Spatial atomic layer deposition of zinc oxide thin films

Zinc oxide thin films have been deposited at high growth rates (up to ~1 nm/s) by spatial atomic layer deposition technique at atmospheric pressure. Water has been used as oxidant for diethylzinc (DEZ) at deposition temperatures between 75 and 250 °C. The electrical, structural (crystallinity and morphology), and optical properties of the films have been analyzed by using Hall, four-point probe, X-ray diffraction, scanning electron microscopy, spectrophotometry, and photoluminescence, respectively. All the films have c-axis (100) preferential orientation, good crystalline quality and high transparency (～ 85%) in the visible range. By varying the DEZ partial pressure, the electrical properties of ZnO can be controlled, ranging from heavily n-type conductive (with 4 mOhm.cm resistivity for 250 nm thickness) to insulating. Combining the high deposition rates with a precise control of functional properties (i.e., conductivity and transparency) of the films, the industrially scalable spatial ALD technique can become a disruptive manufacturing method for the ZnO-based industry.     

Control of ZnO thin film surface by ZnS passivation to enhance photoluminescence

To enhance the optical property of zinc oxide (ZnO) thin film, zinc sulfide (ZnS) thin films were formed on the interfaces of ZnO thin film as a passivation and a substrate layer. ZnO and ZnS thin films were deposited by atomic layer deposition (ALD) using diethyl zinc, H₂O, and H₂S as precursors. Investigations by X-ray diffraction and transmission electron microscopy showed that ZnS/ZnO/ZnS multi-layer thin films with clear boundaries were achieved by ALD and that each film layer had its own polycrystalline phase. The intensity of the photoluminescence of the ZnO thin film was enhanced as the thickness of the ZnO thin film increased and as ZnS passivation was applied onto the ZnO thin film interfaces.     

透明致密ZnO薄膜的恒电流沉积及生长过程研究

采用阴极恒电流沉积方法, 以Zn(NO ₃)₂水溶液为电沉积液, 在经电化学预处理后的ITO导电玻璃上生长了具有c轴高度择优取向、均匀致密的透明ZnO薄膜. 采用X射线衍射、扫描电镜和光学透过谱等技术, 对不同沉积时间条件下薄膜的结晶特性、表面和断面结构、光学性质等进行了研究. 结果表明, 沉积时间对ZnO薄膜质量影响明显: 在薄膜生长后期(120min), ZnO薄膜的结晶性和表面平整度明显降低, 晶粒尺寸增大, 可见光透过率下降, 表明高质量ZnO薄膜的电化学沉积有一最佳生长时间; 此外, 薄膜厚度随时间呈线性变化, 表明可通过生长时间实现对ZnO薄膜厚度的精确控制.     

Controlling the crystallinity and roughness of atomic layer deposited titanium dioxide films

The surface roughness of thin films is an important parameter related to the sticking behaviour of surfaces in the manufacturing of microelectomechanical systems (MEMS). In this work, TiO2 films made by atomic layer deposition (ALD) with the TiCl4-H2O process were characterized for their growth, roughness and crystallinity as function of deposition temperature (110-300 degrees C), film thickness (up to approximately 100 nm) and substrate (thermal SiO2, RCA-cleaned Si, Al2O3). TiO2 films got rougher with increasing film thickness and to some extent with increasing deposition temperature. The substrate drastically influenced the crystallization behaviour of the film: for films of about 20 nm thickness, on thermal SiO2 and RCA-cleaned Si, anatase TiO2 crystal diameter was about 40 nm, while on Al2O3 surface the diameter was about a micrometer. The roughness could be controlled from 0.2 nm up to several nanometers, which makes the TiO2 films candidates for adhesion engineering in MEMS.     

衬底温度对PLD方法生长的ZnO薄膜结构和发光特性的影响

在不同的衬底温度下, 通过脉冲激光淀积的方法在Si衬底上生长出c轴高度取向的ZnO薄膜. ZnO薄膜的结构和表面形貌通过X射线衍射和原子力显微镜表征. 同时以He-Cd激光和同步辐射作为激发源来测试样品的发光特性. 实验结果表明, 在衬底温度为500℃时生长的ZnO薄膜具有非常好的晶体质量, 并且表现出很强的紫外发射. 在用同步辐射为激发源的低温(18K)光致发光谱中, 还观察到了一个位于430nm处的紫光发射, 我们认为这个紫光发射与存在于晶粒间界的界面势阱所引起的缺陷态有关, 这个势阱可能起源于Zn填隙(Zn _i)     

Deposition and characterization of PEDOT/ZnO layers onto PET substrates

ZnO thin films of different thicknesses were deposited by pulsed direct-current magnetron sputtering onto poly(ethylene terephthalate) (PET) substrates and afterwards poly 3, 4-ethylenedioxythiophene:polystyrenesulfonate (PEDOT:PSS) was spin-coated onto the ZnO film. Spectroscopic ellipsometry in the Vis–fUV energy range (1.5–6.5 eV), X-ray diffraction and atomic force microscopy were used to reveal the properties of the deposited films. The size of crystallites increased from 5.1 to 7.4 nm, whereas the crystallinity of the ZnO films has been improved. The influence of different ZnO thickness on the optical properties of the PEDOT:PSS layer was studied as well. As the thickness of ZnO films increased, the surface roughness increased but the energy gap decreased after a critical thickness. Concerning the consequences to the PEDOT:PSS optical properties, no major changes occurred in the transition energies.     

Electrical resistivity of Ti-Zn mixed oxide thin films deposited by atomic layer deposition

Ti-Zn mixed oxide thin films, with thickness less than 50 nm, were grown with atomic layer deposition (ALD) technique at low temperature (90 °C) varying the composition. ALD is a powerful chemical technique to deposit thin films with thickness of few atomic layers. ALD oxide material growth is achieved by dosing sequentially the metal precursor and the oxidizing agent. Thanks to ALD nature of layer by layer growth it was possible to realize mixed metal, Ti and Zn, oxide thin films with controlled composition, simply by changing the number of cycles of each metal oxide layer. Structural and electrical properties of the prepared thin films were studied as a function of their composition. Synchrotron radiation X-ray diffraction technique was used to follow thin film crystallization during sample annealing, performed in situ. It was observed that the onset temperature of crystallization raises with Ti content, and sample structure was Zn₂TiO4 phase. Electrical resistivity measurements were performed on crystalline samples, annealed at 600 °C, revealing an increase in resistivity with Ti content.     

Effect of thickness on nanostructured SnO2 thin films by spray pyrolysis as highly sensitive H2S gas sensor

Nanostructured SnO2 thin films were prepared by spray pyrolysis technique onto glass substrates with different thickness by varying quantity of precursor solution. The structural, optical and electrical properties of these films have been studied. The crystallographic structure of the films was studied by X-ray diffraction (XRD). It is found that the films are tetragonal with (110) orientation. The grain size increases with thickness. Atomic Force Microscopy (AFM) showed that the nanocrystalline nature of the films with porous nature. The grain size increased 14 to 29 nm with increase in film thickness. The studies on the optical properties show that the direct band gap value decreases from 3.75 to 3.50 eV. The temperature dependence of the electrical conductivity was studied. The activation energies of the films are calculated from the conductance temperature characteristics. The nanostructured SnO2 thin films were used as sensing layers for resistive gas sensors. The dependence of gas sensing properties on the thickness of SnO2 thin films was investigated. The gas response of the SnO2 thin films towards the H2S gas was determined at an operating temperature of 150 degrees C. The sensitivity towards H2S gas is strongly depending on surface morphology of the SnO2 thin films.     

Properties of atomic layer deposited HfO2 thin films

The growth, composition and morphology of HfO₂ films that have been deposited by atomic layer deposition (ALD) are examined in this article. The films are deposited using two different ALD chemistries: i) tetrakis ethylmethyl amino hafnium and H₂O at 250° and ii) tetrakis dimethyl amino hafnium and H₂O at 275 °C. The growth rates are 1.2 Å/cycle and 1.0 Å/cycle respectively. The main impurities detected both by X-ray Photoelectron Spectroscopy and Fourier transform infrared spectroscopy (FTIR) are bonded carbon (~ 3 at.%) and both bulk and terminal OH species that are partially desorbed after high temperature inert anneals up to 900 °C. Atomic Force Microscopy reveals increasing surface roughness as a function of increasing film thickness. X-ray diffraction shows that the morphology of the as-deposited films is thickness dependent; films with thickness around 30 nm for both processes are amorphous while ~ 70 nm films show the existence of crystallites. These results are correlated with FTIR measurements in the far IR region where the HfO₂ peaks are found to provide an easy and reliable technique for the determination of the crystallinity of relatively thick HfO₂ films. The index of refraction for all films is very close to that for bulk crystalline HfO₂.     

Growth of ZnO thin films at low temperature by plasma-enhanced atomic layer deposition using H2O and O2 plasma oxidants

Zinc oxide (ZnO) thin films were grown at 70 °C by plasma-enhanced atomic layer deposition using H₂O and O₂ plasmas. Plasma oxidants were used in order to improve the ZnO crystallinity and optoelectronic properties, avoiding high-temperature synthesis. The deposition parameters were optimized to achieve saturation in each reaction step. X-ray photoelectron spectroscopy (XPS) reveals high purity of the obtained ZnO films. X-ray diffraction (XRD) measurements indicate that the grown layers are polycrystalline and that the H₂O plasma synthesis leads to better crystallinity than the O₂ plasma as inferred from the intensity of the (100) and (002) peaks. The films are with high optical transmission, ~90%, as inferred from UV–visible (UV–Vis) transmittance measurements, and optical band gaps of 3.22 and 3.23 eV for H₂O and O₂ plasma, respectively. Atomic force microscopy (AFM) indicates that the films are smooth, with an average roughness of ~?0.22 nm. The growth rate was found to be in the range of 1.2–1.4 Å/cycle. The XPS, XRD, UV–Vis, and AFM results prove the possibility to obtain high-quality ZnO films by O₂ and H₂O plasma processes at 70 °C with chemical, structural, and optical properties promising for flexible electronics. ZnO films were successfully deposited on polyethylene terephthalate substrates using the optimal conditions for H₂O plasma process. No damage of the film surface or substrate was observed.

     

Optical properties of electrochemically deposited ZnO thin films on colloidal crystal film of SiO2 microspheres

The optical properties of electrochemically deposited ZnO thin films on colloidal crystal film of SiO2 microspheres structures were studied. Colloidal crystal film of SiO2 microspheres were self-assembled by evaporation using SiO2 in solution at a constant 0.1 wt%. ZnO in thin films was then electrochemically deposited on to colloidal crystal film of SiO2 microspheres. During electrochemical deposition, the content of Zn(NO3)2 x 6H2O in solution was 5 wt%, and the process's conditions were varied between of 2-4 V and 30-120 s at room temperature, with subsequent heat-treatment between 200 and 400 degrees C. A smooth surface and uniform thickness of 1.8 microm were obtained at 3 V for 90 s. The highest PL peak intensity was obtained in the ZnO thin film heat-treated at 400 degrees C. The double layered ZnO/SiO2 colloidal crystals showed clearly better emission properties than the SiO2/ZnO and ZnO structures.     

Evolution of the properties of ZnO thin films subjected to heating treatments

Structural and optical properties of ZnO thin films (200 nm thickness) deposited using magnetron sputtering technique are influenced by structural defects. Therefore, we applied various heating treatments in order to control and improve the crystallinity of the samples. These treatments were realized in air at temperatures of 350 °C, 550 °C and 700 °C respectively, each for a duration of 1 h. The properties of the samples were investigated both before and after the heating treatment. Modern methods like X-ray Diffraction, Atomic Force Microscopy and Scanning Electron Microscopy were used to analyze the structure and morphology of the heated ZnO thin films. These heating treatments may be held responsible for rearrangements in the morphology of the thin films. Thus, it was observed that an increase of porosity and agglomeration of the crystallites is followed by an increase in the size of the crystallites. Inter-crystalline borders will migrate determining a coalescence of several crystallites during the heating process, as well. As a consequence, an increase of the band gap width from 3.26 eV to 3.30 eV (at 350 °C) and 3.32 eV (at 550 °C) respectively, occurred.     

Structural and optical properties of high quality ZnO thin film on Si with SiC buffer layer

ZnO thin films are grown on Si substrates with SiC buffer layer using ion plasma high frequency magnetron sputtering. These substrates are fabricated using a technique of solid phase epitaxy. With this technique SiC layer of thickness 20-200 nm had been grown on Si substrates consisting pores of sizes 0.5-5 μm at SiC and Si interface. Due to mismatching in lattice constants as well as thermal expansion coefficients, elastic stresses have been developed in ZnO film. Pores at the interface of SiC and Si are acting as the elastic stress reliever of the ZnO films making them strain free epitaxial. ZnO film grown on this especially fabricated Si substrate with SiC buffer layer exhibits excellent crystalline quality as characterized using X-ray diffraction. Surface topography of the film has been characterized using Atomic Force Microscopy as well as Scanning Electron Microscopy. Chemical compositions of the films have been analyzed using Energy Dispersive X-ray Spectroscopy. Optical properties of the films are investigated using Photoluminescence Spectroscopy which also shows good optical quality.     

Laser damage properties of TiO2/Al2O3 thin films grown by atomic layer deposition

Research on thin film deposited by atomic layer deposition (ALD) for laser damage resistance is rare. In this paper, it has been used to deposit TiO(2)/Al(2)O(3) films at 110 °C and 280 °C on fused silica and BK7 substrates. Microstructure of the thin films was investigated by x-ray diffraction. The laser-induced damage threshold (LIDT) of samples was measured by a damage test system. Damage morphology was studied under a Nomarski differential interference contrast microscope and further checked under an atomic force microscope. Multilayers deposited at different temperatures were compared. The results show that the films deposited by ALD had better uniformity and transmission; in this paper, the uniformity is better than 99% over 100 mm Φ samples, and the transmission is more than 99.8% at 1064 nm. Deposition temperature affects the deposition rate and the thin film microstructure and further influences the LIDT of the thin films. As to the TiO(2)/Al(2)O(3) films, the LIDTs were 6.73±0.47 J/cm(2) and 6.5±0.46 J/cm(2) at 110 °C on fused silica and BK7 substrates, respectively. The LIDTs at 11 °C are notably better than 280 °C.     

Using fence post designs to speed the atomic layer deposition of optical thin films

Atomic layer deposition (ALD) at this time is much slower than conventional optical thin-film deposition techniques. A more rapid ALD process for SiO(2) has been developed than for other ALD materials. A fence post design for optical thin films has thin layers of high-index posts standing above a broad low-index ground. If a design for ALD can be predominantly composed of SiO(2) layers with thin high-index layers, the deposition times can be correspondingly shortened, and it is shown that the required performance can still be nearly that of more conventional designs with high- and low-index layers of equal thickness. This combination makes the ALD benefits of conformal coating and precise thickness control more practical for optical thin-film applications.     

Microstructure and optical properties of Al2O3/ZrO2 nano multilayer thin films prepared by pulsed laser deposition

The aluminium oxide/zirconium oxide (Al₂O₃/ZrO₂) nanolaminate thin films (5/20 nm with 4 bilayers, 5/15 nm with 5 bilayers and 5/10 nm with 7 bilayers) were deposited on Si (100) and quartz substrates at an optimized oxygen partial pressure of 3 × 10⁻² mbar at room temperature using pulsed laser deposition. The multilayer films were characterized using X-ray diffraction, X-ray reflectivity, Atomic force microscopy and UV–Visible spectroscopy. The X-ray diffraction studies showed amorphous nature for 5/20 nm film, whereas 5/15 nm and 5/10 nm multilayers showed only tetragonal zirconia at room temperature. X-ray reflectivity studies showed the Kiessig fringes and Bragg peaks, indicating the well defined formation of individual layers and bilayer periodicity in the multilayer films. The AFM studies showed the RMS roughness values of 0.7 nm, 0.9 nm and 1.1 nm for 5/10 nm, 5/15 nm and 5/20 nm multilayers respectively. The optical performance of the combined Al₂O₃/ZrO₂ nanolaminates showed that the refractive indices of the films increased from 1.75 to 1.99 with the decrease of ZrO₂ layer thickness from 20 to 10 nm.     

Structural and functional properties of ZnO thin films grown on Si substrates by air assisted USP method from non-aqueous solutions at low-temperature

In this work, we deals with the processing and characterization of transparent conducting ZnO thin films on p-type Silicon substrates (1 0 0) by air assisted Ultrasonic Spray Pyrolysis (USP) method. The thin films from different Zn acetate precursor solution concentrations (0.1, 0.2, 0.3 and 0.4 M) were deposited at several temperatures (400, 450 and 500 °C) with thickness from ～100 to ～500 nm. The effects of precursor solution concentration, deposition time and temperature on the structural, morphological, optical, and electrical properties of ZnO films were studied by X-ray Diffraction (XRD), Atomic Force Microscopy (AFM), UV–Vis-NIR spectroscopy, and Hall Effect techniques, respectively. It has been shown that on the ZnO film surface, the preferred orientation, the average crystallite size, the electrical resistivity and the RMS surface roughness depend on the substrate temperature. The grown films have showed a good adhesion and an excellent optical transmission of about 80–95% within the visible range (400–800 nm) and a direct band gap from 3.35 to 3.23 eV with the increase of the substrate temperature and the deposition time. All the PL spectra have exhibited a typical green-yellow emission band. Additionally photovoltaic (PV) activities of n-ZnO/p-Si heterostructures fabricated are investigated.     

层数变化对ZnO/In2 O3多层膜微观结构及光电性能的影响

用直流磁控溅射和热氧化法在玻璃衬底上制备ZnO/In2O3透明导电多层膜,当总厚度一定时,调节溅射沉积的层数与相应各层膜的厚度,研究该多层膜微观结构、光学性能和电学性能的变化.XRD和SEM分析表明:随着溅射沉积层数的增加,In2O3衍射峰的强度不断地减弱,ZnO衍射峰出现了不同的晶面择优取向;多层膜表面的ZnO晶粒粒径变小,光洁度增加.四探针法方块电阻测试表明:低温热氧化时,ZnO/In2O3多层膜的方块电阻随层数的增加而上升;高温氧化时,ZnO/In2O3多层膜的方块电阻随层数的增加而下降.可见光光谱分析表明:随着溅射沉积层数的增加,ZnO/In2O3多薄膜在可见光区的平均透过率增大,透过率的峰值向短波方向偏移.     

Fabrication and characterization of epitaxial Ba0.7Sr0.3TiO3 thin films for optical waveguide applications

The optical properties of barium strontium titanate (Ba0.7Sr0.3TiO3; BST) thin films are described. The BST thin films were epitaxially grown upon MgO (001) substrates by pulsed laser deposition. The crystallographic properties of the BST thin films were examined by x-ray diffraction. The BST thin films were highly optically transparent in the visible region. The optical waveguide properties were characterized by a prism coupling technique. An inverse-WBK method was employed to determine the refractive-index profile along the thickness of the BST films. Optical losses were measured by a moving fiber method, and the optical losses were found to be 0.93 dB/cm for the TE0 mode and 1.29 dB/cm for the TM0 mode at 1550 nm. Electro-optic (E-O) properties were measured by a phase-modulation detection method at 632.8 nm, and the BST films exhibited a predominantly quadratic E-O effect with a quadratic E-O coefficient of 6.64 x 10(-18) m2/V2.     

Quantum confinement in amorphous TiO(2) films studied via atomic layer deposition

Despite the significant recent increase in quantum-based optoelectronics device research, few deposition techniques can reliably create the required functional nanoscale systems. Atomic layer deposition (ALD) was used here to study the quantum effects attainable through the use of this ?ngstr?m-level controlled growth process. Size-dependent quantum confinement has been demonstrated using TiO(2) layers of nanoscale thickness applied to the surfaces of silicon wafers. TiO(2) films were deposited at 100?°C using TiCl(4) and H(2)O(2) in a viscous flow ALD reactor, at a rate of 0.61??/cycle. The low-temperature process was utilized to guarantee the amorphous deposition of TiO(2) layers and post-deposition thermal annealing was employed to promote crystallite-size modification. Hydrogen peroxide significantly reduced the residual chlorine that remained from a typical TiCl(4)-H(2)O ALD process at this temperature, down to 1.6%. Spectroscopic ellipsometry was used to quantify the optical properties both below and above the bandgap energy. A central composite design was employed to map the surface response of the film thickness-dependent bandgap shift for the as-deposited case and up to a thermal annealing temperature of 550?°C. The Brus model was used to develop a correlation between the amorphous TiO(2) film thickness and the quantum length to promote equivalent bandgap shifts.