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Luminescence properties of defects in GaN
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Luminescence properties of defects in GaN,×îÈ«µÄGaN PL¹âÆ×·ÖÎö ×÷ÕߣºMichael A. Reshchikova! and Hadis Morko ×÷Õßµ¥Î»£ºDepartment of Electrical Engineering and Physics Department, Virginia Commonwealth University, Richmond, Virginia 23284 ³ö°æÓÚJOURNAL OF APPLIED PHYSICS 97, 061301 s2005d Ŀ¼ I. INTRODUCTION. . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 II. FORMATION AND ENERGY LEVELS OF POINT DEFECTS IN GaN. . . . . . . . . . . . . . . . . . . . 5 A. Theoretical approach. . . . . . . . . . . . . . . . . . . . 5 B. Native point defects. . . . . . . . . . . . . . . . . . . . . 6 1. Vacancies. . . . . . . . . . . . . . . . . . . . . . . . . . . 6 a. Gallium vacancy.. . . . . . . . . . . . . . . . . . . 7 b. Nitrogen vacancy.. . . . . . . . . . . . . . . . . . 7 c. Divacancy.. . . . . . . . . . . . . . . . . . . . . . . . 7 2. Interstitials and antisite defects. . . . . . . . . . 7 a. Gallium interstitial.. . . . . . . . . . . . . . . . . 7 b. Nitrogen interstitial.. . . . . . . . . . . . . . . . . 7 c. Gallium antisite.. . . . . . . . . . . . . . . . . . . 8 d. Nitrogen antisite.. . . . . . . . . . . . . . . . . . . 8 C. Impurities. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 1. Shallow donors. . . . . . . . . . . . . . . . . . . . . .8 2. Substitutional acceptors. . . . . . . . . . . . . . . . 8 3. Isoelectronic impurities. . . . . . . . . . . . . . . . 9 4. Hydrogen. . . . . . . . . . . . . . . . . . . . . . . . . . . 9 D. Complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 1. Shallow donor¡ªgallium vacancy complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . 10 2. Shallow acceptor¡ªnitrogen vacancy complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . 10 3. Hydrogen-related complexes. . . . . . . . . . . . 10 4. Other complexes. . . . . . . . . . . . . . . . . . . . . 11 E. Role of dislocations in the point defect formation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 III. LUMINESCENCE METHODS. . . . . . . . . . . . . . . . 12 A. Steady-state photoluminescence. . . . . . . . . . . . 12 1. Recombination statistics. . . . . . . . . . . . . . . 12 2. Effect of temperature on PL intensity. . . . . 13 3. Estimates of quantum efficiency. . . . . . . . . 14 4. Effect of excitation intensity on PL intensity. . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 5. Estimates of acceptor concentration in n-type GaN. . . . . . . . . . . . . . . . . . . . . . . . . . 15 B. Time-resolved luminescence. . . . . . . . . . . . . . 15 C. Vibrational properties of deep-level defects.. 16 D. Photoluminescence excitation spectra. . . . . . . 17 E. Spatially and depth-resolved cathodoluminescence. . . . . . . . . . . . . . . . . . . . 18 F. Optically detected magnetic resonance. . . . . . 18 IV. LUMINESCENCE RELATED TO POINT DEFECTS IN UNDOPED GaN. . . . . . . . . . . . . . . . 18 A. Yellow luminescence band. . . . . . . . . . . . . . . . 19 1. Effect of temperature. . . . . . . . . . . . . . . . . . 20 2. Effect of excitation intensity. . . . . . . . . . . . 22 3. Effect of hydrostatic pressure. . . . . . . . . . . 22 4. Effect of electron irradiation. . . . . . . . . . . . 23 5. Time-resolved PL. . . . . . . . . . . . . . . . . . . . . 23 6. Resonant excitation. . . . . . . . . . . . . . . . . . . 25 7. Vibrational model of the YL. . . . . . . . . . . . 26 8. Comparison with the positron annihilation results. . . . . . . . . . . . . . . . . . . . 26 9. ODMR on the YL. . . . . . . . . . . . . . . . . . . . 27 10. Effect of doping on the YL. . . . . . . . . . . . . 27 B. Yellow and green luminescence in high-purity GaN. . . . . . . . . . . . . . . . . . . . . . . . 28 1. Effect of excitation intensity. . . . . . . . . . . . 29 2. Resonant excitation. . . . . . . . . . . . . . . . . . . 30 3. Time-resolved PL. . . . . . . . . . . . . . . . . . . . . 31 4. Effect of temperature. . . . . . . . . . . . . . . . . . 33 C. Ultraviolet sshallow DAPd band. . . . . . . . . . . 34 1. Steady-state PL. . . . . . . . . . . . . . . . . . . . . . 34 2. Time-resolved PL. . . . . . . . . . . . . . . . . . . . . 36 3. ODMR and identification of the shallow acceptor. . . . . . . . . . . . . . . . . . . . . . . . . . . . 37 D. Blue luminescence band. . . . . . . . . . . . . . . . . . 38 1. Steady-state PL. . . . . . . . . . . . . . . . . . . . . . 38 2. Time-resolved PL. . . . . . . . . . . . . . . . . . . . . 40 3. Spatially and depth-resolved cathodoluminescence. . . . . . . . . . . . . . . . . . 40 4. Origin of the BL band in undoped GaN... 40 E. Red luminescence band. . . . . . . . . . . . . . . . . . 41 F. Red and green luminescence bands in Ga-rich GaN grown by MBE. . . . . . . . . . . . . . 42 1. Effect of excitation intensity. . . . . . . . . . . . 42 2. Effect of temperature. . . . . . . . . . . . . . . . . . 43 3. Time-resolved PL. . . . . . . . . . . . . . . . . . . . . 44 4. Resonant excitation of the GL2 and RL2 bands. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45 5. Origin and model of the GL2 and RL2 bands. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45 G. Other broad bands in undoped GaN. . . . . . . . 46 H. Characteristics and identification of radiative defects in undoped GaN. . . . . . . . . . 47 V. INTENTIONALLY INTRODUCED IMPURITIES AND NATIVE DEFECTS. . . . . . . . . . . . . . . . . . . . . 48 A. Luminescence in Zn-doped GaN. . . . . . . . . . . 48 1. Blue luminescence band. . . . . . . . . . . . . . . 49 a. Effect of temperature.. . . . . . . . . . . . . . . 49 b. Effect of excitation intensity.. . . . . . . . . 50 c. Time-resolved PL.. . . . . . . . . . . . . . . . . . 51 d. Resonant excitation and vibrational properties.. . . . . . . . . . . . . . . . . . . . . . . . 51 e. ODMR and defect identification.. . . . . . 52 2. Green, yellow, and red luminescence bands. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52 B. Luminescence in Mg-doped GaN. . . . . . . . . . 52 1. Ultraviolet luminescence band in lightly Mg-doped GaN. . . . . . . . . . . . . . . . . . . . . . 53 2. Effect of potential fluctuations on PL. . . . . 54 3. UVL and BL bands in compensated and heavily Mg-doped GaN. . . . . . . . . . . . . . . . 56 a. Effects of growth conditions and annealing.. . . . . . . . . . . . . . . . . . . . . . . . . 56 b. Effect of excitation intensity.. . . . . . . . . 57 c. Effect of temperature.. . . . . . . . . . . . . . . 58 d. Time-resolved PL.. . . . . . . . . . . . . . . . . . 60 e. Effect of hydrostatic pressure.. . . . . . . . 60 f. Effect of electron irradiation.. . . . . . . . . 60 g. Optically detected magnetic resonance.. 61 h. DLTS, positron annihilation, and the infrared spectra.. . . . . . . . . . . . . . . . . . . . 61 4. Yellow and red luminescence bands. . . . . . 62 5. Luminescence in GaN:Mg codoped with shallow donors. . . . . . . . . . . . . . . . . . . . . . . 62 6. Identification of defects in Mg-doped GaN. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 C. Luminescence in GaN doped with other impurities. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 1. Doping with shallow donors. . . . . . . . . . . . 62 a. Silicon doping.. . . . . . . . . . . . . . . . . . . . . 62 b. Oxygen doping.. . . . . . . . . . . . . . . . . . . . 63 c. Selenium doping.. . . . . . . . . . . . . . . . . . . 63 d. Germanium doping.. . . . . . . . . . . . . . . . . 63 2. Doping with acceptors. . . . . . . . . . . . . . . . . 63 a. Carbon doping.. . . . . . . . . . . . . . . . . . . . 63 b. Beryllium doping.. . . . . . . . . . . . . . . . . . 64 c. Calcium doping.. . . . . . . . . . . . . . . . . . . 64 d. Cadmium doping.. . . . . . . . . . . . . . . . . . 65 e. Manganese doping.. . . . . . . . . . . . . . . . . 65 f. Other acceptors in GaN.. . . . . . . . . . . . . 65 3. Doping with isoelectronic impurities. . . . . 65 a. Arsenic doping.. . . . . . . . . . . . . . . . . . . . 65 b. Phosphorus doping.. . . . . . . . . . . . . . . . . 66 4. Radiative defects introduced by irradiation. . . . . . . . . . . . . . . . . . . . . . . . . . . 66 5. Transition and rare-earth elements. . . . . . . 67 a. Transition metals.. . . . . . . . . . . . . . . . . . 67 b. Rare-earth elements.. . . . . . . . . . . . . . . . 67 VI. DEFECT-RELATED LUMINESCENCE IN CUBIC GaN. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67 A. Undoped material. . . . . . . . . . . . . . . . . . . . . . . 67 1. Exciton emission. . . . . . . . . . . . . . . . . . . . . 67 2. Shallow DAP band. . . . . . . . . . . . . . . . . . . 67 3. Deep defects. . . . . . . . . . . . . . . . . . . . . . . . . 68 B. Doped material. . . . . . . . . . . . . . . . . . . . . . . . . 68 1. Carbon doping. . . . . . . . . . . . . . . . . . . . . . . 68 2. Magnesium doping. . . . . . . . . . . . . . . . . . . 69 3. Silicon doping. . . . . . . . . . . . . . . . . . . . . . . 69 VII. EXCITONS BOUND TO POINT DEFECTS. . . . 69 A. Free excitons. . . . . . . . . . . . . . . . . . . . . . . . . . . 69 B. Bound excitons. . . . . . . . . . . . . . . . . . . . . . . . . 71 1. Excitons bound to shallow donors. . . . . . . 71 2. Excitons bound to acceptors. . . . . . . . . . . . 73 3. Haynes rule in GaN. . . . . . . . . . . . . . . . . . . 74 VIII. UNUSUAL LUMINESCENCE LINES IN GaN. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75 A. Yi lines. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75 1. Effects of sample treatments and experimental conditions on the Yi lines. . . 76 a. Effect of hot wet chemical etching.. . . . 76 b. Effect of photoelectrochemical etching.. . . . . . . . . . . . . . . . . . . . . . . . . . . 77 c. Evolution of PL and memory effect.. . . 77 d. Effect of excitation intensity.. . . . . . . . . 77 e. Effect of temperature.. . . . . . . . . . . . . . . 77 2. Characteristics of the Yi lines. . . . . . . . . . . 78 a. The 3.45-eV line sY1d.. . . . . . . . . . . . . . 78 b. The 3.42-eV line sY2d.. . . . . . . . . . . . . . 79 c. The 3.38-eV line sY3d.. . . . . . . . . . . . . . 79 d. The 3.35-eV line sY4d.. . . . . . . . . . . . . . 79 e. The 3.34-eV line sY5d.. . . . . . . . . . . . . . 79 f. The 3.32-eV line sY6d.. . . . . . . . . . . . . . 79 g. The 3.21-eV line sY7d.. . . . . . . . . . . . . . 80 h. The 3.08-, 2.85-, 2.80- and 2.66-eV lines sY8¨CY11d.. . . . . . . . . . . . . . . . . . . . . 80 3. Yi lines and structural defects. . . . . . . . . . . 80 a. Atomic force microscopy.. . . . . . . . . . . . 80 b. X-ray diffraction.. . . . . . . . . . . . . . . . . . . 80 c. Transmission electron microscopy.. . . . . 81 B. Oil-related 3.31- and 3.36-eV lines. . . . . . . . . 81 C. Identification of the Yi lines. . . . . . . . . . . . . . . 82 IX. UNSTABLE LUMINESCENCE FROM DEFECTS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82 A. Unstable luminescence bands. . . . . . . . . . . . . . 82 1. Blue band from the etched GaN surface. . 83 2. Blue and yellow unstable bands. . . . . . . . . 83 B. Manifestation of surface states in photoluminescence. . . . . . . . . . . . . . . . . . . . . . 85 1. Band bending at the surface of GaN. . . . . 85 2. Effect of UV illumination on PL. . . . . . . . 86 3. Effect of ambient on intensity and shape of PL bands. . . . . . . . . . . . . . . . . . . . . . . . . 86 4. Effect of passivation on PL. . . . . . . . . . . . . 87 X. SUMMARY. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88 |
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