As the demand for p-type semiconductors increases, much effort is being put into developing new p-type materials. This demand has led to the development of novel new p-type semiconductors that go beyond existing p-type semiconductors. Copper iodide (CuI) has recently received much attention due to its wide band gap, excellent optical and electrical properties, and low temperature synthesis. However, there are limits to its use as a semiconductor material for thin film transistor devices due to the uncontrolled generation of copper vacancies and excessive hole doping. In this work, p-type CuI semiconductors were fabricated using the chemical vapor deposition (CVD) process for thin-film transistor (TFT) applications. The vacuum process has advantages over conventional solution processes, including conformal coating, large area uniformity, easy thickness control and so on. CuI thin films were fabricated at various deposition temperatures from 150 to 250 °C The surface roughness root mean square (RMS) value, which is related to carrier transport, decreases with increasing deposition temperature. Hall effect measurements showed that all fabricated CuI films had p-type behavior and that the Hall mobility decreased with increasing deposition temperature. The CuI TFTs showed no clear on/off because of the high concentration of carriers. By adopting a Zn capping layer, carrier concentrations decreased, leading to clear on and off behavior. Finally, stability tests of the PBS and NBS showed a threshold voltage shift within ±1 V.
CoSi2 was formed through annealing of atomic layer deposition Co thin films. Co ALD was carried out using bis(N,N'-diisopropylacetamidinato) cobalt (Co(iPr-AMD)2) as a precursor and NH3 as a reactant; this reaction produced a highly conformal Co film with low resistivity (50 μΩcm). To prevent oxygen contamination, ex-situ sputtered Ti and in-situ ALD Ru were used as capping layers, and the silicide formation prepared by rapid thermal annealing (RTA) was used for comparison. Ru ALD was carried out with (Dimethylcyclopendienyl)(Ethylcyclopentadienyl) Ruthenium ((DMPD)(EtCp)Ru) and O2 as a precursor and reactant, respectively; the resulting material has good conformality of as much as 90% in structure of high aspect ratio. X-ray diffraction showed that CoSi2 was in a poly-crystalline state and formed at over 800˚C of annealing temperature for both cases. To investigate the as-deposited and annealed sample with each capping layer, high resolution scanning transmission electron microscopy (STEM) was employed with electron energy loss spectroscopy (EELS). After annealing, in the case of the Ti capping layer, CoSi2 about 40 nm thick was formed while the SiOx interlayer, which is the native oxide, became thinner due to oxygen scavenging property of Ti. Although Si diffusion toward the outside occurred in the Ru capping layer case, and the Ru layer was not as good as the sputtered Ti layer, in terms of the lack of scavenging oxygen, the Ru layer prepared by the ALD process, with high conformality, acted as a capping layer, resulting in the prevention of oxidation and the formation of CoSi2.
Electrolessly deposited Co (Re,P) was investigated as a possible capping layer for Cu wires. 50 nm Co (Re,P) films were deposited on Cu/Ti-coated silicon wafers which acted as a catalytic seed and an adhesion layer, respectively. To obtain the optimized bath composition, electroless deposition was studied through an electrochemical approach via a linear sweep voltammetry analysis. The results of using this method showed that the best deposition conditions were a CoSO4 concentration of 0.082 mol/l, a solution pH of 9, a KReO4 concentration of 0.0003 mol/l and sodium hypophosphite concentration of 0.1 mol/L at 80˚C. The thermal stability of the Co (Re,P) layer as a barrier preventing Cu was evaluated using Auger electron spectroscopy and a Scanning calorimeter. The measurement results showed that Re impurities stabilized the h.c.p. phase up to 550˚C and that the Co (Re,P) film efficiently blocked Cu diffusion under an annealing temperature of 400˚C for 1hr. The good barrier properties that were observed can be explained by the nano-sized grains along with the blocking effect of the impurities at the fast diffusion path of the grain boundaries. The transformation temperature from the amorphous to crystal structure is increased by doping the Re.