Amorphous alumina coatings: processing, structure and remarkable barrier properties

Amorphous aluminium oxide coatings were processed by metalorganic chemical vapour deposition (MOCVD); their structural characteristics were determined as a function of the processing conditions, the process was modelled considering appropriate chemical kinetic schemes, and the properties of the obtained material were investigated and were correlated with the nanostructure of the coatings. With increasing processing temperature in the range 350 degrees C-700 degrees C, subatmospheric MOCVD of alumina from aluminium tri-isopropoxide (ATI) sequentially yields partially hydroxylated amorphous aluminium oxides, amorphous Al2O3 (415 degrees C-650 degrees C) and nanostructured gamma-Al2O3 films. A numerical model for the process allowed reproducing the non uniformity of deposition rate along the substrate zone due to the depletion of ATI. The hardness of the coatings prepared at 350 degrees C, 480 degrees C and 700 degrees C is 6 GPa, 11 GPa and 1 GPa, respectively. Scratch tests on films grown on TA6V titanium alloy reveal adhesive and cohesive failures for the amorphous and nanocrystalline ones, respectively. Alumina coating processed at 480 degrees C on TA6V yielded zero weight gain after oxidation at 600 degrees C in lab air. The surface of such low temperature processed amorphous films is hydrophobic (water contact angle 106 degrees), while the high temperature processed nanocrystalline films are hydrophilic (48 degrees at a deposition temperature of 700 degrees C). It is concluded that amorphous Al2O3 coatings can be used as oxidation and corrosion barriers at ambient or moderate temperature. Nanostructured with Pt or Ag nanoparticles, they can also provide anti-fouling or catalytic surfaces.     

In-situ observation of transition between surface relief and wrinkling in thin film shape memory alloys

Significant surface morphology evolution between relief and wrinkling was observed on a 3.5 microm thick TiNiCu film sputter-deposited on a silicon substrate. At room temperature, variation in surface relief morphology (from separated martensite crystals embedded in amorphous matrix to fully interweaved martensite plates) was observed with slight change in film composition. The phenomenon was attributed to variations in crystallization temperatures of as-deposited amorphous films during annealing because of the compositional difference. During thermal cycling between room temperature and 100 degrees C, reversible surface morphology changes can be observed between surface relief and wrinkling patterns. The formation of the surface wrinkling is attributed to the large compressive stress in the film during high temperature post-annealing and crystallization, whereas surface relief is caused by the martensitic transformation to relieve the large tensile stress in the film. Compositional effect on this surface morphology evolution is discussed. Results also indicate that there is a critical dimension for the wrinkling to occur, and a small circular island can only relax by in-plane expansion.     

Thin transparent W-doped indium-zinc oxide (WIZO) layer on glass

Annealing effect on structural and electrical properties of W-doped IZO (WIZO) films for thin film transistors (TFT) was studied under different process conditions. Thin WIZO films were deposited on glass substrates by RF magnetron co-sputtering technique using indium zinc oxide (10 wt.% ZnO-doped In2O3) and WO3 targets in room temperature. The post annealing temperature was executed from 200 degrees C to 500 degrees C under various O2/Ar ratios. We could not find any big difference from the surface observation of as grown films while it was found that the carrier density and sheet resistance of WIZO films were controlled by O2/Ar ratio and post annealing temperature. Furthermore, the crystallinity of WIZO film was changed as annealing temperature increased, resulting in amorphous structure at the annealing temperature of 200 degrees C, while clear In2O3 peak was observed for the annealed over 300 degrees C. The transmittance of as-grown films over 89% in visible range was obtained. As an active channel layer for TFT, it was found that the variation of resistivity, carrier density and mobility concentration of WIZO film decreased by annealing process.     

Effects of temperature on columnar microstructure and recrystallization of TiO2 film produced by ion-assisted deposition

Titanium oxide thin films were deposited by electron-beam evaporation with ion-beam-assisted deposition. The effect of the substrate temperature and annealing temperature on the columnar microstructure and recrystallization of titanium oxide was studied. The values of the refractive index varied from 2.26 to 2.4, indicating that the different substrate temperatures affected the film density. X-ray diffraction revealed that all films were amorphous as deposited. At annealing temperatures from 100 degrees C to 300 degrees C, only the anatase phase was formed. As the substrate temperature increased from 150 degrees C to 200 degrees C to 250 degrees C, the recrystallization temperature fell from 300 degrees C through 250 degrees C to 200 degrees C. Changing the substrate temperature resulted in the formation of various types of columnar microstructure, as determined by scanning-electron microscopy. Different columnar structures resulted in different surface morphologies, as measured by atomic-force microscopy.     

Crystallization of Au-Si/glass thin film: a real-time synchrotron X-ray scattering study

The crystallization of amorphous, Si-rich, Au28Si72/glass thin film was studied in real-time synchrotron X-ray scattering experiments. The amorphous film crystallizes first into Au and Si phases at a low temperature of 206 degrees C. At annealing temperatures above eutectic temperature (T(E) = 360 degrees C), the Au phase melts while the Si phase rapidly grows further. The crystallized Au28Si72 thin film has nanowire-type grains with 1000-nm-length and 10-nm-diameter. We confirm that the Au liquid phase contributes to the low-temperature crystallization of the Si solid phase for Si-nanowire growth.     

Interaction between sputtered beta-Ta films and diamond-like carbon with Ru intermediate layer

Interaction between beta-tantalum film and Diamond-like Carbon (DLC) film was studied with and without ruthenium intermediate barrier layer. Phase identification using X-ray Diffraction showed that the phase transformation of tantalum film from beta to alpha crystalline structure was delayed by 100 degrees C and the formation of tantalum carbide was also hindered when ruthenium interlayer is present. X-ray reflectivity measurements indicate that the surface and interfacial area of C/Ta film was maintained to achieve desired magnetic and tribological performance even after N2 annealing at 400 degrees C. In C/Ru/Ta film there is minimum intermixing between tantalum and DLC. In C/Ta film, severe reaction between tantalum and carbon took place. Raman spectroscopy analysis revealed the as-deposited carbon film possessed amorphous structure regardless of the existence of Ru interlayer. Graphitization of carbon film was observed in both structures, upon annealing, however the films with Ru layer was thermodynamically more stable thus desirable in magnetic recording.     

Anomalous absorption of isolated silver nanoparticulate films in visible region of electromagnetic field

Anomalous absorption of isolated silver nanoparticulate films with different morphological patterns prepared by the wet colloidal route and followed by thermal treatment were investigated. A polymer embedded silver nanoparticulate film thermally treated at 200 degrees C showed maximum absorbance at approximately 412 nm. The peak position of the surface plasmon band was slightly different but still consistent with theoretical prediction derived by the Mie theory. An isolated nanopariculate film thermally treated at 300 degrees C showed anomalous absorption. Its maximum absorption band was shifted to green regime of 506.9 nm and the bandwidth at half-maximum absorbance of the surface plasmon band was greatly broadened. The plasmon band and its bandwidth were much deviated compared to the theoretical prediction calculated for the silver nanoparticles in the surrounding medium of air and poly(vinyl pyrrolidone) or soda-lime-silica glass. Even though there was no significant growth of silver nanoparticles during thermal treatment at 300 degrees C, the anomalous absorption was observed. The anomalous absorption was not attributed to effects of particle shape and size but to effects of pores induced by development of a great number of pores in the nanoparticulate film. The anomalous absorption greatly decreased with increase in heating temperature from 400 degrees C to 500 degrees C. The extraordinary plasmon damping of the isolated film decreased and the plasmon absorption band was re-shifted to violet regime of 416 nm because of large decrease in size of particles with dramatic change of pore morphology from circular pores with rim to small continuous pores induced by spontaneous formation of new silver nanoparticles.     

Single lamella nanoparticles of polyethylene

We present a complete analysis of the structure of polyethylene (PE) nanoparticles synthesized and stabilized in water under very mild conditions (15 degrees C, 40 atm) by a nickel-catalyzed polymerization in aqueous solution. Combining cryogenic transmission electron microscopy (cryo-TEM) with X-ray scattering, we demonstrate that this new synthetic route leads to a stable dispersion of individual PE nanoparticles with a narrow size distribution. Most of the semicrystalline particles have a hexagonal shape (lateral size 25 nm, thickness 9 nm) and exhibit the habit of a truncated lozenge. The combination of cryo-TEM and small-angle X-ray scattering demonstrates that the particles consist of a single crystalline lamella sandwiched between two thin amorphous polymer layers ("nanohamburgers"). Hence, these nanocrystals that comprise only ca. 14 chains present the smallest single crystals of PE ever reported. The very small thickness of the crystalline lamella (6.3 nm) is related to the extreme undercooling (more than 100 degrees C) that is due to the low temperature at which the polymerization takes place. This strong undercooling cannot be achieved by any other method so far. Dispersions of polyethylene nanocrystals may have a high potential for a further understanding of polymer crystallization as well as for materials science as, e.g., for the fabrication of extremely thin crystalline layers.     

Elevated temperature nanoindentation and viscoelastic behaviour of thin poly(ethylene terephthalate) films

A commercial nanoindentation system fitted with a heating stage and heated indenter has been used to investigate how the elevated temperature nanoscale mechanical properties of poly(ethylene terephthalate) films vary with their processing history and crystallinity over the temperature range 60-110 degrees C. Three additive-free thin films were tested; an undrawn amorphous film, a uniaxially drawn film, and a commercial biaxially drawn Melinex film. A sharp decrease in mechanical properties was observed between 70 and 80 degrees C on the undrawn and uniaxial film consistent with the presence of a glass transition over this temperature range in agreement with literature values for bulk materials. In contrast, a gradual decrease in properties was observed over the same temperature range on the biaxially oriented film. The high crystallinity of the biaxial film could be beneficial in extending the operating temperature of the film. There is a minimum in the elastic recovery parameter around 80 degrees C on both the amorphous and biaxial film. This indicates that the elastic recovery parameter may be more sensitive to changes in mechanical properties occurring at/near the glass transition region than the hardness or modulus alone. A recently introduced dimensionless parameter for creep, A/d(0), was also found to be a promising way to characterise the increased time-dependent deformation around the glass transition region.     

Anomalous elastic properties of RF-sputtered amorphous TeO2+x thin film for temperature-stable SAW device applications.

The anomalous elastic properties of TeO2+x thin films deposited by rf diode sputtering on substrates at room temperature have been studied. The deposited films are amorphous, and IR spectroscopy reveals the formation of Te-O bond. X-ray photoelectron spectroscopy confirms the variation in the stoichiometry of TeO2+x film from x=0 to 1 with an increase in the oxygen percentage in processing gas composition. The elastic parameters of the films in comparison to the reported values for TeO2+x single crystal are found to be low. However, the temperature coefficients of elastic parameters of all deposited films exhibit anomalous behavior showing positive values for TC(C11) in the range (32.0 to 600.0)x10(-4) degrees C(-1) and TC(C44)=(35.0 to 645.5)x10(-4) degrees C(-1) against the negative values TC(C11)=-2.7x10(-4) degrees C(-1) and TC(C44)=-0.73x10(-4) degrees C(-1) reported for TeO2+x single crystal. The variation in the elastic parameters and their temperature coefficients is correlated with the change in the three-dimensional network of Te-O bonding. The anomalous elastic properties of the TeO2+x films grown in 100% O2 are useful for potential application in the design of temperature stable surface acoustic wave devices.     

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.     

Coating of LaCoO3 thin film with sol-gel dip coating method

LaCoO3 thin film was coated on Al2O3 single crystal by sol-gel route. Appropriate composition of precursors, chelating agents and the solvent put together into a flask and magnetically stirred on a magnetic stirrer. After having the red transparent solution, it was stirred for 12 hours before coating. Ultrasonically cleaned substrate is dipped into the solution and taken immediately into vertical furnace which is preheated at 550 degrees C. A dense amorphous film is coated on the substrate. Fired amorphous films are annealed at temperature between 900 degrees C and 1000 degrees C for 20 minutes in the air. Then coated film was characterized by means of XRD, AFM, and SEM. Conductivity of the film was measured to be -0.1819 for 881 degrees C for the log sigma value by assuming the thickness as     

Effect of thermal annealing on the optical properties and residual stress of TiO2 films produced by ion-assisted deposition

The effects of thermal annealing of titanium oxide films deposited by ion-beam assistance at annealing temperatures from 100 degrees C to 300 degrees C on the residual stress and optical properties of the films was investigated. The refractive indices and extinction coefficients increased gradually as the temperature was increased from 100 degrees C to 200 degrees C and then declined gradually as the temperature was increased further from 200 degrees C to 300 degrees C. The film lost oxygen and slowly generated lower suboxides as the annealing temperature was reduced below 200 degrees C, as determined by x-ray photoelectron spectroscopy (XPS). As the annealing temperature increased above 200 degrees C, the lower suboxides began to capture oxygen and form stable oxides. XPS measurements were made to verify both the binding energy associated with the Ti 2p line and the variation of the O 1s line. A Twyman-Green interferometer was employed for phase-shift interferometry to study the residual stress. The residual stress declined as the temperature was reduced from 100 degrees C to 200 degrees C because the lower suboxides reduced the stress in the film. Above 200 degrees C, the film began to capture oxygen, so the residual stress rose. At 300 degrees C, the film was no longer amorphous as the anatase was observed by x-ray diffraction.     

Effects of annealing conditions on microstructures of thin film using crystalline silicon nanoparticles for printable electronics

Silicon thin film was formed by dropping silicon ink on a single-crystalline silicon substrate and further annealing. The effects of the annealing conditions on the microstructures of thin film were investigated in order to obtain a crystalline silicon thin film for application in the field of printable electronics. Silicon ink was prepared by dispersing silicon nanoparticles synthesized using inductive coupled plasma in a solvent, namely, propylene glycol. The silicon nanoparticles in the as-synthesized film were observed to melt at a temperature of less than 1000 degrees C, and a highly crystalline silicon thin film was obtained by annealing at 800 degrees C for 180 min.     

Temperature effects on resistance of aligned multiwalled carbon nanotube films

Electrical transport in vertically aligned films of multiwalled carbon nanotubes has been investigated in the -150 degrees C to 300 degrees C temperature range (all the tests were conducted in air at atmospheric pressure). In all the cases, the nanotube film exhibited a semi-conducting behavior, with the film resistance decreasing with increasing temperature. Removal of amorphous carbon contamination (via plasma etching) significantly improved the nanotube film's sensitivity to temperature changes (particularly in the 20 degrees C to 200 degrees C temperature range). All the of films tested in this study showed a consistent, repeatable behavior that was independent of the nanotube film length. The temperature sensitivity of the nanotube films was also found to be independent of the heating/cooling rates and without hysteresis. Because of the excellent repeatability and stability of the results, it is conceived that miniaturized temperature sensors could be designed using such aligned multiwalled nanotube films.     

Aluminum-induced in situ crystallization of HWCVD a-Si:H films

Aluminum-induced in situ crystallization (AIC) of amorphous silicon films deposited by hot wire chemical vapor deposition (HWCVD) on glass is demonstrated. Aluminum was deposited at temperatures varying from room temperature to 300 °C on HWCVD a-Si:H films. The AIC was observed to take place in situ during the deposition of Al films, when the glass/a-Si:H temperature is kept 300 °C. A 20-nm Al film was effective in inducing crystallization of about 63% in the a-Si:H film. Thus, separate post-deposition annealing step can be avoided. For an Al film thickness comparable to the amorphous silicon film deposited at an optimum deposition rate, crystallization at temperature as low as 200 °C is observed. It was also observed that the growth pattern of c-Si in case of AIC without post-deposition annealing was identical to AIC with annealing step.     

Dependence of electrical properties on thermal temperature in nanocrystalline SnO2 thin films

Nanocrystalline SnO2 thin films were prepared by pulsed laser deposition techniques on clean glass substrates, and the films were then annealed for 30 min from 50 to 550 degrees C with a step of 50 degrees C, respectively. The investigation of X-ray diffraction confirmed that the various SnO2 thin films were consisted of nanoparticles with average grain size in the range of 23.7-28.9 nm. Root-mean-square surface roughness of the as-prepared SnO2 thin film was measured to be 25.6 nm which decreases to 16.2 nm with thermal annealing. Electrical resistivity and refractive index were measured as a function of annealing temperature, and found to lie between 1.24 to 1.45 momega-cm, and 1.502 to 1.349, respectively. The results indicate that nearly opposite actions to root-mean-square surface roughness and electrical resistivity make a unique performance with thermal annealing temperature. The post annealing shows greater tendency to affect the structural and electrical properties of SnO2 thin films which composed of nanoparticles.     

High coercivity of ordered macroporous FePt films synthesized via colloidal templates

The preparation of a three-dimensionally (3D) ordered macroporous iron-platinum (FePt) film derived from monodisperse FePt nanoparticles (approximately 3 nm in diameter) and polystyrene latex particles (254 nm in diameter) is described. The prepared film has a hexagonally ordered porous structure and coercivity up to 10 kOe after annealing at a temperature of 600 degrees C. We also found that size of FePt particles was maintained at around 3 nm, even after annealing at a temperature of 600 degrees C.     

A study of the morphology and microstructure of LPCVD polysilicon

The morphology and microstructure of polysilicon films deposited by low-pressure chemical vapour deposition (LPCVD) have been investigated as a function of deposition conditions. The deposition temperature was varied from 540–640C. As-deposited polysilicon films had a rough surface with (110) textured columnar grain structure, while as-deposited amorphous films had a smooth surface. The polysilicon film deposited at the amorphous to polycrystalline transition temperature had an extra-rough, rugged surface with (311) texture. At the transition temperature, the grain structure tended to shift from the polycrystalline to the amorphous state with increasing deposition pressure and film thickness. It was found that nucleation of amorphous film duringin situ annealing at the transition temperature without breaking the vacuum began to occur from surface silicon atom migration, in contrast to a heterogeneous nucleation during film deposition.     

The structure and optical properties of silicon nanowires prepared by inductively coupled plasma chemical vapor deposition

Silicon nanowires were prepared by vapor-liquid-solid (VLS) mechanism at a growth temperature as low as 380 °C in an inductively coupled plasma chemical vapor deposition system. The nanowires consist of crystalline core surrounded by a thick amorphous silicon shell. An increase in plasma power produces dense and long nanowires with thick amorphous shell, accompanied with a thick uncatalyzed amorphous silicon film on the silicon substrate. Small catalyst nanoparticles are easier activated by plasma to grow the dense and thin nanowires in comparison with the large-size nanoparticles. Moreover, an enhanced optical absorption is achieved due to the strong light trapping and anti-reflection effects in the thin and tapered silicon nanowires with high density.