Polymeric films can be grown by a sequential, self-limiting surface chemistry process known as molecular layer deposition (MLD). The MLD reactants are typically bifunctional monomers for stepwise condensation polymerization and can yield completely organic films. The MLD of organic–inorganic hybrid polymers can also be accomplished using a bifunctional organic monomer and a multifunctional inorganic monomer. In this work, the growth of a poly(aluminum ethylene glycol) polymer is demonstrated using the sequential exposures of trimethylaluminum (TMA) and ethylene glycol (EG). These hybrid polymers, known as alucones, were grown over a wide range of temperatures from 85 to 175 °C. In situ quartz crystal microbalance and ex situ X-ray reflectivity experiments confirmed linear growth of the alucone film versus number of TMA/EG reaction cycles at all temperatures. The alucone growth rates decreased at higher temperatures. Growth rates varied from 4.0 Å per cycle at 85 °C to 0.4 Å per cycle at 175 °C. In situ Fourier transform infrared spectroscopy was used to monitor the surface reactions during alucone MLD. Ex situ FTIR spectroscopy, X-ray photoelectron spectroscopy, and X-ray reflectivity measurements were also employed to determine the chemical composition, thickness, and density of the alucone films. These ex situ studies revealed that the alucone films grown on Al2O3 ALD surfaces evolved under ambient conditions before reaching a stable state. Alucone films capped with rapid SiO2 ALD displayed much more stability than alucone films grown on Al2O3 ALD surfaces. These results indicated that H2O may facilitate the chemical transformation of the alucone MLD films. The alucone films represent a new class of organic–inorganic hybrid polymers. Modification of this basic alucone MLD chemistry with use of other diols or other bifunctional monomers can produce different alucone polymers with variable properties.

Al2O3 atomic layer deposition (ALD) is a model ALD system and Al2O3 ALD films are excellent gas diffusion barrier on polymers. However, little is known about the response of Al2O3 ALD films to strain and the potential film cracking that would restrict the utility of gas diffusion barrier films. To understand the mechanical limitations of Al2O3 ALD films, the critical strains at which the Al2O3 ALD films will crack were determined for both tensile and compressive strains. The tensile strain measurements were obtained using a fluorescent tagging technique to image the cracks. The results showed that the critical tensile strain is higher for thinner thicknesses of the Al2O3 ALD film on heat-stabilized polyethylene naphthalate (HSPEN) substrates. A low critical tensile strain of 0.52% was measured for a film thickness of 80 nm. The critical tensile strain increased to 2.4% at a film thickness of 5 nm. In accordance with fracture mechanics modeling, the critical tensile strains and the saturation crack densities scaled as (1/h)1/2 where h is the Al2O3 ALD film thickness. The fracture toughness for cracking, KIC, of the Al2O3 ALD film was also determined to be KIC = 2.30 MPa m1/2. Thinner Al2O3 ALD film thicknesses also had higher critical strains for cracking from compressive strains. Field-emission scanning electron microscopy (FE-SEM) images revealed that Al2O3 ALD films with thicknesses of 30–50 nm on Teflon fluorinated ethylene propylene (FEP) substrates cracked at a critical compressive strain of ∼1.0%. The critical compressive strain increased to ∼2.0% at a film thickness of ∼20 nm. A comparison of the critical tensile strains on HSPEN substrates and critical compressive strains on Teflon FEP substrates revealed some similarities. The critical strain was ∼1.0% for film thicknesses of 30–50 nm for both tensile and compressive strains. The critical compressive strain then increased more rapidly than the critical tensile strain for thinner films with thicknesses < 30 nm. The high critical tensile and compressive strains for thin Al2O3 ALD films should be very useful for flexible gas diffusion barriers on polymers.

The mechanical robustness of atomic layer deposited alumina and recently developed molecular layer deposited aluminum alkoxide ͑"alucone"͒ films, as well as laminated composite films composed of both materials, was characterized using mechanical tensile tests along with a recently developed fluorescent tag to visualize channel cracks in the transparent films. All coatings were deposited on polyethylene naphthalate substrates and demonstrated a similar evolution of damage morphology according to applied strain, including channel crack initiation, crack propagation at the critical strain, crack densification up to saturation, and transverse crack formation associated with buckling and delamination. From measurements of crack density versus applied tensile strain coupled with a fracture mechanics model, the mode I fracture toughness of alumina and alucone films was determined to be K IC = 1.89Ϯ 0.10 and 0.17Ϯ 0.02 MPa m 0.5 , respectively. From measurements of the saturated crack density, the critical interfacial shear stress was estimated to be c = 39.5Ϯ 8.3 and 66.6Ϯ 6.1 MPa, respectively. The toughness of nanometer-scale alumina was comparable to that of alumina thin films grown using other techniques, whereas alucone was quite brittle. The use of alucone as a spacer layer between alumina films was not found to increase the critical strain at fracture for the composite films. This performance is attributed to the low toughness of alucone. The experimental results were supported by companion simulations using fracture mechanics formalism for multilayer films. To aid future development, the modeling method was used to study the increase in the toughness and elastic modulus of the spacer layer required to render improved critical strain at fracture. These results may be applied to a broad variety of multilayer material systems composed of ceramic and spacer layers to yield robust coatings for use in chemical barrier and other applications.Public reporting burden for the collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data needed, and completing and reviewing the collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information, including suggestions for reducing this burden, to Washington Headquarters Services, Directorate for Information Operations and Reports, 1215 Jefferson Davis Highway, Suite 1204, Arlington VA 22202-4302. Respondents should be aware that notwithstanding any other provision of law, no person shall be subject to a penalty for failing to comply with a collection of information if it does not display a currently valid OMB control number.

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