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[资源] Luminescence properties of defects in GaN

Luminescence properties of defects in GaN,最全的GaN PL光谱分析
作者：Michael A. Reshchikova! and Hadis Morko
作者单位：Department of Electrical Engineering and Physics Department, Virginia Commonwealth University, Richmond, Virginia 23284
出版于JOURNAL OF APPLIED PHYSICS 97, 061301 s2005d
目录
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—gallium vacancy
complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2. Shallow acceptor—nitrogen 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–Y11d.. . . . . . . . . . . . . . . . . . . . . 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