Growth and properties of hafnicone and HfO(2)/hafnicone nanolaminate and alloy films using molecular layer deposition techniques.

Molecular layer deposition (MLD) of the hafnium alkoxide polymer known as "hafnicone" was grown using sequential exposures of tetrakis(dimethylamido) hafnium (TDMAH) and ethylene glycol (EG) as the reactants. In situ quartz crystal microbalance (QCM) experiments demonstrated self-limiting reactions and linear growth versus the number of TDMAH/EG reaction cycles. Ex situ X-ray reflectivity (XRR) analysis confirmed linear growth and measured the density of the hafnicone films. The hafnicone growth rates were temperature-dependent and decreased from 1.2 Å per cycle at 105 °C to 0.4 Å per cycle at 205 °C. The measured density was ∼3.0 g/cm(3) for the hafnicone films at all temperatures. Transmission electron microscopy images revealed very uniform and conformal hafnicone films. The XRR studies also showed that the hafnicone films were very stable with time. Nanoindentation measurements determined that the elastic modulus and hardness of the hafnicone films were 47 ± 2 and 2.6 ± 0.2 GPa, respectively. HfO2/hafnicone nanolaminate films also were fabricated using HfO2 atomic layer deposition (ALD) and hafnicone MLD at 145 °C. The in situ QCM measurements revealed that HfO2 ALD nucleation on the hafnicone MLD surface required at least 18 TDMAH/H2O cycles. Hafnicone alloys were also fabricated by combining HfO2 ALD and hafnicone MLD at 145 °C. The composition of the hafnicone alloy was varied by adjusting the relative number of TDMAH/H2O ALD cycles and TDMAH/EG MLD cycles in the reaction sequence. The electron density changed continuously from 8.2 × 10(23) e(-)/cm(3) for pure hafnicone MLD films to 2.4 × 10(24) e(-)/cm(3) for pure HfO2 ALD films. These hafnicone films and the HfO2/hafnicone nanolaminates and alloys may be useful for flexible thin-film devices.

Metalcones: hybrid organic-inorganic films fabricated using atomic and molecular layer deposition techniques.

Hybrid organic-inorganic films can be deposited using atomic layer deposition (ALD) and molecular layer deposition (MLD) techniques. A special set of hybrid organic-inorganic films based on metal precursors and various organic alcohols yields metal alkoxide films that can be described as "metalcones." Many metalcone films are possible such as the "alucones" and "zincones" based on the reaction of trimethylaluminum and diethylzinc, respectively, with various organic alcohols such as ethylene glycol (EG). This paper reviews the previous work on metalcone MLD and discusses a variety of new metalcone systems. "Titanicones" are grown using TiCl4 and glycerol or EG and "zircones" are grown using zirconium tetra-tert-butoxide and EG. In addition, the organic alcohol can also be varied to change the properties within one metalcone family. For example, the glycerol triol precursor allows for more cross-linking and higher toughness in alucones than the EG diol precursor. Alloys can also be formed by combining metalcone MLD and metal oxide ALD. By varying the relative number of cycles of MLD and ALD, the composition and properties of the hybrid organic-inorganic films can be tuned from pure metalcone MLD to pure metal oxide ALD.

Vapor-phase molecular layer deposition of self-assembled multilayers for organic thin-film transistor.

We report a vapor-phase molecular layer deposition (MLD) of self-assembled multilayer thin films for organic thin-film transistor. In the present MLD process, alkylsiloxane self-assembled multilayers (SAMs) were grown under vacuum by repeated sequential adsorptions of C=C-terminated alkylsilane and aluminum hydroxide with ozone activation. The MLD method is a self-controlled layer-by-layer growth process, and is perfectly compatible with the atomic layer deposition (ALD) method. The SAMs films prepared exhibited good mechanical flexibility and stability, excellent insulating properties, and relatively high dielectric capacitances of 374 nF/cm2 with a high dielectric strength of 4 MV/cm. They were then used as a 12 nm-thick dielectric for pentacene-based thin-film transistors (TFTs), which showed a maximum field effect mobility of 0.57 cm2/V s, operating at -4 V with an on/off current ratio of approximately 10(3).

Low-temperature atomic layer deposition of copper metal thin films: self-limiting surface reaction of copper dimethylamino-2-propoxide with diethylzinc.

A uniform, conformal, pure copper metal thin film was grown at very low substrate temperatures (100-120 degrees C) on Si(100) substrates by atomic layer deposition involving the ligand exchange of [Cu(OCHMeCH(2)NMe(2))(2)] with Et(2)Zn (see scheme). Patterned copper thin films of Cu nanotubes (diameter 150 nm, length 12 microm) were fabricated.

Gas-phase formation of self-assembled monolayers on MgO for protection against hydration.

The gas-phase adsorption of octyltrichlorosilane onto MgO produces self-assembled monolayers that can provide protection against hydration of the underlying MgO surfaces. MgO thin film has attracted attention for application as a protecting layer of alternating current plasma display panel. On exposure to air, the clean MgO surface interacts with water and quickly hydrates to Mg(OH)2, which reduces the secondary electron emission yield. The gas-phase deposition of octyltrichlorosilane on the clean MgO has produced self-assembled monolayers because of high reactivity of the MgO surface. The ultra-thin organic layer of the octylsiloxane can provide significant protection against hydration to the MgO surface, and improves secondary electron emission yield for the MgO samples. The secondary electron emission coefficient y for the monolayer-coated MgO sample is about 25% higher than that for the clean MgO after 24 hr exposing to air.

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.

Rapid vapor-phase fabrication of organic-inorganic hybrid superlattices with monolayer precision.

We report a new layer-by-layer growth method of self-assembled organic multilayer thin films based on gas-phase reactions. In the present molecular layer deposition (MLD) process, alkylsiloxane self-assembled multilayers (SAMs) were grown under vacuum by repeated sequential adsorptions of C=C-terminated alkylsilane and titanium hydroxide. The MLD method is a self- limiting layer-by-layer growth process, and is perfectly compatible with the atomic layer deposition (ALD) method. The SAMs films prepared exhibited good thermal and mechanical stability, and various unique electrical properties. The MLD method, combined with ALD, was applied to the preparation of organic-inorganic hybrid nanolaminate films in the ALD chamber. The organic-inorganic hybrid superlattices were then used as active mediums for two-terminal electrical bistable devices. The advantages of the MLD method with ALD include accurate control of film thickness, large-scale uniformity, highly conformal layering, sharp interfaces, and a vast library of possible materials. The MLD method with ALD is an ideal fabrication technique for various organic-inorganic hybrid superlattices.