Details
| Original language | English |
|---|---|
| Pages (from-to) | 1930-1943 |
| Number of pages | 14 |
| Journal | Chemistry of materials |
| Volume | 8 |
| Issue number | 8 |
| Publication status | Published - Dec 1996 |
| Externally published | Yes |
Abstract
The composition-dependent optical and electronic tunability of the sodalite analogues with stoichiometries Zn8X2[BO2] 12 (X = O, S, Se) and [CdyZn(1-y)] 8X2[BeSixGe(1-x)O4] 6 (X = S, Se and Te) have been demonstrated. The materials strongly photoluminesce, and a comparison of the photoluminescence behavior of the single crystals with the as-synthesized powder analogues shows that the visible emission is intrinsic to the sodalite analogue and not due to impurities such as bulk semiconductor. The emission maxima of these materials can be varied by as much as 100 nm with subtle modifications in the host sodalite framework composition and excitation energies can be stored over, at minimum, several minutes. The materials can be prepared either hydrothermally or by high-temperature solid-state reactions. The local and average long-range structures of composition Zn8X2[BO2] 12 (X = O, S, Se) and M8X2[BeSi xGe1-xO4]6 (M = Zn, Cd; X ) S, Se, Te) are described based on the results of polycrystalline X-ray diffraction, multinuclear solid-state MAS NMR, CdL3 XANES, UV/visible and photoluminescence spectroscopic measurements. Additionally, the crystal structures of the synthetic helvite solid solutions Zn8S 2[BeSixGe1-xO4]6 (x = 0.03, 0.37, 0.74) are presented based on refinement of single-crystal X-ray diffraction and selected area electron diffraction data; these materials crystallize in the acentric, cubic space group P23 (No. 195) with unit-cell parameters a = 8.250(4), 8.221(2), and 8.163(1) Å, respectively. In all these sodalite analogues, the anionic, rigid sodalite framework encloses [M 4X]6+ tetrahedra in a crystalline cubic array, separating each tetrahedron from its eight nearest neighbors by at least 6.4 Å, center to center. This electrostatic isolation results in dramatic high-energy shifts in the optical absorption spectra of the materials and low-frequency shifts in the MAS NMR spectra of the cage center anions, relative to the bulk semiconductors. 113Cd MAS NMR and CdL3 XANES spectra show that the influence of the anion type on the electronic structure at the Cd 2+ ions in the cadmium sodalites is small.
ASJC Scopus subject areas
- Chemistry(all)
- General Chemistry
- Chemical Engineering(all)
- General Chemical Engineering
- Materials Science(all)
- Materials Chemistry
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In: Chemistry of materials, Vol. 8, No. 8, 12.1996, p. 1930-1943.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Synthesis, characterization and tunable electronic/optical properties of II-VI semiconductor species included in the sodalite structure
AU - Moran, Kelly L.
AU - Harrison, William T.A.
AU - Kamber, Ivo
AU - Gier, Thurman E.
AU - Bu, Xianhui
AU - Herren, Daniel
AU - Behrens, Peter
AU - Eckert, Hellmut
AU - Stucky, Galen D.
PY - 1996/12
Y1 - 1996/12
N2 - The composition-dependent optical and electronic tunability of the sodalite analogues with stoichiometries Zn8X2[BO2] 12 (X = O, S, Se) and [CdyZn(1-y)] 8X2[BeSixGe(1-x)O4] 6 (X = S, Se and Te) have been demonstrated. The materials strongly photoluminesce, and a comparison of the photoluminescence behavior of the single crystals with the as-synthesized powder analogues shows that the visible emission is intrinsic to the sodalite analogue and not due to impurities such as bulk semiconductor. The emission maxima of these materials can be varied by as much as 100 nm with subtle modifications in the host sodalite framework composition and excitation energies can be stored over, at minimum, several minutes. The materials can be prepared either hydrothermally or by high-temperature solid-state reactions. The local and average long-range structures of composition Zn8X2[BO2] 12 (X = O, S, Se) and M8X2[BeSi xGe1-xO4]6 (M = Zn, Cd; X ) S, Se, Te) are described based on the results of polycrystalline X-ray diffraction, multinuclear solid-state MAS NMR, CdL3 XANES, UV/visible and photoluminescence spectroscopic measurements. Additionally, the crystal structures of the synthetic helvite solid solutions Zn8S 2[BeSixGe1-xO4]6 (x = 0.03, 0.37, 0.74) are presented based on refinement of single-crystal X-ray diffraction and selected area electron diffraction data; these materials crystallize in the acentric, cubic space group P23 (No. 195) with unit-cell parameters a = 8.250(4), 8.221(2), and 8.163(1) Å, respectively. In all these sodalite analogues, the anionic, rigid sodalite framework encloses [M 4X]6+ tetrahedra in a crystalline cubic array, separating each tetrahedron from its eight nearest neighbors by at least 6.4 Å, center to center. This electrostatic isolation results in dramatic high-energy shifts in the optical absorption spectra of the materials and low-frequency shifts in the MAS NMR spectra of the cage center anions, relative to the bulk semiconductors. 113Cd MAS NMR and CdL3 XANES spectra show that the influence of the anion type on the electronic structure at the Cd 2+ ions in the cadmium sodalites is small.
AB - The composition-dependent optical and electronic tunability of the sodalite analogues with stoichiometries Zn8X2[BO2] 12 (X = O, S, Se) and [CdyZn(1-y)] 8X2[BeSixGe(1-x)O4] 6 (X = S, Se and Te) have been demonstrated. The materials strongly photoluminesce, and a comparison of the photoluminescence behavior of the single crystals with the as-synthesized powder analogues shows that the visible emission is intrinsic to the sodalite analogue and not due to impurities such as bulk semiconductor. The emission maxima of these materials can be varied by as much as 100 nm with subtle modifications in the host sodalite framework composition and excitation energies can be stored over, at minimum, several minutes. The materials can be prepared either hydrothermally or by high-temperature solid-state reactions. The local and average long-range structures of composition Zn8X2[BO2] 12 (X = O, S, Se) and M8X2[BeSi xGe1-xO4]6 (M = Zn, Cd; X ) S, Se, Te) are described based on the results of polycrystalline X-ray diffraction, multinuclear solid-state MAS NMR, CdL3 XANES, UV/visible and photoluminescence spectroscopic measurements. Additionally, the crystal structures of the synthetic helvite solid solutions Zn8S 2[BeSixGe1-xO4]6 (x = 0.03, 0.37, 0.74) are presented based on refinement of single-crystal X-ray diffraction and selected area electron diffraction data; these materials crystallize in the acentric, cubic space group P23 (No. 195) with unit-cell parameters a = 8.250(4), 8.221(2), and 8.163(1) Å, respectively. In all these sodalite analogues, the anionic, rigid sodalite framework encloses [M 4X]6+ tetrahedra in a crystalline cubic array, separating each tetrahedron from its eight nearest neighbors by at least 6.4 Å, center to center. This electrostatic isolation results in dramatic high-energy shifts in the optical absorption spectra of the materials and low-frequency shifts in the MAS NMR spectra of the cage center anions, relative to the bulk semiconductors. 113Cd MAS NMR and CdL3 XANES spectra show that the influence of the anion type on the electronic structure at the Cd 2+ ions in the cadmium sodalites is small.
UR - http://www.scopus.com/inward/record.url?scp=0001025122&partnerID=8YFLogxK
U2 - 10.1021/cm960168c
DO - 10.1021/cm960168c
M3 - Article
AN - SCOPUS:0001025122
VL - 8
SP - 1930
EP - 1943
JO - Chemistry of materials
JF - Chemistry of materials
SN - 0897-4756
IS - 8
ER -