Investigation of optical and electrical properties of ZnO thin films

Zinc oxide (ZnO) thin films were deposited on Si substrates using various working pressures by magnetron sputter. The resistivity of the deposited ZnO films decreases with working pressure, and the resistivity of 4.3 × 10⁻³ Ω cm can be obtained without post annealing. According to the optical transmittance measurements, the optical transmittance above 90% in the wavelength longer than 430 nm and about 80% in the wavelength of 380 nm can be found. Using time-resolved photoluminescence measurement, the carrier lifetime increases with working pressure due to the reduction of nonradiative recombination rate. The reduction of nonradiative recombination rate is originated from the decrease of oxygen vacancies in the ZnO films deposited at a higher working pressure. This result is verified by the photoluminescence measurements. Besides, by increasing the working pressure, the absorption coefficient was decreased and the associated optical energy gap of ZnO thin films was increased.     

退火条件对Sn掺杂ZnO薄膜光电性能的影响

采用溶胶-凝胶法在普通载玻片上制备Sn掺杂ZnO薄膜(SZO薄膜)。研究空气退火、低真空退火、高真空退火、氮气退火、三高退火、循环退火6种不同退火条件对SZO薄膜光电性能的影响。结果表明:6种不同的退火条件制备的SZO薄膜均为纤锌矿结构且具有c轴择优取向生长的特性。高真空退火下,SZO薄膜的结晶状况和电学性质最优,最低电阻率可达到5.4×10~(-2)Ω·cm。薄膜的可见光区平均透过率均大于85%。薄膜在390nm和440nm附近(325nm光激发下)都出现光致发光峰,在空气、氮气、低真空中退火后薄膜440nm处发光强度最为显著。     

The effect of rapid thermal annealing on structural and electrical properties of TiB2 thin films

This work reports on the effect of post-deposition rapid thermal annealing on the structural and electrical properties of deposited TiB₂ thin films. The TiB₂ thin films, thicknesses from 9 to 450 nm, were deposited by e-beam evaporation on high resistivity and thermally oxidized silicon wafers. The resistivity of as-deposited films varied from 1820 μΩ cm for the thinnest film to 267 μΩ cm for thicknesses greater than 100 nm. In the thickness range from 100 to 450 nm, the resistivity of TiB₂ films has a constant value of 267 μΩ cm.

A rapid thermal annealing (RTA) technique has been used to reduce the resistivity of deposited films. During vacuum annealing at 7 × 10⁻³ Pa, the film resistivity decreases from 267 μΩ cm at 200 °C to 16 μΩ cm at 1200 °C. Heating cycles during RTA were a sequence of 10 s. According to scanning tunneling microscopy analysis, the decrease in resistivity may be attributed to a grain growth through polycrystalline recrystallization, as well as to an increase in film density.

The grain size and mean surface roughness of annealed films increase with annealing temperature. At the same time, the conductivity of the annealed samples increases linearly with grain size. The obtained results show that RTA technique has a great potential for low resistivity TiB₂ formation.     

Tungsten-doped ZnO transparent conducting films deposited by direct current magnetron sputtering

Highly conducting and transparent thin films of tungsten-doped ZnO (ZnO:W) were prepared on glass substrates by direct current (DC) magnetron sputtering at low temperature. The effect of film thickness on the structural, electrical and optical properties of ZnO:W films was investigated. All the deposited films are polycrystalline with a hexagonal structure and have a preferred orientation along the c-axis perpendicular to the substrate. The electrical resistivity first decreases with film thickness, and then increases with further increase in film thickness. The lowest resistivity achieved was 6.97 × 10⁻⁴ Ω cm for a thickness of 332 nm with a Hall mobility of 6.7 cm² V⁻¹ s⁻¹ and a carrier concentration of 1.35 × 10²¹ cm⁻³. However, the average transmittance of the films does not change much with an increase in film thickness, and all the deposited films show a high transmittance of approximately 90% in the visible range.     

Annealing effect of ZnO/Au/ZnO transparent conductive films

Au intermediate ZnO (ZAZ) thin films were prepared by radio frequency and direct current magnetron sputtering on glass substrates and then vacuum annealed. The thickness of each layer of the ZAZ films was set at 50 nm, 3 nm, and 47 nm, respectively. The structural, electrical, and optical properties of ZAZ films were investigated with respect to the variation of annealing temperature.As-deposited AZO films showed X-ray diffraction peaks corresponding to ZnO (002) and Au (111) planes and those peak intensities increased with post-deposition vacuum annealing. The optical and electrical properties of the films were strongly influenced by post-deposition annealing. Although the optical transmittance of the films deteriorated with an Au interlayer, as-deposited ZAZ films showed a low resistivity of 2.0 × 10⁻⁴ Ω cm, and the films annealed at 300 °C had a lower resistivity of 9.8 × 10⁻⁵ Ω cm. The work function of the films increased with annealing temperature, and the films annealed at 300 °C had a higher work function of 4.1 eV than the films annealed at 150 °C. The experimental results indicate that vacuum-annealed ZAZ films are attractive candidates for use as transparent electrodes in large area electronic applications such as solar cells and large area displays.     

Preparation of aluminum doped zinc oxide films and the study of their microstructure, electrical and optical properties

Aluminum doped zinc oxide (AZO) polycrystalline thin films were prepared by sol-gel dip-coating process on optical glass substrates. Zinc acetate solutions of 0.5 M in isopropanol stabilized by diethanolamine and doped with a concentrated solution of aluminum nitrate in ethanol were used. The content of aluminum in the sol was varied from 1 to 3 at.%. Crystalline ZnO thin films were obtained following an annealing process at temperatures between 300 °C and 500 °C for 1 h. The coatings have been characterized by X-ray diffraction, UV-Visible spectrophotometry, scanning electron microscopy, and electrical resistance measurement. The ZnO:Al thin films are transparent (∼ 90%) in near ultraviolet and visible regions. With the annealing temperature increasing from 300 °C to 500 °C, the film was oriented more preferentially along the (0 0 2) direction, the grain size of the film increased, the transmittance also became higher and the electrical resistivity decreased. The X-ray diffraction analysis revealed single-phase ZnO hexagonal wurtzite structure. The best conductors were obtained for the AZO films containing 1 at.% of Al, annealed at 500 °C, 780 nm film thickness.     

Dependence of the electrical and optical properties of sputter-deposited ZnO:Ga films on the annealing temperature,time, and atmosphere

Effects of annealing process parameters such as annealing temperature, time, and atmosphere on the electrical resistivity and transmittance properties of Ga-doped ZnO (ZnO:Ga) thin films deposited on glass by rf magnetron sputtering were investigated. The electrical resistivity of a ZnO:Ga thin film is effectively decreased with increasing annealing temperature and time in a reducing atmosphere such as N₂ + 5%H₂. This is attributed to passivation of grain boundaries and zinc ions by hydrogen atoms resulting in increases in carrier concentration and mobility. Also the resistivity of 4.9 × 10⁻⁴Ω cm was obtained by annealing at 200°C for 15 h in the same atmosphere, which is not bad for a transparent conductor for solar cell applications. However, annealing at a temperature higher than 400°C is less effective. The lowest resistivity of 2.3 × 10⁻⁴Ω cm was obtained by annealing at 400°C for 1 h in an N₂ + 5%H₂ atmosphere. The optical transmittance of the ZnO:Ga film is improved by annealing regardless of the annealing atmosphere. Annealing in N₂ + 5%H₂ atmosphere widens the optical band gap, while annealing in an O₂ atmosphere makes the band gap narrower, which can be explained as a blue shift phenomenon.     

The properties of aluminum-doped zinc oxide thin films prepared by rf-magnetron sputtering from nanopowder targets

Aluminum-doped zinc oxide (ZnO:Al) films were deposited onto glass substrates by rf-magnetron sputtering at ambient temperature using, for the first time, doped nanocrystalline powder synthesized by the sol–gel method. The effects of aluminum on structural, electrical, morphological and optical properties were investigated. The films showed a hexagonal wurtzite structure and high preferential orientation in the (002) crystallographic direction. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to study the films morphology. The obtained samples have a typical columnar structure and a very smooth surface. The optical transmittance spectra showed transmittance higher than 90% within the visible wavelength region. A minimum resistivity of 5.436 · 10^− 5 Ω cm at room temperature was obtained for the 3.0 at.% Al-doped film.     

Growth and characterization of indium oxide thin films prepared by spray pyrolysis

Highly transparent and conducting indium oxide thin films are prepared on glass substrates from precursor solution of indium chloride. These films are characterized by X-ray diffraction, scanning electron microscopy and optical transmission. The preferential orientation of these films is found to be sensitive to deposition parameters. A comparative study has been made on the dependence on the thickness of the film on substrate temperatures with aqueous solution and 1:1 C₂H₅OH and H₂O as precursors. Films deposited at optimum conditions have 167 nm thickness and exhibited a resistivity of 2.94 × 10⁻⁴ Ω m along with transmittance better than 82% at 550 nm. The analytical expressions enabling the derivation of the optical constants of these films from their transmission spectrum only have successfully been applied. Finally, the refractive index dispersion is discussed in terms of the single-oscillator Wemple and Didomenico model.     

Structural and optical properties of Ti-doped ZnO thin films prepared by the cathodic vacuum arc technique with different annealing processes

Highly transparent Ti-doped ZnO thin films were prepared on glass substrates at a deposition rate of approximately 33 nm/min using the cathodic vacuum arc technique with a Zn target power of 550 W and a Ti target power of 750 W, respectively. X-ray diffraction measurements have shown that the Ti-doped ZnO thin film with a vacuum post-annealing condition is c-axis oriented but an amorphous phase at the other post-annealing atmosphere and as-deposited condition. Transmittance measurements show that the best optical quality of the Ti-doped ZnO thin films occurred at a post-annealing atmosphere of N₂/H₂ mixed gases. Additionally, the optical transmittance of all films has been found more than 85% in a range of 500-700 nm. The lowest electrical resistivity was 3.48 × 10⁻³ Ω cm, obtained on as-deposited films. However, the post-annealing condition greatly increased the resistivity.     

Transparent conductive In2O3:Mo thin films prepared by reactive direct current magnetron sputtering at room temperature

An amorphous transparent conductive oxide thin film of molybdenum-doped indium oxide (IMO) was prepared by reactive direct current magnetron sputtering at room temperature. The films formed on glass microscope slides show good electrical and optical properties: the low resistivity of 5.9 × 10^− 4 Ω cm, the carrier concentration of 5.2 × 10²⁰ cm^− 3, the carrier mobility of 20.2 cm² V^− 1 s^− 1, and an average visible transmittance of about 90.1%. The investigation reveals that oxygen content influences greatly the carrier concentration and then the photoelectrical properties of the films. Atomic force microscope evaluation shows that the IMO film with uniform particle size and smooth surface in terms of root mean square of 0.8 nm was obtained.     

Properties of SnO2 films fabricated using a rectangular filtered vacuum arc plasma source

Transparent and conducting SnO₂ films of 57–200nm thickness were deposited on microscope glass slide substrates, using a rectangular filtered vacuum arc deposition system. The 40 glass slides were equally distributed on a 400 × 420mm substrate carriage, and were exposed to a Sn plasma beam, produced by a rectangular vacuum arc plasma gun with a Sn cathode, and passed through a rectangular magnetic macroparticle filter towards the substrates. The carriage with the substrates was transported past the 94 × 494mm filter outlet. The SnO₂ films were fabricated on the glass substrates at room temperature by maintaining the chamber oxygen background pressure at 0.52Pa. The film composition, and electrical and optical properties were studied as a function of the film thickness. The films were stored under ambient air conditions, and their electrical resistance was measured as a function of storage time over a period of several months.

The average resistivity of films was 10–17mΩ cm for films with thickness (t) less than 100nm, but that of t > 100nm it was 5–9mΩ cm. The resistivity of the films with t > 100nm did not change significantly after 8months of storage in ambient air. The optical transmittance of the films in the visible spectrum was in the range of 75–90%. The optical constants, i.e., the refractive index and the extinction coefficient of the films at wavelength λ = 550nm were in the range of 2.02–2.09 and 0.013–0.023, respectively, and the optical band gap energy was 4.15–4.21eV. Unlike the electrical resistivity, the optical parameters weakly depended on t.     

Effects of annealing temperature and thickness on microstructure and properties of sol–gel derived multilayer Al-doped ZnO films

Transparent conductive multilayer Al-doped ZnO (AZO) films were prepared by the spin-on technique with rapid thermal annealing process at low temperature. The effects of annealing temperature and thickness on microstructure, growth behavior, electrical properties and optical properties of AZO films were investigated. It was found that AZO films exhibited stronger preferred c-axis-orientation, the electrical resistivity decreased as it would be expected with the increase of annealing temperature from 400 to 500 °C and the increase of the number of layers in the film from 1 to 6, but the electrical resistivity tended to keep at a certain lowest value of 2.7 × 10⁻⁴ Ω cm when the annealing temperature was above 500 °C and the number of layers did not exceed 6. The average optical transmittance of AZO films was over 90% when number of layers in the film did not exceed 4 and decreased as this number increases, but the annealing temperature had little effect on the average optical transmittance of AZO films.     

Electrical properties of Na/Mg co-doped ZnO thin films

Conducting and transparent Na-Mg co-doped ZnO thin films were deposited on glass substrates by sol-gel method. Zn (CH₃COO)₂·2H₂O(AR), MgCl₂·6H₂O(AR)) and NaCl (AR) were selected as precursors. They were dissolved in methanol to form a mixed solution with a designed doping ion concentration. Diethanolamine (HN(CH₂CH₂OH)₂, DEA, AR) was added into the mixed solution as a stabilizer in a DEA/Zn(OAC)₂ molar ratio of 1:1. The electrical properties, phase structure, and surface morphology of the films were analyzed via Hall coefficient analyses, X-ray diffraction and scanning electron microscopy, respectively. The films exhibited an obscure (002) preferential growth in all the cases. Surface morphology studies showed that an increase in the films' thickness causes an increase in the grain size. Films with 0.25 μm thickness, prepared under optimal deposition conditions followed by an annealing treatment in vacuum, showed an electrical resistivity in the level of 10² Ω cm and p-type conduction. These results make Na-Mg co-doped ZnO thin films an attractive material for transparent electrodes in thin film devices.     

Electrical,optical, and structural properties of thin films with tri-layers of AZO/ZnMgO/AZO grown by filtered vacuum arc deposition

Transparent conductive oxides (TCO) are indispensable as front electrode for most of thin film electronic devices such as transparent electrodes for flat panel displays, photovoltaic cells, windshield defrosters, transparent thin film transistors, and low emissivity windows. Thin films of aluminum-doped zinc oxide (AZO) have shown to be one of the most promising TCOs. In this study, three layered Al-doped ZnO (AZO)/ZnMgO/AZO heterostructures were prepared by filtered cathodic arc deposition (FCAD) on glass substrates. The objective is to find a set of parameters that will allow for improved optical and electrical properties of the films such as low resistivity, high mobility, high number of charge carriers, and high transmittance. We have investigated the effect of modifications in thickness and doping of the ZnMgO inner layer on the structural, electrical, and optical characteristics of the stacked heterostructures.     

Substrate temperature dependence of the properties of Ga-doped ZnO films deposited by DC reactive magnetron sputtering

Ga-doped zinc oxide (ZnO:Ga) transparent conductive films were deposited on glass substrates by DC reactive magnetron sputtering. The influence of substrate temperature on the structural, electrical, and optical properties of ZnO:Ga films was investigated. The X-ray diffraction (XRD) studies show that higher temperature helps to promote Ga substitution more easily. The film deposited at 350 °C has the optimal crystal quality. The morphology of the films is strongly related to the substrate temperature. The film deposited is dense and flat with a columnar structure in the cross-section morphology. The transmittance of the ZnO:Ga thin films is over 90%. The lowest resistivity of the ZnO:Ga film is 4.48×10⁻⁴ Ω cm, for a film which was deposited at the substrate temperature of 300 °C.     

Pulsed laser deposited ZnO:In as transparent conducting oxide

Zinc oxide (ZnO) and indium doped ZnO (IZO) thin films with different indium compositions were grown by pulsed laser deposition technique on corning glass substrate. The effect of indium concentration on the structural, morphological, optical and electrical properties of the film was studied. The films were oriented along c-direction with wurtzite structure and highly transparent with an average transmittance of more than 80% in the visible wavelength region. The energy band gap was found to decrease with increasing indium concentration. High transparency makes the films useful as optical windows while the high band gap values support the idea that the film could be a good candidate for optoelectronic devices. The value of resistivity observed to decrease initially with doping concentration and subsequently increases. IZO with 1% of indium showed the lowest resistivity of 2.41 × 10⁻² Ω cm and large transmittance in the visible wavelength region. Especially 1% IZO thin film was observed to be a suitable transparent conducting oxide material to potentially replace indium tin oxide.     

Electrical and optical properties of Zn-In-Sn-O transparent conducting thin films

Indium tin oxide (ITO) is one of the widely used transparent conductive oxides (TCO) for application as transparent electrode in thin film silicon solar cells or thin film transistors owing to its low resistivity and high transparency. Nevertheless, indium is a scarce and expensive element and ITO films require high deposition temperature to achieve good electrical and optical properties. On the other hand, although not competing as ITO, doped Zinc Oxide (ZnO) is a promising and cheaper alternative. Therefore, our strategy has been to deposit ITO and ZnO multicomponent thin films at room temperature by radiofrequency (RF) magnetron co-sputtering in order to achieve TCOs with reduced indium content. Thin films of the quaternary system Zn-In-Sn-O (ZITO) with improved electrical and optical properties have been achieved.The samples were deposited by applying different RF powers to ZnO target while keeping a constant RF power to ITO target. This led to ZITO films with zinc content ratio varying between 0 and 67%. The optical, electrical and morphological properties have been thoroughly studied. The film composition was analysed by X-ray Photoelectron Spectroscopy. The films with 17% zinc content ratio showed the lowest resistivity (6.6 × 10^− 4 Ω cm) and the highest transmittance (above 80% in the visible range). Though X-ray Diffraction studies showed amorphous nature for the films, using High Resolution Transmission Electron Microscopy we found that the microstructure of the films consisted of nanometric crystals embedded in a compact amorphous matrix. The effect of post deposition annealing on the films in both reducing and oxidizing atmospheres were studied. The changes were found to strongly depend on the zinc content ratio in the films.     

直流磁控溅射法制备掺钛氧化锌透明导电薄膜

采用直流磁控溅射法在室温水冷玻璃衬底上制备出高质量的掺钛氧化锌(ZnO:Ti)透明导电薄膜,研究了溅射功率对ZnO:Ti薄膜结构、形貌和光电性能的影响,结果表明,溅射功率对ZnO:Ti薄膜的结构和电阻率有显著影响.XRD表明,ZnO:Ti薄膜为六角纤锌矿结构的多晶薄膜,且具有c轴择优取向.当溅射功率为130W时,实验制备的ZnO:Ti薄膜的电阻率具有最小值9.67×10~(-5)Ω·cm.实验制备的ZnO:Ti薄膜具有良好的附着性能,可见光区平均透过率超过91%.ZnO:Ti薄膜可以用作薄膜太阳能电池和液晶显示器的透明电极.     

Structural, optical and electrical characterization of spray-deposited TiO2 thin films

Titanium oxide (TiO₂) thin films were deposited onto glass substrates by means of spray pyrolysis method using methanolic titanyl acetyl acetonate as precursor solution. The thin films were deposited at three different temperatures namely 350, 400 and 450 °C. As-deposited thin films were amorphous having 100–300 nm thickness. The thin films were subsequently annealed at 500 °C in air for 2 h. Structural, optical and electrical properties of TiO₂ thin films have been studied. Polycrystalline thin films with rutile crystal structure, as evidenced from X-ray diffraction pattern, were obtained with major reflexion along (1 1 0). Surface morphology and growth stages based on atomic force microscopy measurements are discussed. Electrical properties have been studied by means of electrical resistivity and thermoelectric power measurements. Optical study shows that TiO₂ possesses direct optical transition with band gap of 3.4 eV.