Thermal Desorption Studies of Isotopically-Labeled Oxygen from La2CuO4+δ


Isotopically-labeled oxygen enrichment and thermal desorption mass spectroscopy (TDMS) have been combined to study interstitial oxygen desorption from superconducting La2CuO4+δ(δ ≤ 0.032). Single crystal samples of magnetic, insulating La2CuO4.00 were annealed at 860K under 1-3 kbar oxygen pressure for 12-100 hours to yield hole-doped, superconducting La2CuO4+δ samples with 35K <Tc <40K. Whereas no TDMS signals were observed for the insulator, rapid bursts (FWHM < 0.5 sec) of molecular oxygen were observed above 350K while heating the superconductor at less than 1 K sec{-1} in high vacuum. A kinetic model is proposed in which the interstitial oxygen diffuses to internal grain boundaries and defects during heating, thereby inducing stress in the lattice as it attempts to revert to the LaCuO4.00 crystal structure. This stress is relieved by lattice fracture at grain boundaries during the TDMS experiment, releasing the trapped oxygen from the sample as micro-cracks are formed. In addition, the facile oxygen exchange between interstitial and latticeoxygen sites has been discovered by TDMS and weight gain measurements from isotopically-enriched crystals, supporting thestructural model of Chaillout, et al. in which the interstitial oxygen atom dimerizes with a lattice oxygen ion.

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This work is supported by the United States Department of Energy, Office of Basic Energy Sciences, Division of Material Sciences, under contract DE-AC04-76DP00789 with Sandia National Laboratories. Illuminating discussions with Edwin Beauchamp and Bruno Morosin are gratefully acknowledged.

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Shinn, N.D., Bartram, M.E., Schirber, J.E. et al. Thermal Desorption Studies of Isotopically-Labeled Oxygen from La2CuO4+δ. MRS Online Proceedings Library 209, 825–830 (1990).

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