Silver nanowire-based contacts represent one of the major new directions in transparent contacts for opto-electronic devices with the added advantage that they can have Indium-Tin-Oxide-like properties at substantially reduced processing temperatures and without the use of vacuum-based processing. However, nanowires alone often do not adhere well to the substrate or other film interfaces; even after a relatively high-temperature anneal and unencapsulated nanowires show environmental degradation at high temperature and humidity. Here we report on the development of ZnO/Ag-nanowire composites that have sheet resistance below 10 Ω/sq and >90% transmittance from a solution-based process with process temperatures below 200 °C. These films have significant applications potential in photovoltaics and displays.

Beta-gallium oxide (β-Ga2O3) is of increasing interest to the optoelectronic community for transparent conductor and power electronic applications. Considerable variability exists in the literature on the growth and doping of Ga2O3 films, especially as a function of growth approach, temperature, and oxygen partial pressure. Here pulsed laser deposition (PLD) was used to grow high-quality β-Ga2O3 films on (0001) sapphire and (−201) Ga2O3 single crystals and to explore the growth, stability, and dopability of these films as function of temperature and oxygen partial pressure. There is a strong temperature dependence to the phase formation, morphology, and electronic properties of β-Ga2O3 from 350 to 550 °C.

Radio frequency (rf) magnetron sputtering is used to deposit Ti0.85Nb0.15O2 and Ti0.8Ta0.2O2 films on glass substrates at substrate temperatures (TS) ranging from ∼250 to 400 °C. The most conducting Nb-doped TiO2 films were deposited at TS = 370 °C, with conductivities of ∼60 S/cm, carrier concentrations of 1.5 × 1021 cm−3 and mobilities <1 cm2/V·s. The conductivity of the films was limited by the mobility, which was more than 10 times lower than the mobility for films deposited epitaxially on SrTiO3. The difference in properties is likely caused by the randomly oriented crystal structure of the films deposited on glass compared with biaxially textured films deposited on SrTiO3. The anatase phase could not be stabilized in the Ta-doped TiO2 films, likely because of the high dopant concentration.

Hydrogenated amorphous silicon (a-Si:H) films of high and low hydrogen content were deposited directly on molybdenum, carbon-coated TEM grids by hot-wire chemical vapor deposition. The material was annealed at 600°C and 630°C for variable times to achieve various degrees of crystallinity. The films thickness of 100-nm allowed characterization by TEM without additional thinning. The grain growth in such thin films is nearly two-dimensional, allowing clear identification of crystalline and amorphous regions. Thus, the crystalline volume fraction can be tracked by simple image-processing methods. The evolution of crystallization by grain nucleation and growth for these films is accurately described by classical phase-change kinetics. Analysis of the randomly distributed grains at early stages of crystallization also provides the average areal grain number density and grain size. From the image analysis, we determine the grain nucleation rate and the grain growth velocity. The final grain size is then estimated by extrapolation to the fully crystallized state, assuming the kinetic parameters remain constant after the onset of crystallization.

The results of structural and electrical characterizations of SrTiO3 thin films deposited onto LaAlO3 substrates by pulsed laser deposition technique are presented. The appearance of the ferroelectric phase in these films has been experimentally documented, the transition temperature being in the range of 90–120K. The hysteresis loops have been monitored in a wide temperature range by using thin film planar capacitors, the driving field being predominantly in the plane of the film. The switching properties of the films has been studied at low temperatures (∼25K) and well saturated loops have been observed with relatively low coercive field (<6kV/cm for 10μm gap). The presence of the imprint phenomenon has been also found at low temperatures.

The microstructure of the investigated SrTiO3 thin films has been studied by using a high resolution transmission electron microscope (TEM). It has been found that the annealed and as-deposited thin films, being of the same composition, have quite different microstructures. The difference observed in the polarization response of the films is related to that in their microstructure.

Direct-write technologies offer the potential for low-cost materials-efficient deposition of contact metallizations for photovoltaics. We report on the inkjet printing of metal organic decomposition (MOD) inks with and without nanoparticle additions. Near-bulk conductivity of printed and sprayed metal films has been achieved for Ag and Ag nanocomposites. Good adhesion and ohmic contacts with a measured contact resistance of 400μΩ•cm2 have been observed between the sprayed silver films and a heavily doped n-type layer of Si. Silver deposited using the MOD ink burns through the Si3N4 antireflection coating when annealed at 850°C to form an ohmic contact to the n-Si underneath. An active solar cell device was fabricated using a top contact that was spray printed using the Ag MOD ink. Inkjet printed films show adhesion differences as a function of the process temperature and solvent. Silver lines with good adhesion and conductivity have been printed on glass with 100 μm resolution.

The electrical and structural properties of sputtered indium oxide (In2O3) thin films doped with Mo, Zr, and Ti were studied. Properties of these films are compared to undoped In2O3 and tin-doped In2O3 (ITO). The as-sputtered films, doped with Mo (IO:Mo), exhibited high mobility (45 cm2V-1s-1). Pulsed laser deposition (PLD) was also used to deposit IO:Mo films. The highest mobility achieved for an as-deposited PLD IO:Mo film deposited onto a glass substrate was 42.7 cm2V-1s-1. However, PLD IO:Mo films deposited on single-crystal yttria-stabilized zirconia (YSZ) substrates exhibited a higher mobility of 53.6 cm2V-1s-1 and a greater degree of structural orientation than the sputtered films. Following post-deposition annealing, both the sputtered films on glass, and the PLD films on YSZ, exhibited improved mobilities of 47 and 66 cm2V-1s-1, respectively.

Metal-organic and hybrid metal-organic/metal nanoparticle inkswere evaluated for use in the inkjet printing of copper and silver conducting lines. Pure, smooth, dense, highly conductive coatings were produced by spray printing with (hexafluoroacetylacetonato)copper(I)-vinyltrimethylsilane Cu(hfa)·VTMS) and (hexafluoroacetylacetonato)silver(I)(1,5-cyclooctadiene) (Ag(hfa)COD) metal-organic precursors on heated substrates. Good adhesion to the substrates tested, glass, Kapton tape and Si, has been achieved without use of adhesion promoters. The silver metal-organic ink has also beenused to print metal lines and patterns with a commercial inkjet printer. Hybrid inks comprised of metal nanoparticles mixed with the metal-organic complexes above have also been used to deposit Cu and Ag films by spray printing.This approach gives dense, adherent films that are much thicker than those obtained using the metal-organic inks alone. The conductivities of the silvercoatings obtained by both approaches are near that of bulk silver (2 μΩ·cm). The copper coatings had conductivities at least an order ofmagnitude less than bulk.

We have found that by varying only the substrate temperature and oxygen pressure five different crystallographic orientations of V2O5 thin films can be grown, ranging from amorphous to highly textured crystalline. Dense, phase-pure V2O5 thin films were grown on SnO2/glass substrates and amorphous quartz substrates by pulsed laser deposition over a wide range of temperatures and oxygen pressures. The films' microstructure, crystallinity, and texturing were characterized by electron microscopy, x-ray diffraction, and Raman spectroscopy. Temperature and oxygen pressure appeared to play more significant roles in the resulting crystallographic texture than did the choice of substrate. A growth map summarizes the results and delineates the temperature and O2 pressure window for growing dense, uniform, phase-pure V2O5 films.

Composite thin films of 60 wt% Ba0.6Sr0.4TiO3 and 40 wt% MgO were produced by Pulsed Laser Deposition. The biaxial texture of the BST component on the MgO substrate has been established with XRD. All as-deposited films had an enlarged BST out-of-plane lattice parameter. A more relaxed lattice constant as well as higher degree of texture has been obtained in the films deposited at higher temperature and lower deposition rate. Post-deposition annealing in flowing oxygen results in a further relaxation and alignment of the BST lattice. The as-deposited films were not tunable at room temperature. The greatest dielectric tuning was achieved in films annealed at 1200 °C. The observed difference in tunability for the films annealed at different temperatures may result from a spatial redistribution of BST material on the substrate surface during annealing.

We have employed inks containing nanometer-sized particles of Ag and Al (nano-Ag and nano-Al, respectively) as precursor inks for the formation of contacts to n- and p-type Si, respectively. The particles as formed by the electroexplosion process were dispersed in toluene, applied to Si and annealed above the respective eutectic temperatures. In the case of nano-Ag, this directly yields an ohmic contact. However, the nano-Al was found to be coated with an oxide layer that impairs the formation of an ohmic contact. A chelating chemical etch involving treatment with hexafluoroacetylacetone was developed to remove this oxide coat. This treated nano-Al produced a good ohmic contact. Smooth, pure Ag films have also been deposited by spray printing organometallic inks prepared from Ag(hfa)(SEt2) and Ag(hfa)(COD). These films are deposited in one step onto heated glass and Si substrates at one atmosphere pressure. The films show resistivities of ∼2 µΩ·cm. These inks appear to be amenable to ink-jet printing of Ag lines and as a low temperature glue for the Ag nanoparticles for thicker metallizations.

We grew BaxSr1−xTiO3 (BST) films on MgO single crystal substrates by pulsed laser deposition (PLD). We report the in-plane (a) and out-of-plane (c) lattice parameters of BST films deposited in a range of O2 deposition pressures [P(02)], as measured by asymmetric rocking curve diffraction. As P(O2) increases, the films' biaxial strain changes from compression (a < c), to cubic (a = c), and then to tension (a > c). Furthermore, both a and c are larger than the lattice constant for bulk BST of the same composition. This indicates the presence of a hydrostatic strain component in addition to the biaxial component. From the measured lattice parameters, we calculate the total residual strain in terms of biaxial and hydrostatic components. We also examine the effects of a post-deposition anneal. Characterizing residual strain and understanding its origin(s) are important since strain affects the dielectric properties of BST films and thereby the properties of devices which incorporate them.

Highly crystalline, textured thin films of LiCoxAl1-xO2 (x=0, 0.5) have been grown by pulsed laser deposition. Films of both stoichiometries were dense and uniaxially textured with Li, Co (or Co, A1) layers parallel to the substrate. It was found that crystal quality depended strongly on oxygen partial pressure, substrate temperature, and substrate material. The deposition of LiCo0.5Al0.5O2 is also highly dependent upon laser fluence, requiring at least 12.8 J/cm2 for high quality films. Chemical diffusion measurements were performed over a wide range of lithium contents using the potentiostatic intermittent titration technique. Maximum and minimum effective for LiCoO2 were 4.0 × 10−11 and 1.2 × 10−2 cm2/s, respectively, and for LiCo0.5A10.5O2, 2.2 × 10−12 and 8.0 × 10−17 cm2/s, respectively.

We report the performance of 16-element phased array antennas operating at 30 GHz and ambient temperature. These antennas use BaxSr1−xTiO3(BST)-based phase shifters to produce the beam steering. Ferroelectric phase shifters offer advantages over current semiconductor and ferrite devices including faster switching speeds and lower costs. Also, ferroelectric phase shifters offer higher power handling capability than semiconductor devices and also have high radiation resistance. We made phase shifters from laser-ablated epitaxial BST films as well as from polycrystalline BST-oxide composite films. Although neither the devices nor the materials themselves are fully optimized, phase shifters have shown > 360° of phase shift with < 350 V DC bias (E < 9 V/µm) and ∼8 dB insertion loss. With ferroelectric phase shifters incorporated, antennas show radiation patterns with central-lobe half-power widths of ∼13° and side lobe intensities down by more than 10 dB. Using the phase shifters, the central lobe can be shifted, or “steered,” by ±18° in either direction. These results demonstrate a first step toward a prototype steerable antenna for 20–30 GHz satellite communications as well as other applications.

Thin films of crystalline and amorphous V2O5 were deposited by pulsed laser deposition (PLD) and the chemical diffusion coefficients, , were measured by the potentiostatic intermittent titration technique (PITT). In crystalline V2O5 films, the maximum and minimum were found to be 1.7 × 10−2 cm2/s and 5.8 × 10−15 cm2/s respectively, with a general trend for to rise in single-phase regions. The changes in correlated well to the known phases in LiV2O5. In amorphous V2O5 films, exhibited a smooth, continuous decrease as the Li concentration increased.

Our team has been investigating the use of particle-based contacts in CdTe solar cell technologies. Toward this end, particles of Cu-doped HgTe (Hg-Cu-Te) and Sb-Te have been applied as contacts to CdTe/CdS/SnO2 heterostructures. These metal telluride materials were characterized by standard methods. Hg-Cu-Te particles in graphite electrodag contacts produced CdTe solar cells with efficiencies above 12% and series resistance (Rse) of 6 Ω or less. Metathesis preparation of Cu(I) and Cu(II) tellurides (i.e., Cu2Te and CuTe, respectively) were attempted as a means of characterizing the valence state of Cu in the Hg-Cu-Te ink. For Sb-Te contacts to CdTe, open circuit voltages (Vocs) in excess of 800 mV were observed, however, efficiencies were limited to 9%; perhaps a consequence of the marked increase in the Rse (i.e., >20 Ω) in these non-graphite containing contacts. Acetylene black was mixed into the methanolic Sb-Te colloid as a means of reducing Rse, however, no improvement in device properties was observed.

The use of nanoparticle precursors for electronic materials including sulfides, selenides, oxides and the elements has potentially wide ranging implications for improving device properties and substantially reducing the deposition costs. To realize this goal the complex interfacial chemistry of these small particles must be controlled. In this paper we present a number of cases demonstrating the complexity of this chemistry. These include CuInSe2 where the kinetics of phase formation dominate the sintering process; CdTe where sintering proceeds with and without the sintering enhancement of CdCl2, but produces materials different electronically than bulk materials; and the use of compound and elemental nanoparticles ( Ag, Al, Hg-Cu-Te and Sb-Te) for contacts to elemental and compound semiconductors (Si and CdTe).

The use of nanoparticle colloids for spray deposition of Cu-In-Se precursor films and subsequent thermal treatment to form CuInSe2 (CIS) films has been investigated. In the present study, the metathesis reaction between Na2Se in methanol and metal salts (i.e., Cu(BF4)2 and/or InI3) in pyridine produced CuSe, In2Se3, and CuInSe2.5 nanoparticle colloids. Purified colloid was sprayed onto heated molybdenum-coated sodalime glass substrates to form CuInSe2.5/Mo and In2Se3/CuSe/Mo precursor films. These precursor films were subjected to various thermal treatments in an effort to produce large-grained CIS films from the nano-sized precursors. The annealed CIS films were characterized by scanning electron microscopy (SEM) and x-ray diffraction (XRD). Results of this continuing effort will be discussed.

We report on the use of pulsed laser depositon (PLD) to grow thin films of LiCoO2 on a number of low cost substrates including SnO2 coated Upilex, stainless steel and SnO2 coated glass. Highly textured (001) films grown on CVD deposited SnO2 films on 7059 glass, were obtained at 200 to 500 mTorr O2 and a temperature of 500 C. Similar texture was not obtained on the stainless or Upilex however dense films from crystalline to amorphous were obtained. The films were characterized by x-ray diffraction and Raman spectroscopy.