Preventing Thin Film Dewetting via Graphene Capping

A monolayer 2D capping layer with high Young's modulus is shown to be able to effectively suppress the dewetting of underlying thin films of small organic semiconductor molecule, polymer, and polycrystalline metal, respectively. To verify the universality of this capping layer approach, the dewetting experiments are performed for single‐layer graphene transferred onto polystyrene (PS), semiconducting thienoazacoronene (EH‐TAC), gold, and also MoS₂ on PS. Thermodynamic modeling indicates that the exceptionally high Young's modulus and surface conformity of 2D capping layers such as graphene and MoS₂ substantially suppress surface fluctuations and thus dewetting. As long as the uncovered area is smaller than the fluctuation wavelength of the thin film in a dewetting process via spinodal decomposition, the dewetting should be suppressed. The 2D monolayer‐capping approach opens up exciting new possibilities to enhance the thermal stability and expands the processing parameters for thin film materials without significantly altering their physical properties.     

Self-organized patterned arrays of Au and Ag nanoparticles by thickness-dependent dewetting of template-confined films

In this work we report on the formation of self-organized and multimodal sized patterned arrays of Au and Ag nanoparticles on SiO₂ surface exploiting the thickness-dependent solid-state dewetting properties of template-confined deposited nanoscale films. In this approach, the Au and Ag surface pattern order, on the SiO₂ substrate, is established by the template confined deposition on a micrometric scale, while the solid-state dewetting phenomenon is induced by thermal processes (below the Au and Ag melting temperature). The deposited films have not an uniform thickness. They, instead, present a controlled thickness due to shadowing mask effects during depositions. Such an inhomogeneity can be further controlled by changing the deposition angle. After the dewetting process, scanning electron microscopy analyses allowed us to correlate the mean diameter 〈D〉 and spacing 〈s〉 of the formed nanoparticles by the thickness h of the deposited films. Despite the dewetting process of the Au and Ag films occurs in the solid state, relations describing the evolution of 〈D〉 and 〈s〉 with 〈h〉 typical of the linear hydrodynamic spinodal dewetting process of liquid films, 〈D〉 ∝ h ^5/3 and 〈s〉 ∝ h ², were verified within a 20 % experimental error. As a consequence we call this process “pseudo-spinodal dewetting”.     

Improvement of ultrathin polystyrene film stability by addition of poly(styrene-stat-chloromethylstyrene) copolymer: An atomic force microscopy study

A method to improve the stability of ultrathin polystyrene (PS) films on SiO_x/Si substrate is introduced. In this method, interfacial interactions between PS film and substrate are enhanced by addition of poly(styrene-stat-chloromethylstyrene(ClMS)) copolymer containing 5 mol% of ClMS group. The resulting slight structural modification of the copolymer does not cause phase separation in the polymer blend. On the other hand, the existence of polar ClMS groups provides anchoring sites on the polar SiO_x surface via dipolar interactions. In this study, ratios of the copolymers are varied from 0 to 40 wt.% in the thin films resulting in a systematic increase of the interfacial interactions. The dewetting behaviors of all films subjected to the same annealing conditions are explored via atomic force microscopy. The analyses of root mean square roughness and dewetting area as a function of annealing time and copolymer ratio provide information about the film stability. Our results indicate that blending small quantity of the copolymer with PS significantly increases the stability of ultrathin films.     

Morphological and optical properties of PdxAg1-x alloy nanoparticles

Alloy nanoparticles (NPs) can offer a wide range of opportunities for various applications due to their composition and structure dependent properties such as multifunctionality, electronic heterogeneity, site-specific response, and multiple plasmon resonance bands. In this work, the fabrication of self-assembled Pd_xAg_1-x NPs alloy nanostructures with distinct size, density, shape, and composition is demonstrated via the solid-state dewetting of sputtered Pd/Ag thin films on c-plane sapphire. The initial stage of bilayer dewetting exhibits the nucleation of voids, followed by the expansion of voids and cluster breakdown and finally shape transformation along with the temperature control. Bilayer composition shows a substantial influence on the dewetting such that the overall dewetting is enhanced along with the increased Ag composition, i.e. Pd_0.25Ag_0.75 > Pd_0.5Ag_0.5 > Pd_0.75Ag_0.25. On the other hand, the size and density of NPs can be efficiently controlled by varying the initial thickness of bilayers. Reflectance peaks in UV and near-infrared (NIR) regions and a wide absorption band in the visible region arisen from the surface plasmon resonance are observed in reflectance spectra. The peak intensity depends on the composition of Pd_xAg_1-x NPs and the NIR peaks gradually blue-shift with the size decrement.     

Influences of poly[(styrene)x-stat-(chloromethylstyrene)y]s additives on dewetting behaviors of polystyrene thin films: effects of polar group ratio and film thickness

This contribution investigates the addition of poly(styrene-stat-chloromethylstyrene (ClMS))s as dewetting inhibitors of polystyrene (PS) thin films with thicknesses ranging from 12 to 38 nm. The ClMS ratios in the copolymers are 5, 25 and 45 mol%. Atomic force microscopy and optical microscopy are utilized to follow morphological changes of blended PS/copolymer films upon annealing above their glass transition temperatures. We have found that thermal stability of the PS films is greatly improved when a small amount of the copolymers is added into the system. The polar ClMS groups provide anchoring sites with the polar SiO_x/Si substrate while the styrene segments favorably interact with the PS matrix. The effectiveness of the copolymers as dewetting inhibitors is also found to increase with mole ratio of ClMS group. While the stability of PS films is systematically improved upon addition of the highly substituted copolymers, using the copolymer with relatively low ratio of ClMS group could lead to the opposite result. This class of copolymers can be utilized for improving thermal stability of ultrathin PS films. The fundamental knowledge from this study is also important for designing or selecting structure of additives used to improve the stability of polymeric thin films.     

Technological conditions for optimization of the optoelectronic parameters of the (As2S3)x(As2Se3)1−x glassy semiconductor films on a polymer roll base

We have experimentally studied dependence of the optoelectronic parameters (resistance, photosensitivity, drift mobility, and optical absorption edge) of thin (As₂S₃)_x(As₂Se₃)_1−x glassy semiconductor films on the rate of their thermal deposition in vacuum onto a Lavsan (Dacron) roll base. Films obtained at the optimum deposition rates, ranging from 4 to 7×10⁻³ μm/s, are characterized by greater values of the resistance, photosensitivity, and drift mobility, while the absorption edge approaches a value typical of a bulk glassy semiconductor. The influence of pores, formed in the volume of the deposit, on the physical properties of the films is discussed.     

Preparation of Zr1−x AlxO2 by annealing of ZrOx/Al thin films in the air atmosphere

Preparation of Zr_1−xAl_xO₂ by annealing of ZrO_x/Al thin layers in the reactive medium is presented in this work. At first ZrO_x thin films were deposited by reactive cathodic arc evaporation. Cathodic arc evaporation is the most versatile PVD coating technology. The process uses arc evaporation to create highly ionized plasma. It allows the “droplets” to escape into the coating under special condition in the chamber. After complete analysis of the process of arc deposition, ZrO_x thin films with thickness of ∼600 nm were deposited on Al₂O₃ and quartz substrates. Using vaporization on ZrO_x thin films 10% mol of Al was deposited and these ZrO_x/Al thin films were annealed at 500–900 °C in the air medium. The Zr_0.9Al_0.1O₂ thin films with nanocrystallite and two phases, monoclinic and cubic, were produced using the above-mentioned technique. The structure and optical properties of films were investigated by XRD, ellipsometry, photospectometry, respectively.     

Electrical properties and phase transition of Ge1−x Sn x Se2.5 thin films

The Ge_1–x Sn _x Se_2.5 system was prepared by melting the correct ratio of high purity elements in quartz evacuated ampoules followed by quenching in ice. It was found that, within the Ge_1–x Sn _x Se_2.5 system, a glassy state can be formed when 0 x 0.4. On increasing x to 0.6 a glassy state could not be obtained, as is confirmed by X-ray diffraction. Differential thermal analysis (DTA) was carried out to study the effect of composition on the stability of amorphous phase. Ge_1–x Sn _x Se_2.5 (where 0 x 0.6) thin films have been prepared by the thermal evaporation technique. The electrical conductivity of the thin films have been studied as a function of composition and film thickness.     

Structural and optical properties of In doped Se–Te phase-change thin films: A material for optical data storage

Se_75−xTe₂₅In_x (x = 0, 3, 6, & 9) bulk glasses were obtained by melt quench technique. Thin films of thickness 400 nm were prepared by thermal evaporation technique at a base pressure of 10⁻⁶ Torr onto well cleaned glass substrate. a-Se_75−xTe₂₅In_x thin films were annealed at different temperatures for 2 h. As prepared and annealed films were characterized by X-ray diffraction and UV–Vis spectroscopy. The X-ray diffraction results show that the as-prepared films are of amorphous nature while it shows some poly-crystalline structure in amorphous phases after annealing. The optical absorption spectra of these films were measured in the wavelength range 400–1100 nm in order to derive the extinction and absorption coefficient of these films. It was found that the mechanism of optical absorption follows the rule of allowed non-direct transition. The optical band gap of as prepared and annealed films as a function of photon energy has been studied. The optical band gap is found to decrease with increase in annealing temperature in the present glassy system. It happens due to crystallization of amorphous films. The decrease in optical band gap due to annealing is an interesting behavior for a material to be used in optical storage. The optical band gap has been observed to decrease with the increase of In content in Se–Te glassy system.     

Influence of laser-irradiation on the optical constants Se75S25 − xCdx thin films

Amorphous thin films of glassy alloys of Se₇₅S_25 − xCd_x (x = 2, 4 and 6) were prepared by thermal evaporation onto chemically cleaned glass substrates. Optical absorption and reflection measurements were carried out on as-deposited and laser-irradiated thin films in the wavelength region of 500-1000 nm. Analysis of the optical absorption data shows that the rule of no-direct transitions predominates. The laser-irradiated Se₇₅S_25 − xCd_x films showed an increase in the optical band gap and absorption coefficient with increasing the time of laser-irradiation. The results are interpreted in terms of the change in concentration of localized states due to the shift in Fermi level. The value of refractive index increases decreases with increasing photon energy and also by increasing the time of laser-irradiation. With the large absorption coefficient and change in the optical band gap and refractive index by the influence of laser-irradiation, these materials may be suitable for optical disc application.     

Carbon nitride as a buffer layer for magnetic thin films

Amorphous carbon nitride (CN_{x, 0.1<x<0.3}) thin films present a unique combination of hardness and compliance and may be useful for incorporation into ferromagnetic multilayers. We present a study of the use of amorphous CN_x as a buffer layer for NiFe magnetic thin films. The surface roughness of the NiFe films is comparable to films on Ta or Cu buffer layers and is stable with annealing at 200 °C. Effects on the magnetization and coercivity are seen, and may be due to several mechanisms, including chemical reactions at the interface and interdiffusion.     

Influences of carbon content and power density on the uniformity of PECVD grown a-Si1−x:Cx:H thin films

Large area electronics require large size thin films whose eventual inhomogeneities arise as a problem. Hydrogenated amorphous silicon carbide thin films (a-Si_1−xC_x:H) for four different source gas mixtures at two power densities were deposited by plasma enhanced chemical vapor deposition (PECVD) technique. The degree of film homogeneity was investigated through measurements of deposition rate, refractive index and optical energy gap along the radial direction of bottom electrode. Both ellipsometer at various incident angles and optical transmittance at normal incidence were used in mutual control as diagnosing tools. It seems there is a critical power density beyond which inhomogeneities of the deposited films along the radial direction of the electrode are unavoidable.     

Solid-state dewetting of Pt on (100) SrTiO3

Continuous thin films of Pt on (100) SrTiO₃ substrates were dewetted to form Pt particles at 1,150 °C, using an oxygen partial pressure of 10^?20 atm. After retraction of thick (50 or 100 nm) Pt films, SrTiO₃ anisotropic rods, slightly depleted in Ti, were found on the surface of the substrate. Rods did not form after dewetting of thinner (10 nm) Pt films. After dewetting, a ~10 nm thick interfacial phase was found between the Pt and the SrTiO₃. The interfacial phase, based on Sr and containing ~25 at% oxygen, is believed to be a transient state, formed due to Ti depletion from the substrate, resulting in a Pt(Ti) solution in the particles. The interfacial phase forms due to the low oxygen partial pressure used to equilibrate the system, and is expected to influence the electrical properties of devices based on Pt–SrTiO₃.     

Annealing effect on crystallization behavior of cubic MgxZn1−xO films on A-plane and M-plane sapphire

Cubic Mg_xZn_1−xO thin films with Mg composition around 70% were deposited on A-plane and M-plane sapphire substrates by rf-reactive magnetron sputtering. Measured structural and optical properties of these thin films indicated an optimal annealing temperature of 700 °C which produced high quality cubic MgZnO thin films on both substrates. Moreover, when the annealing temperature exceeded 750 °C, a much rougher surface resulted, and several large mosaic particles on the surface of the annealed films appeared. From EDX results, the Mg composition was lower than that found in other sections of the annealed films. We attributed this to thermally induced reconstruction of the crystallites. This phenomenon was more obvious for annealed MgZnO films on A-plane sapphire than that on M-plane sapphire. Thermal expansion mismatch with the substrate is the principal reason.     

Optical and electrical properties of hydrogenated amorphous Si1-xGex alloy thin films prepared by planar magnetron sputtering

Thin films of hydrogenated amorphous Si_1-xGe_x were prepared by the r.f. diode planar magnetron sputtering method using composite targets of silicon and germanium in an atmosphere of H₂ diluted with argon. The optical absorption coefficient, d.c. conductivity, photoconductivity and IR transmission spectra were measured, and the dependence of these characteristics on the germanium content x was investigated. For films with x ≈ 0.1, it is found that the dark conductivity decreases and the ratio of the photoconductivity to the dark conductivity increases by about one order of magnitude compared with those for hydrogenated amorphous silicon. This phenomenon seems to be caused by a reorganization of the tetrahedrally bonded structure. Films of this composition are considered to be of interest as an opto-electronic material requiring a high resistance. Photoconductive effects are not observed for films with x > 0.3. This is considered to be due to an alloying effect. The decrease in the amount of bonded hydrogen in the films becomes appreciable for the films with x > 0.6.     

反应溅射NiCrOx薄膜过程及其光学性质的研究

研究了反应气体流量对磁控反应溅射ＮｉＣｒＯｘ薄膜成分和光学常数的影响,在反应溅射过程中,ＮｉＣｒ靶随着Ｏ２流量的增大出现毒化现象,在不同氧流量条件下可沉积出近于透明的介电薄膜和不透明的吸收薄膜,对薄膜光学常数的研究可应用到太阳能光谱选择摹制备。     

Thin films preparation by rf-sputtering of copper/iron ceramic targets with Cu/Fe = 1: From nanocomposites to delafossite compounds

In the Cu-Fe-O phase diagram, delafossite CuFeO₂ is obtained for the Cu^I oxidation state and for the Cu/Fe = 1 ratio. By decreasing the oxygen content, copper/spinel oxide composite can be obtained because of the reduction and the disproponation of cuprous ions. Many physical properties as for instance, electrical, optical, catalytic properties can then be affected by the control of the oxygen stoichiometry.In rf-sputtering technique, the bombardment energies on the substrate can be controlled by the deposition conditions leading to different oxygen stoichiometry in the growing layers.By this technique, thin films have been prepared from two ceramic targets: CuFeO₂ and CuO + CuFe₂O₄. We thus synthesized either Cu⁰/Cu_xFe_1−xO₄ nanocomposites thin films with various Cu⁰ quantities or CuFeO₂-based thin films.Two-probes conductivity measurements were permitted to comparatively evaluate the Cu⁰ content, while optical microscopy evidenced a self-assembly phenomenon during thermal annealing.     

Absorbing TiOx thin film enabling laser welding of polyurethane membranes and polyamide fibers

We report on the optical properties of thin titanium suboxide (TiO_x) films for applications in laser transmission welding of polymers. Non-absorbing fibers were coated with TiO_x coatings by reactive magnetron sputtering. Plasma process parameters influencing the chemical composition and morphology of the deposited thin films were investigated in order to optimize their absorption properties. Optical absorption spectroscopy showed that the oxygen content of the TiO_x coatings is the main parameter influencing the optical absorbance. Overtreatment (high power plasma input) of the fiber surface leads to high surface roughness and loss of mechanical stability of the fiber. The study shows that thin substoichiometric TiO_x films enable the welding of very thin polyurethane membranes and polyamide fibers with improved adhesion properties.     

Optical properties of amorphous, erbium-doped yttrium alumino-borate thin films

In this paper, we report on the optical characterizations of erbium-doped yttrium alumino-borate glassy thin films prepared by the polymeric precursor and sol-gel routes and the spin-coating technique. High quality planar waveguides were produced by a multilayer processing of Y_1−xEr_xAl₃(BO₃)₄ compositions with x = 0.02, 0.05, 0.10, 0.30, and 0.50. Their optical properties were investigated using transmission, photoluminescence, and m-lines spectroscopy, whereas high resolution scanning electron microscopy (HR-SEM) was applied to check film thickness and surface homogeneity. The refractive indices determined from transmission and m-lines spectroscopy are in good agreement just like the film thickness measured by HR-SEM and transmission spectroscopy. We observed low propagation losses, together with efficient photoluminescence emission for polymeric precursor thin films, involving low cost and environment friendly reactants.     

CuIn1 − xAlxSe2 thin films obtained by selenization of evaporated metallic precursor layers

CuIn_1 − xAl_xSe₂ (CIAS) thin films were grown by a two stage process. Cu, In and Al layers were sequentially evaporated and subsequently heated with elemental selenium in a quasi-closed graphite box. Different x values (0 ≤ x ≤ 0.6) were obtained by varying the Al and In precursor layers thicknesses. Selenization conditions such as Se amount provided during the selenization process were adjusted in order to optimize the film properties. Polycrystalline CuIn_1 − xAl_xSe₂ thin films with chalcopyrite structure were obtained. Referred to CuInSe₂ thin films the lattice parameters, the (112) orientation and the average crystallite size decreased and the band gap energy increased with increasing Al content. To optimize structural properties of the CIAS films a higher Se amount was required as the x value increased. The incorporation of Al changed the thin film morphology towards smaller grain sizes and less compact structures.