S. E. Asher

Abstract We report the growth and characterization of record‐efficiency ZnO/CdS/CuInGaSe 2 thin‐film solar cells. Conversion efficiencies exceeding 19% have been achieved for the first time, and this result indicates that the 20% goal is within reach. Details of the experimental procedures are provided, and material and device characterization data are presented. Published in 2003 by John Wiley & Sons, Ltd.

Nitrogen-doped films of ZnO grown by two methods, metalorganic chemical vapor deposition (MOCVD) and reactive sputtering, were studied with x-ray and ultraviolet photoelectron spectroscopy (XPS and UPS). Systematic differences in the N chemical states were observed between films grown by sputtering and MOCVD: only two N chemical states were observed in films grown by reactive sputtering, whereas four N chemical states were observed in MOCVD films. To aid in the assignment of the N chemical states, photoemission data from the polycrystalline films were compared with data taken on N2+-implanted Zn metal and N2+-implanted ZnO. High-resolution core level spectra of the N1s region indicated that nitrogen can occupy at least four different chemical environments in ZnO; these include the NO acceptor, the double donor (N2)O, and two carbon–nitrogen species. Valence band spectra indicate that the Fermi energy of all films studied was near the conduction band minimum, implying that the films remained n-type after nitrogen doping. Analysis of the relative amounts of acceptors and donors identified by XPS in the sputter-grown films provides clues as to why only a small percentage of incorporated nitrogen is found to contribute to carriers, and points toward possible paths to higher quality ZnO:N films.

The role of hydrogen in nitrogen-doped ZnO thin films was studied by Fourier transform infrared (FTIR) absorption and modeled by first-principles calculations to understand the difficulty of doping ZnO p-type with nitrogen. Nitrogen-doped ZnO films were fabricated by low-pressure metal-organic chemical vapor deposition (MOCVD). High levels of nitrogen incorporation were observed, but the acceptor concentrations remained low. Theoretical analysis suggests there is a high probability that NO− and H+ charged defects combine to form the neutral defect complexes, thereby compensating the nitrogen-related acceptors. Calculated values of the vibrational frequencies of the related infrared modes agree well with the measured spectra. Thus, we believe the difficulty of achieving p-type doping in MOCVD-grown ZnO films is due, at least partially, to inadvertent passivation by hydrogen.

A discussion of the modeling of the proton exchange fabrication process is given, including a brief review of results of analytical measurements of concentration and concentration/index relation, as well as some presentation of the speculations made as to mechanisms of resulting index profiles. Discussion is then given to modeling of the exchange process itself via the ion exchange equations. The concentration profiles of protons and lithium in proton-exchanged LiNbO3 crystals measured by secondary ion mass spectroscopy are then presented. The proton concentration profiles are found to be nearly rectangular in shape. The diffusion characteristics of the ion exchange process are empirically modeled by solving the ion exchange equations with concentration dependent self-diffusion coefficients. Secondary ion mass spectroscopy (SIMS) measurements on annealed H+:LiNbO3 samples show proton and lithium concentration profiles to be Gaussian in nature. The proton and lithium concentration profiles of annealed H+:LiNbO3 samples are fit to the solutions of diffusion equations obtained from standard thermal diffusion theory. The fit has resulted in values of diffusion coefficient for protons during annealing (Dp=0.77 μm2/h). Index profiles are then calculated from these equations and are found to agree with the profiles reported elsewhere. Optical mode measurements on channel waveguides fabricated under various diffusion conditions and annealed for various times, are carried out. The mode-tailoring ability of the proton exchange process is demonstrated by fabricating low-loss single-mode channel guides (λ=0.83 μm) having channel widths as large as 6 and as small as 2.5 μm, simply by changing the diffusion conditions. Some anomalous results obtained in waveguides fabricated under extreme conditions are discussed.

Abstract This communication reports an MgF 2 /ZnO/CdS/Cu(In,Ga)Se 2 /Mo/glass polycrystalline solar cell with a confirmed total‐area conversion efficiency of 16.4%. the thin‐film Cu(In,Ga)Se 2 absorber was fabricated by computer‐controlled physical vapor deposition (PVD) from the elemental sources. the resulting absorber has a Gal/In compositional grading that we refer to as a notch. Capacitance‐voltage (C‐V) measurements also reveal a graded doping profile in the region near the electronic p‐n junction. the enhanced device performance is characterized by an open‐circuit voltage (V oc ) of 660 mV and a particularly high fill factor (FF) of 78.7%.