Realization of intrinsic p-type ZnO thin films by metal organic chemical vapor deposition

P-type ZnO thin films were grown on sapphire substrates with and without nitrous oxide (N₂O) by metal organic chemical vapor deposition (MOCVD). The intrinsic p-type ZnO films were achieved by controlling the Zn:O ratio in the range of 0.05–0.2 without N₂O flow. Secondary ion mass spectroscopy (SIMS) showed that the films contained little or no nitrogen (N) impurities for all samples. The p-type behavior of the samples should be due to the intrinsic acceptor-like defects V_Zn, for ZnO film grown without nitrous oxide, and N, occupying O sites as acceptors for ZnO film grown with nitrous oxide. The best p-type ZnO film has low resistivity of 0.369 Ω-cm, high carrier density of 1.62×10¹⁹ cm⁻³, and mobility of 3.14 cm²/V-s. The obtained p-type ZnO films possess a transmittance of nearly 100% in the visible region and strong near-band-edge emission.     

Relaxing the Conductivity/Transparency Trade‐Off in MOCVD ZnO Thin Films by Hydrogen Plasma

Increasing the conductivity of polycrystalline zinc oxide films without impacting the transparency is a key aspect in the race to find affordable and high quality material as replacement of indium‐containing oxides. Usually, ZnO film conductivity is provided by a high doping and electron concentration, detrimental to transparency, because of free carrier absorption. Here we show that hydrogen post‐deposition plasma treatment applied to ZnO films prepared by metalorganic low‐pressure chemical vapor deposition allows a relaxation of the constraints of the conductivity/transparency trade‐off. Upon treatment, an increase in electron concentration and Hall mobility is observed. The mobility reaches high values of 58 and 46 cm²V^?1s^?1 for 2‐μm‐ and 350‐nm‐thick films, respectively, without altering the visible range transparency. From a combination of opto‐electronic measurements, hydrogen is found, in particular, to reduce electron trap density at grain boundaries. After treatment, the values for intragrain or optical mobility are found similar to Hall mobility, and therefore, electron conduction is found to be no longer limited by the phenomenon of grain boundary scattering. This allows to achieve mobilities close to 60 cm²V^?1s^?1, even in ultra‐transparent films with carrier concentration as low as 10¹⁹ cm^?3.     

UV and IR emission intensity in ZnO films,nanorods, and bulk single crystals doped with Er and additionally introduced impurities

For ZnO films, nanorods, and bulk single crystals doped with Er⁺ ions, it is shown that the effect of codopants introduced into the cation and ion sublattices and the observation of a high-intensity emission band at the wavelength λ_max = 1535 nm are defined by the local environment of the Er⁺ ion. Doping of the films and single crystals with Er⁺ ions by diffusion brings about an infrared (IR) emission band with a low intensity because of an inadequate concentration of impurity ions. The emission intensity of this band can be raised by introducing additional Ag, Au, or N⁺ impurities into the ZnO films. The UV-emission intensity of the Er-doped films and single crystals at λ_max = 368–372 nm is identical to that of the undoped films. ZnO nanorods doped with Er only or together with Al or Ga codopants exhibit only one IR band (at λ_max = 1535 nm), whose intensity decreases upon the introduction of codopants. Doping of the nanorods with the N⁺ gaseous impurity during growth (930 < T < 960°C) and then with the Er⁺ impurity by diffusion does not yield a substantial increase in the IR-emission intensity compared to the that of the corresponding band for nanorods not doped with the N⁺ impurity. In the Er-doped nanorods, whose photoluminescence spectra exhibit a high-intensity band at λ_max = 1535 nm, the UV emission band at λ_max = 372 nm is practically lacking.     

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.     

Optical and electrical properties of epitaxial (Mg,Cd)xZn1−xO, ZnO, and ZnO:(Ga,Al) thin films on c-plane sapphire grown by pulsed laser deposition

A consistent set of epitaxial, n-type conducting ZnO thin films, nominally undoped, doped with Ga or Al, or alloyed with Mg or Cd, was grown by pulsed laser deposition (PLD) on single-crystalline c-plane sapphire (0 0 0 1) substrates, and characterized by Hall measurement, and UV/VIS optical transmission spectroscopy.The optical band gap of undoped ZnO films at nearly 3.28 eV was shifted by alloying with Mg up to 4.5 eV and by alloying with Cd down to 3.18 eV, dependent on the alloy composition. In addition, highly doped ZnO:Al films show a blue-shifted optical absorption edge due to filling of electronic states in the conduction band.The Hall transport data of the PLD (Mg,Zn,Cd)O:(Ga,Al) thin films span a carrier concentration range of six orders of magnitude from 3 × 10¹⁴ to 3 × 10²⁰ cm⁻³, which corresponds to a resistivity from 5 × 10⁻⁴ to 3 × 10³ Ω cm. Structurally optimized, nominally undoped ZnO films grown with ZnO nucleation and top layer reached an electron mobility of 155 cm²/V s (300 K), which is among the largest values reported for heteroepitaxial ZnO thin films so far.Finally, we succeeded in combining the low resistivity of ZnO:Ga and the band gap shift of MgZnO in MgZnO:Ga thin films. This results demonstrate the unique tunability of the optical and electrical properties of the ZnO-based wide-band gap material for future electronic devices.     

Properties of conducting zinc oxide films prepared by R.F. Sputtering

An effective method of dopant incorporation in rf sputtered ZnO film is reported. The electrical, optical and structural properties of zinc doped ZnO films are investigated. Electron mobility of∼10 cm² /V-sec and electron concentration of∼10¹⁹ cm⁻³ have been measured at room temperature. X-ray diffraction data obtained on films prepared on Corning 7059 glass show (002) peak, dominating. The high electrical conductivity and transmission makes ZnO films very attractive as a component for heterojunction solar cells.     

Growth of Heteroepitaxial ZnO Thin Films on GaN‐Buffered Al2O3 (0001) Substrates by Low‐Temperature Hydrothermal Synthesis at 90 °C

Heteroepitaxial ZnO films are successfully grown on nondoped GaN‐buffered Al₂O₃ (0001) substrates in water at 90 °C using a two‐step process. In the first step, a discontinuous ZnO thin film (ca. 200 nm in thickness) consisting of hexagonal ZnO crystallites is grown in a solution containing Zn(NO₃)·6 H₂O and NH₄NO₃ at ca. pH 7.5 for 24 h. In the second step, a dense and continuous ZnO film (ca. 2.5 μm) is grown on the first ZnO thin film in a solution containing Zn(NO₃)·6 H₂O and sodium citrate at ca. pH 10.9 for 8 h. Scanning electron microscopy, X‐ray diffraction, UV‐vis absorption spectroscopy, photoluminescence spectroscopy, and Hall‐effect measurement are used to investigate the structural, optical, and electrical properties of the ZnO films. X‐ray diffraction analysis shows that ZnO is a monocrystalline wurtzite structure with an epitaxial orientation relationship of (0001)[11 0]_ZnO∥(0001)[11 0]_GaN. Optical transmission spectroscopy of the two‐step grown ZnO film shows a bandgap energy of 3.26 eV at room temperature. A room‐temperature photoluminescence spectrum of the ZnO film reveals only a main peak at ca. 380 nm without any significant defect‐related deep‐level emissions. The electrical property of ZnO film showed n‐type behavior with a carrier concentration of 3.5 × 10¹⁸ cm^–3 and a mobility of 10.3 cm² V^–1 s^–1.     

Low temperature Solution-Processed ZnO film on flexible substrate

Transparent conductive ZnO films were directly deposited on unseeded polyethersulfone (PES) substrates with a spin-spray method using aqueous solution at a low substrate temperature of 85 °C. All ZnO films were crystalline with wurtzite hexagonal structure and impurity phases were not detected. ZnO films deposited without citrate ions in the reaction solution had a rod array structure. In contrast, ZnO films deposited with citrate ions in the reaction solution had a continuous, dense structure. The transmittance of the ZnO films was improved from 11.9% to 85.3% as their structure changed from rod-like to continuous. After UV irradiation, the ZnO films with a continuous, dense structure had a low resistivity of 9.1×10⁻³ Ω cm, high carrier concentration of 2.7×10²⁰ cm⁻³ and mobility of 2.5 cm² V⁻¹ s⁻¹.     

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.     

Structural and Electrical Characterization of ZnO Films Grown by Spray Pyrolysis and Their Application in Thin‐Film Transistors

The role of the substrate temperature on the structural, optical, and electronic properties of ZnO thin films deposited by spray pyrolysis using a zinc acetate precursor solution is reported. Analysis of the precursor compound using thermogravimentry and differential scanning calorimetry indicates complete decomposition of the precursor at around 350 °C. Film characterization using Fourier Transform Infrared Spectroscopy (FTIR), photoluminescence spectroscopy (PL), and ultraviolet–visible (UV–Vis) optical transmission spectroscopy suggests the onset of ZnO growth at temperatures as low as 100 °C as well as the transformation to a polycrystalline phase at deposition temperatures >200 °C. Atomic force microscopy (AFM) and X‐ray diffraction (XRD) reveal that as‐deposited films exhibit low surface roughness (rms ≈ 2.9 nm at 500 °C) and a crystal size that is monotonously increasing from 8 to 32 nm for deposition temperatures in the range of 200–500 °C. The latter appears to have a direct impact on the field‐effect electron mobility, which is found to increase with increasing ZnO crystal size. The maximum mobility and current on/off ratio is obtained from thin‐film transistors fabricated using ZnO films deposited at >400 °C yielding values on the order of 25 cm² V^?1s^?1 and 10⁶, respectively.     

Electrostatic Tuning of Spray‐Deposited ZnO for Controlled Mobility Enhancement

Spray‐deposited nanocrystalline ZnO films are produced in order to establish empirical relationships between synthetic conditions and the density of states as a means of achieving electrostatic control. By varying the spray‐pyrolysis deposition conditions, i.e., substrate temperature, precursor concentration, and flow rate, a wide range of exponentially distributed density of localized states profiles and field‐effect mobility values ranging over three orders of magnitude (0.02–30 cm² V^?1 s^?1) are obtained for analysis. It is found that mobility can be controlled by appropriately tuning the shape of the density of states profile, increasing the band tail slope and reducing the band edge concentration of shallow states. Most significantly, it is shown that the shape of the density of states can be modified by adjusting the spray‐pyrolysis deposition conditions for electrostatic control. It is found that higher Zn precursor concentration in solution increases the slope of the band tails, leading to higher mobility. Additionally, the band edge concentration is reduced with increased substrate temperature also leading to higher mobility. These results quantify the relationship between defect electrostatics and electron transport while demonstrating electrostatic control via synthetic modification of localized states.     

Solution‐Deposited Zinc Oxide and Zinc Oxide/Pentacene Bilayer Transistors: High Mobility n‐Channel,Ambipolar, and Nonvolatile Devices

A solution processed n‐channel zinc oxide (ZnO) field effect transistor (FET) was fabricated by simple dip coating and subsequent heat treatment of a zinc acetate film. The field effect mobility of electrons depends on ZnO grain size, controlled by changing the number of coatings and zinc acetate solution concentration. The highest electron mobility achieved by this method is 7.2 cm² V^?1 s^?1 with On/Off ratio of 70. This electron mobility is higher than for the most recently reported solution processed ZnO transistor. We also fabricated bilayer transistors where the first layer is ZnO, and the second layer is pentacene, a p‐channel organic which is deposited by thermal evaporation. By changing the ZnO grain size (or thickness) this type of bilayer transistor shows p‐channel, ambipolar and n‐channel behavior. For the ambipolar transistor, well balanced electron and hole mobilities are 7.6 × 10^?3 and 6.3 × 10^?3 cm² V^?1 s^?1 respectively. When the ZnO layer is very thin, the transistor shows p‐channel behavior with very high reversible hysteresis. The nonvolatile tuning function of this transistor was investigated.     

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.     

Highly conductive ZnO films with high near infrared transparency

We present an approach for deposition of highly conductive nominally undoped ZnO films that are suitable for the n‐type window of low band gap solar cells. We demonstrate that low‐voltage radio frequency (RF) biasing of growing ZnO films during their deposition by non‐reactive sputtering makes them as conductive as when doped by aluminium (ρ≤1·10⁻³Ω cm). The films prepared with additional RF biasing possess lower free‐carrier concentration and higher free‐carrier mobility than Al‐doped ZnO (AZO) films of the same resistivity, which results in a substantially higher transparency in the near infrared region (NIR). Furthermore, these films exhibit good ambient stability and lower high‐temperature stability than the AZO films of the same thickness. We also present the characteristics of Cu(InGa)Se₂, CuInSe₂ and Cu₂ZnSnSe₄‐based solar cells prepared with the transparent window bilayer formed of the isolating and conductive ZnO films and compare them to their counterparts with a standard ZnO/AZO bilayer. We show that the solar cells with nominally undoped ZnO as their transparent conductive oxide layer exhibit an improved quantum efficiency for λ > 900 nm, which leads to a higher short circuit current density J_SC. This aspect is specifically beneficial in preparation of the Cu₂ZnSnSe₄ solar cells with band gap down to 0.85 eV; our champion device reached a J_SC of nearly 39 mAcm⁻², an open circuit voltage of 378mV, and a power conversion efficiency of 8.4 %. Copyright © 2015 John Wiley & Sons, Ltd.     

Characteristics of GZO thin films deposited by sol–gel dip coating

Zinc oxide (ZnO) films were deposited by sol–gel dip coating using the acrylamide route. The films were doped with different concentrations of gallium in the range 250–1200 ppm. The films exhibited hexagonal structure. The grain size decreased from 100 to 10 nm as the dopant concentration increased. The resistivity of the doped samples decreased from 10³ to 3×10⁻³ Ω cm. The band gap value shifted towards the short-wavelength region as the dopant concentration increased. XPS studies indicated doping of Ga in ZnO     

Cellulose‐Based Ionogels for Paper Electronics

A new class of biofriendly ionogels produced by gelation of microcellulose thin films with tailored 1‐ethyl‐3‐methylimidazolium methylphosphonate ionic liquids are demonstrated. The cellulose ionogels show promising properties for application in flexible electronics, such as transparency, flexibility, transferability, and high specific capacitances of 5 to 15 μF cm^?2. They can be laminated onto any substrate such as multilayer‐coated paper and act as high capacitance dielectrics for inorganic (spray‐coated ZnO and colloidal ZnO nanorods) and organic (poly[3‐hexylthiophene], P3HT) electrolyte‐gated field‐effect transistors (FETs), that operate at very low voltages (<2 V). Field‐effect mobilities in ionogel‐gated spray‐coated ZnO FETs reach 75 cm² V^?1 s^?1 and a typical increase of mobility with decreasing specific capacitance of the ionogel is observed. Solution‐processed, colloidal ZnO nanorods and laminated cellulose ionogels enable the fabrication of the first electrolyte‐gated, flexible circuits on paper, which operate at bending radii down to 1.1 mm.     

High‐Performance Amorphous Multilayered ZnO‐SnO2 Heterostructure Thin‐Film Transistors: Fabrication and Characteristics

Multilayered ZnO‐SnO₂ heterostructure thin films consisting of ZnO and SnO₂ layers are produced by alternating the pulsed laser ablation of ZnO and SnO₂ targets, and their structural and field‐effect electronic transport properties are investigated as a function of the thickness of the ZnO and SnO₂ layers. The performance parameters of amorphous multilayered ZnO‐SnO₂ heterostructure thin‐film transistors (TFTs) are highly dependent on the thickness of the ZnO and SnO₂ layers. A highest electron mobility of 43 cm²/V·s, a low subthreshold swing of a 0.22 V/dec, a threshold voltage of 1 V, and a high drain current on‐to‐off ratio of 10¹⁰ are obtained for the amorphous multilayered ZnO(1.5 nm)‐SnO₂(1.5 nm) heterostructure TFTs, which is adequate for the operation of next‐generation microelectronic devices. These results are presumed to be due to the unique electronic structure of amorphous multilayered ZnO‐SnO₂ heterostructure film consisting of ZnO, SnO₂, and ZnO‐SnO₂ interface layers.     

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.     

Structural and Electrical Properties of Atomic Layer Deposited Al‐Doped ZnO Films

Structural and electrical properties of Al‐doped ZnO (AZO) films deposited by atomic layer deposition (ALD) are investigated to study the extrinsic doping mechanism of a transparent conducting oxide. ALD‐AZO films exhibit a unique layer‐by‐layer structure consisting of a ZnO matrix and Al₂O₃ dopant layers, as determined by transmission electron microscopy analysis. In these layered AZO films, a single Al₂O₃ dopant layer deposited during one ALD cycle could provide ≈4.5 × 10¹³ cm^?2 free electrons to the ZnO. The effective field model for doping is suggested to explain the decrease in the carrier concentration of ALD‐AZO films when the interval between the Al₂O₃ layers is reduced to less than ≈2.6 nm (>3.4 at% Al). By correlating the electrical and structural properties, an extrinsic doping mechanism of ALD‐AZO films is proposed in which the incorporated Al atoms take oxygen from the ZnO matrix and form doubly charged donors, such as oxygen vacancies or zinc interstitials.     

ZnO Thin Film, Device, and Circuit Fabrication using Low-Temperature PECVD Processes

We report undoped ZnO films deposited at low temperature (200°C) using plasma-enhanced chemical vapor deposition (PECVD). ZnO thin-film transistors (TFTs) fabricated using ZnO and Al₂O₃ deposited in situ by PECVD with moderate gate leakage show a field-effect mobility of 10 cm²/V s, threshold voltage of 7.5 V, subthreshold slope <1 V/dec, and current on/off ratios >10⁴. Inverter circuits fabricated using these ZnO TFTs show peak gain magnitude (dV _out/dV _in) ~5. These devices appear to be strongly limited by interface states and reducing the gate leakage results in TFTs with lower mobility. For example, ZnO TFTs fabricated with low-leakage Al₂O₃ have mobility near 0.05 cm²/V s, and five-stage ring-oscillator integrated circuits fabricated using these TFTs have a 1.2 kHz oscillation frequency at 60 V, likely limited by interface states.