Possible mechanisms for strain relaxation in ferroelectric thin films are developed. The models are applicable to tetragonal thin film ferroelectrics grown epitaxially on (001) cubic single crystal substrates. We assume growth at temperatures in excess of the Curie temperature (Tc). The extent of strain accommodation by misfit dislocations is considered at the growth temperature (Tg). On cooling to Tc, further misfit dislocation generation is possible due to differences in thermal expansion behavior of the film and substrate. During the paraelectric to ferroelectric transition (PE→FE) additional strains develop in the film. The total strain for the FE phase may be relieved either by further misfit generation or by domain formation. We have developed temperature dependent stability maps that predict the stable domain structure that forms during the PE→FE transition. The stability maps incorporate the role of the following parameters: (i) substrate lattice parameter, (ii) differential thermal expansion characteristics between the film and substrate, (iii) cooling rate, and (iv) depolarizing fields and electrode geometry. Further, the role of dislocation stabilization of domain patterns is discussed.
Preparation of Colloidal Sols: A magnetite colloid was prepared in alkaline solution according to the procedure published by Massart [11]. An aqueous solution containing 2.3 g (8.5 mmol) FeCl 3 ×6H 2 O in 4 mL H 2 O and 1.69 g (4.3 mmol) Fe(NH 4 ) 2 (SO 4 ) 2 in 1 mL of 2 M HCl, was added to 50 mL of 1 M (CH 3 ) 4 NOH×5H 2 O. The resulting black suspension was stirred for 1 h at room temperature and then sonicated in an ultrasonic bath for 1 h. The colloid was then centrifuged at 20 000 g for 1 h. The supernatant was decanted and the slurry resuspended in 20 mL water by sonication before being passed through a 0.2 mm pore cellulose nitrate membrane.A titanium dioxide sol was prepared by hydrolysis of titanium tetraisopropoxide under a nitrogen atmosphere following the procedure described by O'Regan et al. [12]. 25 mL of titanium tetraisopropoxide was mixed with 4 mL of isopropanol in a dropping-funnel under a nitrogen atmosphere. This mixture was added slowly over a period of 5 min to 150 mL of vigorously stirred double-distilled, deionized water in a 250 mL three-neck flask equipped with heater, thermometer and stirrer. Ten minutes after the final alkoxide addition, 1 mL of 69 % HNO 3 was added. The white hydrolysis mixture was then stirred for 8 h at 80 C to remove the isopropanol, filtered through a 0.2 mm pore cellulose nitrate membrane, and sonicated for 1 h to produce a stable colloidal solution with a bluish-white coloration.Preparation of the Composites and Method of Calcination: Typically, a sample of the sliced copolymer gel (ca. 5 mm thick) was added to the colloidal sol and left for the desired period of time. The colloid-loaded gels were removed, washed with water and allowed to dry in air. Thermogravimetric analysis (TGA) measurements were made using a NETZSCH STA 409EP machine. Samples were heated under air in an alumina crucible to a final temperature of 800 C at a rate of 5 K/min. Large samples of the mineralized gels were calcined by heating to a temperature of 450 or 500 C in a Carbolite furnace (type ELF11/6) at a heating rate of 1 C min ±1 .
We present measurements of the electrical conductivity of metallic nanowires which have been fabricated by chemical deposition of a thin continuous palladium film onto single DNA molecules to install electrical functionality. The DNA molecules have been positioned between macroscopic Au electrodes and are metallized afterwards. Low-resistance electrical interfacing was obtained by pinning the nanowires at the electrodes with electron-beam-induced carbon lines. The investigated nanowires exhibit ohmic transport behavior at room temperature. Their specific conductivity is only one order of magnitude below that of bulk palladium, confirming that DNA is an ideal template for the production of electric wires, which can be utilized for the bottom-up construction of miniaturized electrical circuits.
The microscopic mechanism of platinum cluster nucleation on DNA templates is studied by first-principle molecular dynamics simulations. We find that Pt(II) complexes bound to DNA can form strong Pt−Pt bonds with free Pt complexes after a single reduction step, and may thus act as preferential nucleation sites. This is confirmed by a series of reduction experiments, in which we achieve purely heterogeneous platinum growth on DNA, and use it to fabricate metal cluster necklaces of unprecedented thinness and regularity.
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