Correlation between native defects, conductivity

and green luminescence in ZnO single crystals

Naresh Adhikari, Pooneh Saadaktia, Petr Stepanov, Micah Haseman, G.E.Jellison, L.A.
Boatner, Farida Selim
Center for Pure and Applied Photosciences, Bowling Green State University, Bowling
Green, OH 43403, USA
Center for Radiation Detection Materials and Systems, Oak Ridge National
Laboratory, TN 37830, USA
13-September-2018
 Introduction

• ZnO is a direct wide band-gap (3.37

eV) compound semiconductor that is
suitable for short wavelength
optoelectronic applications.

• ZnO is transparent to visible light

and can be made highly conductive
by doping.

• Exciton binding is very high energy

– 60 meV, which is especially
important for optoelectronic Oxygen atom Zinc atom
application.

Samanta PK., J Tissue Sci Eng. 2017;8(197):2.

2
Applications of ZnO

Rubber industry Fillers, activator of rubber compounds

Pharmaceutical
and cosmetic
Component of creams, powders, dental
industry pastes, Absorber of UV radiation

Textile industry Absorber of UV radiation

Electronics and
electrotechnology
Used in: photoelectronic, field emitters,
industries sensors, V lasers, solar cells

Photocatalysis Photocatalyst

More Production of zinc silicates, typographical and

Applications offset inks, criminology biosensor, process of
3
producing and packing vegetables products
Kołodziejczak-Radzimska A, Materials. 2014; 7(4):2833
Samples Grown by different methods :
• B: ZnO Hydrotherm growth c-axis (0001)
• C: Praxair Ceramic ZnO 77 Mpa 30 ramp to 800℃, 30 min
hold at 800℃
• D: ZnO multiple heat treatments (Praxair, ceramic, 80 Mpa,
initial ramp to 800℃)
• E: ZnO c-perp (Eagle Picher CVT grown)
• F: ZnO c-para (Eagle Picher CVT grown)
• H: ZnO (DENPA) hydrothermal (Tokyo)
• J: ZnO Cermet M-plane melt grown (Skull melting) High O2
pressure
• K: ZnO Cermet A-plane melt grown (Skull melting) High O2
pressure
4
 ZnO E

ZnO C

ZnO H

5
Characterization

• Photoluminescence

• Van der Pauw Hall effect

• Thermoluminescence

• Positron Annihilation Lifetime Spectroscopy (PALS)

• Digital coincidence Doppler broadening spectroscopy

6
Photoluminescence
measurements:

Sample B: Hydrothermal

Power PL(376) PL(570) Ratio

High A 1.55 0.06 0.04
High B 1.55 0.06 0.04
Low A 0.80 0.26 0.32
Low B 0.80 0.30 0.38

• Peak excitonic PL = 376

nm
• Peak “green” PL = 570
nm
7
Sample C: Praxair Ceramic

Power PL(376) PL(550) Ratio

High A 1.50 0.34 0.23

High B ---- 0.34 ----
Low A 1.25 0.94 0.75
Low B 1.7 1.10 0.65

 Peak excitonic PL = 377 nm

 Peak “green” PL = 550 nm

8
Sample D : Praxair Ceramic

Power PL(376) PL(550) Ratio

High A 0.62 0.08 0.13
High B 0.90 0.32 0.36
Low A 0.58 0.16 0.28
Low B 0.82 0.62 0.76

 Peak excitonic PL = 376 nm

 Peak “green” PL = 520-580 nm
 Big difference between
different spots
 Still, ratio High < Low

9
 Sample E : CVT Growth

 Peak excitonic PL = 376 Power PL(376) PL(510) Ratio

nm
High A 0.021 0.031 1.5
 Peak “green” PL = 510 nm
High B 0.034 0.046 1.4
 Very low PL for all
Low A 0.031 0.068 2.2
 PL(510) > PL(376)
Low B 0.040 0.083 2.1
 Still, ratio High < Low 10
Sample F : CVT Growth

 Peak excitonic PL = 377 nm

 Peak “green” PL = 550 nm
 Very low PL for all Power PL(376) PL(550) Ratio
 PL(550) > PL(377) High A 0.0075 0.024 3.2
 PL was so low could not see High B 0.0040 0.013 3.2
low power PL
 Can see the 706 and
possibly the 727 lines
11
 Sample H : Hydrothermal, DENPA

Power PL(376) PL(550) Ratio

 Peak excitonic PL = 376 nm High A 20.0 1.7 0.085
 Peak “green” PL = 580 nm High B 19.8 1.6 0.081
 Very strong PL; High laser power = Low A 15.7 3.1 0.20
3.38 mW (saturates) Low B 15.0 2.85 0.19
 Still, ratio High < Low 12
 Sample J, K Cermet (High O2 Pressure)

 Peak excitonic PL = 377 nm

 Very little “green” PL in either
 Very little difference between spots
 Did not try low power---no signal
13
TL Glow Curve

5x105
A
B
4x105
E
TL Intensity (a.u.)

G
3x105 H

2x105

1x105

-150 -100 -50 0

Temperature (oC)
14
TL Emission Peak

1200
A
1000 B -151C
B -113C
E -151C
TL Intensity (a.u.)

800 E -77C
F
600 G -168C
G -77C
H
400

200

200 300 400 500 600 700 800

Wavelength (nm)
15
Positron Annihilation Lifetime Spectroscopy

16
Digital Coincidence Doppler Spectrometer System

Energy resolution: 1.1 keV FWHM at 511 keV Novelties:

Preamplifier signal width: 1 μs (max count rate ~105 cps) Absence of the coincidence unit.

Maximum binning: 32768 (16384, 8192) channels Every analyzer continuously saves independent series of energy
and time events.
Coincidence count rate: ~50 cps at ~4.5% dead time
The two-dimensional energy spectrum is reconstructed on-the-fly
Signal-to-noise ratio: 105 during acquisition. 17
Various measurements on samples :
Sample Resistivity (W Mobility Density “Green” PL Average S W
cm) (cm2/Vs) (cm3) Emission Wavelength Positron parameter parameter
(nm) lifetime (ns)

B(Hydrotherm 673 1.0697288 9.85E+15 570 0.172 0.4302 0.06232

)

C(Praxiar, Highly 550 0.195 0.4504 0.05332

Ceramic) Conductive
D (Praxair, Highly 520-580 0.198 0.4484 0.05422
Ceramic) Conductive
E(CVT) 6.99x105 0.4047047 2.75E+13 510 0.209 0.4549 0.05043

F(CVT) 6.88x10-2 93.599808 9.69E+17 550 0.205 0.4536 0.05038

H(DENPA, 68.5 580 0.197 0.4486 0.05331

Hydrotherm)
92.814066 9.82E+14

J, K (Cermet, 0.355, 174.45258 0.172, 0.4503 0.05544

melt with high
1.01E+17,
0.474 180.32338 7.30E+16 0.172 0.4487 0.05614
O2 Pressure

Thermoluminescence data reveals that the presence of H-donors in samples B, J and K.

18
Continued ….

19
PALS Results :
Average positron lifetime vs conductivity

20
S parameter vs conductivity

21
S parameter vs W parameter

22
23
24
25
Summary

 Samples which exhibit weak green luminescence and these

samples are highly conductive. This is due to the decrease
in Zn vacancies as shown by positron lifetime data.
 Samples grown by different growth methods exhibits
different defect structures.

 The ratio between green luminescence emission and near

band emission decreases with increasing laser intensity.

 Positron annihilation measurements revealed the presence

of Zn vacancy decorated by Hydrogen defects.

26
Acknowledgement

• Dr. Jellison
• Dr. Boatner
• Dr. Stepanov
• Entire Selim lab

27