Selective atomic layer deposition of metal oxide thin films on patterned self-assembled monolayers formed by microcontact printing

We demonstrate a selective atomic layer deposition of TiO2, ZrO2, and ZnO thin films on patterned alkylsiloxane self-assembled monolayers. Microcontact printing was done to prepare patterned monolayers of the alkylsiloxane on Si substrates. The patterned monolayers define and direct the selective deposition of the metal oxide thin films using atomic layer deposition. The selective atomic layer deposition is based on the fact that the metal oxide thin films are selectively deposited only on the regions exposing the silanol groups of the Si substrates because the regions covered with the alkylsiloxane monolayers do not have any functional group to react with precursors.     

Electromechanical Behavior of Al/Al2O3 Multilayers on Flexible Substrates: Insights from In Situ Film Stress and Resistance Measurements

A series of Al and Al/Al₂O₃ thin-film multilayer structures on flexible polymer substrates are fabricated with a unique deposition chamber combining magnetron sputtering (Al) and atomic layer deposition (ALD, Al₂O₃, nominal thickness 2.4–9.4 nm) without breaking vacuum and thoroughly characterized using transmission electron microscopy (TEM). The electromechanical behavior of the multilayers and Al reference films is investigated in tension with in situ X-ray diffraction (XRD) and four-point probe resistance measurements. All films exhibit excellent interfacial adhesion, with no delamination in the investigated strain range (12%). For the first time, an adhesion-promoting naturally forming amorphous interlayer is confirmed for thin films sputter deposited onto polymers under laboratory conditions. The evolution of Al film stresses and electrical resistance reveal changes in the deformation behavior as a function of oxide thickness. Strengthening of Al is observed with increasing oxide thickness. Significant embrittlement can be avoided for oxide layer thicknesses ≤2.4 nm.     

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.     

Effects of different needles and substrates on CuInS2 deposited by electrostatic spray deposition

Copper indium disulphide (CuInS₂) thin films were deposited using the electrostatic spray deposition method. The effects of applied voltage and solution flow rate on the aerosol cone shape, film composition, surface morphology and current conversion were investigated. The effect of aluminium substrates and transparent fluorine doped tin oxide (SnO₂:F) coated glass substrates on the properties of as-deposited CuInS₂ films were analysed. An oxidation process occurs during the deposition onto the metallic substrates which forms an insulating layer between the photoactive film and substrate. The effects of two different spray needles on the properties of the as-deposited films were also studied. The results reveal that the use of a stainless steel needle results in contamination of the film due to the transfer of metal impurities through the spray whilst this is not seen for the glass needle. The films were characterised using a number of different analytical techniques such as X-ray diffraction, scanning electron microscopy, Rutherford back-scattering and secondary ion mass spectroscopy and opto-electronic measurements.     

The effect of sputtering gas pressure on structure and photocatalytic properties of nanostructured titanium oxide self-cleaning thin film

Titanium oxide thin films were deposited by DC reactive magnetron sputtering on ZnO (80 nm thickness)/soda-lime glass and SiO₂ substrates at different gas pressures. The post annealing on the deposited films was performed at 400 °C in air atmosphere. The results of X-ray diffraction (XRD) showed that the films had anatase phase after annealing at 400 °C. The structure and morphology of deposited layers were evaluated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface grain size and roughness of TiO₂ thin films after annealing were around 10-15 nm and 2-8 nm, respectively. The optical transmittance of the films was measured using ultraviolet-visible light (UV-vis) spectrophotometer and photocatalytic activities of the samples were evaluated by the degradation of Methylene Blue (MB) dye. Using ZnO thin film as buffer layer, the photocatalytic properties of TiO₂ films were improved.     

SiO2层上沉积的纳米多晶硅薄膜及其特性

采用低压化学气相沉积(LPCVD)系统以高纯SiH4为气源,在p型10.16 cm<100>晶向单晶硅衬底SiO2层上制备纳米多晶硅薄膜,薄膜沉积温度为620℃,沉积薄膜厚度分别为30 nm、63 nm和98 nm.对不同薄膜厚度的纳米多晶硅薄膜分别在700℃、800℃和900℃下进行高温真空退火.通过X射线衍射(XRD)、Raman光谱、扫描电子显微镜(SEM)和原子力显微镜(AFM)对SiO2层上沉积的纳米多晶硅薄膜进行特性测试和表征,随着薄膜厚度的增加,沉积态薄膜结晶显著增强,择优取向为<111>晶向.通过HP4145B型半导体参数分析仪对沉积态掺硼纳米多晶硅薄膜电阻I-V特性测试发现,随着薄膜厚度的增加,薄膜电阻率减小,载流子迁移率增大.     

A study of titanium thin films in transmission laser micro-joining of titanium-coated glass to polyimide

Electron beam evaporation (EB-PVD) and cathodic arc physical vapor deposition (CA-PVD) techniques were used for the preparation of titanium (Ti) thin films onto Pyrex borosilicate 7740 glass wafers and the deposited films were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) techniques. The microstructure and surface morphology of the films were studied as a function of the film deposition techniques. Film properties such as, adherence, microstructure and roughness were interconnected to the laser joint strength between Ti coated glass wafers and polyimide films. Ti thin films on glass had a natural oxide layer on the surface as found from XPS. AFM study showed the formation of a uniform Ti coating consisted of packed crystallites with average size of 35 nm by EB-PVD. The root-mean-square surface roughness of the films was 1-2 nm. Whereas, films prepared by CA-PVD had crystallites with an average size of 120 nm and defects in the form of macro-particles which is a common attribute of this deposition system. The surface roughness of the film was 125 nm. The laser joint strength was found to be influenced by the Ti film quality on the glass substrate.     

Charge-trapping characteristics of Al2O3/Cu/Al2O3 nanolaminate structures prepared through atomic layer deposition

The nanolaminate Al2O3/Cu/Al2O3 structures were constructed on p-type Si (001) substrates using atomic layer deposition (ALD) process with the aim to fabricating nonvolatile charge-trap memories. Low temperature Cu thin layers were deposited through plasma-enhanced atomic layre depositon of Cu aminoalkoxide (Cu(dmamb)2) combined with hydrogen plasma and Al2O3 layers were prepared by thermal atomic layer deposition of trimethylaluminum (TMA) combined with H2O. Nonvolatile features were confirmed using capacitance-voltage (C-V) measurements. The copper film functions as a charge-trapping layer and the Al2O3 thin layers were employed as tunneling and control oxide layers. Line shapes and binding energies of Cu metal and the thin layer of 6 nm Cu in nanolaminate structures were observed in the X-ray photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (TEM) image. The V(FB) shift width of the Al2O3 (28 nm)/Cu (6 nm)/Al2O3 (4.2 nm)/Si laminate structure is found to be 4.75 V in voltage sweeping between -10 and +10 V, leading to the trap density of 1.68 x 10(18) cm(-3).     

The role of the Zn buffer layers in the structural and photoluminescence properties of ZnO films on Zn buffer layers deposited by RF magnetron sputtering

Highly c-axis oriented ZnO thin films were grown on Si (100) substrates with Zn buffer layers. Effects of the Zn buffer layer thickness on the structural and optical qualities of ZnO thin films were investigated for the ZnO films with the buffer layers 90, 110, and 130 nm thick using X-ray diffraction (XRD), photoluminescence (PL) and atomic force microscopy (AFM) analysis techniques. It was confirmed that the quality of a ZnO thin film deposited by RF magnetron sputtering was substantially improved by using a Zn buffer layer. The highest ZnO film quality was obtained with a Zn buffer layer 110 nm thick. The surface roughness of the ZnO thin film increases as the Zn buffer layer thickness increases.     

Structural and electrical properties of RuO2 thin films prepared by rf-magnetron sputtering and annealing at different temperatures

Conductive ruthenium oxide (RuO₂) thin films have been deposited at different substrate temperatures on various substrates by radio-frequency (rf) magnetron sputtering and were later annealed at different temperatures. The thickness of the films ranges from 50 to 700 nm. Films deposited at higher temperatures show larger grain size (about 140 nm) with (200) preferred orientation. Films deposited at lower substrate temperature have smaller grains (about 55 nm) with (110) preferred orientation. The electrical resistivity decreases slightly with increasing film thickness but is more influenced by the deposition and annealing temperature. Maximum resistivity is 861 μΩ cm, observed for films deposited at room temperature on glass substrates. Minimum resistivity is 40 μΩ cm observed for a thin film (50 nm) deposited at 540°C on a quartz substrate. Micro-Raman investigations indicate that strain-free well-crystallized thin films are deposited on oxidized Si substrates.     

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.     

Nano-polycrystalline vanadium oxide thin films prepared by pulsed laser deposition

Nano-polycrystalline vanadium oxide thin films have been successfully produced by pulsed laser deposition on Si(100) substrates using a pure vanadium target in an oxygen atmosphere. The vanadium oxide thin film is amorphous when deposited at relatively low substrate temperature (500 degrees C) and enhancing substrate temperature (600-800 degrees C) appears to be efficient in crystallizing VOx thin films. Nano-polycrystalline V3O7 thin film has been achieved when deposited at oxygen pressure of 8 Pa and substrate temperature of 600 degrees C. Nano-polycrystalline VO2 thin films with a preferred (011) orientation have been obtained when deposited at oxygen pressure of 0.8 Pa and substrate temperatures of 600-800 degrees C. The vanadium oxide thin films deposited at high oxygen pressure (8 Pa) reveal a mix-valence of V5+ and V4+, while the VOx thin films deposited at low oxygen pressure (0.8 Pa) display a valence of V4+. The nano-polycrystalline vanadium oxide thin films prepared by pulsed laser deposition have smooth surface with high qualities of mean crystallite size ranging from 30 to 230 nm and Ra ranging from 1.5 to 22.2 nm. Relative low substrate temperature and oxygen pressure are benifit to aquire nano-polycrystalline VOx thin films with small grain size and low surface roughness.     

Effects of the substrate temperature on the Cu seed layer formed using atomic layer deposition

Cu has replaced Al as the main interconnection material in ultra-large integrated circuits, reducing resistance capacitance delay and yielding higher electro-migration reliability. As feature size decreases, however, it has become more difficult to produce reliable Cu wiring. We studied a Cu seed layer deposited using plasma enhanced atomic layer deposition (PEALD). The electrical properties of the PEALD Cu thin film with sub-10 nm thickness were determined by the continuities and morphologies of the films. At a deposition temperature of 150 °C, the resistivity of Cu thin films was 5.2 μΩ-cm and the impurity content was below 5 atomic %. Based on these results, Cu seed layers were deposited on 32-nm Ta/SiO2 trench substrates, and electrochemical plating was performed under conventional conditions. A continuous seed layer was deposited using PEALD, resulting in a perfectly filling of the 32-nm sized trench.     

Preparation of silica thin films by novel wet process and study of their optical properties

Silicon dioxide (SiO2) thin films have gained considerable attention because of their various industrial applications. For example, SiO2 thin films are used in superhydrophilic self-cleaning surface glass, UV protection films, anti-reflection coatings, and insulating materials. Recently, many processes such as vacuum evaporation, sputtering, chemical vapor deposition, and spin coating have been widely applied to prepare thin films of functionally graded materials. However, these processes suffer from several engineering problems. For example, a special apparatus is required for the deposition of films, and conventional wet processes are not suitable for coating the surfaces of substrates with a large surface area and complex morphology. In this study, we investigated the film morphology and optical properties of SiO2 films prepared by a novel technique, namely, liquid phase deposition (LPD). Images of the SiO2 films were obtained by scanning electron microscopy (SEM) and atomic force microscopy (AFM) in order to study the surface morphology of these films: these images indicate that films deposited with different reaction times were uniform and dense and were composed of pure silica. Optical properties such as refractive index and transmittance were estimated by UV-vis spectroscopy and ellipsometry. SiO2 films with porous structures at the nanometer scale (100-250 nm) were successfully produced by LPD. The deposited film had excellent transmittance in the visible wavelength region.     

Investigation of ZnO films on Si<111> substrate grown by low energy O+ assisted pulse laser deposited technology

Zinc oxide thin films (ZnO) with different thickness were prepared on Si (111) substrates using low energy O⁺ assisted pulse laser deposition (PLD). The structural and morphological properties of the films were investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM) measurements, respectively. The quality of ZnO films was also examined by using Rutherford backscattering spectroscopy/ion channeling (RBS/C) techniques. XRD showed that there was only one sharp diffraction peak at 2θ = 34.3° with the full width at the half maximum (FWHM) of around 0.34° for two ZnO samples, which also indicated that ZnO thin films had a good c-axis preferred orientation. Results of Rutherford backscattering and ion channeling clearly indicated that the Zn:O ratio in zinc oxide thin film approached to unity and the ZnO thin film grown by low energy O⁺ assisted pulse laser deposition had a polycrystalline structure. In the case of ZnO film fabricated by low energy O⁺ assisted pulse laser deposited under identical experimental conditions except growth time, AFM analysis has shown that the root mean square (RMS) roughness (2.37 nm) of thinner ZnO film (35 nm) was far below that (13.45 nm) of the thicker ZnO film (72 nm).     

Epitaxial growth of titanium oxide thin films on MgO(100) single-crystal substrates by reactive deposition methods

We synthesized titanium oxide thin films on MgO(100) single-crystal substrates by two reactive deposition methods and compared the structures of the thin films formed by these methods. In one method (pulsed-molecular-beam deposition method), molecular oxygen is supplied to the substrates by using a pulsed-molecular-oxygen beam source and deposition of one unit layer of titanium and subsequent supply of molecular oxygen are repeatedly performed. In the other method (radical beam deposition method), atomic oxygen is irradiated to the substrates by using an atomic oxygen beam generated by the radical beam source and irradiation of the atomic oxygen and deposition of titanium are simultaneously performed. In the case of the pulsed-molecular-beam deposition method, the crystal structure was changed by increasing the number of oxygen pulses supplied from the beam source. We found that the crystal structure of titanium oxide depended on the composition ratio of O:Ti in the film. The maximum ratio of O:Ti attainable by this method was 1.85, and at this ratio, (100)-oriented pseudorutile was formed. In the case of the radical beam deposition method, (100)-oriented anatase was formed below the titanium deposition rate of 0.10 nm/s and pseudorutile (TiO_2−δ) was formed above 0.15 nm/s. The pseudorutile structure synthesized on this experiment was very stable in air. We concluded that the crystal structure of the pseudorutile is a new crystal structure of titanium oxide.     

Lanthanum concentration dependence of electrical properties in tin oxide thin films

Lanthanum doped tin oxide thin films were prepared on boron-silicon glass substrates by spray pyrolysis. Lanthanum concentration was varied from 0 to 1.0 wt%. The microstructures, sheet resistance and thermal stabilities of the lanthanum doped tin oxide thin films have been investigated in order to determine the role of this dopant on electrical properties. X-ray diffraction (XRD) result shows the deposited thin film is mainly rutile SnO₂. And atomic force microscopy (AFM) reveals that the thin film has smooth surface with no cracks and defects. And it exhibits a typical bimodal grain size distribution with an average grain size of 95 nm. The sheet resistances of the thin films have a complex dependence on the lanthanum concentration. With increasing lanthanum concentration, the sheet resistances of tin oxide thin films were slightly increased and then abruptly decreased. Moreover, when the lanthanum concentration of 0.5 wt% was reached, the specimen exhibits excellent electrical properties. Because of its effectiveness in improving homogeneity of operating surface temperature and thermal stability, lanthanum appears to be an attractive additive for the tin oxide thin films.     

Liquid phase deposition of BiFeO3 thin film on self-assembly monolayers

BiFeO₃ (BFO) thin films were successfully deposited on self-assembled monolayers (SAMs) by the liquid phase deposition method. The measurement of contact angle and atomic force microscopy (AFM) showed that after immersion in an octadecyl trichlorosilane (OTS) solution for 30 min, the surface of the substrate was covered with a smooth, hydrophobic layer. After UV irradiation for 30 min, the smooth hydrophobic layer changed into a serrated hydrophilic layer. This indicated that the OTS-SAMs played an active role as chemical templates in controlling nucleation and growth of the BFO thin film. The phase and the surface topography of the BFO film were investigated respectively by X-ray diffraction, Field emission scanning electron microscopy (FE-SEM) and AFM. The results showed that the optimum annealing temperature and deposition temperature for preparing the BFO thin film were 600 and 70 °C respectively. The films were annealed at 600 °C for 2 h. As-prepared thin films were smooth, uniform, and dense with the height varying between 20 and 100 nm. Moreover, patterned BFO nanoarrays were prepared.     

Magnetic Domain Studies of Cobalt Nanostructures

The pulsed laser deposition technique associated with a low energy cluster beam is used to deposit cobalt thin films with a thickness 100?C200?nm and cobalt dots of a diameter 100?C200?nm on silicon substrates. The deposited thin films of Co are composed of clusters of a?size 10?C50?nm, with very few large grains as revealed by atomic force microscopy. The observations performed by magnetic force microscopy on as-grown thin films reveal randomly distributed out-of-plane magnetic domain structures. These magnetic domains are aligned linearly by applying an external magnetic field either perpendicular or parallel to the substrate during the deposition. In addition, the effect of film thickness and roughness on multidomains is reported. The increase of roughness resulted in the decrease of magnetic domain width from 200 to 100?nm. This decrease is accompanied by the appearance of instability in the stripe domain pattern. Well separated cobalt dots of diameter in the range of 100?C200?nm are also deposited on silicon substrates, which show arc-like multidomains. The domains seem to be oriented along the long axis of the dots. The domain structure of Co nanodots is similar to that of Co thin films indicating strong magnetic coupling of clusters.     

Atomic layer deposition of SiO2 thin films using tetrakis(ethylamino)silane and ozone

We examined the atomic layer deposition (ALD) of silicon dioxide thin films on a silicon wafer by alternating exposures to tetrakis(ethylamino)silane [Si(NHC2H5)4] and O3. The growth kinetics of silicon oxide films was examined at substrate temperatures ranging from 325 to 514 degrees C. The deposition was governed by a self-limiting surface reaction, and the growth rate at 478 degrees C was saturated at 0.17 nm/cycle for Si(NHC2H5)4 exposures of 2 x 10(6) L (1 L = 10(-6) Torr x s). The films deposited at 365-404 degrees C exhibited a higher deposition rate of 0.20-0.21 nm/cycle. However, they contained impurities, such as carbon and nitrogen, and showed poor film qualities. The concentration of impurities decreased with increasing substrate temperature. It was found that the films deposited in the high-temperature regime (478-514 degrees C) showed excellent physical and electrical properties equivalent to those of LPCVD films.