Influence of substrate temperature on the electrical behaviour of zinc stannate thin films deposited by electron beam evaporation technique

Summary  A series of zinc stannate (Zn₂ SnO₄) thin films were prepared at four different substrate temperatures; namely, room-temperature (25°C), 50°C, 100°C and 200°C. Direct-current resistivity measurements were performed on these samples in the temperature range from room temperature (∼290 K) up to about 500 K. A phase transition (of positive temperature coefficient (PTC) of resistance) was observed in the thin film grown at room temperature at about 385 K. Other investigated samples showed a semiconducting behaviour of three distinct conduction mechanisms extending from intrinsic to thermal freeze-out conduction. The width of the band gapE _g was found to depend on the substrate temperature and was discussed in terms of a formation of a band tailing. Thermal freeze-out was dominant at the lower temperature region. On leave from Department of Physics, Faculty of Science, Alexandria University, Alexandria, Egypt.     

The characteristics of surface acoustic waves on AlN/LiNbO3 substrates

The characteristics of surface-acoustic-wave (SAW) devices on various substrates were measured by a network analyzer in the temperature range from 0 to 80 °C. Based on the structure of IDT/AlN/LiNbO₃, it was revealed that the magnitude of the temperature coefficient of frequency (TCF) of a SAW on a LiNbO₃ substrate was significantly decreased due to the thickness increase of AlN thin film deposited on the LiNbO₃ substrate. The TCF of a SAW on an AlN/LiNbO₃ device was measured to be about -51 ppm/°C at h/λ=0.1, where h is the thickness of the AlN film and λ is the wavelength of the SAW. This indicates that the deposition of an AlN film on a LiNbO₃ substrate could improve the temperature stability, as compared with that of a SAW on a LiNbO₃ substrate (-73 ppm/°C). The SAW device on the ST-X quartz is shown to have a positive TCF as the AlN thin film is deposited on the surface of the ST-X quartz. In addition, the phase velocity (V_p) of the SAW on an AlN/LiNbO₃ substrate was significantly increased by the increase of AlN thickness (h/λ). Received: 14 October 2002 / Accepted: 15 October 2002 / Published online: 29 January 2003 RID="*" ID="*"Corresponding author. Fax: +886-7/525-4199, E-mail: ycc@ee.nsysu.edu.tw     

Development of conductive transparent indium tin oxide (ITO) thin films deposited by direct current (DC) magnetron sputtering for photon-STM applications

Highly conductive and transparent indium tin oxide (ITO) thin films, each with a thickness of 100 nm, were deposited on glass and Si(100) by direct current (DC) magnetron sputtering under an argon (Ar) atmosphere using an ITO target composed of 95% indium oxide and 5% tin oxide for photon-STM use. X-ray diffraction, STM observations, resistivity and transmission measurements were carried out to study the formation of the films at substrate temperatures between 40 and 400 °C and the effects of thermal annealing in air between 200 and 400 °C for between1 and 5 h. The film properties were highly dependent on deposition conditions and on post-deposition film treatment. The films deposited under an Ar atmosphere pressure of ∼1.7×10^-3 Torr by DC power sputtering (100 W) at substrate temperatures between 40 and 400 °C exhibited resistivities in the range 3.0–5.7×10^-5 Ω m and transmissions in the range 71–79%. After deposition and annealing in air at 300 °C for 1 h, the films showed resistivities in the range 2.9–4.0×10^-5 Ω m and transmissions in the range 78–81%. Resistivity and transmission measurements showed that in order to improve conductive and transparent properties, 2 h annealing in air at 300 °C was necessary. X-ray diffraction data supported the experimental measurements of resistivity and transmission on the studies of annealing time. The surface roughness and film uniformity improve with increasing substrate temperature. STM observations found the ITO films deposited at a substrate temperature of 325 °C, and up to 400 °C, had domains with crystalline structures. After deposition and annealing in air at 300 °C for 1 h the films still exhibited similar domains. However, after deposition at substrate temperatures from 40 °C to 300 °C, and annealing in air at 300 °C for 1 h, the films were shown to be amorphous. More importantly, the STM studies found that the ITO film surfaces were most likely to break after deposition at a substrate temperature of 325 °C and annealing in air at 300 °C for 2 or 3 h. Such findings give some inspiration to us in interpreting the effects of annealing on the improvement of conductive and transparent properties and on the transition of phases. In addition, correlations between the conductive/transparent properties and the phase transition, the annealing time and the phase transition, and the conductive/transparent properties and the annealing time have been investigated. Received: 10 July 2000 / Accepted: 27 October 2000 / Published online: 9 February 2001     

Highly frequency-, temperature-, and bias-stable dielectric properties of 500 °C processed Bi2SiO5 thin films with low dielectric loss

Excellent dielectric frequency, bias, and temperature stability of bismuth silicate (Bi₂SiO₅, BSO) thin films with a low dielectric loss has been obtained in this study. The thin films were prepared on Pt/Ti/SiO₂/Si substrates by a chemical solution deposition method at a relatively low annealing temperature of 500 °C. The BSO films have a preferred growth along (200) orientation with dense fine-grained surface morphology. The dielectric constant and dielectric loss of the thin film annealed at 500 °C are 57 and 0.01, respectively, at 100 kHz, with little change between 1 kHz and 100 kHz and in the bias electric field range between −250 kV/cm and 250 kV/cm, indicating that the thin film exhibits a low dielectric loss as well as excellent frequency and bias field stability. The dielectric-temperature measurements confirmed that the BSO thin film annealed at 500 °C also has good temperature stability between 150 K and 450 K. Our results suggest that the BSO thin films have potential applications in the next-generation integrated capacitors.     

Thickness dependent anomalous magnetic behavior in pulsed-laser deposited cobalt ferrite thin film

Cobalt ferrite thin films of different thicknesses were pulsed-laser deposited onto a fused quartz substrate held at ambient temperature (RT) by varying deposition time. The samples were ex-situ annealed at 750°C in air for 2 hours. All the films were characterized by X-ray diffraction, Raman spectroscopy and energy dispersive X-ray analysis. The spontaneous magnetization, 4πM _S , was found to be 6130 G for the 50 nm thick sample, and this is higher than that for the bulk cobalt ferrite of 5300 G, by 16%. The 4πM _S was found to decrease with the increase in film thickness and an overall decrease of 32% was observed, when the film thickness increased from 50 nm to 600 nm. In contrast the films of the same thicknesses, when deposited at substrate temperature of 750°C showed an increase of 4πM _S with the increase in film thickness. The thickness dependence of 4πM _S in these nanocrystalline thin films has been explained in terms of the cation distribution and the grain size, which are sensitive to the substrate temperature during deposition.     

Preparation of cadmium stannate films by spray pyrolysis technique

Cadmium stannate thin films were prepared by spray pyrolysis technique using cadmium acetate and tin(II) chloride precursors at substrate temperatures 450 °C and 500 °C. XRD pattern confirms the formation of orthorhombic (1 1 1) cadmium stannate phase for the film prepared at substrate temperature of 500 °C, whereas, films prepared at 450 °C are amorphous. Film formation does not occur at substrate temperature from 300 to 375 °C. SEM images reveal that the surface of the prepared Cd₂SnO₄ film is smooth. The average optical transmittance of ∼86% is obtained for the film prepared at substrate temperature of 500 °C with the film thickness of 400 nm. The optical band gap value of the films varies from 2.7 to 2.94 eV. The film prepared at 500 °C shows a minimum resistivity of 35.6 × 10⁻⁴ Ω cm.     

Deposition of aluminum nitride thin film on Si(1 1 1) by KrF excimer laser and its characterizations

We present the deposition of aluminum nitride (AlN) thin film by KrF excimer laser sputtering and the study of the effects of substrate temperature and laser fluences. Deposition rate of AlN thin film at 0.3 Å/pulse has been achieved with laser fluence of 1500 mJ/cm² and at substrate temperature of 250 K, and this shows the enhancement of the deposition rate at low substrate temperature. Surface morphology of the deposited films is characterized by atomic force microscopy (AFM). In addition, the electrical performance of the MIS devices with AlN thin films prepared in this experiment has been characterized.     

Effect of substrate temperature on the magnetic properties and internal stresses of CoPt/AlN multilayer deposited by dc magnetron sputtering

Magnetic properties and internal stresses of AlN(20 nm)/[CoPt(2 nm)/AlN(20 nm)]₅ multilayer structure deposited at different substrate temperatures by dc magnetron sputtering have been studied. It is found that with increasing the substrate temperature from room temperature to 400 °C, in-plane magnetic anisotropy field of the film becomes smaller, and the out-of-plane magnetization becomes stronger. Especially when the film is deposited at substrate temperature of 400 °C, the out-of-plane magnetization becomes as strong as the in-plane magnetization. On the other hand, the total in-plane residual stress of the film changes gradually from compressive to tensile. The compressive intrinsic stress is generated during deposition process and decreases with increasing the substrate temperature. After annealing at high temperatures, the films show strong perpendicular magnetic anisotropy. With increasing the annealing temperature, the in-plane thermal stress also increases and becomes dominant, which is considered to result in the perpendicular magnetic anisotropy of the films.     

Thermal and optical properties of Cd2SnO4 thin films using photoacoustic spectroscopy

Cadmium stannate (Cd₂SnO₄) thin films were prepared by the RF magnetron sputtering technique on glass substrates with substrate temperatures of room temperature (RT), 100°C, 200°C and 300°C. Photoacoustic analyses were made to obtain the thermal diffusivity and the optical bandgap values of the Cd₂SnO₄ thin films. The change in thermal diffusivity of the films with the substrate temperature was analyzed. The optical bandgap values obtained from the photoacoustic spectroscopy were compared with the values obtained from the optical transmittance spectra. X-ray photoelectron spectroscopic (XPS) studies confirm the formation of stoichiometric films. Surface morphological studies by atomic force microscopy (AFM) revealed the crystalline nature of the films deposited at 100°C.     

Curie temperatures of CoPt ultrathin continuous films

The effects of layer thickness and thermal annealing on Curie temperature have been studied for CoPt ultrathin continuous layers in AlN/CoPt multilayer structures. It is found that there exists a critical thickness below which Curie temperature rapidly decreases due to the loss of spin-spin interactions in the vicinity of interface. After high temperature annealing, the in-plane lattice constant of CoPt film is increased and the exchange coupling parameter is decreased. Consequently, Curie temperatures decrease for some films with large thickness, compared with as-deposited state. Upon annealing at 600?^°C, CoPt undergoes ordering transformation, which also contributes to the degradation of the Curie temperature. However, when the CoPt film thickness is below 2?nm, the Curie temperature is increased after annealing. Especially for 1?nm thick film, the Curie temperature is strikingly increased from 173?^°C to 343?^°C after annealing at 600?^°C. This effect is attributed to the out-of-plane lattice deformation of CoPt thin layers in AlN/CoPt multilayer structures.     

Properties of Eu-doped zinc oxide thin films grown on glass substrates by radio-frequency magnetron sputtering

Eu-doped ZnO (EZO) thin films were prepared on glass substrates at various growth temperatures by radio-frequency magnetron sputtering. The properties of deposited thin films showed a significant dependence on the growth temperature. The preferential growth orientation of all the thin films was occurred along the ZnO (002) plane. The maximum crystallite size and the minimum average transmittance in the wavelength range of 450–1100 nm were observed for the EZO thin film deposited at 25 °C. A red shift of the optical band gap was observed in the growth temperature range of 25–300 °C. The highest figure of merit, an index for evaluating the performance of transparent conducting thin films, was obtained at 200 °C of growth temperature. These results indicated that the high-quality EZO film was obtained at a growth temperature of 200 °C.     

The effects of substrate temperatures on the electrical properties of CaZrO3 thin films prepared by RF magnetron sputtering

The radio frequency magnetron sputtering technology (RFMS) was employed to deposit perovskite structure orthogonal phase CaZrO₃ thin films on Pt/Ti/SiO₂/Si substrates. The effects of substrate temperatures on structure and electrical properties of these films were investigated in detail. The CaZrO₃ thin films were systematically characterized by means of X-ray diffraction (XRD), Scanning electron microscope (SEM), Multi-frequency LCR meter (HP4294A) and Radiant Precision Workstation to study the phase structure, cross-section morphology, dielectric and ferroelectric properties at different substrate temperatures. The result indicates that these films can withstand 80 V DC Bias voltage and have excellent stability of frequency, voltage and temperature. The CaZrO₃ thin film prepared at 550 °C turned out to be mainly orthorhombic CaZrO₃ phase with high permittivity, low dielectric loss, extremely low leakage current (at 1 MHz, the dielectric constant is 39.42, the dielectric loss is 0.00455, the quality factor is 220 and the leakage current density is 9.11 × 10⁻⁷A/cm² at 80 V applied voltage.). This work demonstrates that higher substrate temperature can boost the formation of orthorhombic CaZrO₃ phase and the CaZrO₃ thin film prepared by RF magnetron sputtering is a very promising paraelectric material in the application of thin film capacitor.     

A facile two-step preparation of compact and crystalline Sb2S3 thin film for efficient solar cells

The two-step preparation of compact and crystalline Sb₂S₃ thin films was firstly reported using the pyrolysis of the Sb-butyldithiocarbamate complex solution in DMF. The porous and amorphous Sb₂S₃ thin films were successfully prepared at 170 °C for 30 min, and then can be converted to compact and crystalline Sb₂S₃ thin films at 200 °C for 30 min or 300 °C for 2 min. The corresponding solar cells with the architecture of FTO/TiO₂ compact layer/Sb₂S₃/spiro-OMeTAD/Au achieved the photoelectric conversion efficiency of 4.16% at 200 °C and 5.05% at 300 °C. The two-step preparation of the compact and crystalline Sb₂S₃ thin films can provide the feasible approach for the fabrication of various microstructure thin film solar cells and the low preparation temperature of 200 °C was also attractive to assemble the flexible Sb₂S₃ thin film solar cells.     

Structural, optical and electrical properties of tin oxide thin film deposited by APCVD method

Tin oxide (SnO₂) thin films have been grown on glass substrates using atmospheric pressure chemical vapour deposition (APCVD) method. During the deposition, the substrate temperature was kept at 400°C–500°C. The structural properties, surface morphology and chemical composition of the deposited film were studied by X-ray diffraction (XRD), scanning electron microscope (SEM) and Rutherford back scattering (RBS) spectrum. XRD pattern showed that the preferred orientation was (110) having tetragonal structure. The optical properties of the films were studied by measuring the transmittance, absorbance and reflectance spectra between λ = 254 nm to 1400 nm and the optical constants were calculated. Typical SnO₂ film transmits ∼ 94% of visible light. The electrical properties of the films were studied using four-probe method and Hall-voltage measurement experiment. The films showed room temperature conductivity in the range 1.08 × 10² to 1.69 × 10² Ω⁻¹cm⁻¹.     

Solid state photoelectrochemical cells utilising graphite thin films counter electrode

This paper reports the use of graphite thin films as a counter electrode of a solid state photoelectrochemical cells of ITO/TiO₂/PVC-LiClO₄/graphite. The photoelectrochemical cells material was a screen-printed layer of titanium dioxide onto an ITO-covered glass substrate which was used as a working electrode of the device. The solid electrolyte used was PVC-LiClO₄ that was prepared by solution casting technique. The graphite films which serve as a counter electrode were prepared onto glass substrate by electron beam evaporation technique at substrate temperatures variation of 25, 50, 100, 150 and 200 °C. The dependence of sheet resistance and surface morphology of the graphite films on substrate temperature were studied. The films deposited at 25 °C shows the smoothest surface morphology and the smallest grain size. Bigger grain size, rougher surface morphology of graphite film counter electrode. The current-voltage characteristics of four devices utilising the graphite counter electrode with different substrate temperature in dark as well as under illumination of 100 mWcm⁻² light from a tungsten halogen lamp were recorded at room temperature and at 50 °C, respectively. It was found that the photovoltaic parameters of the device such as short-circuit current density, J_sc and open-circuit voltage, V_oc increases with the decreasing average grain size of the graphite counter electrode. The device whose graphite film counter electrode was deposited onto the glass substrate at 25 °C gave the highest J_sc of 0.32 μA/cm² and V_oc of 117 mV, respectively.     

Aluminum-assisted crystallization and <Emphasis Type="Italic">p</Emphasis>-type doping of polycrystalline Si

Aluminum-doped p-type polycrystalline silicon thin films have been synthesized on glass substrates using an aluminum target in a reactive SiH₄+Ar+H₂ gas mixture at a low substrate temperature of 300 °C through inductively coupled plasma-assisted RF magnetron sputtering. In this process, it is possible to simultaneously co-deposit Si–Al in one layer for crystallization of amorphous silicon, in contrast to the conventional techniques where alternating metal and amorphous Si layers are deposited. The effect of aluminum target power on the structural and electrical properties of polycrystalline Si films is analyzed by X-ray diffraction, Raman spectroscopy, scanning electron microscopy and Hall-effect analysis. It is shown that at an aluminum target power of 100 W, the polycrystalline Si film features a high crystalline fraction of 91%, a vertically aligned columnar structure, a sheet resistance of 20.2 kΩ/□ and a hole concentration of 6.3×10¹⁸ cm⁻³. The underlying mechanism for achieving the semiconductor-quality polycrystalline silicon thin films at a low substrate temperature of 300 °C is proposed.     

等离子增强原子层沉积低温生长AlN薄膜

采用等离子增强原子层沉积技术在单晶硅基体上成功制备了AlN晶态薄膜, 利用椭圆偏振仪、原子力显微镜、小角掠射X射线衍射仪、高分辨透射电子显微镜、 X射线光电子能谱仪对样品的生长速率、表面形貌、晶体结构、薄膜成分进行了表征和分析, 结果表明, 采用等离子增强原子层沉积制备AlN晶态薄膜的最低温度为200 ℃, 薄膜表面平整光滑, 具有六方纤锌矿结构与(100)择优取向, Al_2p与N_1S的特征峰分别为74.1 eV与397.0 eV, 薄膜中Al元素与N元素以Al-N键相结合, 且成分均匀性良好. 关键词： 氮化铝 等离子增强原子层沉积 低温生长 晶态薄膜     

Preparation of Pb2CrO5 thin films by an electron-beam evaporation technique

Pb₂CrO₅ thin films have been prepared by an electron-beam evaporation deposition technique on glass substrates using ceramic disks. The thin film fabrication conditions are studied by x-ray diffraction, replica electron micrography and scanning electron microscopy as parameters of substrate temperature, annealing temperature and annealing time. As-deposited Pb₂CrO₅ thin films in the amorphous state are crystallized by heat treatment. Annealed thin films are structurally classified into three types according to the preferred orientations which depend on substrate temperatures (T _s:

1. (i)

   (020) atT _s=room temperature

2. (ii)

   mainly (310) atT _s=100 ‡C, and

3. (iii)

   (200) atT _s=350 ‡C.

The substrate temperature contributes to film orientations; annealing temperature and time-enhance film crystallinity. The annealing temperature is fixed between 400 and 500 ‡C in making appropriate Pb₂CrO₅ thin films. These thin films, ranging between 0.3 and 2.0 Μm in thickness, are prepared at a deposition rate of 1500 å/m.

     

The Effects of Thermal Treatments on Microstructure Phosphorus-Doped ZnO Layers Grown by Thermal Evaporation

The ZnO films doped with 3 wt% phosphorus (P) were produced by activating phosphorus doped ZnO (ZnO:P) thin films in oxygen (O₂) ambient at 600°C for 30, 60, 90 and 120 min, respectively. As-deposited films doped with phosphorus are highly conductive and n type. All the films showed p-type conduction after annealing, in an O₂ ambient atmosphere. The activation energies of the phosphorus dopant in the p-type ZnO under O₂ ambient gases indicate that phosphorus substitution on the O site yielded a deep level in the gap. With a further increase of the annealed durations, the crystalline quality of the ZnO:P sample is degraded. The best p-type ZnO:P film deposited at 600°C for 30 min shows a resistivity of 1.85 Ω cm and a relatively high hole concentration of 5.1 × 10¹⁷cm^–3 at room temperature. The films exhibit a polycrystalline hexagonal wurtzite structure without preferred orientation. The mean grain sizes are calculated to be about 60, 72, 78, 85 and 90 nm for the p-type ZnO films prepared at 600°C for 30, 60, 90 and 120 min, respectively. Room temperature photoluminescence (PL) spectra of the ZnO film exhibit two emission bands — paramount excitonic ultraviolet (UV) emission and weak deep level visible emission. The excellent emission from the film annealed at 600°C for 30 min is attributed to the good crystalline quality of the p-type ZnO film and the low rate of formation of intrinsic defects at such short duration. The visible emission consists of two components in the green range.     

Growth of thin, crystalline oxide, nitride, and oxynitride films on NiAl and CoGa surfaces

At 300 K, an amorphous Al-oxide film is formed on NiAl(001) upon oxygen adsorption. Annealing of the oxygen-saturated NiAl(001) surface to 1200 K leads to the formation of thin well-ordered θ-Al₂O₃ films. At 300 K, and low-exposure oxygen atoms are chemisorbed on CoGa(001) on defects and on step edges of the terraces. For higher exposure up to saturation, the adsorption of oxygen leads to the formation of an amorphous Ga-oxide film. The EEL spectrum of the amorphous film exhibits two losses at ≈400 and 690 cm^-1. After annealing the amorphous Ga-oxide films to 550 K thin, well-ordered β-Ga₂O₃ films are formed on top of the CoGa(001) surface. The EEL spectrum of the β-Ga₂O₃ films show strong Fuchs-Kliewer (FK) modes at 305, 455, 645, and 785 cm^-1. The β-Ga₂O₃ films are well ordered and show (2×1) LEED pattern with two domains, oriented perpendicular to each other. The STM study confirms the two domains structure and allows the determination of the two-dimensional lattice parameters of β-Ga₂O₃. The vibrational properties and the structure of β-Ga₂O₃ on CoGa(001) and θ-Al₂O₃ on NiAl(001) are very similar. Ammonia adsorption at 80 K on NiAl(111) and NiAl(001) and subsequent thermal decomposition at elevated temperatures leads to the formation of AlN. Well-ordered and homogeneous AlN thin films can be prepared by several cycles of ammonia adsorption and annealing to 1250 K. The films render a distinct LEED pattern with hexagonal [AlN/NiAl(111)] or pseudo-twelve-fold [AlN/NiAl(001)] symmetry. The lattice constant of the grown AlN film is determined to be a_AlN= 3.11 Å. EEL spectra of AlN films show a FK phonon at 865 cm^-1. The electronic gap is determined to be E_g= 6.1±0.2 eV. GaN films are prepared by using the same procedure on the (001) and (111) surfaces of CoGa. The films are characterized by a FK phonon at 695 cm^-1 and an electronic band gap E_g= 3.5±0.2 eV. NO adsorption at 75 K on NiAl(001) and subsequent annealing to 1200 K leads to the formation of aluminium oxynitride (AlON). An oxygen to nitrogen atomic ratio of ≈2:1 was estimated from the analysis of AES spectra. The AlON films shows a distinct (2×1) LEED pattern and the EEL spectrum exhibits characteristic Fuchs-Kliewer modes. The energy gap is determined to be E_g= 6.6±0.2 eV. The structure of the AlON film is derived from that of θ-Al₂O₃ formed on NiAl(001). Received: 21 March 1997/Accepted: 12 August 1997