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Pressure evolution of localized nitrogen cluster states in GaAsN alloys
Paul R. C. Kent and Alex ZungerSolid State Theory Group
National Renewable Energy Laboratory
U.S. Department of EnergyOffice of ScienceBasic Energy SciencesDivision of Materials Sciences
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Kent and Zunger PRL 86 2613 (2001)
Localized-Delocalized Transition in GaAsN
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Experimental Pressure & Composition EvolutionCourtesy B. Weinstein (Buffalo) ICPS2002, APS2002
Pressure coefficient of CS reduced compared to bulkDisappearance of highest energy CS!
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How do the nitrogen CS evolve with pressure and composition?
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Computational Modeling of Dilute Alloys
Use large supercells (10^3-10^6 atoms) containing many nitrogensStatistically average properties of many random configurationsUse VFF for structural relaxationUse Empirical pseudopotential method for wavefunctions
Small SupercellApproach
Large SupercellApproach
Kent and Zunger PRB 64 115208 (2001)
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Computational Modeling
64000 atom supercells
1. Create nitrogen clusterin dilute alloy
2. Follow localized state withpressure & nitrogen concentration
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Isolated nitrogen in bulk GaAs
L=Localized D=Delocalized
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Nitrogen triplet in Bulk GaAs
Localized state remains in gapLow pressure coefficient
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Developed alloy
Delocalized states at band edges
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Developed alloy with triplet
Delocalized states at band edgesTriplet not within gap or at band edge, as expected
Expected
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Isosurfaces
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Summary [email protected]
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Model Comparison
Band anticrossing Good fit of band edge bowingNo cluster states (CS)
Impurity band Predicts broadening of localized statesPressure exposes either broad impurity band, or nothingNo discrete CS to expose
Atomistic model Conduction states overtake discrete CS(This work) Some hybridization at higher pressures
Consistent with experiment
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Summary
In dilute GaAsN
• Deep (low energy) CS emergeinto gap with pressure
• Shallowest CS can hybridize– Pressure coefficient increased– Do not emerge into gap
Kent and Zunger Appl. Phys. Lett. 82 370 (2003)
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Anticrossing/repulsion between band edge and
localized statesdrives band gap down
Band gap reduction
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GaPN Pressure dependence
–14 meV/GPa
PressureE
nerg
y
Bulk GaP
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Red Shift of PL vs PLE
Majority stateabsorbs
Minority stateemits
I. A. Buyanova et al. MRS IJNSR 6 2 (2001)
- Emission from localized minority states
- Absorption to majority states