Molecular layer deposition of functional thin films for advanced lithographic patterning

Photoresist materials comprise one of the main challenges faced by lithography to meet the requirements of electronic device size scaling. Here we report for the first time the use of molecular layer deposition (MLD) to produce photoresist materials with controllable placement of functional moieties. Polyurea resists films are deposited by MLD using urea coupling reactions between 1,4-phenylene diisocyanate (PDIC) and ethylenediamine (ED) or 2,2'-(propane-2,2-diylbis(oxy))diethanamine (PDDE) monomers in a layer-by-layer fashion with a linear growth rate, allowing acid-labile groups to be incorporated into the film at well-controlled positions. The films are deposited with stoichiometric compositions and have highly uniform surface morphology as investigated using atomic force microscopy. We show that acid treatment can cleave the backbone of the polyurea film at positions where the acid-labile groups are embedded. We further show that after soaking the polyurea film with photoacid generator (PAG), it acts as a photoresist material and we present several UV patterning demonstrations. This approach presents a new way to make molecularly designed resist films for lithography.     

Pulsed laser deposition of YBCO thin films in a shadow mask configuration

We present an investigation on a modified pulsed laser deposition method (PLD) that employs plume geometric shadowing (Nd:YAG laser, 1.06 μm, 2.5 J/cm², YBCO target). A plane shadow mask and a newly proposed helical mask were used. The aim of our approach was to improve the film surface morphology. The study investigated the influence of the main geometrical parameters of the two configurations on the plume propagation and film morphology. Using the shadow plane mask method we deposited extremely smooth YBCO films with a roughness of 4–5 nm (RMS), which is an improvement of two orders of magnitude compared with standard PLD. The helical shadow mask allows deposition of films of the same roughness as in the plane mask case, but brings further improvement by eliminating the film thickness non-uniformity, typical for plane mask configuration. In both cases the deposition rate decreased up to 7–12 times compared with standard PLD.     

Laser-ablated plasma for deposition of ZnO thin films on various substrates

We report optical and structural properties of ZnO films deposited by pulsed laser deposition technique on 1100) n-typesilicon and quartz substrates at various pressures of back ground gas. ZnO plasma was created using KrF laser 1248 nm) atvarious pressures of the ambient gas, oxygen. Laser induced plasma at varying fluence on the target was investigated using optical emission spectroscopy and 2-D images of the expanding plumes. X-ray diffraction, atomic force microscopy, and spectro-photometry were used to characterize as grown films.     

Laser-ablated plasma for deposition of ZnO thin films on various substrates

We report optical and structural properties of ZnO films deposited by pulsed laser deposition technique on (100) n-type silicon and quartz substrates at various pressures of back ground gas. ZnO plasma was created using KrF laser (248 nm) at various pressures of the ambient gas, oxygen. Laser induced plasma at varying fluence on the target was investigated using optical emission spectroscopy and 2-D images of the expanding plumes. X-ray diffraction, atomic force microscopy, and spectro-photometry were used to characterize as grown films.     

Deposition of thermal and hot-wire chemical vapor deposition copper thin films on patterned substrates

In this work we study the hot-wire chemical vapor deposition (HWCVD) of copper films on blanket and patterned substrates at high filament temperatures. A vertical chemical vapor deposition reactor was used in which the chemical reactions were assisted by a tungsten filament heated at 650 degrees C. Hexafluoroacetylacetonate Cu(I) trimethylvinylsilane (CupraSelect) vapors were used, directly injected into the reactor with the aid of a liquid injection system using N2 as carrier gas. Copper thin films grown also by thermal and hot-wire CVD. The substrates used were oxidized silicon wafers on which trenches with dimensions of the order of 500 nm were formed and subsequently covered with LPCVD W. HWCVD copper thin films grown at filament temperature of 650 degrees C showed higher growth rates compared to the thermally ones. They also exhibited higher resistivities than thermal and HWCVD films grown at lower filament temperatures. Thermally grown Cu films have very uniform deposition leading to full coverage of the patterned substrates while the HWCVD films exhibited a tendency to vertical growth, thereby creating gaps and incomplete step coverage.     

Optical and electrochemical properties of multilayer polyelectrolyte thin films incorporating spherical, gold colloid nanomaterials

Polyelectrolyte multilayer (PEM) films incorporating various types of spherical, gold nanomaterials (NMs) were investigated to assess the existence of electrochemical and/or optical signal enhancement effects directly attributable to embedded NMs and the relationship of these effects to film structure and composition. Specifically, electrostatically assembled films of cationic poly-l-lysine (PLL) and anionic poly(4-styrene sulfonate) (PSS) incorporating one of four types of spherical, gold colloid NMs were constructed on 3-(aminopropyl)trimethoxysilane (3-APTMS)-modified glass substrates for optical studies or 11-mercaptoundecanoic (MUA)-modified gold electrodes for electrochemical studies. The NMs inserted into the PEM films include citrate-stabilized gold nanoparticles, thioctic acid-stabilized gold nanoparticles (TAS-NPs), MUA-modified monolayer protected gold clusters, and hollow gold nanoshells (Au-NSs). Optical sensitivity of the NM-embedded films, in terms of absorbance, surface plasmon band shifts, and the dependence of these optical responses on film thickness, varied depending on the type of NM within the film (e.g., TAS-NPs versus Au-NSs) but exhibited no corresponding electrochemical effects in the diffusional voltammetry of a ferricyanide redox probe. While not correlated to optical responses, the increased Faradaic current achieved during voltammetry at NM-embedded PEM films suggested that electrochemical effects of NMs were less dependent on the type of NMs and were, instead, more related to their location within the film and the electrostatic interactions built into the interfacial chemistry of the films. These results should prove useful for developing strategies constructing thin films with NMs that are specifically designed for optical or electrochemical sensing, taking full advantage of the signal enhancements provided by individual types of NMs.     

Spray pyrolysis deposition of lanthanum telluride thin films and their characterizations

Spray pyrolysis method is used to deposit lanthanum telluride (La₂Te₃) thin films on glass substrates. The films are deposited by pyrolysis of sprayed solutions of LaCl₃ and Te metal dissolved in concentrated HCl and HNO₃ along with hydrazine hydrate as a reducing agent. X-ray diffraction analyses show that the films are polycrystalline with La₂Te₃ phase. The films have a direct optical band gap of 2.2 eV. The films are p-type semiconductors with an electrical resistivity of the order of 10⁴ Ω cm at ambient temperature (27 °C).     

Deposition of CNx thin films by plasma-activated chemical vapour deposition using various precursors as carbon source

CNx-thin films have been deposited by plasma-activated chemical vapour deposition with capacitively or inductively coupled r.f. plasma. Acetylene, methane, carbon monoxide and tetracyanoethylene have been used as carbon precursor. A strong dependence of the layer properties on the precursor was found. In some films the nitrogen to carbon ratio was close to that of C3N4. The highest nitrogen content was observed in films made from carbon monoxide as precursor in an inductively coupled argon/nitrogen plasma. The nitrogen was mainly incorporated with covalent nitrogen–carbon single bonds. X-ray diffraction measurements showed no reflections indicating crystallinity. In small grains (length ∼10 μm) found on the layer surface the stoichiometry corresponded nearly to that of C3N4, the oxygen content is very low. Further characterizations by TEM are intended. This revised version was published online in November 2006 with corrections to the Cover Date.     

The deposition of amorphous carbon thin films for hard mask applications by reactive particle beam assisted sputtering process

In this work, amorphous carbon thin films for hard mask applications were deposited by a reactive particle beam (RPB) assisted sputtering system at room temperature. The deposition characteristics of the films were investigated as functions of operating parameters such as reflector bias voltage and RF plasma power. By spectroscopic ellipsometry, the decrease in the refractive index of films at the wavelengths of 633 and 248 nm was observed with the increasing plasma power. In Raman spectra, the positions of G line shifted to higher wavenumbers with increasing plasma power. When the reflector bias voltage increases, the deposition rate was increased but the positions of G line remained nearly unchanged.     

Nanoparticulate magnetite thin films as electrode materials for the fabrication of electrochemical capacitors

Magnetite nanoparticles in stable colloidal suspension were prepared by the co-precipitation method. Nanoparticulate magnetite thin films on supporting stainless steel plates were prepared by drop-coating followed by heat treatment under controlled conditions. The effects of calcination temperature and atmosphere on the microstructure and electrochemical properties of nanoparticulate magnetite thin films were investigated. Nanoparticulate magnetite thin films prepared under optimized conditions exhibited a specific capacitance value of 82 F/g in mild aqueous 1.0 M Na₂SO₄ solution. Due to their high charge capacity, good cycling reversibility, and stability in a mild aqueous electrolyte, nanoparticulate magnetite thin films appear to be promising electrode materials for the fabrication of electrochemical capacitors.     

Preparation of nitrogen-doped YSZ thin films by pulsed laser deposition and their characterization

The pulsed laser deposition technique was applied to deposit nitrogen-doped yttria stabilized zirconia (YSZ) thin films. The working parameters were varied in order to achieve a maximal nitrogen content. The films were characterized by SIMS, XPS, X-ray diffraction and optical spectroscopy. The surface topography was studied by AFM and HRSEM. The influence of the deposition parameters on the film properties is discussed.

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Magnetic anisotropy of Co-Cr thin films as a function of substrate temperature during deposition

A sequence of Co78Cr22films, 500 nm in thickness, was prepared by deposition on glass in a modified Varian D.C. magnetron S-gun sputtering system. The substrate temperature during deposition, Ts, was fixed at various values with an upper limit of 300°C. Specimens were examined by VSM, TM, FMR and TEM. Msrises significantly with increasing Ts, peaking at 200°C at 370 emu/cm³. The effective volume-averaged anisotropy drops for Ts>110°C from +1.6 KOe to progressively negative values (-4.3 KOe at 300°C). From FMR we find indications of the presence, in addition to the transition and bulk layers, of a highly negative anisotropy constituent (sim-11.5KOe anisotropy field). This resonance appears at Tsvalues of 150°C and above. TEM plane and cross-section views taken on a Ts= 150°C specimen show islands composed of tilted columns within the bulk. For vertical recording, specimens prepared at Tsvalues between 50 and 100°C are recommended. On the other hand, for longitudinal recording applications, films prepared at Tsvalues above 250°C would seem to be appropriate.     

Atomic layer deposition process with TiF4 as a precursor for depositing metal fluoride thin films

A novel atomic layer deposition process for the preparation of fluoride thin films in a temperature range of 225 degrees C-400 degrees C is introduced. The crystallinity, morphology, composition, thicknesses, refractive indices, and transmittance of the films are analyzed. Low impurity levels are obtained at 350 degrees C-400 degrees C with good stoichiometry. Refractive indices of 1.34-1.42 for MgF(2), 1.43 for CaF(2), and 1.57-1.61 for LaF(3) films are obtained.     

Effect of deposition time on sputtered ZnO thin films and their gas sensing application

Nowadays, advanced industrialization and population growth have led to increasing the environmental related issues. This paper reports the effect of deposition time on ZnO films deposited on to the glass substrate by using rf magnetron sputtering technique and their further use for gas sensing applications. Herein, deposition time is considered to be changed from 300 s, 800 s (S1, S2). The thickness of deposited films lies in the range of 130–180 nm. The synthesized films were characterized by various techniques in terms of structural, morphological, optical and gas sensing properties. The typical crystal size of ZnO films was found to be in the range of 15–27 nm. FESEM analysis revealed the growth of nanospheres was lies in the range of 80–120 nm. Fourier transform infrared spectroscopy confirmed the ZnO bonding located at a wavelength of 430 cm^?1. The average optical transmittance of the film was about 90–95% in the visible range. The optical band gap of ZnO films was decreased from 3.31 to 3.29 eV. The detailed characterization study showed 800 s is an optimum deposition time for good optoelectronic properties. For gas sensing application, highest sensitivity was obtained at operating temperature of 205 °C. Prepared films have a quick response and fast recovery time in the range of 128 s and 163 s respectively. These response and recovery time characteristics were explained by valence ion mechanism.     

Spray deposition process of polycrystalline thin films of CuWO4 and study on its photovoltaic electrochemical properties

The preparation of copper tungstate (CuWO₄) thin film for the first time by Spray Pyrolysis (SP) process using its ammonical solution as precursor is presented here. The growth of the film takes place by pyrolytic decomposition of the spraying precursor solution onto the preheated glass substrates. X-ray diffraction (XRD) study confirms the polycrystalline, single-phase nature of the sintered films. Scanning electron microscope (SEM) images clearly show the uniform aggregate of crystallites of dimensions 1–2 μm. The study of optical absorption spectrum in the wavelength range 350–850 nm shows direct as well as indirect optical transitions in both the materials. The films are semiconducting in nature and highly resistive at room temperature as evident from their d.c. electrical conductivity measurements obtained by the Two Point Probe method in the temperature range 310–600 K. The thin films deposited on fluorine doped tin oxide (FTO) coated conducting glass substrates are then used as photoanode in photovoltaic electrochemical (PVEC) cell. The PVEC cell configuration is: CuWO₄ |Ce⁴⁺, Ce³⁺| Pt; 0.1 M in 0.1 N H₂SO₄. The PVEC characterization reveals the fill factor and power conversion efficiency to be 0.33 and 0.64%, respectively. The flat band potential is found to be − 0.14 V (SCE).     

Mesoscopic and submicroscopic patterning in thin polymer films: Impact of the solvent

Formation of mesoscopic and submicrometric self-assembled patterns in polystyrene and polycarbonate films produced by a fast dip-coating process was studied. Mixtures of chloroform and dichloromethane were used as a solvent. The mixture's composition plays a decisive role in the patterning. Close-packed honeycomb structures comprised of 200–2000 nm pores dispersed in polymer matrix were obtained. The mechanism of self-assembling is discussed.     

Direct patterning of double-layered metal thin films by a pulsed Nd:YAG laser beam

Metal thin-film patterning is of technological significance because modern electronic devices commonly require an electrode or metallization pattern. There are many cases where this pattern consists of two different metallic layers in order to improve the mechanical and electrical contact. We here show that double-layered metal thin films evaporated on glass can be directly patterned by a spatially-modulated pulsed Nd-YAG laser beam incident from the backside of the substrate. This method utilizes a pulsed laser-induced thermo-elastic force exerting on the film which plays a role to detach it from the substrate. Since the film is polycrystalline with nano-sized grains, a spatially-modulated thermo-elastic force may enable selective removal of the material by shearing along the weakly-bonded grain boundary regions. Many different combinations of Al, Ag, and Au layers have been investigated and their pattern fidelity and morphology are discussed, along with the simulation results for double-layered nanocystalline films.     

ZnO thin films prepared by atomic layer deposition and rf sputtering as an active layer for thin film transistor

Recently, the application of ZnO thin films as an active channel layer of transparent thin film transistor (TFT) has become of great interest. In this study, we deposited ZnO thin films by atomic layer deposition (ALD) from diethyl Zn (DEZ) as a metal precursor and water as a reactant at growth temperatures between 100 and 250 °C. At typical growth conditions, pure ZnO thin films were obtained without any detectable carbon contamination. For comparison of key film properties including microstructure and chemical and electrical properties, ZnO films were also prepared by rf sputtering at room temperature. The microstructure analyses by X-ray diffraction have shown that both of the ALD and sputtered ZnO thin films have (002) preferred orientation. At low growth temperature T_s ≤ 125 °C, ALD ZnO films have high resistivity (> 10 Ω cm) with small mobility (< 3 cm²/V s), while the ones prepared at higher temperature have lower resistivity (< 0.02 Ω cm) with higher mobility (> 15 cm²/V s). Meanwhile, sputtered ZnO films have much higher resistivity than ALD ZnO at most of the growth conditions studied. Based upon the experimental results, the electrical properties of ZnO thin films depending on the growth conditions for application as an active channel layer of TFT were discussed focusing on the comparisons between ALD and sputtering.