We review prior and on-going works in using laser annealing (LA) techniques in the development of chalcogenide-based [CdTe and Cu(In,Ga)(S,Se)2] solar cells. LA can achieve unique processing regimes as the wavelength and pulse duration can be chosen to selectively heat particular layers of a thin film solar cell or even particular regions within a single layer. Pulsed LA, in particular, can achieve non-steady-state conditions that allow for stoichiometry control by preferential evaporation, which has been utilized in CdTe solar cells to create Ohmic back contacts. Pulsed lasers have also been used with Cu(In,Ga)(S,Se)2 to improve device performance by surface-defect annealing as well as bulk deep-defect annealing. Continuous-wave LA shows promise for use as a replacement for furnace annealing as it almost instantaneously supplies heat to the absorbing film without wasting time or energy to bring the much thicker substrate to temperature. Optimizing and utilizing such a technology would allow production lines to increase throughput and thus manufacturing capacity. Lasers have also been used to create potentially low-cost chalcogenide thin films from precursors, which is also reviewed.
For the production of high efficiency thin film, Cu(In,Ga)Se2 solar cells, absorber layers with grain sizes of a few hundred nanometers and without detrimental secondary phases are favored. Co-electrodeposition offers a low-cost and material efficient synthesis route, where, in a single step, films containing CuInSe2 are formed. However, the material is nanocrystalline, constitutes multiple phases and has poor photovoltaic properties 1. Therefore a subsequent annealing step is required to produce absorber layers suitable for use in photovoltaic devices. Laser annealing has been demonstrated to improve crystallinity, stimulate atomic diffusion and develop opto-electronic properties when compared to the precursor 2. In this work, high resolution X-ray diffraction was used in order to assess the presence of secondary phases in the absorber layer. All diffractograms of laser annealed films exhibited an additional, unknown peak, measurable through the full depth of the material which is independent of precursor composition, annealing time or laser flux. Evaluation of literature on codeposited CuInSe2, combined with Rietveld refinement suggests a number of possible identities for this peak. The candidates in order of most likely to least likely are structural defects, In2Se3, and CuIn3Se5. We consider the impact that each of these would have on a device formed via this process and thus its success as a new manufacturing route for CuInSe2 solar cells.
In order to upscale the production of thin film solar cells a cost effective and simple synthesis technique is required.
Keeping this in mind we have investigated the effect of electrochemical deposition (ED) and inherently low thermal
budget rapid thermal annealing (RTA) processing of CuInSe2 in sulfur atmosphere. X-ray diffraction (θ-2θ) scans
indicate increased grain size and improved crystallinity after RTA of ED films. Scanning electron microscopy images
(SEM) suggest changes in surface morphology after sulfur incorporation. Raman spectroscopy results and temperature
dependent conductivity measurements are also discussed in the paper.
Cu(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.