm HfO₂ layers, and mid-gap density of interface states, D_it = 3 × 10¹¹ cm^?2 eV^?1, was obtained. In contrast to the Ge case, where an engineered interface layer greatly improves electrical characteristics, we show that ALD-Al₂O₃ deposited on the In_0.53Ga_0.47As (1 0 0) ? 4 × 2 surface after in situ thermal desorption in the ALD chamber of a protective As cap results in an atomically-abrupt and unpinned interface. By avoiding subcutaneous oxidation of the InGaAs channel during Al₂O₃ deposition, a relatively passive gate oxide/III–V interface is formed.     

Effect of gate insulator thickness on device performance of InGaZnO thin-film transistors

Top-contact thin-film transistors (TFTs) are fabricated in this work using atomic layer deposition (ALD) Al₂O₃ as the gate insulator and radio frequency sputtering InGaZnO (IGZO) as the channel layer so as to investigate the effect of Al₂O₃ thickness on the performance of IGZO-TFTs. The results show that TFT with 100-nm-thick Al₂O₃ (100 nm-Al₂O₃-TFT) exhibits the best electrical performance; specifically, field-effect mobility of 5 cm²/Vs, threshold voltage of 0.95 V, I_on/I_off ratio of 1.1×10⁷ and sub-threshold swing of 0.3 V/dec. The 100 nm-Al₂O₃-TFT also shows a substantially smaller threshold voltage shift of 1.1 V after a 10 V gate voltage is applied for 1 h, while the values for TFTs with an Al₂O₃ thickness of 220 and 280 nm are 1.84 and 2 V, respectively. The best performance of 100 nm-Al₂O₃-TFT can be attributed to the larger capacitance and the smaller amount of total trap centers possessed by a thinner insulator compared to the thicker ones.     

Effect of four different zinc salts and annealing treatment on growth,structural, mechanical and optical properties of nanocrystalline ZnS thin films by chemical bath deposition

ZnS thin films were deposited from four different zinc salts on glass substrates by chemical bath deposition method. Different anions of zinc salts affect the deposition mechanism and growth rate, which influence the properties of the films significantly. The ZnS thin film deposited from ZnSO₄ is smoother, thicker, more homogeneous and compact, nearly stoichiometric, comparing with the films deposited from Zn(CH₃COO)₂ and Zn(NO₃)₂, and ZnCl₂. The scratch test of bonding force between ZnS film and substrate shows that the ZnS film deposited from ZnSO₄ has the most excellent adhesion with the substrate. The presence of SO₄²⁻ promotes heterogeneous ZnS thin film growth via ions by ions deposition, and the films deposited from Zn(CH₃COO)₂ and Zn(NO₃)₂ are formed via clusters by clusters deposition. XRD and HRTEM results show that cubic ZnS films are obtained after single deposition, and the grain size of ZnS thin film deposited from ZnSO₄ for 2.5 h is 10 nm. The average transmission of all films is greater than 85% in the wavelength ranging from 600 to 1100 nm, and the transmission of films deposited from ZnSO₄ or Zn(NO₃)₂ for 1.5, 2 and 2.5 h is greater than 85% in the wavelength varying from 340 to 600 nm, which can enhance the blue response. The band gaps of all ZnS thin films are in the range of 3.88–3.99 eV. After annealing treatment, the mechanical and optical properties of the ZnS thin film deposited from ZnSO₄ are improved significantly.     

Ultra-low-energy ion-beam-synthesis of Ge nanocrystals in thin ALD Al2O3 layers for memory applications

Structural and electrical properties of ALD-grown 5 and 7 nm-thick Al₂O₃ layers before and after implantation of Ge ions (1 keV, 0.5–1 × 10¹⁶ cm^?2) and thermal annealing at temperatures in the 700–1050 °C range are reported. Transmission Electron Microscopy reveals the development of a 1 nm-thick SiO₂-rich layer at the Al₂O₃/Si substrate interface as well as the formation of Ge nanocrystals with a mean diameter of ～5 nm inside the implanted Al₂O₃ layers after annealing at 800 °C for 20 min. Electrical measurements performed on metal–insulator–semiconductor capacitors using Ge-implanted and annealed Al₂O₃ layers reveal charge storage at low-electric fields mainly due to location of the Ge nanocrystals at a tunnelling distance from the substrate and their spatial dispersion inside the Al₂O₃ layers.     

Study on thermal solid-phase crystallization of amorphous ZnO thin films stacked on vanadium-doped ZnO films

Thermal solid-phase crystallization (SPC) of an amorphous ZnO film stacked on a vanadium-doped ZnO (VZO) film was investigated. ZnO films were deposited on 30-nm-thick amorphous VZO films on c-face sapphire substrates at room temperature by RF magnetron sputtering. Stacked film was subsequently calcined at 800 °C in a nitrogen atmosphere. ZnO film grew in an amorphous state up to about 150-nm thick on the amorphous VZO film, but self-orientation occurred in a thicker layer. Any secondary phase such as Zn₂VO₄ was not formed in the case of total film thickness (t_total) ≥100 nm. V concentration decreased by thermal diffusion of V through the ZnO layer from the VZO film, and thereby the formation of secondary phase was effectively avoided. The amorphous ZnO layer was crystallized from highly-aligned initial thin layer of VZO film when t_total ≤200 nm and crystal orientation of the stacked film was superior to single VZO film. However, the c-axis orientation was deteriorated drastically at t_total ≈400 nm due to SPC affected by the tilted regions existed in the as-deposited ZnO film. Therefore, it is suggested that careful selection of ZnO film thickness is necessary to obtain the high-quality ZnO films in this method.     

Synthesis and some surface studies of laminated ZnO/TiO2 transparent bilayer by two-step growth

A laminated bilayer was prepared by first depositing titanium dioxide (TiO₂) nanocrystals on indium tin oxide (ITO) coated glass by a two-electrode cell. Zinc oxide (ZnO) thin film was thereafter deposited on the TiO₂ by two different techniques: electrochemical deposition and vacuum evaporation. The films were characterized by some surface probing techniques. Morphological study revealed that particle size of the TiO₂ underlayer increases between 110 and 138 nm with increase in deposition voltage. It also showed that ZnO thin film (overlayer) completely covered the underlying TiO₂ without chemical interaction between constituents of both layers. Cross-sectional FESEM study gave values of layered film thickness below 55 µm. Exhibition of strong diffraction peak at plane (121) indicated preference of TiO₂ film's growth orientation. It also suggested a feature of phase-pure brookite. Optical studies showed that each film exhibited strong absorption edge at λ=~330 nm and transmitted fairly across visible light region. Energy band gap lied between 3.24 and 3.43 eV. This study demonstrated successive layer deposition of transparent metal oxide structures from inorganic reagents. It also reaffirmed TiO₂ as a recipe for barrier layer that can hinder transition of holes from absorber to transparent front contact of nanostructured photonic devices.     

Composition,structure and electrical properties of DC reactive magnetron sputtered Al2O3 thin films

Thin films of alumina (Al₂O₃) were deposited over Si 〈1 0 0〉 substrates at room temperature at an oxygen gas pressure of 0.03 Pa and sputtering power of 60 W using DC reactive magnetron sputtering. The composition of the as-deposited film was analyzed by X-ray photoelectron spectroscopy and the O/Al atomic ratio was found to be 1.72. The films were then annealed in vacuum to 350, 550 and 750 °C and X-ray diffraction results revealed that both as-deposited and post deposition annealed films were amorphous. The surface morphology and topography of the films was studied using scanning electron microscopy and atomic force microscopy, respectively. A progressive decrease in the root mean square (RMS) roughness of the films from 1.53 nm to 0.7 nm was observed with increase in the annealing temperature. Al–Al₂O₃–Al thin film capacitors were then fabricated on p-type Si 〈1 0 0〉 substrate to study the effect of temperature and frequency on the dielectric property of the films and the results are discussed.     

Influence of Sn content on properties of ZnO:SnO2 thin films deposited by ultrasonic spray pyrolysis

The present work is devoted to the preparation of zinc oxide (ZnO): tin oxide (SnO₂) thin films by ultrasonic spray technique. A set of films are deposited using a solution formed with zinc acetate and tin chloride salts mixture with varied weight ratio R=[Sn/(Zn+Sn)]. The ratio R is varied from 0 to 100% in order to investigate the influence of Sn concentration on the physical properties of ZnO:SnO₂ films. The X rays diffraction (XRD) analysis indicated that films are composed of ZnO and SnO₂ distinct phases without any alloys or spinnel phase formations. The average grain size of crystallites varies with the ratio R from 17 to 20 nm for SnO₂ and from 24 to 40 nm for ZnO. The obtained films are highly transparent with a transmission coefficient equal to 80%. An increase in Sn concentration increases both the effective band gap energy from 3.2 to 4.01 eV and the photoluminescence intensity peak assigned defects to SnO₂. The films electrical characterization indicated that films are resistive. Their resistivities vary between 1.2×10² and 3.3×10⁴ (Ω cm). The higher resistivity is measured in film deposited with a ratio R equal to 50%.     

Growth behavior and improved water–vapor-permeation-barrier properties of 10-nm-thick single Al2O3 layer grown via cyclic chemical vapor deposition on organic light-emitting diodes

We have investigated the growth behavior and water vapor permeation barrier properties of cyclic chemical vapor deposition (C-CVD)-grown 10-nm-thick single layer of Al₂O₃. Al₂O₃ layers grown by C-CVD showed a high density of 3.298 g/cm³ and were amorphous without grain boundaries. A deposition rate of 0.46 nm/cycle was obtained. The C-CVD system was self-limiting, as in the case of atomic layer deposition, which enables precise control of the thickness of the Al₂O₃ layer. A water vapor transmission rate of 1.51 × 10⁻⁵ (g/m²)/day was obtained from a Ca degradation test performed at 85 °C and 85% relative humidity. Moreover, the performance of organic light-emitting diodes, passivated by a C-CVD-grown 10-nm-thick Al₂O₃ single layer, was not affected after 24,000 h of turn-on time; this is strong evidence that C-CVD-grown Al₂O₃ layers effectively prevent water vapor from diffusing into the active organic layer.     

Electronic and chemical properties of ZnO in inverted organic photovoltaic devices

Photo-conversion efficiency of inverted polymer solar cells incorporating pulsed laser deposited ZnO electron transport layer have been found to significantly increase from 0.8% to up to 3.3% as the film thickness increased from 4 nm to 100 nm. While the ZnO film thickness was found to have little influence on the morphology of the resultant ZnO films, the band structure of ZnO was found to evolve only for films of thickness 25 nm or more and this was accompanied by a significant reduction of 0.4 eV in the workfunction. The films became more oxygen deficient with increased thickness, as found from X-ray photoelectron spectroscopy (XPS) and valence band XPS (VBXPS). We attribute the strong dependence of device performance to the zinc to oxygen stoichiometry within the ZnO layers, leading to improvement in the band structure of ZnO with increased thickness.     

Magneto-optical characteristics of Mn-doped ZnO films deposited by ultrasonic spray pyrolysis

This work considers a Mn-doped ZnO (ZnO:Mn) film deposited on a slide glass substrate by ultrasonic spray pyrolysis. ZnO:Mn (Mn at 1.5 at%) film with and without an applied magnetic field, is demonstrated to have absorption edges at 2.74 and 2.84 eV, respectively. These values are lower than that of a pure ZnO film because the Mn-doping causes the exchange of s–d and p–d interactions or high carrier concentration. When the ZnO:Mn film is placed in a magnetic field B_z of 0.5 T, an absorption edge and a photoluminescence (PL) shift of about 0.1 eV and 85 meV, respectively, are observed. This shift is attributed to the interband magneto-optic absorption associated with the Landau splitting. The observed shift increases with the amount of Mn dopant.     

Structural,morphological, electrical and optical studies of Cr doped SnO2 thin films deposited by the spray pyrolysis technique

Tin oxide (SnO₂) and chromium (Cr) doped tin oxide (Cr:SnO₂) thin films were deposited on the preheated glass substrates at 673 K by spray pyrolysis. Concentration of Cr was varied in the solution by adding chromium (III) chloride hexahydrate from 0 to 3 at%. The effect of Cr doping on the structural, electrical and optical properties of tin oxide films is reported. X-ray diffraction pattern confirms the tetragonal crystal structure for undoped and Cr doped tin oxide films. Scanning electron microscopic photographs show the modification of surface morphology of tin oxide film due to varying concentration of Cr. X-ray photoelectron spectra of Cr:SnO₂ (3 at%) thin film revealed the presence of carbon, tin, oxygen, and chromium. Carrier concentration and mobility of the SnO₂ films decrease with increasing concentration of Cr and 0.5 at% Cr doped tin oxide film acquires a mobility of 70 cm²/V s. Average optical transmittance in the 550–850 nm range varies from 38% to 47% with varying Cr concentration in the solution.     

Thickness-dependent optoelectronic properties of CuCr0.93Mg0.07O2 thin films deposited by reactive magnetron sputtering

CuCr_0.93Mg_0.07O₂ thin films were successfully deposited by DC reactive magnetron sputtering at 1123 K from metallic targets. The influence of film thickness on the structural and optoelectronic properties of the films was investigated. X-ray diffraction (XRD) results revealed that all the films had a delafossite structure with no other phases. The optical and electrical properties were investigated by UV–VIS spectrophotometer and Hall measurement, respectively. It was found that the optoelectronic properties exhibited a thickness-dependent behavior. The optical band gap and the average transmittance of the films showed a monotonous decrease with respect to the increase in thickness. The average transmittance in the visible region decreased from 67% to 47% as the thickness increased from ~70 nm to ~280 nm. Simultaneously, the conductivity of the films fell from 1.40 S∙cm⁻¹ to 0.27 S∙cm⁻¹. According to Haacke's figure of merit (FOM), a film with a maximum FOM value of about 1.72×10⁻⁷ Ω⁻¹ can be achieved when the thickness is about 70 nm (σ≈ 1.40 S·cm⁻¹ and T_av. ≈67%).