Lithium Acceptors and Hydrogen in ZnO

Caleb Corolewski

Rough Draft
1 Introduction

Semiconductor devices have had tremendous impact on our society. They offer
smaller, more efficient replacements to older technologies. The most commonly known
example of this is how silicon transistors replaced vacuum tubes. Computers that once
consumed 175 kW and occupied hundreds of cubic feet now consume a mere 0.4325
W and occupy a pants pocket[20][1].

Another field poised to be changed as dramatically as that of computing is the field of

optoelectronics. Optoelectronics are devices that convert between light and electricity.
A well known accomplishment in this field has been the light emitting diode (LED),
which is poised to replace light bulbs similar to how the transistor replaced the vacuum
tube. Another attractive application uses semiconducting devices to convert light into
electricity; these are photo-voltaic solar cells. As it stand today, photo-voltaic solar
cells suffer from a dearth of maladies: low efficients, short lifetime, poor reliability,
large performance effects due to local environments. Needless to say, progress must
be made before many optoelectronic devices can be placed into the consumer’s hands.
Zinc Oxide (ZnO) is a material with the potential to solve a great many of the problems
plaguing optoelectronic devices.

The wurtzite Zinc Oxide materials system generates significant interest for applica-
tions in optoelectronics because of its possibility of fulfilling many device requirements.
ZnO has a room temperature bandgap of 3.37 eV [3]; making it transparent over the
entire visible spectrum. It has efficient light emission and recombination due to a 60
meV exciton binding energy [9]. Unlike many other wide bandgap compound semicon-
ductors, large diameter single crystalline wafers can be grown [15][18][21]. In many
aspects, the material is environmentally friendly; it can be processed with relatively

1
harmless chemicals such as hydrogen peroxide, the compound and its constituents
are abundant in the earth’s crust, and the material itself is relatively inert.

The physical structure of ZnO is the hexagonal wurtzite crystal structure. This is the
stablest and naturally occurring allotrope of ZnO. Wurtzite ZnO is a hexagonal lattice
with a=3.8227 Å, c=5.2071 Å, and a unit cell volume of 47.63 Å3 [7]. ZnO differs 1.8%
p
from an ideal wurtzite lattice, with c/a =1.6021 as opposed to 8/3 .The crystal structure
has 6mm point group symmetry and belongs to the P63 mc space group[7].

With its melange of properties, ZnO sees widespread use in many applications. Its
crystal structure, high thermal conductivity, and large diameter growth allows it to be
used as a substrate for growing many compound semiconductors. ZnO is often used
as rubber additive in tires to reduce thermal and static buildup. High radiation hard-
ness and the ability to block UV radiation has led to its inclusion in beauty products,
sunscreens, and paints. ZnO is often found in varistors due to its strong nonlinear
resistance, transducers due to its piezeoelectricity, phosphors for its strong lumines-
cence, and catalysts because of a high surface sensitivity.

As grown ZnO in almost any form, film bulk, or nano, is n-type. The charge neutrality
level in ZnO lies very close to, if not in the conduction band. As a semiconducting oxide,
ZnO is classified as either: oxygen deficient having V+2 +2
O or a zinc excess having Zni

depending on the growth conditions. While both classifications contain intrinsic donor
defects, recent studies have shown that these are not the source of n-type conductivity.
Extrinsic defects, such as aluminum or gallium, incorporated during growth, have been
shown to be responsible for the high n-type conductivity[11].

ZnO has yet to see widespread use in optoelectronics because they require, at the
most basic level, a p-n junction; holding ZnO back from such devices is a lack of p-
type conductivity. Reasons for the lack of p-type material are many: low solubility
of acceptor defects, high formation energies, self and hydrogen compensation, and

2
lowhole mobilities. Furthermore, the shallowest theoretically predicted acceptors is
90 meV whereas the experimentally determined level is 800meV. With ZnO being an
”old” material, there exists studies on nearly every acceptor species in ZnO.

Starting with J. J. Lander in 1960, many have investigated lithium due to its having
a similar oxygen bond length, high diffusivity, and high solubility[8]. It is believed that
these properties would allow high doping concentrations and thus overcome the native
donors and the passivation and compensation mechanisms. This study provides new
evidence for a deep, 800 meV, lithium acceptor through a combination of spectroscopy
and electrical measurements.

2 Experimental Methodology

2.1 Material Processing - Doping

Single Crystal ZnO wafers from Cermet Inc (bridgeman melt grown - MG) and MTI
(Hydrothermally grown - HT) were used in this study. These crystals were doped
through three thermal and environmental treatments. Based on Li diffusion kinetics
measured by J.J. Lander, the doping process is as follows[8].

2.1.1 Lithium Doping

Single crystals of 10 mm x 10 mm x 0.5 mm were buried in a 15:1 ZnO:Li2 O powder

◦
mixture in a quartz ampoule, and annealed at 700 in air for 24 hours. 4.5 g of ZnO
and 0.3 g of Li2 O were used per crystal. Together these powders occupy a volume of
Li
less than 5 cc. This gives an order magnitude approximation of 1021 , and with
cm3
1021 Li atoms outside the crystal, and can be considered to be an infinite source of Li
for diffusion models.

3
 Li2 O was mixed with ZnO to lower the activity of the the Li source, thereby prevent-
ing dissolution of the ZnO crystal. Small surface pitting and damage still occurred.
Screening experiments ere used to determine the lowest usable ratio.

At 700◦ the diffusivity of Li is roughly equivalent to that of Zn (DLi u DZn ); but

the solubility of Li is about 100 times that of Zn (SLi u 100SZn )[8].In this way, the
concentration of Li within the ZnO crystal was maximized. Additionally the effects of Zn
migration are trivialized in this regime. The furnace was open to the ambient air to limit
the problems (exploding ampules) due to out gassing of the powders. After 24 hours,
the samples were cooled slowly, on the order of 10 minutes, to room temperature. Slow
cooling has been shown to increase the concentration of substitutional Li as opposed
to quenching [22]. Once cool, the samples were polished on both sides to remove
surface damage (pitting). Final polishing was done with 0.3 micron diamond lapping
films.

2.1.2 Post Processing: Vacuum Annealing

Polished crystals were sealed under vacuum (≈ 1 Torr) in a quartz ampoule and
annealed at 500◦ for 30 min. As before, the samples were slow cooled. At 500◦ C
DLi is roughly 3 orders of magnitude less then DZn [8]. During Li diffusion a space
charge region is created within the crystal which forms an interface inhibiting furtherer
Li diffusion. The depth of this interface within the crystal is inversely proportion al
to the partial pressure of oxygen, PO2 [8]. Additionally, the solubility of interstitial Li is
also inversely proportion al to PO2 [8]. and means that vacuum annealing increases the
spatial homogeneity of interstitial Li throughout the crystal.

2.1.3 Post Processing: Oxygen Annealing

The final step’s purpose is two fold, to promote interstitial Li to substitutional sites
and to reduce the concentration of interstitial Li and Zn. In this step, the sample was
sealed in a quartz ampoule under a pressure of O2 such that at the annealing tem-

4
perature of 500 ◦ C is PO2 u 1 atm. The sample was annealed for 15 min and cooled
slowly.

2.2 Characterization Methods

After each of the above steps, the samples were characterized to map the evolu-
tion of their properties with processing. Spectroscopic and electrical characterizations
were performed.

2.2.1 Spectroscopy

Low temperature (8K) Fourier transform infrared spectroscopy (FTIR) was performed
with a Bomem DA8 vacuum FTIR spectrometer with a KBr beamsplitter and an InSb
detector. Low temperature measurements were done in a cryostat with wedged ZnSe
windows. Spectra were measured with a 1 cm-1 resolution over a 1800-4000 cm−1
spectral range. Particular attention was given to the evolution of the free carrier ab-
sorption (FCA) and hydrogen local vibrational modes (LVMs). Spectra were collected
both normal to and 45◦ to the c-axis.

Photoluminescence emission (PL) and excitation (PLE) measurements were per-

formed at 8K with a JY-Horiba Flourolog-3 spectrometer. PL and PLE probe radiative
transitions due to in gap energy levels. Figure 1 helps to illustrate the difference in
collection modes. In emission, PL, measurements, the sample is excited with a fixed
energy of light and the emission is collected over a set range. In excitation, PLE, mea-
surements, a specific emission is collected - normally chosen from a defect band - and
the excitation is varied. Emission, PL, measurements can give information about a
number of energetic transitions, whereas excitation, PLE, studies only one. A 450 W
Xe lamp and monochromator was used in conjunction with a cryostat allowing mea-
surements to be made at 8K.

5
Figure 1: A schematic illustrating two modes photoluminescence specroscopy: emis-
sion and excitation. The gray arrows on the left correspond to possible energetic ex-
citations an electron in the sample could undergo. The colored arrows on the right
correspond to luminescent transitions possible after excitation.

2.2.2 Electrical Measurements

Van der Pauw geometry DC Hall effect measurements were attempted, but the sam-
ples were too resistive, the mobilities too low, and the Hall voltages below the threshold
for DC measurements. The equations below illustrate the Hall voltage issue. Numbers
used in the calculation are representative of samples from this study in terms of sample
(ex. resistance) experimental (ex. magnetic field) parameters.

IB
VH =
ned
Vsupply
I=
R
Vsupply =2.4V

R =1GΩ
2.4V · 1.3T
VH =
109 Ω · 1020 m−3 · 1.6 · 10−19 C · 0.5 · 10−3 m
=3.9nV

In these equations, VH is the Hall voltage, I is the current applied to the sample, B is
the magnetic field, n is the carrier density, e is the fundamental charge, d is the sample
thickness, Vsupply is the maximum output voltage of the system, and R is the two-point
resistance of the sample.

6
 With DC Hall effect measurements fundamentally impossible, variable temperature
- van der Pauw geometry - resistivity measurements were performed instead. Resis-
tivity was measured on a MMR Technologies Inc. Hall effect system with a variable
temperature vacuum sealed sample compartment.

Electrical contacts were made to samples with nano particle molybdenum dioxide
(MoO2 ) through electrospray deposition (ELD). MoO2 is a semi-metal that behaves as
a metal or degenerate semiconductor with a work function of 6.5 eV. MoO2 is used as
a contacted due to having a work function higher then any elemental metal; platinum
is the metal with the highest work function, 5.5 eV. Figure 2 Shows the band offsets
and Fermi levels for ZnO with a 800meV acceptor level with respect to Pt and MoO2 .
MoO2 allows the build in potential to be decreased by 1eV, down to around 700meV.

Figure 2: A drawing illustrating the failure of metals to work as a contact to hypothetical

p-type ZnO. The left half corresponds to ZnO with a 800 meV Li acceptor level, and
the right to the metal platinum and the metastable MoO2

7
3 Results and Discussion

3.1 Photoluminescence

The photoluminescence of lithium doped ZnO was originally studied by Schirmer

and Zwingel in the early 70s [17]. By tracing the broad yellow band, they used their
trace to estimate the zero phonon line of the band to be 0.8eV above the valence
band[17]. More recent work by Meyers suggests that the Li and Na levels are shallow,
approximately 400 meV [13]. However, Meyers suggests that both have the nearly
identical peak positions and shapes, which points to a more likely possibility of defect
native to ZnO, such as the vacancy[13].

Figure 3 shows the PL and PLE spectra for before and after Li doping. PLE is only
shown for after doping. Before doping, many near band edge features are present, the
first and second donor bound excitons, and the 3.2eV donor acceptor pair transition[12].
After Li doping, none of these features are discernible, and the band edge lumines-
cence is noticeably smeared out. This change is consistent with photoluminescence
from highly strained crystals, in this case a crystal containing a high concentration of
lithium. Prior to doping, the PL spectrum shows a broad, 580 nm feature, after Li
doping, this feature is no longer present, instead a 565 band is found.

It has been stated that the broad yellow, 2.2 eV, band originates from 800 meV
lithium acceptor level, Figure 4 illustrates how this occurs. Figure 4 is a coordinate con-
figuration diagram for the photolumenscent excitation and emission of the Li acceptor.
From the PLE data in Figure 3, it was found that the onset of photoluminescence for
LiZn is 3.1 eV, as shown by the blue upward pointing arrow. Illumination with 3.1 eV
will excite an electron from the Li− , creating a neutral lithium and an electron in the
conduction band. This electron will then relax to a minimum energy in the conduction
band (0.5 ev), and finally fall across the band gap and return to this neutral lithium,
creating Li− , and releasing a yellow photon. The verticle arrows represent instanta-

8
Figure 3: PL spectra for ZnO:Li. PLE was collected for the broad 565nm band at-
tributed to LiZn .

neous, hence optical, transitions. Any transition involving horizontal movement on this
diagram requires some form of structural relaxation. Structural relaxation is specifi-
cally slower then optical processes. After the electron returns to the Li− , it will relax
to its minimum, shown by the 0.35 eV energy along the bottom curve. The relaxation
energies shown in Figure 4 were not measured in this study, but instead represent
realistic values seen in other materials, and were chosen to show the agreement with
Schirmer’s work.

Figure 4: Configuration coordinate diagram for ZnO:Li photoluminescence processes.

9
3.2 Variable Temperature Resistivity

As received ZnO crystals from MTI, are weakly n-type. After doping with lithium,
the samples undergo dramatic changes. As mentioned previously, the lithium doped
samples were not measurable with conventional metal contacts (In,Au, and Ti were
tested), it wasn’t until MoO2 was stumbled upon that electrical measurements could
be made. See Figure 2 for an explanation of the contacts.

Figure 5 shows the variable temperature resistivity measurements for an undoped

and lithium doped sample. Before doping, the room temperature resistivity was on
the order of 103 Ω cm. Data for the before doping was collected from 100-500K, for
comparison purposes, the low temperature data are not shown. A fit to the resistivity
data found a 0.33eV activation energy when fit with a surface conduction term. The
inclusion of the surface conduction term has been shown to be necessary by Allen
et. al. [2]. This activation energy is in good agreement with Deep Level Transient
Spectroscopy (DLTS) work done by Simpson et. al. who found and assigned a level
300 meV to singly ionized oxygen vacancies [19].

Figure 5: Resistivity versus temperature data and fits comparing before and after Li
doping in ZnO. Data were fit to include a surface conduction term.

After lithium doping the room temperature resistivity increases to 109 Ω cm, 6 or-
ders of magnitude. Measurements below room temperature were not possible; room

10
temperature measurements were barely possible, 109 Ω cm material require special
testing apparati for insulators or power electronics. As the temperature was increased,
the resistivity dropped to more manageable levels. At the highest temperature studied,
600K, the resistivity was 105 Ω cm, and improvement of 4 orders of magnitude. Fitting
the data for the lithium doped sample, again with a surface conduction term, found an
activation of 0.88 eV.

Typically activation energies from electrical measurements are taken from ”Freeze-
Out” curves, fitting carrier density versus temperature. As mentioned previously, this
was not possible for the lithium doped ZnO. However, if the mobility of the material is
relatively unchanging with temperature and conduction mechanisms such as hopping
or tunneling are not present, the resistivity and carrier density curves should be closely
related. ρ(T ) = (e · n(T ) · µ(T ))−1 . The validity of this statement can be seen in the
back of the envelop type calculations shown below. In these calculations, the carrier
densities as calculated from energy band statistics (theoretical) are compared with
those calculated from the resistivity (experimental). The mobility value is justified since
the valence band of ZnO shows very little dispersion.

Experimentally: p u(ρeµ)−1
cm2 −1
p400K u(109 cm · 10−19 · 1 )
V ·s
u1010 cm−3
cm2 −1
p600K u(105 cm · 10−19 · 1 )
V ·s
u1014 cm−3
EA
Theoretically: p uNV · e− kT
0.8eV
p400K u1019 cm−3 · e− k·400K

u109 cm−3
0.8eV
p600K u1019 cm−3 · e− k·600K

u1013 cm−3

11
 While there is an order of magnitude difference between the numbers, the agree-
ment is acceptable. Many computational studies in the literature have shown less
agreement. Furthermore at both temperatures, the resistivity of the sample is more
akin to that of a semi-insulator than a semiconductor, and is consistent with conduc-
tion from thermally activated deep levels. A 800 meV level should remain inactive until
relatively high temperatures; the convention in semiconductors is that a shallow dopant
is ionizable with room temperature thermal energy.

12
3.3 FTIR

Fourier transform infrared spectroscopy is unique in its ability to study low energy
electronic transitions and LVMs of defects. Of particular interest are hydrogen LVMs.
Hydrogen is an omnipresent impurity in materials. In semiconducting oxides, hydrogen
is always positively charged. Within the crystal, hydrogen is either a donor (often
shallow) and forms complexes with acceptors, passivating them. Hydrogen will also
bond with any dangling bonds at the crystal’s surface.

3.3.1 LiZn -OH Local Vibrational Modes

In lithium doped ZnO, hydrogen will complex with the lithium acceptor and the axial
oxygen atom, forming a Li-OH complex [4]. The reason for this specific orientation is
that the hole from a lithium acceptor is on the axial oxygen, this orientation is 15 meV
less than that of the non-axial configuration [16]. loc Halliburton and company found
this complex to have a vibrational energy of 3577 cm−1 wavenumbers [4]. Because
this complex lies along the c-axis, it is normally not IR active; by tilting the sample
45◦ with respect to the incident IR beam, this LVM can be detected. All lithium doped
samples in this study contain this complex as can be seen below in Figure 6. The
presence of 3577 cm−1 correlates to the presence of Li acceptors in ZnO; statistically,
every acceptor cannot be passivated.

Figure 6: FTIR spectrum snapshot illustrating shape and location of the Li-OH LVM in
ZnO.

13
3.3.2 Hydrogen Local Vibrational Modes

After doping, numerous LVMs appear, as shown in Figure –XX–. The majority of
these have not been reported in literature, and their origins are unknown. The dom-
inant feature in the spectrum is a 3677 cm−1 peak, which has been attributed to a
monolayer of OH groups on the oxygen terminated surface of ZnO. [14]. Outside of
the previously mentioned 3577cm−1 Li-OH feature, the only other previously identified
peak is 3326 cm−1 . While the existence of a 3326 cm−1 peak is known, the source is
still debated; it has been attributed to hydrogen donors [6] and proposed to arrise from
either Ca-H or a zinc vacancy hydrogen mode [11]. All other features in the spectra
shown in Figure 7 have yet to be identified.

Figure 7: FTIR spectrum containing numerous, as of yet, unidentified LVMs in ZnO.

The boxed area corresponds to a x20 magnification of the absorbance.

Annealing a sample in deuterium, an isotope of hydrogen with an extra neutron, will

replace the hydrogen in hydrogen LVMs with deuterium. This process will cause any
LVMs containing hydrogen to shift to lower wavenumbers, and is frequently used in
spectroscopy to identify LVMs originating from hydrogen complexes. In ZnO, it has
been shown that deuterating a sample shifts hydrogen LVMS by a factor of 1.34 [10].

14
Figure 8 shows the spectra of a lithium doped ZnO sample after both hyrdogenation
and deueration. Peaks in the deuterated, blue, spectrum correspond to peaks in the
hydrogenated spectra by the factor of 1.34 found by McCluskey et. al.[10].

Figure 8: Comparison of hydrogen and deuterium LVMs in ZnO:Li.

3.3.3 Hydrogen Local Vibrational Modes and the Fermi Level

Two points were mentioned previously; the charge neutrality level in ZnO is near the
conduction band and hydrogen in ZnO passivates acceptors. Thermodynamically, the
Fermi level of a material wants to be at the charge neutrality level. As lithium acceptors
are doped into the crystal, the Fermi level is lowered. To combat this, hydrogen will
form complexes with acceptors in the crystal in attempt to bring the Fermi level back
near the charge neutrality level. It is believed that this hydrogen comes from the bulk
of the ZnO crystal. Hydrogen concentrations of 1017 cm−1 have been typically seen in
single crystalline ZnO [5]. The hydrogen and deuterium LVMs of Figure –XX– indicate
a large number of acceptor hydrogen complexes; their number is too large to be due
to the hydrogen donor. The large number of acceptor hydrogen complexes that form
after lithium doping is evidence that post lithium doping, the Fermi level is below mid
gap; the evolution of the acceptor hydrogen complexes is much less likely for above
mid gap states.

15
4 Future Work

This work presented here focused solely on lithium related results. In the FTIR
results section, the presence of other acceptor LVMs was mentioned. The proposed
future work on ZnO is to conclude the results of lithium doping in a definitive matter, the
literature is rife with debate on many aspects. As this paper was being written, work
has already began on sodium doping of ZnO, with the eventual plan to co-dope single
crystal ZnO wafers. The reason for co-doping is that sodium is believed to be more
shallow than lithium, but is known to be much less soluble, by created a background
of insulating lithium doped material, the hope is to create a thin, near surface layer of
highly Na doped material. From there it would be a natural progression to expand the
study to encompass the entirety of the Group I metals as well as to look for the illusive
zinc vacancy signals (no concrete evidence exists on anything electronic or hydrogen
related).

5 Conclusion

Lithium doped zinc oxide has been studied from the impurity perspective. Photolu-
minescence emission and excitation measurements found a dramatic increase in they
yellow band with Li doping and suggest a deep 800 meV level. Electrical resistivity
measurements find Li doping creates semi-insulating ZnO with an activation energy
of 880 meV as found through conductivity mechanisms. The two strongly suggest a
p-type semi-insulating state has been created in ZnO through Li doping. Further, albeit
indirect, proof for the p-type ZnO:Li is the presence of numerous hydrogen LVMs after
Li doping which arise in attempt to raise the Fermi level nearer the charge neutrality
level.

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