Property variations of direct-current reactive magnetron sputtered copper oxide thin films deposited at different oxygen partial pressures

Cuprous oxide (Cu₂O) and cupric oxide (CuO) thin films were deposited on glass substrates at different oxygen partial pressures by direct-current reactive magnetron sputtering of pure copper target in a mixture of argon and oxygen gases. Oxygen partial pressure was found to be a crucial parameter in controlling the phases and, thus, the physical properties of the deposited copper oxide thin films. Single-phase Cu₂O thin films with cubic structure were obtained at low oxygen partial pressure between 0.147 Pa and 0.200 Pa while higher oxygen partial pressure promoted the formation of CuO thin films with base-centered monoclinic structure. Polycrystalline Cu₂O thin films deposited with oxygen partial pressure at 0.147 Pa possessed the lowest p-type resistivity of 1.76 Ω cm as well as an optical band gap of 2.01 eV. On the other hand, polycrystalline CuO thin films deposited with oxygen partial pressure at 0.320 Pa were also single phase but showed a n-type resistivity of 0.19 Ω cm along with an optical band gap of 1.58 eV.     

Structural and optical studies on dc reactive magnetron sputtered Cu2O films

Cuprous oxide (Cu₂O) thin films were deposited by dc reactive magnetron sputtering technique onto glass substrates by sputtering of pure copper target in a mixture of argon and oxygen gases under various oxygen partial pressures in the range 8 × 10^− 3–1 × 10^− 1 Pa at a constant substrate temperature of 473 K and a sputtering pressure of 4 Pa. The dependence of cathode potential on the oxygen partial pressure was explained in terms of cathode poisoning effect. The influence of oxygen partial pressure on the structural and optical properties of Cu₂O films was systematically studied. Single phase films of Cu₂O were obtained at an oxygen partial pressure of 2 × 10^− 2 Pa. The films formed at an oxygen partial pressure of 2 × 10^− 2 Pa were polycrystalline with cubic structure and exhibited an optical band gap of 2.04 eV.     

Preparation and characterization of sol-gel derived copper-strontium-oxide thin films

P-type transparent conductive oxides have potential applications in photovoltaics, transparent electronics, and organic optoelectronics. In this paper, results are presented on the synthesis of Cu₂SrO₂ thin films, a p-type transparent conducting oxide by a sol-gel route. Cu(II)methoxide and Sr-metal dissolved in anhydrous isopropanol were used as precursor for the sol preparation. For potassium (K) doping, K-acetate dissolved in anhydrous isopropanol was used as the precursor. Films were spin-coated onto substrates and partially pyrolysed in air at 225°C. After partial pyrolization, a two stage annealing sequence was used to achieve the final film microstructure and composition. Although combinations of oxygen pressure, annealing time, and annealing temperature were used to obtain phase pure Cu₂SrO₂ thin films, X-ray diffraction consistently showed the presence of Cu₂O as a second phase with Cu₂SrO₂−the desired phase. Microstructural studies showed similar phase separation in the films and confirmed the microcrystalline nature. The best conductivities obtained for the undoped and 1% K-doped films were 2 × 10^− 3 and 1.2 × 10^− 2 S/cm, respectively. Both films showed a broad optical absorption edge in the visible range.     

Growth and characterisation of CaCu2Ox thin films by pulsed injection MOCVD

Oxides with the structure MCu₂O₂ (M = Ca, Ba, Mg and Sr) are promising materials for the development of new p-type transparent conducting oxide thin films. This paper reports preliminary results on the growth and characterisation of CaCu₂O_x thin films by pulsed injection MOCVD. By using as precursors calcium and copper tetramethylheptanedionate dissolved in meta-xylene, mixed calcium-copper films have been grown in the temperature range from 450 °C to 550 °C. At these temperatures, deposited films exhibited a high mirror reflection effect, good adherence and were reasonably uniform with the cationic composition of the films being easily controlled by adjusting the copper-calcium ratio in the precursor solution. In CaCu₂O₂, copper is in the Cu¹⁺ oxidation state and depending on the oxygen partial pressure used, the films either contained CaCu₂O₃ or a mixture of CaO, CuO and Cu₂O. Optimisation of annealing conditions increased the presence of Cu¹⁺ in the film. Films had a maximum transmittance of 50% in the visible range and were highly resistive. Appropriate annealing conditions reduced the resistivity of the films.     

Low temperature (< 100 °C) deposited P-type cuprous oxide thin films: Importance of controlled oxygen and deposition energy

With the emergence of transparent electronics, there has been considerable advancement in n-type transparent semiconducting oxide (TSO) materials, such as ZnO, InGaZnO, and InSnO. Comparatively, the availability of p-type TSO materials is more scarce and the available materials are less mature. The development of p-type semiconductors is one of the key technologies needed to push transparent electronics and systems to the next frontier, particularly for implementing p-n junctions for solar cells and p-type transistors for complementary logic/circuits applications. Cuprous oxide (Cu₂O) is one of the most promising candidates for p-type TSO materials. This paper reports the deposition of Cu₂O thin films without substrate heating using a high deposition rate reactive sputtering technique, called high target utilisation sputtering (HiTUS). This technique allows independent control of the remote plasma density and the ion energy, thus providing finer control of the film properties and microstructure as well as reducing film stress. The effect of deposition parameters, including oxygen flow rate, plasma power and target power, on the properties of Cu₂O films are reported. It is known from previously published work that the formation of pure Cu₂O film is often difficult, due to the more ready formation or co-formation of cupric oxide (CuO). From our investigation, we established two key concurrent criteria needed for attaining Cu₂O thin films (as opposed to CuO or mixed phase CuO/Cu₂O films). First, the oxygen flow rate must be kept low to avoid over-oxidation of Cu₂O to CuO and to ensure a non-oxidised/non-poisoned metallic copper target in the reactive sputtering environment. Secondly, the energy of the sputtered copper species must be kept low as higher reaction energy tends to favour the formation of CuO. The unique design of the HiTUS system enables the provision of a high density of low energy sputtered copper radicals/ions, and when combined with a controlled amount of oxygen, can produce good quality p-type transparent Cu₂O films with electrical resistivity ranging from 10² to 10⁴ Ω-cm, hole mobility of 1-10 cm²/V-s, and optical band-gap of 2.0-2.6 eV. These material properties make this low temperature deposited HiTUS Cu₂O film suitable for fabrication of p-type metal oxide thin film transistors. Furthermore, the capability to deposit Cu₂O films with low film stress at low temperatures on plastic substrates renders this approach favourable for fabrication of flexible p-n junction solar cells.     

The effect of deposition parameters on the properties of SrCu2O2 films fabricated by pulsed laser deposition

SrCu₂O₂ (SCO) thin films have been fabricated by pulsed laser deposition at oxygen partial pressures between 5 × 10^− 5-5 × 10^− 2 mbar and substrate temperatures from 300 °C to 500 °C. All films were single-phase SrCu₂O₂, p-type materials. Films deposited at a substrate temperature of 300 °C and oxygen pressure 5 × 10^− 4 mbar exhibited the highest transparency (∼ 80%), having conductivity 10^− 3 S/cm and carrier concentration around 10¹³ cm^− 3. Films deposited at oxygen partial pressure higher than 10^− 3 mbar exhibited higher conductivity and carrier concentration but lower transmittance. Depositions at substrate temperatures higher than 300 °C gave films of high crystallinity and transmittance even for films as thick as 800 nm. The energy gap of SrCu₂O₂ thin films was found to be around 3.3 eV.     

Structural, optical and electrical properties of reactively sputtered Ag2Cu2O3 films

Ag₂Cu₂O₃ thin films were deposited on glass substrates by RF magnetron sputtering of an equiatomic silver-copper target (Ag_0.5Cu_0.5) in reactive Ar-O₂ mixtures. The reactive sputtering was done at varying power, oxygen flow rate and deposition temperature to study the influence of these parameters on the deposition of Ag₂Cu₂O₃ films. The film structure was determined by X-ray diffraction, while the optical properties were examined by spectrophotometry (UV-vis-NIR) and photoluminescence. Furthermore, the film thickness and resistivity were measured by tactile profilometry and 4-point probe, respectively. Additional mobility, resistivity and charge carrier density Hall effect measurements were done on a few selected samples. The best films in terms of stoichiometry and crystallography were achieved with a sputtering power of 100 W, oxygen and argon flow rates of 20 sccm (giving a deposition pressure of 1.21 Pa) and a deposition temperature of 250 °C. The optical transmittance and photoluminescence spectra of films deposited with these parameters indicate several band gaps, most prominently, a direct one of around 2.2 eV. Electrical characterization reveals charge carrier concentrations and mobilities in the range of 10²¹-10²² cm^− 3 and 0.01-0.1 cm²/Vs, respectively.     

Effect of high temperature post-annealing of La0.7Sr0.3MnO3 films deposited by radio frequency magnetron sputtering on SiO2/Si substrates heated at low temperature

La_0.7Sr_0.3MnO₃ thin films were deposited on SiO₂/Si substrates by RF magnetron sputtering under different oxygen gas flow rates with a sputtering power of 100 W. During deposition, the substrate was heated at 623 K. To investigate post-annealing effects, the as-deposited La_0.7Sr_0.3MnO₃ thin films were thermal-treated at 973 K for 1 h. The effects of oxygen gas flow rate and post-annealing treatment on the physical properties of the films were systematically studied. X-ray diffraction results show that the growth orientation and crystallinity of the films were greatly affected by the oxygen gas flow rate and substrate heating during deposition. The sheet resistance of the films gradually decreased with increasing oxygen gas flow rate, while the post-annealed films showed the opposite behavior. The temperature coefficient of resistance at 300 K of La_0.7Sr_0.3MnO₃ thin films deposited at an oxygen gas flow rate of 40 sccm decreased from − 2.40%/K to − 1.73%/K after post annealing. The crystalline state of the La_0.7Sr_0.3MnO₃ thin films also affected its electrical properties.     

Electrical and optical properties of ITO:Ca composite thin films for TEOLED cathode

ITO:Ca composite thin films were deposited on glass substrate by the rf magnetron co-sputtering method with various numbers of Ca chips and oxygen partial pressures. The carrier concentration of the ITO:Ca thin film was 7 × 10²⁰ cm^− 3 when the number of Ca chips was 4 at an oxygen partial pressure of 1.4%. The sheet resistance and optical transmittance of the ITO:Ca thin films were 68.2 Ω/sq. and 87%, respectively. The work function of the ITO:Ca thin films with 8 Ca chips was changed from 4.6 eV to 5.0 eV when the oxygen partial pressure was increased from 0.8% to 2.2%. When the oxygen partial pressure was 1.2%, a low work function of 4.6 eV was obtained for the ITO:Ca thin films.     

Copper doped nickel oxide transparent p-type conductive thin films deposited by pulsed plasma deposition

Transparent p-type conductive Ni_0.9Cu_0.1O thin films were prepared by pulsed plasma deposition (PPD) method. The effects of substrate temperature and oxygen pressure on the structural, electrical and optical properties of the films were investigated respectively. The film deposited at room temperature exhibits the highest conductivity of 5.17 S cm⁻¹, with an average transmittance of 60% in the visible region. A transparent p-Ni_0.9Cu_0.1O/n-In₂O₃:W (IWO) hetero-junction diode was fabricated exhibiting rectifying current-voltage characteristics.     

Low resistivity transparent conducting CdO thin films deposited by DC reactive magnetron sputtering at room temperature

Transparent conducting cadmium oxide (CdO) films were deposited on PET (polyethylene terephthalate) substrate by DC reactive magnetron sputtering at room temperature. All the films deposited at room temperature were polycrystalline in rock-salt structure. Dependences of the physical properties of the CdO films on the oxygen partial pressure were systematically studied. The films deposited at low oxygen flow rate were (200) oriented, while the films deposited at an oxygen flow rate greater than 20 sccm were (111) oriented. The average grain size of the CdO films decreased as the oxygen flow rate increases as determined by XRD and SEM. The Hall effect measurement showed that CdO films have high concentration, low resistivity, and high mobility. Both the mobility and the concentration of the carrier decreased with the increase of the oxygen flow rate. A minimum sheet resistance of 36.1 Ω/□, or a lowest resistivity of 5.44 × 10^− 4 Ω cm (6.21 × 10²⁰/cm³, μ = 19.2 cm²/Vs) was obtained for films deposited at an oxygen flow rate of 10 sccm.     

Influence of the growth conditions on the stoichiometry and on the optical properties of titanium oxide thin films prepared by reactive sputtering

Titanium oxide thin films are deposited at room temperature by reactive DC sputtering onto glass and Si (100) substrates. Different conditions of deposition were varied such as sputtering power, deposition time and oxygen partial pressure to study their influence on the titanium oxide thin films growth. The absolute amount of oxygen and the relative O/Ti composition of films have been determined by Nuclear Reaction Analysis and Rutherford Backscattering Spectroscopy, respectively. Additionally, the band-gap was determined by measuring the optical absorption and its behavior correlated with the oxygen film content. From the present study, it is possible to establish that the optical band-gap energy depends mainly on the sputtering oxygen partial pressure used at the preparation and that films prepared with a partial oxygen pressure of 4 × 10^− 2 Pa allows titanium oxide with near stoichiometric composition. Additionally, from the optical point of view, band-gap energies of 3.4 eV are obtained for near stoichiometric films and a decrease is observed for samples prepared with higher oxygen concentrations.     

Analysis of precursors for crystal growth of YBaCuO thin films in magnetron sputtering deposition

We correlated the crystallinity of YBaCuO films prepared by magnetron sputtering deposition using Ar/O₂ mixture gas with the atomic and molecular composition in the gas phase. YBaCuO films were deposited on MgO substrates at 670 °C. Two-dimensional distributions of Y, Ba, Cu, YO, BaO, and CuO densities and one-dimensional distribution of O density were measured by laser-induced fluorescence spectroscopy. The Y and Ba densities decreased significantly with the increase of the O₂ partial pressure, and they were below the detection limit at an O₂ flow ratio of 10% and a total gas pressure of 53 Pa. The decrease in the Y and Ba densities was compensated by an increase in the YO and BaO densities. The decrease in the Cu density with the increase of the O₂ partial pressure was less significant, while the CuO density was below the detection limit at all the discharge conditions. The O density was evaluated to be 10¹²-10¹³ cm^− 3, which was much higher than the Cu density. On the other hand, YBaCuO films with high crystallinity were obtained at total gas pressures of 53-80 Pa and O₂ flow ratios of 50-70%. Therefore, it is concluded that the precursors for the deposition of YBaCuO films with high crystallinity are Cu, YO, BaO, and O.     

Overview about the optical properties and mechanical stress of different dielectric thin films produced by reactive-low-voltage-ion-plating

Thin films of Ta₂O₅, Nb₂O₅, and HfO₂ were deposited by reactive-low-voltage-ion-plating (RLVIP) on unheated glass and silicon substrates. The film thickness was about 200 nm. Optical properties as well as mechanical film stress of these layers were investigated in dependence of various deposition parameters, i.e. arc current and oxygen partial pressure. For an arc current in the range between 40 and 50 A and an oxygen partial pressure of at least 11 · 10^− 4 mbar good results were obtained. The refractive index and film thickness were calculated from spectrophotometric transmission data using the Swanepoel theory. For example at 550 nm wavelength the refractive index for thin RLVIP-Nb₂O₅-films was found to be n₅₅₀ = 2.40. The optical absorption was obtained by photo-thermal deflection spectrometry. For the investigated materials absorption coefficients in the range of k = 5 · 10^− 4 at 515 nm wavelength were measured. The mechanical film stress was determined by measuring the difference in bending of silicon substrates before and after the deposition process. For dense films, i.e. no water vapour sorption on atmosphere, the mechanical film stress was always compressive with values of some hundred MPa. In case of films deposited with higher arc currents (I_arc > 60A) and lower oxygen pressure (< 15 · 10^− 4 mbar) the influence of a post deposition heat treatment at 350 °C for 4 h on air was also investigated. For these films the properties could clearly be improved by such treatment. However, by using lower arc currents and higher oxygen partial pressure during the ion plating process, immediately dense and environmental stable films with good optical as well as mechanical properties could be achieved without post deposition heat treatment. All the results obtained will be presented in graphs and diagrams.     

Thin films preparation by rf-sputtering of copper/iron ceramic targets with Cu/Fe = 1: From nanocomposites to delafossite compounds

In the Cu-Fe-O phase diagram, delafossite CuFeO₂ is obtained for the Cu^I oxidation state and for the Cu/Fe = 1 ratio. By decreasing the oxygen content, copper/spinel oxide composite can be obtained because of the reduction and the disproponation of cuprous ions. Many physical properties as for instance, electrical, optical, catalytic properties can then be affected by the control of the oxygen stoichiometry.In rf-sputtering technique, the bombardment energies on the substrate can be controlled by the deposition conditions leading to different oxygen stoichiometry in the growing layers.By this technique, thin films have been prepared from two ceramic targets: CuFeO₂ and CuO + CuFe₂O₄. We thus synthesized either Cu⁰/Cu_xFe_1−xO₄ nanocomposites thin films with various Cu⁰ quantities or CuFeO₂-based thin films.Two-probes conductivity measurements were permitted to comparatively evaluate the Cu⁰ content, while optical microscopy evidenced a self-assembly phenomenon during thermal annealing.     

Chemical vapor deposition of phase-rich WC thin films on silicon and carbon substrates

Chemical vapor deposition was used to deposit tungsten carbide from a mixture of WCl₆, H₂ and C₃H₈ at 750-1050 °C on silicon and carbon substrates. The phase composition of the films was correlated with substrate temperature, substrate position in the reactor, and total flow rates. X-ray diffraction and X-ray photoelectron spectroscopy were employed to investigate the surface and bulk properties of the thin films. Thick, adherent films of phase-rich hexagonal WC were deposited using 1.3 × 10³ Pa total pressure, 1050 °C substrate temperature, and reactant flow rates of H₂/C₃H₈/Ar/WCl₆ = 1.8 × 10^− 2/3.6 × 10^− 3/8.9 × 10^− 4/1.8 × 10^− 4 mol/min, where Ar is the carrier gas. The surface composition was oxygen and carbon rich as compared with the bulk.     

Growth and characterization of tin oxide thin films and fabrication of transparent p-SnO/n-ZnO p–n hetero junction

p-Type and n-type tin oxide thin films were deposited by rf-magnetron sputtering of metal tin target by varying the oxygen pressure. Chemical composition of SnO thin film according to the intensity of the XPS peak is about 48.85% and 51.15% for tin and oxygen respectively. Nearest neighbor distance of the atoms calculated from SAED patterns is 2.9 Åand 2.7 Åfor SnO and SnO₂ respectively. The Raman scattering spectrum obtained from SnO thin films showed two peaks, one at 113 cm⁻¹ and the other at 211 cm⁻¹. Band gap of as-deposited SnO_x thin films vary from 1.6 eV to 3.2 eV on varying the oxygen partial pressure from 3% to 30% which indicates the oxidization of metallic phase Sn to SnO and SnO₂. p-Type conductivity of SnO thin films and n-type conductivity of SnO₂ thin films were confirmed through Hall coefficient measurement. Transparent p–n hetero junction fabricated in the structure glass/ITO/n-ZnO/p-SnO shows rectification with forward to reverse current ratio as 12 at 4.5 V.     

Characterization of copper oxide nanolayers deposited by direct current magnetron sputtering

Direct current reactive magnetron sputtering was used to deposit the thin layers of copper oxide (Cu₂O) on glass substrates. A solid disc of pure copper as the target was sputtered in an argon gas under sputtering pressures varying from 0.133 to 4 Pa. The effects of the sputtering power and pressure on the structural and optical properties of Cu₂O thin films were systematically studied. The deposited layers were characterized using X-ray diffraction, atomic force microscopy, profilometry and spectrophotometry. The optical transmission of the films was measured in the visible region. The increase in pressure resulted in a higher growth rate than increasing sputtering power. The increase in power produced Cu₂O thin films that were detrimental to the optical transmission of the films.     

Effects of periodicity and oxygen partial pressure on the crystallinity and dielectric property of artificial SrTiO3/BaTiO3 superlattices integrated on Si substrates by pulsed laser deposition method

Epitaxial SrTiO₃(STO)/BaTiO₃(BTO) artificial superlattices have been grown on TiN buffered Si (001) substrates by pulsed laser deposition method and the effects of stacking periodicity and processing oxygen partial pressure on their crystallinity and dielectric properties were studied. The crystal orientation, epitaxy nature, and microstructure of STO/BTO superlattices were investigated using X-ray diffraction and transmission electron microscopy. The TiN buffer layer and superlattice thin films were grown with cube-on-cube epitaxial orientation relationship of [110](001)_films∣∣[110](001)_TiN∣∣[110](001)_Si. The c-axis lattice parameter of the STO/BTO superlattice decreased from 0.412 nm to 0.406 nm with increasing oxygen partial pressure and the dielectric constants, measured at the frequency of 100 kHz at room temperature, of the superlattices with 2 nm/2 nm periodicity increased from 312 at 1 × 10^− 5 Torr to 596 at 1 × 10^− 3 Torr. The dielectric constants of superlattices grown at oxygen partial pressure of 1 × 10^− 3 Torr increased from 264 to 678 with decreasing periodicity of the superlattices from 10 nm/10 nm to 1 nm/1 nm.     

Atmospheric pressure PECVD of SiO2 thin film at a low temperature using HMDS/O2/He/Ar

SiO₂-like thin films were deposited at a low temperature (< 50 °C) by a remote-type, atmospheric pressure plasma enhanced chemical vapor deposition (AP-PECVD) using a pin-to-plate-type, dielectric barrier discharge with gas mixtures containing hexamethyldisilazane (HMDS)/O₂/He/Ar. The film characteristics were investigated according to the HMDS and O₂ flow rates. To obtain a more SiO₂-like thin film, an adequate combination of HMDS and oxygen flow rates was required to remove the -(CH₃)_x bonding in the HMDS and to oxidize the Si in HMDS effectively. At the optimized flow rates, the surface roughness of the SiO₂-like thin film was also the lowest. By using HMDS (50 sccm) and O₂ (500 sccm) flow rates in the gas mixture of HMDS/O₂/He (2 slm)/Ar (600 sccm), SiO₂-like thin films with a low impurity (< 6.35% C) were obtained at a deposition rate of approximately 10.7 nm/min.