Polystyrene (PS) grafted to silicon oxide (SiO2, referred to as gPS-SiO2) bilayers generated via a polymer grafting method were used as organic-oxide hybrid gate dielectrics to fabricate solution-processed triethylsilylethynyl anthradithiophene (TES-ADT) organic field-effect transistors (OFETs). The dielectric surface properties were significantly altered by the areal grafting densities of different molecular weight (Mw) PS chains with end-functionalized dimethylchlorosilane attached to the SiO2 surfaces. Lesser grafting densities of longer PS chains increased the surface roughness of the treated SiO2 surfaces from 0.2 to 1.5 nm, as well as the water contact angles from 94° to 88°. Below a critical Mw of end-functionalized PS, the gPS chains on the SiO2 surfaces appeared to form a brush-like conformation with an areal density value greater than 0.1 chains nm(-2), but other high-Mw gPS chains formed pancake structures in which the polymeric layers were easily incorporated with solution-processed TES-ADT as a solute. These findings indicate that low-density gPS layers interfered with the self-assembly of TES-ADT in cast films, causing great decreases in crystal grain size and π-conjugated orientation. The presence of compact gPS chains on the SiO2 surface could yield high electrical performance of TES-ADT OFETs with a field-effect mobility of 2.1 cm2 V(-1) s(-1), threshold voltage of -2.0 V, and on/off current ratio of greater than 10(7) when compared to those developed using less-concentrated gPS-SiO2 surfaces.

A highly π-conjugated nanofibrillar network of poly(3-hexyl thiophene) (P3HT) embedded in polydimethylsiloxane (PDMS) elastomer films on SiO2 dielectrics was facilely developed via solution-blending of an ultrasound-assisted dilute P3HT solution with a PDMS precursor followed by spin-casting and curing. In contrast, simple blending without ultrasonication against the dilute P3HT solution yielded large agglomerates in cast films owing to a great difference in solubility parameter (δ) values (P3HT = 9.5 cal(1/2) cm(-3/2), PDMS = 7.3 cal(1/2) cm(-3/2)). In the ultrasound-assisted 0.1 vol % P3HT solutions, the π-conjugated polymer could develop crystalline nanofibrils surrounded by nonpolar hexyl side chains with the same δ value as that of PDMS, yielding homogeneously dispersed 10 wt % loaded P3HT/PDMS blend films. Spun-cast P3HT/PDMS blend films could yield high electrical properties in organic field-effect transistor, including mobilities of up to 0.045 cm(2) V(-1) s(-1) and on/off current ratios of >5 × 10(5), as well as excellent environmental stability owing to the outer PDMS layer.

Natural diamonds were (and are) formed (some, billions of years ago) in the Earth’s upper mantle in metallic melts in a temperature range of 900–1400°C and at pressures of 5–6 GPa1,2; indeed, diamond is thermodynamically stable under high pressure and high temperature (HPHT) conditions as per the phase diagram of carbon3. Scientists at General Electric invented and used a HPHT apparatus in 1955 to synthesize diamonds from melted iron sulfide at about 7 GPa and 1600°C4–6. There is an existing paradigm that diamond can be grown using liquid metals only at both high pressure (typically 5–6 GPa) and high temperature (typically 1300–1600°C) where it is the stable form of carbon7. Here, we describe the growth of diamond crystals and polycrystalline diamond films with no seed particles using liquid metal but at 1 atmosphere pressure, and at 1025°C, breaking this paradigm. Diamond grew at the interface of liquid metal composed of gallium, iron, nickel, and silicon and a graphite crucible, by catalytic activation of methane and diffusion of carbon atoms in the subsurface region of the liquid metal. Raman spectroscopy with 13C-labeling proves that methane introduced into the growth chamber is the carbon source for many of the regions of newly grown diamond. The new growth diamonds were studied by Raman spectroscopy, scanning and transmission electron microscopy, X-ray diffraction, and photoluminescence. Growth of (metastable) diamond in liquid metal at moderate temperature and 1 atm pressure opens many possibilities for further basic science studies and for the scaling of this type of growth.

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