Highly Photosensitive Lead Sulfide Thin Films Grown by H2 S Free MOCVD Using a Single Source Metal-Organic Precursor.

High-quality lead sulfide (PbS) films are deposited on selected substrate chemistries by an H2 S-free metal-organic chemical vapor deposition (MOCVD) process using a single-source metal-organic complex (Pb(dmampS)2 ). The complex is synthesized via a salt metathesis reaction between PbCl2  and lithium 1-(dimethylamino)-2-methylpropane-2-thiolate (Li(dmampS)) in diethyl ether. Subsequent film deposition is conducted by a simple thermolysis process in the absence of H2 S, yet chemical and structural analysis confirm chemically stoichiometric and homogenous films. Mechanistic studies with electron impact mass spectroscopy (EIMS) and gas chromatography mass spectroscopy (GCMS) suggest the selective cleavage of C-S bonds in the complex as the reason for the facile PbS formation with negligible impurity incorporation. The high crystallinity, low hole concentrations, and charge transport properties comparable and in many cases superior to films produced by atomic layer deposition (ALD) testify to the quality of the films. Lastly, rigid and flexible photodetectors fabricated with the PbS films exhibit considerably high photocurrents, reliable switching characteristics, and high sensitivity over a broad spectral bandwidth, highlighting the potential for realizing practical broadband photodetectors.

Correlating Molecular Precursor Interactions with Device Performance in Solution-Processed Cu2ZnSn(S,Se)4 Thin-Film Solar Cells.

Research efforts aimed at improving the crystal quality of solution-processed Cu2ZnSn(S,Se)4 (CZTSSe) absorbers have largely employed delicate pre- and postprocessing strategies, such as multistep selenization, heat treatment in mixed chalcogen atmospheres, and multinary extrinsic doping that are often complex and difficult to reproduce. On the other hand, understanding and tuning chemical interactions in precursor inks prior to the thin-film deposition have received significantly less attention. Herein, we show for the first time how the complexation of metallic and chalcogen precursors in solution have a stark influence on the crystallization and optoelectronic quality of CZTSSe absorbers. By varying thiourea to metal cation ratios (TU/M) in dimethylformamide (DMF) and isopropyl alcohol (IPA)-based inks, we observed the formation of nanoscale metal-organic complexes and submicron size aggregates which play a key role in the morphology of the precursor layers obtained by spin-coating and drying steps. We also identify the primary cations in the complexation and assembling processes in solution. The morphology of the precursor film, in turn, has an important effect on grain growth and film absorber structure after the reactive annealing in the presence of Se. Finally, we establish a link between metal complexes in precursor solutions and device performance, with power conversion efficiency increasing from approximately 2 to 8% depending on the TU/M and Cu/(Zn + Sn) ratios.

Novel Heteroleptic Tin(II) Complexes Capable of Forming SnO and SnO2 Thin Films Depending on Conditions Using Chemical Solution Deposition.

A new heteroleptic complex series of tin was synthesized by the salt metathesis reaction of SnX2 (X = Cl, Br, and I) with aminoalkoxide and various N-alkoxy-functionalized carboxamide ligands. The complexes, [ClSn(dmamp)]2 (1), [BrSn(dmamp)]2 (2), and [ISn(dmamp)]2 (3), were prepared from the salt metathesis reaction of SnX2 with one equivalent of dmamp; [Sn(dmamp)(empa)]2 (4), [Sn(dmamp)(mdpa)]2 (5), and [Sn(dmamp)(edpa)]2 (6) were prepared via the salt metathesis reaction using complex 2 with one equivalent of N-alkoxy-functionalized carboxamide ligand. Complexes 1-5 displayed dimeric molecular structures with tin metal centers interconnected by µ2-O bonding via the alkoxy oxygen atom. The molecular structures of complexes 1-5 showed distorted trigonal bipyramidal geometries with lone pair electrons in the equatorial position. Using complex 6 as a tin precursor, SnO x films were deposited by chemical solution deposition (CSD) and subsequent post-deposition annealing (PDA) at high temperatures. SnO and SnO2 films were selectively obtained under controlled PDA atmospheres of argon and oxygen, respectively. The SnO films featured a tetragonal romarchite structure with high crystallinity and a preferred growth orientation along the (101) plane. They also exhibited a lower transmittance of >52% at 400 nm due to an optical band gap of 2.9 eV. In contrast, the SnO2 films exhibited a tetragonal cassiterite crystal structure and an extremely high transmittance of >97% at 400 nm was observed with an optical band gap of 3.6 eV.

Synthesis and characterization of novel zinc precursors for ZnO thin film deposition by atomic layer deposition.

A novel series of zinc complexes, [EtZn(dab)]2 (1), [EtZn(damb)]2 (2), [EtZn(damp)]2 (3), and [EtZn(dadb)]2 (4), were prepared via single-step substitution. Further, these were analyzed by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR), elemental analysis, single crystal X-ray diffraction analysis, and thermogravimetric analysis (TGA). The X-ray crystallography analysis revealed that all complexes exist as dimeric structures with distorted tetrahedral geometry having zinc centers that are interconnected via µ2-O bonding of the aminoalkoxy oxygen atom. TGA and thermal analysis of the complexes showed high volatilities and stabilities at sublimation temperatures of 70, 95, 90, and 105 °C at 0.5 Torr for the respective compounds. Precursor 3 was successfully used for ZnO thin film deposition by ALD. A growth rate per cycle (GPC) of 0.125 nm per cycle was obtained at 200 °C and XPS analysis confirmed the growth of highly pure ZnO films without carbon and nitrogen impurities, while XRD analysis revealed the deposition of reasonably crystalline films. Additionally, the high transmittance and wide bandgap of the films are suitable for optoelectronic applications.

Low-Temperature Growth of Indium Oxide Thin Film by Plasma-Enhanced Atomic Layer Deposition Using Liquid Dimethyl(N-ethoxy-2,2-dimethylpropanamido)indium for High-Mobility Thin Film Transistor Application.

Low-temperature growth of In2O3 films was demonstrated at 70-250 °C by plasma-enhanced atomic layer deposition (PEALD) using a newly synthesized liquid indium precursor, dimethyl(N-ethoxy-2,2-dimethylcarboxylicpropanamide)indium (Me2In(EDPA)), and O2 plasma for application to high-mobility thin film transistors. Self-limiting In2O3 PEALD growth was observed with a saturated growth rate of approximately 0.053 nm/cycle in an ALD temperature window of 90-180 °C. As-deposited In2O3 films showed negligible residual impurity, film densities as high as 6.64-7.16 g/cm3, smooth surface morphology with a root-mean-square (RMS) roughness of approximately 0.2 nm, and semiconducting level carrier concentrations of 1017-1018 cm-3. Ultrathin In2O3 channel-based thin film transistors (TFTs) were fabricated in a coplanar bottom gate structure, and their electrical performances were evaluated. Because of the excellent quality of In2O3 films, superior electronic switching performances were achieved with high field effect mobilities of 28-30 and 16-19 cm2/V·s in the linear and saturation regimes, respectively. Furthermore, the fabricated TFTs showed excellent gate control characteristics in terms of subthreshold swing, hysteresis, and on/off current ratio. The low-temperature PEALD process for high-quality In2O3 films using the developed novel In precursor can be widely used in a variety of applications such as microelectronics, displays, energy devices, and sensors, especially at temperatures compatible with organic substrates.