Investigation of combinatorial coevaporated thin film Cu 2ZnSnS4. I. Temperature effect, crystalline phases, morphology, and photoluminescence

pre-printCu2ZnSnS4 is a promising low-cost, nontoxic, earth-abundant absorber material for thin-film solar cell applications. In this study, combinatorial coevaporation was used to synthesize individual thin-film samples spanning a wide range of compositions at low (325 C) and high (475 C) temperatures. Film composition, grain morphology, crystalline-phase and photo-excitation information have been characterized by x-ray fluorescence, scanning electron microscopy, x-ray diffraction, Raman spectroscopy, and photoluminescence imaging and mapping. Highly textured columnar grain morphology is observed for film compositions along the ZnS-Cu2ZnSnS4-Cu2SnS3 tie line in the quasi-ternary Cu2S-ZnS-SnS2 phase system, and this effect is attributed to structural similarity between the Cu2ZnSnS4, Cu2 SnS3, and ZnS crystalline phases. At 475 C growth temperature, Sn-S phases cannot condense because of their high vapor pressures. As a result, regions that received excess Sn flux during growth produced compositions falling along the ZnS-Cu2ZnSnS4-Cu2SnS3 tie line. Room-temperature photoluminescence imaging reveals a strong correlation for these samples between film composition and photoluminescence intensity, where film regions with Cu/Sn ratios greater than 2 show strong hotoluminescence intensity, in comparison with much weaker photoluminescence in regions that received excess Sn flux during growth or subsequent processing. The observed photoluminescence quenching in regions that received excess Sn flux is attributed to the effects of Sn-related native point defects in Cu2ZnSnS4 on non-radiative recombination processes. Implications for processing and performance of Cu2ZnSnS4 solar cells are discussed

SnS thin-films by RF sputtering at room temperature

Journal ArticleTin monosulfide (SnS) is of interest as a potential solar cell absorber material. We present a preliminary investigation of the effects of sputtering conditions on SnS thin-film structural, optical, and electronic properties. Films were RF sputtered from an SnS target using an argon plasma. Resistivity, stoichiometry, phase, grain size and shape, bandgap, and optical absorption coefficient can be varied by modifying argon pressure for a fixed deposition time. Most films have an indirect bandgap in the range of 1.08?1.18 eV. XRD patterns confirmed the films as mostly crystalline, and grain morphology was examined using profile and surface SEM images

Pulsed and continuous wave solid phase laser annealing of electrodeposited CuInSe2 thin films

pre-printCu(In,Ga)Se2 (CIGS) thin film photovoltaic absorber layers are primarily synthesized by vacuum based techniques at industrial scale. In this work, we investigate non-vacuum film synthesis by electrochemical deposition coupled with pulsed laser annealing (PLA) and or continuous wave laser annealing (CWLA) using 1064 nm laser. PLA results indicate that at high fluence (≥100 mJ/cm2) CuInSe2 films melt and dewet on both Mo and Cu substrates. In the submelt PLA regime (≤70 mJ/cm2) no change in XRD results is recorded. However CWLA at 50 W/cm2 for up to 45 s does not result in melting or dewetting of the film. XRD and Raman data indicate more than 80% reduction in full width at half maximum (FWHM) in their respective main peaks for annealing time of 15 s or more. No other secondary phases are observed in XRD or Raman spectrum. These results might help us in setting up the foundation for processing CIGS through an entirely non-vacuum process

Magnetocrystalline anisotropy and magnetization reversal in Ga1-xMnxP synthesized by ion implantation and pulsed-laser melting

Journal ArticleWe report the observation of ferromagnetic resonance (FMR) and the determination of the magnetocrystalline anisotropy in (100)-oriented single-crystalline thin film samples of Ga1−xMnxP with x=0.042. The contributions to the magnetic anisotropy were determined by measuring the angular and the temperature dependencies of the FMR resonance fields and by superconducting quantum interference device magnetometry. The largest contribution to the anisotropy is a uniaxial component perpendicular to the film plane; however, a negative contribution from cubic anisotropy is also found. Additional in-plane uniaxial components are observed at low temperatures, which lift the degeneracy between the in-plane [011] and [011¯] directions as well as between the in-plane [010] and [001] directions. Near T=5 K, the easy magnetization axis is close to the in-plane [011¯] direction. All anisotropy parameters decrease with increasing temperature and disappear above the Curie temperature TC. A consistent picture of the magnetic anisotropy of ferromagnetic Ga1−xMnxP emerges from the FMR and magnetometry data. The latter can be successfully modeled when both coherent magnetization rotation and magnetic domain nucleation are considered

Electronic structure of ferromagnetic semiconductor Ga1-xMnxAs probed by sub-gap magneto-optical spectroscopyElectronic

We employ Faraday and Kerr effect spectroscopy in the infrared range to investigate the electronicstructure ofGa1 xMnxAsnear the Fermi energy. The band structure of this archetypical dilute-momentferromagnetic semiconductor has been a matter of controversy, fueled partly by previous measurements ofthe unpolarized infrared absorption and their phenomenological impurity-band interpretation. Unlike theunpolarized absorption, the infrared magneto-optical effects we study are intimately related to ferromag-netism, and their interpretation is much more microscopically constrained in terms of the orbital characterof the relevant band states. We show that the conventional theory of the disordered valence band with anantiferromatnetic exchange term accounts semiquantitatively for the overall characteristics of themeasured infrared magneto-optical spectra

Temperature dependent conductivity of polycrystalline Cu 2ZnSnS 4 thin films

pre-printThe temperature-dependent conductivity of Cu2ZnSnS4 (CZTS) thin films prepared by sulfurization of different sputtered ZnS/Cu/Sn stacks and also of the same stack annealed for different times was investigated from 30-300 K. Fitting of the through-thickness conductivity requires a model including Mott variable-range hopping (M-VRH), nearest-neighbor hopping (NNH), and thermionic emission over grain boundary (GB) barriers. The GB barrier height varies sensitively from 50-150 (65) meV with annealing and especially with [Cu]/([Zn]þ[Sn]) ratio but is independent of [Zn]/[Sn] ratio. These results are critical for understanding the behavior of solar cells based on polycrystalline CZTS absorber layers

Compositional tuning of ferromagnetism in Ga1-xMnxP

ManuscriptWe report the magnetic and transport properties of Ga1-xMnxP synthesized via ion implantation followed by pulsed laser melting over a range of x, namely 0.018 to 0.042. Like Ga1-xMnxAs, Ga1-xMnxP displays a monotonic increase of the ferromagnetic Curie temperature with x associated with the hole-mediated ferromagnetic phase while thermal annealing above 300 ºC leads to a quenching of ferromagnetism that is accompanied by a reduction of the substitutional fraction of Mn. However, contrary to observations in Ga1- xMnxAs, Ga1-xMnxP is non-metallic over the entire composition range. At the lower temperatures over which the films are ferromagnetic, hole transport occurs via hopping conduction in a Mn-derived band; at higher temperatures it arises from holes in the valence band which are thermally excited across an energy gap that shrinks with x

Heat flow model for pulsed laser melting and rapid solidification of ion implanted GaAs

Journal ArticleIn order to further understand the pulsed-laser melting (PLM) of Mn and N implanted GaAs, which we have used to synthesize thin films of the ferromagnetic semiconductor Ga1−xMnxAs and the highly mismatched alloy GaNxAs1−x, we have simulated PLM of amorphous (a-) and crystalline (c-) GaAs. We present a numerical solution to the one-dimensional heat equation, accounting for phase-dependent reflectivity, optical skin depth, and latent heat, and a temperature-dependent thermal conductivity and specific heat. By comparing the simulations with experimental time-resolved reflectivity and melt depth versus laser fluence, we identify a set of thermophysical and optical properties for the crystalline, amorphous, and liquid phases of GaAs that give reasonable agreement between experiment and simulation. This work resulted in the estimation of thermal conductivity, melting temperature and latent heat of fusion of a-GaAs of 0.008 W/cm K at 300 K, 1350 K, and 2650 J /cm3, respectively. These materials properties also allow the prediction of the solidification velocity of crystalline and ion-amorphized GaAs