Journal ArticleDOI

# A study of the T2 defect and the emission properties of the E3 deep level in annealed melt grown ZnO single crystals

22 Mar 2013-Journal of Applied Physics (American Institute of Physics)-Vol. 113, Iss: 12, pp 124502

AbstractWe report on the space charge spectroscopy studies performed on thermally treated melt-grown single crystal ZnO. The samples were annealed in different ambients at 700 °C and also in oxygen ambient at different temperatures. A shallow donor with a thermal activation enthalpy of 27 meV was observed in the as-received samples by capacitance-temperature, CT scans. After annealing the samples, an increase in the shallow donor concentrations was observed. For the annealed samples, E27 could not be detected and a new shallow donor with a thermal activation enthalpy of 35 meV was detected. For samples annealed above 650 °C, an increase in acceptor concentration was observed which affected the low temperature capacitance. Deep level transient spectroscopy revealed the presence of five deep level defects, E1, E2, E3, E4, and E5 in the as-received samples. Annealing of the samples at 650 °C removes the E4 and E5 deep level defects, while E2 also anneals-out at temperatures above 800 °C. After annealing at 700 °C, the T2 deep level defect was observed in all other ambient conditions except in Ar. The emission properties of the E3 deep level defect are observed to change with increase in annealing temperature beyond 800 °C. For samples annealed beyond 800 °C, a decrease in activation enthalpy with increase in annealing temperature has been observed which suggests an enhanced thermal ionization rate of E3 with annealing.

Topics: Shallow donor (56%), Annealing (metallurgy) (53%)

### A study of the T2 defect and the emission properties of the E3 deep level in annealed melt grown ZnO single crystals

• The authors report on the space charge spectroscopy studies performed on thermally treated melt-grown single crystal ZnO.
• The samples were annealed in different ambients at 700 C and also in oxygen ambient at different temperatures.
• For the annealed samples, E27 could not be detected and a new shallow donor with a thermal activation enthalpy of 35 meV was detected.
• It has also been demonstrated that at some particular temperatures, formation of these deep level defects is ambient related.
• The authors perform a further investigation on the introduction of T2/Ex in ZnO under various annealing conditions and the effects of high temperature oxygen annealing on it using the conventional DLTS measurement techniques.

### II. EXPERIMENT

• Melt grown single crystal ZnO samples obtained from Cermet Inc. with a batch number K3-1553-01 AV were used in this study.
• For ArþO2 annealing, a set of two samples was first annealed in Ar. First the two samples were annealed in O2, after which one of the samples was removed.
• All annealing was performed prior to Schottky and ohmic contact fabrication.
• Prior to contact fabrication, all samples were cleaned as outlined by Mtangi et al.13.

### III. RESULTS AND DISCUSSIONS

• From the IV characteristics of the Schottky contacts fabricated on the ZnO samples used in this study, ideality factors of 1.09–1.40 were calculated.
• This indicates that pure thermionic emission proved to be the dominant current transport mechanism at room temperature.
• Barrier heights of 0.82 eV were measured on the contacts fabricated on the oxygen annealed samples, while lower barrier heights of 0.66 eV were measured for the vacuum annealed samples.
• All the contacts fabricated were suitable for use in space charge spectroscopic techniques.

### A. Shallow donors

• The authors have investigated the effects of annealing on the shallow donors and the net doping concentration of the samples using capacitance temperature (C-T) scans and capacitance-voltage (C-V) measurements (van Opdorp’s method20), respectively.
• From the net doping profiles presented in Figure 1(a), the authors observed that the net doping concentration increases for all the annealed samples.
• This donor has previously been attributed to the Zni. 1,2.
• In the annealed samples, E27 could not be detected and a shallow donor with an activation enthalpy of 35 meV was observed instead.
• The low temperature capacitance values show a pronounced trend with increase in annealing temperature ).

### B. Deep level defects

• DLTS measurements performed on the un-annealed sample reveals the presence of five deep level defects (E1, E2, E3, E4, and E5) .
• Making a follow up of this observation, one might be tempted to assume that oxygen annealing followed by argon annealing might anneal out the T2 level.
• Since this defect (E2/T2) has been observed in material grown using different techniques; and proves to be ambient related (promoted mainly under vacuum in melt-grown [this work] and O2 ambient in hydrothermally grown4), there is a chance that this defect is intrinsic to the ZnO material.
• The authors have separated the E3 DLTS peak from the T2 peak by simulating the E3 defect and subtracting it from the peak that contains E3 and T2.

### D. Emission properties of E3

• The as-received ZnO samples contain the E3 deep level defect in very high concentrations.
• Reuse of AIP content is subject to the terms at: http://jap.aip.org/about/rights_and_permissions techniques.14–18,24–27.
• The microscopic origins of this defect are not clear as yet.
• This gives a hint that annealing of ZnO at high temperatures affects the emission properties of the E3 defect.
• Thus, for samples annealed at high temperatures, the activation enthalpy of E3 is reduced .

### IV. CONCLUSIONS

• As-received ZnO samples contain the E27 shallow donor.
• After annealing, the E27 shallow donor could not be detected.
• As-received ZnO samples contain five deep level defects as determined using DLTS techniques.
• High concentrations of T2 are obtained after annealing samples in ambients with low O2 partial pressures.
• E3 shows an enhanced thermal ionization rate with increase in annealing temperature where its activation enthalpy decreases with increase in annealing temperature above 800 C.

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A study of the T2 defect and the emission properties of the E3 deep level in
annealed melt grown ZnO single crystals
W. Mtangi, M. Schmidt, F. D. Auret, W. E. Meyer, P. J. Janse van Rensburg et al.
Citation: J. Appl. Phys. 113, 124502 (2013); doi: 10.1063/1.4796139
View online: http://dx.doi.org/10.1063/1.4796139
Additional information on J. Appl. Phys.
Journal Homepage: http://jap.aip.org/
Information for Authors: http://jap.aip.org/authors

A study of the T2 defect and the emission properties of the E3 deep level
in annealed melt grown ZnO single crystals
W. Mtangi,
1
M. Schmidt,
1
F. D. Auret,
1
W. E. Meyer,
1
P. J. Janse van Rensburg,
1
M. Diale,
1
J. M. Nel,
1
A. G. M. Das,
2
F. C. C. Ling,
3
and A. Chawanda
4
1
Department of Physics, University of Pretoria, Private Bag X20, Hatﬁeld 0028, South Africa
2
School of Information Technology, Monash South Africa, Roodepoort 1725, South Africa
3
Department of Physics, University of Hong Kong, Pokfulam Road, Hong Kong
4
Department of Physics, Midlands State University, P. Bag 9055, Senga Road, Gweru, Zimbabwe
(Received 2 November 2012; accepted 7 March 2013; published onl ine 22 March 2013)
We report on the space charge spectroscopy studies performed on thermally treated melt-grown
single crystal ZnO. The samples were annealed in different ambients at 700
C and also in oxygen
ambient at different temperatures. A shallow donor with a thermal activation enthalpy of 27 meV
was observed in the as-received samples by capacitance-temperature, CT scans. After annealing the
samples, an increase in the shallow donor concentrations was observed. For the annealed samples,
E27 could not be detected and a new shallow donor with a thermal activation enthalpy of 35 meV
was detected. For samples annealed above 650
C, an increase in acceptor concentration was
observed which affected the low temperature capacitance. Deep level transient spectroscopy
revealed the presence of ﬁve deep level defects, E1, E2, E3, E4, and E5 in the as-received samples.
Annealing of the samples at 650
C removes the E4 and E5 deep level defects, while E2 also
anneals-out at temperatures above 800
C. After annealing at 700
C, the T2 deep level defect was
observed in all other ambient conditions except in Ar. The emission properties of the E3 deep level
defect are observed to change with increase in annealing temperature beyond 800
C. For samples
annealed beyond 800
C, a decrease in activation enthalpy with increase in annealing temperature
has been observed which suggests an enhanced thermal ionization rate of E3 with annealing.
V
C
2013
American Institute of Physics.[http://dx.doi.org/10.1063/1.4796139]
I. INTRODUCTION
ZnO is a wide and direct bandgap semiconductor with a
high exciton binding energy, high saturation velocity, high
electron mobility, and excellent resistance to radiation dam-
age. The latter feature of the material qualiﬁes it for the fabri-
cation of devices that can operate in high radiant conditions,
e.g., in outer space applications and reactor laboratories.
Since in space applications, devices are usually subjected to
very harsh temperature conditions, it is a requirement for the
material to be resistant to high temperature annealing effects
for better operating efﬁciency and lifetime of devices. This is
because annealing tends to modify the operation of devices
by inducing defects, recovering/activating the neutral dop-
ants, increasing the concentration of shallow donors
1,2
result-
ing in surface conduction,
3
and at times annealing out
defects. For devices operating in the UV region, the problem
arises when defects induced in the material due to high tem-
perature exposure are optically active. Optical absorption by
these defects will inﬂuence efﬁcient operation of devices.
Considering the low oxygen and nitrogen partial pres-
sures as well as the high temperatures which a detector on a
space craft is exposed to, there is a need to have knowledge
of the defects that can be introduced at high temperatures
under different ambient conditions. Studies on the annealing
induced defects in ZnO have been performed using deep
level transient spectroscopy (DLTS) techniques in which
deep level defects have been observed. It has also been dem-
onstrated that at some particular temperatures, formation of
these deep level def ects is ambient related. Quemener et al.
4
have investigated the effects of annealing hydrothermally
grown ZnO samples at 1100
C in Ar, O
2
, and Zn. Their
results have revealed the introdu ction of E2 whose formation
strongly depends on the ambient used. Mtangi et al.
5
also
investigated the effects of annealing melt grown single crys-
tals at 300
C in Ar, O
2
, and H
2
and they have revealed the
introduction of E4 in Ar and H
2
ambient. Annealing ZnO at
1100
C in Zn vapour and Ti has been performed by Weber
and Lynn.
6
Selim et al.
7
have also investigated the effects of
annealing ZnO under Zn-rich conditions and reported a red
colouration of ZnO which has been attributed to O
v
, while
Ehret and Greenstone
8
have also reported the changes in the
colour of red ZnO upon heat treatment at different tempera-
tures, a hint which points out to the deep level defects that
are formed at those temperatures. Clearly, the effects of ther-
mal treatm ent have an effect on the optical and electronic
properties of ZnO.
Schmidt et al.
9
have demonstrated the photo-ionisation
of a defect level T2 observed in Pulsed Laser deposited
grown ZnO samples using optical deep level transient spec-
troscopy (ODLTS) while Ellguth et al.
10
showed the photo-
ionisation of the T2 and E4 defects in PLD ZnO thin ﬁlms
also using ODLTS. Such observation has not been reported
in bulk single crystal ZnO and neither has T2 been observed
in as-grown Cermet single cry stal ZnO. Current literature
indicates that the T2 has only been observed in polycrystal-
line ZnO, thin ﬁlms, and also in vapour phase grown material
used by Frank et al.
11
Ye et al.
12
have reported a defect with
0021-8979/2013/113(12)/124502/8/$30.00 V C 2013 American Institute of Physics113, 124502-1 JOURNAL OF APPLIED PHYSICS 113, 124502 (2013) Downloaded 06 May 2013 to 137.215.6.53. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jap.aip.org/about/rights_and_permissions the same activation enthalpy as T2 after O-implantation and subsequent annealing of melt grown ZnO samples in air, while Mtangi et al. 13 reported a defect they labelled Ex with a similar activation enthalpy to that of T2 after annealing melt grown single crystal ZnO samples at 700 CinArþ O 2 . It must be noted that the material used by Ye et al. 12 and Mtangi et al. 13 was obtained from the same supplier. Frank et al. 11 also demonstrates that the E4 is optically active and is a negative-U centre. Therefore, the existence of the T2/Ex and E4 defects in ZnO crystals will deﬁnitely affect device operation within the UV region. Also of interest in ZnO defect studies is a defect labelled E3. This defect has been observed to be present in all ZnO crystals in very high concentrations regardless of material growth technique. The study of this defect and its identity is an interesting topic as it is not clear where it originates from as yet. Research performed on ZnO, however, has the vast majority of reports assigning it to an oxygen vacancy related defect, 1416 while other reports suggest it to be a transition metal ion related defect. 17,18 Debate about the identity of E3 is still raging. With the difﬁculty in growing reproducible p-type ZnO, knowing the identity of E3 and its behaviour, i.e., in terms of its annealing behaviour can be essential as this might assist in controlling material doping. It has since been observed that the conditions under which T2 and E4 are introduced reduce the intensity of the E3 peak. 13 Using the capacitance based DLTS technique, under dark conditions, it has been observed from the DLTS spectra that E3 has a peak height which increases with increase in rate window frequency as has been reported by, 12,19 an indication that it has a temperature activated capture cross-section. However, its capture barrier energy has not been obtained yet as its capture process seems not to follow a simple exponen- tial process. It was also suggested that the electron capture rate for the E3 level is not constant during the ﬁlling pulse as it depends on the occupancy of the defect and the available carriers for electron capture. 19 In this paper, we perform a further investigation on the introduction of T2/Ex in ZnO under various annealing condi- tions and the effects of high temperature oxygen annealing on it using the conventional DLTS measurement techniques. We also report, for the ﬁrst time, on the observed change in emission properties and activation enthalpy of the E3 defect with changes in annealing temperature. II. EXPERIMENT Melt grown single crystal ZnO samples obtained from Cermet Inc. with a batch number K3-1553-01 AV were used in this study. Six sa mples were cut from the same 1 cm 2 wa- fer. The as-received sample was used as the reference sample for this experiment. The rest of the samples were then annealed at 700 C for 1 h in different ambient conditions. Before annealing, the samples were ultrasonically cleaned in methanol for 5 min and blow dried using nitrogen gas. For Ar þ O 2 annealing, a set of two samples was ﬁrst annealed in Ar. One of the samples was then removed from the furnace. The remaining sample was then annealed for another 1 h in O 2 ambient. For the O 2 þ Ar annealing, a set of two samples was also used. First the two samples were annealed in O 2 , af- ter which one of the samples was removed. The remaining sample was annealed in Ar ambient for another 1 h. Vacuum annealing was performed at a pressure of approximately 1 10 6 Torr. For annealing involving Ar and O 2 , a con- trolled ﬂow of gas of 3.0 l/min was used. For samples annealed in O 2 ambient at different temperatures, a 1 cm 2 wafer from the same batch of samples as in the latter case was used. All annealing was performed prior to Schottky and ohmic contact fabrication. Prior to contact fabrication, all samples were cleaned as outlined by Mtangi et al. 13 Pd Schottky contacts of diameter 0.5 mm and thickness 50 nm were fabricated on the Zn-polar face while ohmic contacts of Al/Au with thicknesses of 30/50 nm were fabricated on the O-polar face of the samples. Contact fabrication was done using the resistive evaporation system at a pressure of approximately 1 10 6 Torr. III. RESULTS AND DISCUSSIONS From the IV characteristics of the Schottky contacts fabricated on the ZnO samples used in this study, ideality factors of 1.09–1.40 were calculated. This indicates that pure thermionic emission proved to be the dominant current trans- port mechanism at room temperature. The as-received sam- ple showed a leakage current in the order of 10 9 Aata reverse bias of 2.0 V and a series resistance in the order of 600 X. For the annealed samples, the oxygen annealed sam- ples produced contacts with the least leakage current values in the order of 10 10 A at a reverse bias of 2.0 V and series resistance values in the order of 3 k X, while the vacuum annealed samples gave contacts with high leakage currents, in the order of 10 6 A at 2.0 V and series resistance values which are lower than those obtained in the as-received samples. Barrier heights of 0.82 eV were measured on the contacts fabricated on the oxygen annealed samples, while lower barrier heights of 0.66 eV were measured for the vac- uum annealed samples. All the contacts fabricated were suit- able for use in space charge spectroscopic techniques. A. Shallow donors We have investigated the effects of annealing on the shallow donors and the net doping concentration of the samples using capacitance temperature (C-T) scans and capacitance-voltage (C-V) measurements (van Opdorp’s method 20 ), respectively. In Figure 1(a), the net-doping con- centration of the samples annealed at 700 C in different ambients is presented. From the net doping proﬁles presented in Figure 1(a), we observed that the net doping concentration increases for all the annealed samples. In ambients with low oxygen partial pressures (Ar and vacuum), the net doping concentration is higher within a depth of 0.10 lm below the interface compared to that of the as-received sample. For the samples annealed in oxygen ambient at different temperatures (Figure 1(b)), the net doping concentration for all the annealed samples is observed to increase as compared to that of the as-received samples. This increase is observed to be highly pronounced towards the surface. At a depth of 0.10 lm below the interface, an increase in net doping density 124502-2 Mtangi et al. J. Appl. Phys. 113, 124502 (2013) Downloaded 06 May 2013 to 137.215.6.53. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jap.aip.org/about/rights_and_permissions with annealing is observed up to a temperature of 675 C, after annealing at 700 C and 800 C, there is a decrease in the net doping density. An increase in net doping density is again noticed after annealing between 825 C–875 C and a decrease is observed after annealing at 900 C. The C-T meas- urements in Figure 2(b) can be used to explain this trend, since the C-V measurements were performed at 300 K, where a ﬂuctuation in the capacitance values is also observed. This ﬂuctuation can be attributed to the partial contribution of the E3 level to the capacitance at this temperature which inﬂuen- ces the determination of the net doping concentration. For samples annealed above 650 C, this effect is crucial since the slope in the C-T characteristics at 300 K is very steep. For the C-T scans presented in Figure 2, only in the as-grown samples, a shallow donor previously labelled E27 (Ref. 1) with an activation enthalpy of approximately 27 meV was observed. This donor has previously been attrib- uted to the Zn i . 1,2 In the annealed samples, E27 could not be detected and a shallow donor with an activation enthalpy of 35 meV was observed instead. There are two possibilities explaining the absence of the E27 in the annealed samples: (i) Either it was annealed-out as was also suggested by Mtangi et al., 2 or (ii) There is an increase in the acceptor concentration with annealing, which in turn affects the position of the Fermi level. In the latter case, the lowering of the Fermi level would call for an increase in the degree of acceptor compensation within the annealed material. E27 would then be ionized at all temperatures and, therefore, it will not be observed by space charge spectroscopic techni- ques. With the lowering of the Fermi level, its electrons in the conduction band will easily be taken up by the acceptor states. The failure to observe the E27 in the annealed sam- ples is also in agreement with what was theoretically sug- gested by Janotti and Van de Walle 21 and experimentally by Neuvonen et al. 22 that the Zn i is highly mobile at tempera- tures around 600 C and is not likely to be a stable donor. The concentration of E35 is increased for the Ar and vacuum annealed samples (Figure 2(a)). This increase in the E35 concentration can be related to low oxygen partial pres- sure. For the oxygen annealed samples, E35 has the highest concentration in the sample annealed at 650 C. Annealing at temperatures higher than 650 C resu lts in a decrease in the low temperature capacitance (Figure 2(b)). This decrease in capacitance witnessed for high temperature annealed FIG. 1. Net doping density proﬁles of ZnO samples annealed in different ambient conditions at 700 C. These proﬁles were recorded at room tempera- ture and at a frequency of 50 kHz. Figure 1(b) Net doping density proﬁles of ZnO samples annealed in oxygen ambient at different temperatures. These proﬁles were recorded at room temperature and at a frequency of 50 kHz. FIG. 2. Capacitance temperature scans for ZnO samples annealed in differ- ent ambient conditions at a temperature of 700 C. These were recorded at a reverse bias of 2.0 V scanning up in temperature. Figure 2(b) Capacitance temperature scans for ZnO samples annealed in oxygen ambient at different temperatures. These scans were recorded at a reverse bias of 2.0 V scanning up in temperature. The inset shows the variation of capacitance with anneal- ing temperature at 75 K. 124502-3 Mtangi et al. J. Appl. Phys. 113, 124502 (2013) Downloaded 06 May 2013 to 137.215.6.53. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jap.aip.org/about/rights_and_permissions samples could be due to the increase in acceptor concentra- tion with annealing temperature. The low temperature capac- itance values show a pronounced trend wit h increase in annealing temperature (inset of Figure 2(b)). The inset shows the variation of capacitance with temperature at 75 K. The capacitance increases with increase in annealing temperature and reaches a maximum at an annealing temperature of 650 C, after which it decreases with increase in annealing temperature. B. Deep level defects DLTS measurements performed on the un-annealed sam- ple reveals the presence of ﬁve deep level defects (E1, E2, E3, E4, and E5) (Figure 3). Arrhenius plots of these deep level defects are presented in Figure 4. The activation enthal- pies and apparent capture cross-sections of these defects are presented in Tables I and II. The E4 and E5 deep levels are being observed for the ﬁrst time in the as-received samples from Cermet. Since we have not observed the E4 and E5 in as-received samples before, 13,18,19,23 we attribute these defects to sample growth conditions. A defect with an activa- tion enthalpy similar to the one we have measured has been observed by Frank et al. 11 in vapour phase grown ZnO which they attributed to an oxygen vacancy. Since our E4 defect compares very well to the E4 by Frank et al. 11 in both activa- tion enthalpy and capture cross-section, we can assign our E4 defect to the O-vacancy. Assignment of E4 to the oxygen vacancy in this case implies that there is a high possibility this particular batch of samples was grown under non- equilibrium conditions, i.e., low oxygen partial pressures. The activation enthalpy and apparent capture cross-section of E5 have been obtained as 1.05 eV and 5 10 12 cm 2 , respectively. Interesting enough, annealing samples in different ambi- ent conditions at 700 C anneal out the E4 and E5 deep level defects. For samples annealed in oxygen ambient at different temperatures (Figure 3(b)), below an annealin g temperature of 675 C, E5 is annealed out, but E4 is still present. After annealing at 675 C, both the E4 and E5 defects anneal-out. Above the 800 C annealing temperature, the E2 defect FIG. 3. Normalized DLTS spectra obtained from Pd/ZnO Schottky contacts for ZnO samples annealed at 700 C in different ambient conditions. The spectra were recorded at a rate window frequency of 100 Hz, reverse bias voltage of 2.0 V, ﬁlling pulse of 0.3 V into forward bias and pulse width of 2.0 ms. Figure 3(b) Normalized DLTS spectra obtained from Pd/ZnO Schottky contacts for ZnO samples annealed in oxygen ambient at different temperatures. The spectra were recorded at a rate window frequency of 500 Hz, reverse bias voltage of 2.0 V, ﬁlling pulse of 0.4 V into forward bias and pulse width of 2.0 ms. The inset shows the spectra obtained from the 900 C annealed samples at a rate window frequency of 5 Hz. FIG. 4. Arrhenius plots obtained from the ZnO samples annealed in different ambient conditions at 700 C to calculate the activation enthalpy and appa- rent capture cross-section of the observed defects. Figure 4(b) Arrhenius plots obtained from the ZnO samples annealed at different temperatures in oxygen ambient to calculate the activation enthalpy and apparent capture cross-section of the observed defects. 124502-4 Mtangi et al. J. Appl. Phys. 113, 124502 (2013) Downloaded 06 May 2013 to 137.215.6.53. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jap.aip.org/about/rights_and_permissions ##### Citations More filters Journal ArticleDOI Abstract: The source of n -type conductivity in undoped transparent conducting oxides has been a topic of debate for several decades. The point defect of most interest in this respect is the oxygen vacancy, but there are many conflicting reports on the shallow versus deep nature of its related electronic states. Here, using a hybrid quantum mechanical/molecular mechanical embedded cluster approach, we have computed formation and ionization energies of oxygen vacancies in three representative transparent conducting oxides: In 2 O 3 , SnO 2 , and ZnO. We find that, in all three systems, oxygen vacancies form well-localized, compact donors. We demonstrate, however, that such compactness does not preclude the possibility of these states being shallow in nature, by considering the energetic balance between the vacancy binding electrons that are in localized orbitals or in effective-mass-like diffuse orbitals. Our results show that, thermodynamically, oxygen vacancies in bulk In 2 O 3 introduce states above the conduction band minimum that contribute significantly to the observed conductivity properties of undoped samples. For ZnO and SnO 2 , the states are deep, and our calculated ionization energies agree well with thermochemical and optical experiments. Our computed equilibrium defect and carrier concentrations, however, demonstrate that these deep states may nevertheless lead to significant intrinsic n -type conductivity under reducing conditions at elevated temperatures. Our study indicates the importance of oxygen vacancies in relation to intrinsic carrier concentrations not only in In 2 O 3 , but also in SnO 2 and ZnO. 58 citations Journal ArticleDOI Abstract: Proton implantation is shown to increase the concentration of the so called and commonly observed E3 defect level in zinc oxide (ZnO). Box and single profiles of protons with doses ranging from 6×1010 cm−2 to 4.3×1012 cm−2 were implanted into hydrothermally grown ZnO samples with original concentrations of E3 below 5×1014 cm−3. Capacitance-Voltage profiling and junction spectroscopy measurements showed that the charge carrier concentration and absolute concentration of E3 centers increase by more than one order of magnitude compared to the as-grown samples as well as control samples implanted with He ions. The results provide strong evidence for the involvement of H in the formation of the E3 center, and a complex involving interstitial H and an oxygen sub-lattice primary defect are discussed. 22 citations Journal ArticleDOI G. Shanmuganathan Abstract: Fe and K simultaneously doped ZnO thin films Zn0.99 K0.01 (Fe)x O (, 2, 3, and 4%) were synthesized by chemical bath deposition method. The XRD investigation reveals that all the doped ZnO thin films are in hexagonal wurtzite crystal structure without impurity phases. With increase in Fe concentration, the growth of thin films along c axis is evident from the XRD which indicates the increase in intensity along (002) direction. The same is visible from the surface morphology which shows the formation of hexagonal structure for higher Fe concentration. The topography shows gradual variation with Fe incorporation. The optical energy band gap obtained from the transmittance spectrum decreases from 3.42 to 3.06 eV with increase in Fe concentration indicating the red shift and this trend is consistent with the earlier experimental results. The UV emission is centered around 3.59 eV. The optical constants such as refractive index, extinction coefficient, and absorption coefficient which are essential for the optoelectronic applications were also determined. 15 citations Journal ArticleDOI , H-S Kim2 Abstract: Electrical properties of a ZnO microwire grown by carbo-thermal evaporation, a ZnO thin film grown by pulsed-laser deposition and a hydrothermally grown ZnO bulk crystal are compared. Deep defects were investigated by means of deep-level transient spectroscopy. The defect level E3 was observed in all samples investigated. Additionally, a defect labelled T2 that preferentially forms under Zn-rich condition was detected in the microwire, the thin film and the bulk sample. Our results indicate that V Zn is likely involved in this defect. 14 citations Journal ArticleDOI Thomas Lenz Abstract: In this work, we report on the electrical characterization of nanoparticular thin films of zinc oxide (ZnO) and aluminum-doped ZnO (AZO). Temperature-dependent current–voltage measurements revealed that charge transport for both, ZnO and AZO, is well described by the Poole–Frenkel model and excellent agreement between the experimental data and the theoretical predictions is demonstrated. For the first time it is shown that the nature of the charge-transport is not affected by the doping of the nanoparticles and it is proposed that the Poole–Frenkel effect is an intrinsic and universally limiting mechanism for the charge transport in nanoparticular thin films with defect states within the bandgap. 8 citations ##### References More filters Journal ArticleDOI Abstract: We have performed a comprehensive first-principles investigation of native point defects in ZnO based on density functional theory within the local density approximation (LDA) as well as the$\mathrm{LDA}+U$approach for overcoming the band-gap problem. Oxygen deficiency, manifested in the form of oxygen vacancies and zinc interstitials, has long been invoked as the source of the commonly observed unintentional$n$-type conductivity in ZnO. However, contrary to the conventional wisdom, we find that native point defects are very unlikely to be the cause of unintentional$n$-type conductivity. Oxygen vacancies, which have most often been cited as the cause of unintentional doping, are deep rather than shallow donors and have high formation energies in$n$-type ZnO (and are therefore unlikely to form). Zinc interstitials are shallow donors, but they also have high formation energies in$n$-type ZnO and are fast diffusers with migration barriers as low as$0.57\phantom{\rule{0.3em}{0ex}}\mathrm{eV}$; they are therefore unlikely to be stable. Zinc antisites are also shallow donors but their high formation energies (even in Zn-rich conditions) render them unlikely to be stable under equilibrium conditions. We have, however, identified a different low-energy atomic configuration for zinc antisites that may play a role under nonequilibrium conditions such as irradiation. Zinc vacancies are deep acceptors and probably related to the frequently observed green luminescence; they act as compensating centers in$n$-type ZnO. Oxygen interstitials have high formation energies; they can occur as electrically neutral split interstitials in semi-insulating and$p$-type materials or as deep acceptors at octahedral interstitial sites in$n$-type ZnO. Oxygen antisites have very high formation energies and are unlikely to exist in measurable concentrations under equilibrium conditions. Based on our results for migration energy barriers, we calculate activation energies for self-diffusion and estimate defect-annealing temperatures. Our results provide a guide to more refined experimental studies of point defects in ZnO and their influence on the control of$p\$-type doping.

2,661 citations

Journal ArticleDOI
TL;DR: This study revealed the nature of native defects and their roles in ZnO through positron annihilation and optical transmission measurements and revealed oxygen vacancies are the origin for the shift in the optical absorption band that causes the red or orange coloration.
Abstract: This study revealed the nature of native defects and their roles in ZnO through positron annihilation and optical transmission measurements. It showed oxygen vacancies are the origin for the shift in the optical absorption band that causes the red or orange coloration. It also revealed experimental evidence that the donor nature of oxygen vacancy is approximately 0.7 eV. In addition, this work showed the Zn interstitial was not the donor in the as-grown ZnO and supported recent calculations that predicted hydrogen in an oxygen vacancy forms multicenter bonds and acts as a shallow donor.

296 citations

Journal ArticleDOI
F.D. Auret
Abstract: We report on the electrical characterization of single-crystal ZnO and Au Schottky contacts formed thereon before and after bombarding them with 1.8 MeV protons. From capacitance–voltage measurements, we found that ZnO is remarkably resistant to high-energy proton bombardment and that each incident proton removes about two orders of magnitude less carriers than in GaN. Deep level transient spectroscopy indicates a similar effect: the two electron traps detected are introduced in extremely low rates. One possible interpretation of these results is that the primary radiation-induced defects in ZnO may be unstable at room temperature and anneal out without leaving harmful defects that are responsible for carrier compensation.

292 citations

Journal ArticleDOI
Abstract: An electron trap of 0.3 eV depth was characterized in hydrothermally grown, single‐crystal zinc oxide using deep‐level transient spectroscopy. Specimens were fabricated with Ag Schottky contacts on (0001) surfaces. The capture cross section was determined to be 2.6×10−14 cm2. The defect is a native donor and is attributed to a singly ionized oxygen vacancy V•O.

159 citations

Journal ArticleDOI

Abstract: Temperature dependent current–voltage ( I – V ) and Hall measurements were performed on Pd/ZnO Schottky barrier diodes in the range 20–300 K The apparent Richardson constant was found to be 860 × 10 - 9 A K - 2 cm - 2 in the 60–160 K temperature range, and mean barrier height of 050 eV in the 180–300 K temperature range After barrier height inhomogeneities correction, the Richardson constant and the mean barrier height were obtained as 167 A K - 2 cm - 2 and 061 eV in the temperature range 80–180 K, respectively A defect level with energy at 012 eV below the conduction band was observed using the saturation current plot and ( 011 ± 001 ) eV using deep level transient spectroscopy measurements

76 citations