Atomic layer deposition (ALD) is a process for depositing highly uniform and conformal thin films by alternating exposures of a surface to vapours of two chemical reactants. ALD processes have been successfully demonstrated for many metal compounds, but for only very few pure metals. Here we demonstrate processes for the ALD of transition metals including copper, cobalt, iron and nickel. Homoleptic N,N'-dialkylacetamidinato metal compounds and molecular hydrogen gas were used as the reactants. Their surface reactions were found to be complementary and self-limiting, thus providing highly uniform thicknesses and conformal coating of long, narrow holes. We propose that these ALD layers grow by a hydrogenation mechanism that should also operate during the ALD of many other metals. The use of water vapour in place of hydrogen gas gives highly uniform, conformal films of metal oxides, including lanthanum oxide. These processes should permit the improved production of many devices for which the ALD process has previously not been applicable.
Organic non‐volatile memory (ONVM) based on pentacene field‐effect transistors (FETs) has been fabricated using various chargeable thin polymer gate dielectrics—termed electrets—onto silicon oxide insulating layers. The overall transfer curve of organic FETs is significantly shifted in both positive and negative directions and the shifts in threshold voltage (VTh) can be systemically and reversibly controlled via relatively brief application of the appropriate external gate bias. The shifted transfer curve is stable for a relatively long time—more than 105 s. However, this significant reversible shift in VTh is evident only in OFETs with non‐polar and hydrophobic polymer electret layers. Moreover, the magnitude of the memory window in this device is inversely proportional to the hydrophilicity (determined from the water contact angle) and dielectric polarity (determined from the dielectric constant), respectively. Memory behaviors of ONVM originate from charge storage in polymer gate electret layers. Therefore, the small shifts in VTh in ONVM with hydrophilic and polar polymers may be due to very rapid dissipation of transferred charges through the conductive channels which form from dipoles, residual moisture, or ions in the polymer electret layers. It is verified that the surface or bulk conductivities of polymer gate electret layers played a critical role in determining the non‐volatile memory properties.
A series of homoleptic metal amidinates of the general type [M(R-R'AMD)(n)](x) (R = (i)Pr, (t)Bu, R' = Me, (t)Bu) has been prepared and structurally characterized for the transition metals Ti, V, Mn, Fe, Co, Ni, Cu, Ag, and La. In oxidation state 3, monomeric structures were found for the metals Ti(III), V(III), and La(III). Bridging structures were observed for the metals in oxidation state 1. Cu(I) and Ag(I) are held in bridged dimers, and Ag(I) also formed a trimer that cocrystallized with the dimer. Metals in oxidation state 2 occurred in either monomeric or dimeric form. Metals with smaller ionic radii (Co, Ni) were monomeric. Larger metals (Fe, Mn) gave monomeric structures only with the bulkier tert-butyl-substituted amidinates, while the less bulky isopropyl-substituted amidinates formed dimers. The new compounds were found to have properties well-suited for use as precursors for atomic layer deposition (ALD) of thin films. They have high volatility, high thermal stability, and high and properly self-limited reactivity with molecular hydrogen, depositing pure metals, or water vapor, depositing metal oxides.
We have studied the electronic, physical, and transistor properties of a family of donor-acceptor polymers consisting of diketopyrrolopyrrole (DPP) coupled with different accepting companion units in order to determine the effects of donor-acceptor interaction. Using the electronically neutral benzene (B), the weakly accepting benzothiadiazole (BT), and the strongly accepting benzobisthiadiazole (BBT), the accepting strength of the companion unit was systematically modulated. All polymers exhibited excellent transistor performance, with mobilities above 0.1 cm(2)V(-1)s(-1), even exceeding 1 cm(2)V(-1)s(-1) for one of the BBT-containing polymers. We find that the BBT is the strongest acceptor, enabling the BBT-containing polymers to be strongly ambipolar. The BBT moiety also strengthens interchain interactions, which provides higher thermal stability and performance for transistors with BBT-containing polymers as the active layer.
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