Nanostructure engineering in porous columnar thin films: recent advances

Glancing angle deposition (GLAD) is a physical vapour deposition method used to fabricate highly functional thin films with an engineerable columnar morphology. Recent developments in GLAD technology have produced columnar nanostructures of increased complexity, including periodic, nanofibrous, perforated, and graded porosity thin films for use in applications ranging from sensors and actuators to optical filters, microfluidics, and catalysis. A brief review of GLAD methodology and historical developments is followed by a discussion of the latest developments in this field.     

Fabrication and optical characterization of template-constructed thin films with chiral nanostructure

We report the fabrication of thin films perforated by high aspect ratio helical or chevron pores by an extension of the glancing angle deposition (GLAD) technique. The perforated films were created by transferring the nanostructure of a GLAD template film into target materials such as polymers and spin-on-glasses and subsequently removing the template. The pore shapes are shown to be highly controllable and films designed to suit particular applications are discussed. By a double templating technique, we replicate the structure of the original film using alternate materials, which are typically less suited to the unmodified GLAD technique. Helical films of Cu and Ni were created by this method and the process should be transferable to additional electrodeposited materials. The optical rotatory power of perforated thin films formed on glass substrates was characterized and perforated films were shown to be effective in rotating the polarization plane of linearly polarized incident light by as much as 1.4/spl deg///spl mu/m.     

Correlation lengths, porosity and water adsorption in TiO₂ thin films prepared by glancing angle deposition

This paper reports a thorough microstructural characterization of glancing angle deposited (GLAD) TiO(2) thin films. Atomic force microscopy (afm), grazing-incidence small-angle x-ray scattering (GISAXS) and water adsorption isotherms have been used to determine the evolution of porosity and the existence of some correlation distances between the nanocolumns constituting the basic elements of the film's nanostructure. It is found that the deposition angle and, to a lesser extent, the film thickness are the most important parameters controlling properties of the thin film. The importance of porosity and some critical dimensions encountered in the investigated GLAD thin films is highlighted in relation to the analysis of their optical properties when utilized as antireflective coatings or as hosts and templates for the development of new composite materials.     

纳米结构的倾斜角度沉积及性能优化

纳米材料发展的关键是纳米结构的制备、形貌调控和性能优化.倾斜角度沉积是以较大的角度(大于75°)倾斜入射沉积薄膜,通过控制沉积参数,得到具有特殊形貌纳米结构的方法,具有适用范围广,操作便捷,制备的薄膜面积大、纯度高、结构规整等特点,是一种理想的制备纳米材料的方法.本文介绍了采用倾斜角度沉积技术制备氧化铪抗反射薄膜和银基表面增强拉曼基底,详细分析了该方法的参数调控对纳米结构的形貌和性能的影响,并指出将倾斜角度沉积与其他先进技术相结合(以原子层沉积为例),可进一步优化纳米结构的性能,提高倾斜角度沉积的使用范围.     

Structure and microstructure of EB-PVD yttria thin films grown on Si (111) substrate

Structure and microstructure of yttria thin films grown by electron beam physical vapour deposition on a stationary Si (111) substrate at room temperature (RT), 500° and 700 °C, were investigated by the grazing-incidence X-ray diffraction and scanning electron microscopy, respectively. X-ray photoelectron spectroscopy provided information on the surface contamination from the atmosphere and the Y oxidation state. A strong effect of the deposition temperature and the vapour flux incidence angle was found. The film deposited at RT is polycrystalline with very fine grains of the body-centered cubic (bcc) crystallographic symmetry. An increase of deposition temperature results in a rapid growth of bcc grains with an improved crystalline structure. Moreover, the based-centered monoclinic phase appears for the deposition temperature of 700 °C. Preferred grain orientation (texture) with two main components, (400) and (622), was observed in the films deposited at 500 °C whereas no texture was found for 700 °C. The microstructure exhibits the columnar feather-like structure of different degrees of perfection which can be explained by the shadowing effects caused by an oblique vapour flux incidence angle. Surface morphology of the films is governed by a combination of the triangular and four-sided (square) columns. All films were found to be dense with a little porosity between the columns.     

Indium tin oxide nanowhisker morphology control by vapour-liquid-solid glancing angle deposition

A new growth technique for indium tin oxide nanowhiskers with increased control over feature size and spacing is reported. The technique is based on a unique combination of self-catalysed vapour-liquid-solid (VLS) growth and glancing angle deposition (GLAD). This VLS-GLAD technique provides enhanced control over nanowhisker morphology as the effect of typical VLS growth parameters (e.g.?flux rate, temperature) is amplified at large deposition angles characteristic of GLAD. Spatial modulation of the collimated growth flux controls trunk width, number and orientation of branches, and overall nanowhisker density. Here we report the influence of growth conditions (including deposition angle, flux rate, nominal pitch and substrate temperature) on nanowhisker morphology, with specific focus on the effect of large deposition angles. Sheet resistance and transmission of the films were measured to characterize their performance as transparent conductive oxides. Hybrid nanostructured films grown in this study include high surface area nanowhiskers protruding from a conductive film, ideal for transparent conductive electrode applications.     

Overcoming cap layer cracking for glancing-angle deposited films

Porous thin films deposited by glancing-angle deposition (GLAD) have found application as sensor, micro-electrical mechanical systems and microfluidic devices. However, conventional micro-fabrication techniques can damage the very properties which make GLAD films attractive for these applications. To facilitate integration of GLAD films with these processes, a capping layer may be used. Such capping layers must be as free of defects as possible to ensure that the GLAD film is well protected. Here, the cracking properties of evaporated TiO₂ caps deposited on GLAD films have been investigated as a function of substrate temperature. Our films are a porous vertical post layer 2.7 μm thick capped with a solid 400 nm layer. This material system experiences tensile stress from two sources: thermal mismatch between the film and substrate, and intrinsic stress in the cap from Volmer-Weber coalescence. Crack properties such as crack length distribution, crack density and branch number were quantified. In general, higher substrate temperatures reduced crack density, branch number and preferentially eliminated longer cracks. The onset of crystallinity at substrate temperatures around 300 °C briefly increases crack area and branch number, but a further reduction can be achieved by depositing above this temperature. Applications of films grown by GLAD requiring high-quality capping layers will benefit from this study.     

Characterization of ZrO2 and SiC ceramic thin films prepared by electrostatic atomization

ZrO₂ and SiC ceramic thin films and their bilayer have been successfully prepared by a newly developed electrostatic atomization technique. This technique can generate fine spray of ceramic suspensions in a micrometer sized range with a narrow size distribution which is crucial for preparation of uniform thin films of these ceramic materials. Compared to some other thin film deposition techniques, such as Chemical vapour deposition (CVD), physical vapour deposition (PVD) and plasma spray (PS) etc. the thin film deposition process using electrostatic atomization is not only cheap but also controllable. The prepared ZrO₂ and SiC thin films were investigated using scanning electron microscopy (SEM) and energy dispersion analysis (EDA) techniques. These thin films were observed to be homogenous with a particle size less than 10 m. The ZrO₂-SiC bilayer was found to have an abrupt interface, implying that the deposition process is controllable and also that functionally graded ceramic/ceramic materials can be prepared in this way if the thickness of each layer is accurately controlled.     

Periodically structured glancing angle deposition thin films

Thin films fabricated using the glancing angle deposition technique have a porous microstructure consisting of freestanding columns. Many promising applications of such thin films require that the columns be arranged in periodic arrays using substrate topographies-so-called seed layers-that enforce controlled film nucleation. In this paper, we present the optimized design, fabrication, and characteristics of periodically structured thin films, achieving highly uniform periodic film morphologies. We derive geometrical rules for designing substrate seed layers, and explain how to fabricate large area seed patterns with submicrometer features. Using negative-resist electron-beam lithography and laser direct write lithography, we have reached extremely high pattern densities. An experimental analysis is provided of seed-enforced nucleation and thin-film growth, showing that the elimination of film growth between seeds is crucial, and that the substrate seed layer geometry must match the intended film microstructure. Finally, we discuss the enhanced properties of periodically structured oblique angle thin films and their applications.     

Growth and properties of the CuInS2 thin films produced by glancing angle deposition

We use the glancing angle deposition technique (GLAD) to grow CuInS₂ thin films by a vacuum thermal method onto glass substrates. During deposition, the substrate temperature was maintained at 200 °C. Due to shadowing effect the oblique angle deposition technique can produce nanorods tilted toward the incident deposition flux. The evaporated atoms arrive at the growing interface at a fixed angle θ measured from the substrate normal. The substrate is rotated with rotational speed ω fixed at 0.033 rev s^− 1. We show that the use of this growth technique leads to an improvement in the optical properties of the films. Indeed high absorption coefficients (10⁵–3.10⁵ cm^− 1) in the visible range and near-IR spectral range are reached. In the case of the absence of the substrate rotation, scanning electron microscopy pictures show that the structure of the resulting film consists of nanocolumns that are progressively inclined towards the evaporation source as the incident angle was increased. If a rapid azimuthal rotation accompanies the substrate tilt, the resulting nanostructure is composed of an array of pillars normal to the substrate. The surface morphology show an improvement without presence of secondary phases for higher incident angles (θ > 60°).     

Estimation of vapour pressure and partial pressure of subliming compounds by low-pressure thermogravimetry

A method for the estimation of vapour pressure and partial pressure of subliming compounds under reduced pressure, using rising temperature thermogravimetry, is described in this paper. The method is based on our recently developed procedure to estimate the vapour pressure from ambient pressure thermogravimetric data using Langmuir equation. Using benzoic acid as the calibration standard, vapour pressure-temperature curves are calculated at 80, 160 and 1000 mbar for salicylic acid and vanadyl bis-2,4-pentanedionate, a precursor used for chemical vapour deposition of vanadium oxides. Using a modification of the Langmuir equation, the partial pressure of these materials at different total pressures is also determined as a function of temperature. Such data can be useful for the deposition of multi-metal oxide thin films or doped thin films by chemical vapour deposition (CVD).     

The effect of HfO<Subscript>2</Subscript> second phase in Fe films upon ion irradiation

Ferrum of BCC crystal structure is a typical kind of matrix in structural alloy steels which could be strengthened by introducing some second phase. In the present study, BCC Fe thin films with hafnium oxide (HfO₂) second phase have been synthesized in an electron beam evaporation system. Multi-layered and glancing angle deposition (GLAD) techniques were taken to form some HfO₂ second phase in Fe films. Ion irradiation was conducted to investigate the irradiation resistance of the obtained samples with and without HfO₂ second phase.     

Production of porous carbon thin films by pulsed laser deposition

Pulsed laser deposition (PLD) has been used together with the Glancing Angle Deposition (GLAD) technique [1 and 2] for the first time to produce highly porous structured films. A laser produced carbon plasma and vapour plume was deposited at a highly oblique incident angle onto rotating Si substrates, resulting in films exhibiting high bulk porosity and controlled columnar microstructure. By varying the substrate rotation rate, the shape of the microcolumns can be tailored. These results extend the versatility of the GLAD process to materials not readily deposited by means of traditional physical vapour deposition techniques.     

The effect of HfO2 second phase in Fe films upon ion irradiation

Ferrum of BCC crystal structure is a typical kind of matrix in structural alloy steels which could be strengthened by introducing some second phase. In the present study, BCC Fe thin films with hafnium oxide (HfO₂) second phase have been synthesized in an electron beam evaporation system. Multi-layered and glancing angle deposition (GLAD) techniques were taken to form some HfO₂ second phase in Fe films. Ion irradiation was conducted to investigate the irradiation resistance of the obtained samples with and without HfO₂ second phase.     

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.     

Silver-doped germanium sulphide glass channel waveguides fabricated by chemical vapour deposition and photo-dissolution process

Germanium sulphide glass thin films have been fabricated by chemical vapour deposition directly on commercial glass substrates. Silver (Ag)-doped channel waveguide structures were then prepared in a three step process, first channels were patterned in photo-resist, next a Ag thin film was deposited on the patterned waveguide by thermal evaporation, and finally the silver ions were doped into germanium sulphide glass by a photo-dissolution process. The refractive index of germanium sulphide increased by about 0.02 through the photo-dissolution process. The loss of the channel waveguides measured at 632.8 nm was 0.63 ± 0.05 dB/cm.     

Optical properties of porous helical thin films

Porous dielectric thin films, composed of isolated helical columns, are fabricated by the glancing angle deposition technique. The selective reflection of circularly polarized light and the optical rotation of linearly polarized light are investigated as a function of film material and helical morphology. The strongest chiral optical response is observed for titanium-dioxide films because of its large refractive index. Optical rotatory powers as high as 4.5 degrees are observed in 830-nm-thick helical films. By tailoring the pitch of the helical columns, the wavelength dependence of the circular reflection band is tuned to preferentially reflect red, green, or blue light, a promising quality for display applications.     

Growth of diamond thin films by chemical vapour deposition

Deposition of diamond thin films on non-diamond substrates at low pressures (<760 torr) and low temperatures (<2000°C) by chemical vapour deposition (CVD) has been the subject of intense research in the last few years. The structural and the electrical properties of CVD diamond films grown on p-type 〈111〉 and high-resistivity (>100 kΩ-cm) 〈100〉 oriented silicon substrates by hot filament chemical vapour deposition technique are described in this review paper.     

Herstellung von Präzisionsschichten mittels Ionenstrahlsputtern

Precise thin film synthesis by ion beam sputter deposition Ion beam sputter deposition (IBSD) is a promising technique for the fabrication of high performance thin films because of the well defined and adjustable particle energies, which are rather high in comparison to other PVD techniques. Recent developments concerning long‐term stability and lateral uniformity of the ion beam sources strengthen the position of the IBSD technique in the field of precise thin film synthesis. Furthermore, IBSD offers a more independent choice of relevant deposition parameters like particle energy and flux, process gas pressure and deposition rate. In this paper we present our currently installed large area IBSD facility “IonSys 1600”, which was developed by Fraunhofer IWS Dresden and Roth & Rau company (Hohenstein‐Ernstthal). Substrate sizes of up to 200 mm (circular) or up to 500 mm length (rectangular) can be coated and multilayer stacks with up to six different materials are possible. Tailored 1‐ or 2‐dimensional film thickness distributions with deviations of < 0.1 % can be fabricated by a relative linear motion of the substrate holder above an aperture. In order to demonstrate the advantages of the IBSD technique especially for sophisticated materials and films with high requirements concerning purity, chemical composition or growth structure, several examples of deposited multilayers for various applications are presented.     

Roughness of glancing angle deposited titanium thin films: an experimental and computational study

The characterization of roughness at the nanoscale by the means of atomic force microscopy (AFM) was performed on high aspect ratio glancing angle deposited titanium thin films. With the use of scanning electron microscopy as well as x-ray photoelectron spectroscopy, it was shown that the AFM measurements gave rise to incorrect roughness values for the films consisting of the highest aspect ratio structures. By correcting for this experimental artefact, the difference between the saturated roughness value of a film grown with conventional physical vapour deposition and films grown with a glancing angle of deposition was shown to behave as a power law function of the deposition angle, with a saturated roughness exponent of κ?=?7.1?±?0.2. This power law scaling was confirmed by three-dimensional molecular dynamics simulations of glancing angle deposition, where the saturated roughness exponent was calculated to κ?=?6.7?±?0.4.