Aluminum oxide barrier coating on polyethersulfone substrate by atomic layer deposition for barrier property enhancement

Aluminum oxide layers were deposited on flexible polyethersulfone (PES) substrates via plasma enhanced atomic layer deposition (PEALD) process using trimethylaluminum (TMA) and oxygen as precursor and reactant materials. Several process parameters in PEALD process were investigated in terms of refractive index and layer thickness. Number of process cycle increased the thickness and refractive index of the layer to enhance the barrier properties. Non-physisorbed TMA and unreacted oxygen were purged before and after the plasma reaction, respectively. Identical purge time was applied to TMA and oxygen and it was optimized for 10 s. Thinner and denser layer was formed as substrate temperature increased. However, the PES substrate could be deformed above 120 °C. Aluminum oxide layer formed on PES at optimized conditions have 11.8 nm of thickness and reduced water vapor transmission rate and oxygen transmission rate to below 4 × 10^− 3 g/m² day and 4 × 10^− 3 cm³/m² day, respectively. Polycarbonate and polyethylene naphthalate films were also tested at optimized conditions, and they also showed quite appreciable barrier properties to be used as plastic substrates.     

Atomic layer deposited aluminum oxide barrier coatings for packaging materials

Thin aluminum oxide coatings have been deposited at a low temperature of 80 °C on various uncoated papers, polymer-coated papers and boards and plain polymer films using the atomic layer deposition (ALD) technique. The work demonstrates that such ALD-grown Al₂O₃ coatings efficiently enhance the gas-diffusion barrier performance of the studied porous and non-porous materials towards oxygen, water vapor and aromas.     

Fluorescent tags to visualize defects in Al2O3 thin films grown using atomic layer deposition

Defects and cracks in thin film barriers that are coated on polymers allow the leakage of reactive species through the polymer substrate. Fluorescent tags have been developed to visualize defects and cracks in thin film barriers and to inspect rapidly the barrier quality with minimal sample preparation. For Al₂O₃ films with a thickness of 25 nm deposited on polyethylene naphthalate polymer substrates using atomic layer deposition techniques, the fluorescent tags have identified cracks ~ 20 nm in width after applied strain and have observed individual defects as small as ~ 200 nm in diameter.     

Electrical resistivity of Ti-Zn mixed oxide thin films deposited by atomic layer deposition

Ti-Zn mixed oxide thin films, with thickness less than 50 nm, were grown with atomic layer deposition (ALD) technique at low temperature (90 °C) varying the composition. ALD is a powerful chemical technique to deposit thin films with thickness of few atomic layers. ALD oxide material growth is achieved by dosing sequentially the metal precursor and the oxidizing agent. Thanks to ALD nature of layer by layer growth it was possible to realize mixed metal, Ti and Zn, oxide thin films with controlled composition, simply by changing the number of cycles of each metal oxide layer. Structural and electrical properties of the prepared thin films were studied as a function of their composition. Synchrotron radiation X-ray diffraction technique was used to follow thin film crystallization during sample annealing, performed in situ. It was observed that the onset temperature of crystallization raises with Ti content, and sample structure was Zn₂TiO4 phase. Electrical resistivity measurements were performed on crystalline samples, annealed at 600 °C, revealing an increase in resistivity with Ti content.     

Comparison of some coating techniques to fabricate barrier layers on packaging materials

Atomic layer deposition (ALD), electron beam evaporation, magnetron sputtering and a sol-gel method were used to deposit thin aluminum oxide coatings onto two different fiber-based packaging materials of commercial board grades coated with synthetic and biodegradable polymers. Significant decreases in both the water vapor and oxygen permeation rates were observed. With each technique the barrier performance was improved. However, among the techniques tested ALD was found to be most suitable. Our results moreover revealed that biodegradable polylactic acid-coated paperboard with a 25-nm thick layer of aluminum oxide grown by ALD on top of it showed promising barrier characteristics against water vapor and oxygen.     

Effects of argon and oxygen flow rate on water vapor barrier properties of silicon oxide coatings deposited on polyethylene terephthalate by plasma enhanced chemical vapor deposition

Plasma polymer coatings were deposited from hexamethyldisiloxane on polyethylene terephthalate (PET) substrates while varying the operating conditions, such as the Ar and O₂ flow rates, at a fixed radio frequency power of 300 W. The water vapor transmission rate (WVTR) of the untreated PET was 54.56 g/m²/day and was decreased after depositing the silicon oxide (SiO_x) coatings. The minimum WVTR, 0.47 g/m²/day, was observed at Ar and O₂ flow rates of 4 and 20 sccm, respectively, with a coating thickness of 415.44 nm. The intensity of the peaks for the Si-O-Si bending at 800-820 cm^− 1 and Si-O-Si stretching at 1000-1150 cm^− 1 varied depending on the Ar and O₂ flow rates. The contact angle of the SiO_x coated PET increased as the Ar flow rate was increased from 2 to 8 sccm at a fixed O₂ flow rate of 20 sccm. It decreased gradually as the oxygen flow rate increased from 12 to 28 sccm at a fixed Ar carrier gas flow rate. The examination by atomic force microscopy revealed a correlation of the SiO_x morphology and the water vapor barrier performance with the Ar and O₂ flow rates. The roughness of the deposited coatings increased when either the O₂ or Ar flow rate was increased.     

Magneto-optical Kerr-effect studies on copper oxide thin films produced by atomic layer deposition on SiO2

This work demonstrates the sensitivity of magneto-optical Kerr-effect (MOKE) spectroscopy to ultra-thin nonmagnetic films using the example of copper oxide. The films with an effective thickness between 0.6 nm and 6 nm are produced by atomic layer deposition (ALD) on silicon oxide substrates based on the Cu(I) β-diketonate precursor [(ⁿBu₃P)₂Cu(acac)] (acac = acetylacetonate) at a process temperature of 120 °C. The copper oxide films exhibit magneto-optical activity in the spectral ranges around 2.6 eV and above 4 eV. The evolution of the spectral features as a function of the number of ALD cycles is simulated numerically using the dielectric function and the Voigt constant of Cu₂O as input parameters. The comparison between experimental and simulated MOKE spectra strengthens the conclusion drawn from spectroscopic ellipsometry studies that the thin film optical constants differ markedly from the bulk ones.     

X-ray mirrors on flexible polymer substrates fabricated by atomic layer deposition

Atomic layer deposition (ALD) techniques were used to fabricate W/Al₂O₃ superlattices with high X-ray reflectivity on flexible Kapton® polyimide and polyethylene naphthalate (PEN) polymer substrates. Reflectivities of 78% and 74% at λ = 1.54 Å were measured for 6-bilayer W/Al₂O₃ superlattices on Kapton® polyimide and PEN, respectively. These excellent X-ray reflectivities are attributed to precise bilayer thicknesses and ultrasmooth interfaces obtained by ALD and smoothing of the initial polymer surface by an Al₂O₃ ALD layer. The conformal ALD film growth also produces correlated roughness that enhances the reflectivity. These W/Al₂O₃ superlattices on flexible polymers should be useful for ultralight and adjustable radius of curvature X-ray mirrors.     

Low-Loss Optical Waveguides for the Near Ultra-Violet and Visible Spectral Regions with Al(2)O(3) Thin Films from Atomic Layer Deposition

In this work, we report low-loss single-mode integrated optical waveguides in the near ultra-violet and visible spectral regions with aluminum oxide (Al₂O₃) films using an atomic layer deposition (ALD) process. Alumina films were deposited on glass and fused silica substrates by the ALD process at substrate/chamber temperatures of 200 °C and 300 °C. Transmission spectra and waveguide measurements were performed in our alumina films with thicknesses in the range of 210-380 nm for the optical characterization. Those measurements allowed us to determine the optical constants (n_w and k_w), propagation loss, and thickness of the alumina films. The experimental results from the applied techniques show good agreement and demonstrate a low-loss optical waveguide. Our alumina thin-film waveguides are well transparent in the whole visible spectral region and also in an important region of the UV; the measured propagation loss is below 4 dB/cm down to a wavelength as short as 250 nm. The low propagation loss of these alumina guiding films, in particular in the near ultra-violet region which lacks materials with high optical performance, is extremely useful for several integrated optic applications.     

Plastic substrate with gas barrier layer and transparent conductive oxide thin film for flexible displays

A novel plastic substrate for flexible displays was developed. The substrate consisted of a polycarbonate (PC) base film coated with a gas barrier layer and a transparent conductive thin film. PC with ultra-low intrinsic birefringence and high temperature dimensional stability was developed for the base film. The retardation of the PC base film was less than 1 nm at a wavelength of 550 nm (film thickness, 120 µm). Even at 180 °C, the elastic modulus was 2 GPa, and thermal shrinkage was less than 0.01%. The surface roughness of the PC base film was less than 0.5 nm. A silicon oxide (SiO_x) gas barrier layer was deposited on the PC base film by a roll-to-roll DC magnetron reactive sputtering method. The water vapor transmission rate of the SiO_x film was less than 0.05 g/m²/day at 40 °C and 100% relative humidity (RH), and the permeation of oxygen was less than 0.5 cc/m² day atm at 40 °C and 90% RH. As the transparent conductive thin film, amorphous indium zinc oxide was deposited on the SiO_x by sputtering. The transmittance was 87% and the resistivity was 3.5 × 10^− 4 ohm cm.     

Silicon oxide diffusion barrier coatings on polypropylene

In this study the influence of process conditions for the plasma-enhanced chemical vapor deposition of SiO_x diffusion barrier coatings on polypropylene (PP) is investigated and compared to results obtained on polyethylene terephthalate (PET). It was observed that the thermal load during deposition is much more crucial in the case of PP. If the thermal load is not the limiting factor, the composite parameter (CP) energy input per mass of precursor showed to be valuable to describe plasma conditions at constant oxygen to monomer ratio. Low oxygen transmission rates (OTRs) of 5.1 ± 3.6 and 0.3 ± 0.1 cm³/m²day/atm were achieved on PP and PET foil, respectively, for an optimal CP of 4.1 × 10⁵ J/g. Fourier transform infrared (FTIR) spectroscopy revealed that low carbon and silanol content is necessary for good barrier performance. Low RF power, necessary to reduce thermal load on PP, can be compensated by increasing the oxygen to monomer ratio.For favorable plasma conditions, the dependence of the OTR on the coating thickness follows a similar trend for both substrate materials with a critical thickness of approximately 12 nm. The residual permeation can be correlated to the defect density at each stage of film growth by means of a simple correlation. Further support for permeation through defects is found by the activated rate theory, since the apparent activation energy of oxygen permeation is below typical values of amorphous glasses and remains unchanged due to the deposition of SiO_x on both substrates.     

High resolution Rutherford Backscattering Spectrometry investigations of ZrO2 layer growth in the initial stage on native silicon oxide and titanium nitride

High Resolution Rutherford Backscattering Spectrometry (HR-RBS) with a depth resolution of about 0.3 nm near the surface was used to analyse the interface between ultrathin high-k ZrO₂-layers and the substrate. In order to improve the quality of the analysis, a method was developed that takes local thickness variations, obtained by atomic force microscopy, into account during simulation of the HR-RBS spectra. The initial stages of atomic layer deposition (ALD) growth processes on Si(100) covered with native silicon oxide (SiO₂) or with TiN have been studied. In the first case the interface is sharp, except for a small intermediate ZrSiO₄-layer, and no diffusion of Zr-atoms in SiO₂ could be detected. A quite different behaviour could be derived from high resolution spectra for the growth of ZrO₂ on TiN. In addition, measurements of the surface topography of the TiN-layer revealed non-negligible surface roughness. Diffusion of Zr into polycrystalline TiN was demonstrated after correction for surface roughness. This observation indicates that already during the first ALD reaction cycle a small proportion of the deposited Zr-atoms diffuses - probably along grain boundaries - into the TiN-layer up to a depth of 3 nm.     

Atomic layer deposition grown composite dielectric oxides and ZnO for transparent electronic applications

In this paper, we report on transparent transistor obtained using laminar structure of two high-k dielectric oxides (hafnium dioxide, HfO₂ and aluminum oxide, Al₂O₃) and zinc oxide (ZnO) layer grown at low temperature (60 °C-100 °C) using Atomic Layer Deposition (ALD) technology. Our research was focused on the optimization of technological parameters for composite layers Al₂O₃/HfO₂/Al₂O₃ for thin film transistor structures with ZnO as a channel and a gate layer. We elaborate on the ALD growth of these oxides, finding that the 100 nm thick layers of HfO₂ and Al₂O₃ exhibit fine surface flatness and required amorphous microstructure. Growth parameters are optimized for the monolayer growth mode and maximum smoothness required for gating.     

Protection of polymer from atomic-oxygen erosion using Al2O3 atomic layer deposition coatings

Thin films of Al₂O₃ grown using atomic layer deposition (ALD) techniques can protect polymers from erosion by oxygen atoms. To quantify this protection, polyimide substrates with the same chemical repeat unit as Kapton^® were applied to quartz crystal microbalance (QCM) sensors. Al₂O₃ ALD films with varying thicknesses were grown on the polyimide substrates. The ALD-coated polyimide materials were then exposed to a hyperthermal atomic-oxygen beam. The mass loss versus oxygen-atom exposure time was measured in situ by the QCM. Al₂O₃ ALD film thicknesses of ∼ 35 Å were found to protect the polymer from erosion.     

Surface poisoning in the nucleation and growth of palladium atomic layer deposition with Pd(hfac)2 and formalin

Palladium (Pd) atomic layer deposition (ALD) can be performed with Pd(hfac)₂ (hfac = hexafluoroacetyl-acetone) and formalin as the reactants. For Pd ALD on oxide surfaces, the nucleation of Pd ALD has been observed to require between 20 and 100 ALD cycles. To understand the long nucleation periods, this study explored the surface reactions occurring during Pd ALD nucleation and growth on hydroxylated Al₂O₃ substrates. In situ Fourier transform infrared (FTIR) spectroscopy on high surface area nanopowders was used to observe the surface species. The adsorption of Pd(hfac)₂ on hydroxylated Al₂O₃ substrates was found to yield both Pd(hfac)* and Al(hfac)* surface species. The identity of the Al(hfac)* species was confirmed by separate FTIR studies of hfacH adsorption on the hydroxylated Al₂O₃ substrates. Isothermal loss of the Al(hfac)* species revealed second-order kinetics at 448-523 K with an activation barrier of E_d = 39.4 kcal/mol. The lack of correlation between Al(hfac)* and AlOH* species during the loss of Al(hfac)* species suggested that the Al(hfac)* species may desorb as Al(hfac)₃. After Pd(hfac)₂ exposure and the subsequent formalin exposure on hydroxylated Al₂O₃ substrates, only hfac ligands from Pd(hfac)* species were removed from the surface. In addition, the formalin exposure added formate species. The Al(hfac)* species was identified as the cause of the long nucleation period because Al(hfac)* behaves as a site blocker. The surface poisoning by Al(hfac)* species was corroborated by adsorbing hfacH prior to the Pd(hfac)₂ exposures. The amount of Pd(hfac)* species after Pd(hfac)₂ exposures decreased progressively versus the previous hfacH exposure. Pd ALD occurred gradually during the subsequent Pd ALD cycles as the Al(hfac)* species were slowly removed from the Al₂O₃ surface. Ex situ transmission electron microscopy analysis revealed Pd nanoclusters that grew in size and dispersion with increasing number of Pd ALD cycles. These nanoclusters eventually coalesced to form a continuous Pd ALD film. Surface poisoning by the hfac ligands may help to explain the nucleation difficulties for metal ALD on oxide substrates using β-diketonate reactants.     

Water permeation through organic-inorganic multilayer thin films

We prepared organic (self-assembled monolayer (SAM))-inorganic (TiO₂) multilayer barrier films on polyethylene terephthalate substrate using atomic layer deposition and molecular layer deposition methods in the same deposition chamber. The water permeation was mainly blocked by the inorganic TiO₂ layer. While the lag time was proportional to the thickness of the TiO₂ layer, the steady-state permeation rate was relatively independent of the thickness. The multilayer approach was effective in extending the lag time due to both the tortuous path effect and the internal desiccant effect. Water permeation occurred sequentially in the organic-inorganic multilayer barriers by water accumulation in the organic SAM layers. The water vapor transmission rate was 7.0 × 10^− 4 g/m²·day during the lag time of 155 h at 60 °C and a relative humidity of 85% with 5-dyad barrier film.     

Properties of atomic layer deposited HfO2 thin films

The growth, composition and morphology of HfO₂ films that have been deposited by atomic layer deposition (ALD) are examined in this article. The films are deposited using two different ALD chemistries: i) tetrakis ethylmethyl amino hafnium and H₂O at 250° and ii) tetrakis dimethyl amino hafnium and H₂O at 275 °C. The growth rates are 1.2 Å/cycle and 1.0 Å/cycle respectively. The main impurities detected both by X-ray Photoelectron Spectroscopy and Fourier transform infrared spectroscopy (FTIR) are bonded carbon (~ 3 at.%) and both bulk and terminal OH species that are partially desorbed after high temperature inert anneals up to 900 °C. Atomic Force Microscopy reveals increasing surface roughness as a function of increasing film thickness. X-ray diffraction shows that the morphology of the as-deposited films is thickness dependent; films with thickness around 30 nm for both processes are amorphous while ~ 70 nm films show the existence of crystallites. These results are correlated with FTIR measurements in the far IR region where the HfO₂ peaks are found to provide an easy and reliable technique for the determination of the crystallinity of relatively thick HfO₂ films. The index of refraction for all films is very close to that for bulk crystalline HfO₂.     

Native oxide consumption during the atomic layer deposition of TiO2 films on GaAs (100) surfaces

The consumption of the surface native oxides is studied during the atomic layer deposition of TiO₂ films on GaAs (100) surfaces. Films are deposited at 200 °C from tetrakis dimethyl amido titanium and H₂O. Transmission electron microscopy data show that the starting surface consists of ~2.6 nm of native oxide and X-ray photoelectron spectroscopy indicates a gradual reduction in the thickness of the oxide layer as the thickness of the TiO₂ film increases. Approximately 0.1-0.2 nm of arsenic and gallium suboxide is detected at the interface after 250 process cycles. For depositions on etched GaAs surfaces no interfacial oxidation is observed.     

Thin Laminate Films for Barrier Packaging Application – Influence of Down Gauging and Substrate Surface Properties on the Permeation Properties

A reduction in thickness of barrier laminated film systems generally leads to a quality decrease of the resulting packaging materials' functional properties. Especially for food packaging applications, adequate oxygen and water barrier properties are indispensable. The focus of this study was therefore the development of thin film systems using metallized aluminium or ethyl vinyl alcohol barrier laminates with low oxygen and water vapour transmission properties. Biaxially oriented polyethylene terephthalate and biaxially oriented polypropylene aluminium‐coated thin film laminates as well as corresponding ethyl vinyl alcohol film systems could be successfully produced with oxygen transmission rates of <0.5 cm³(STP)/(m² d bar) and water barrier values of <0.1 g/(m² d). It could be confirmed that the film thickness of these materials within the range of the investigated dimensions does not have an influence on the barrier properties. In fact, the parameters of the production process influence the functional properties of the film systems and must therefore be adapted. Machinability of these excellent thin film systems requires further investigation on packaging lines before they can be transferred to packaging application. Copyright © 2011 John Wiley & Sons, Ltd.     

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.