1. Introduction
Zinc Oxide (ZnO) stands out among the myriad semiconductor materials because of its
rich set of optical, electrical, and piezoelectric properties [1-5]. Its wide bandgap of approximately 3.37 eV at room temperature and its large exciton
binding energy make it an attractive choice for optoelectronic devices, solar cells,
and sensors [6-9]. However, despite its numerous advantages, the intrinsic electrical properties of
ZnO often necessitate modification to render it suitable for specific applications.
To optimize ZnO’s electronic characteristics, researchers have employed various doping
methods, introducing foreign atoms into the ZnO lattice. Doping not only modulates
electrical conductivity but also affects other physical properties, thereby allowing
customization of the material's performance [10, 11]. Among the various dopants studied to enhance ZnO’s electrical properties, Li has
emerged as a promising candidate. Li, being the lightest metal and having a smaller
ionic size compared to zinc, offers unique interactions when introduced into the ZnO
lattice [12-15]. Recent studies have begun to elucidate intriguing potential benefits of Li doping
and the mechanisms behind them. Park et. al reported a boost in the performance of
solution-processed ZnO thin-film transistors (TFTs) by using Li and sodium (Na) as
dopants [16]. A unique low-temperature fabrication method was developed, allowing the creation
of carbon-free ZnO thin films as TFT active layers at just 300°C. Results showed that
both Li-doped and Na-doped ZnO TFTs achieved impressive field-effect mobilities, with
Li-doped devices reaching up to 11.45 cm² V-¹ s-¹. They also exhibited excellent on/off ratios exceeding 107. Importantly, all these devices were processed at low temperatures, making them suitable
for flexible electronics, particularly on plastic substrates.
Bang et. al reported LZO films created through a simple solution process, which exhibited
improved crystallinity and smoother surfaces compared to undoped ZnO films. LZO TFTs
on heavily p-doped Si substrates achieved a peak field-effect mobility of 5.18 cm²
V-¹ s-¹ with an on/off ratio of 107, demonstrating the effectiveness of Li doping for enhancing ZnO film properties and
TFT performance [17]. Aksoy et. al employed microwave-assisted hydrothermal synthesis to create LZO nanopowders
[18]. Their structural properties, morphological characteristics, and photovoltaic performance
in dye-sensitized solar cells (DSSCs) were investigated [14]. Notably, the DSSCs using these nanopowders achieved an efficiency of 1.23%, surpassing
previous studies and demonstrating the potential of LZO for enhancing DSSC performance
[18]. Hjiri et. al. studied Li-doping-induced structural and optical properties associated
with defects [14]. LZO films were produced using sol-gel spin coating, with Li doping levels ranging
from 0% to 10%. XRD analysis confirmed a hexagonal Wurtzite structure in both doped
and undoped films. Li doping induced a red shift in the absorption edge in UV-Vis
spectroscopy. PL spectra didn't reveal distinct Li-related peaks, suggesting that
Li defects were obscured within the band tail width states. This suggests that Li
doping promotes oxygen vacancy defects in ZnO films rather than oxygen interstitial
defects. Rajeevgandhi et. al demonstrated that spherical LZO nanoparticles via coprecipitation
exhibited supercapacitor behavior with a specific capacitance of 401 F/g at a scan
rate of 2 mV/s [19]. Metal oxide semiconducting (MOS) gas sensors using ZnO films were characterized
and evaluated for NO2 gas sensing [20]. Undoped and alkali-metal (Li/Na)-doped ZnO films were compared. The LZO sensors
exhibited higher sensitivity and faster response/recovery times, detecting NO2 at 15 ppm, below the exposure limit (20 ppm).
The current literature presents varying results concerning the electrical, structural,
and optical effects of lithium doping on ZnO [6, 21, 22]. Some suggest an enhancement in conductivity and carrier concentration, while others
have revealed potential challenges [12, 23, 24]. This disparity in outcomes underscores the necessity for a systematic and comprehensive
study of LZO, as groundwork for this research endeavor.
Optimizing the electrical properties of ZnO through Li doping could have a significant
impact on various industries. Enhanced electrical properties could lead to more efficient
electronic devices, better solar cells, or more sensitive sensors. Furthermore, as
the global electronics industry moves towards more sustainable and efficient materials,
understanding and leveraging the potential of LZO will become paramount.
The primary goal of this research is to present a comprehensive understanding of how
lithium doping affects ZnO’s electrical properties. In particular, we focused on the
LZO thin film close to the gate dielectric, by adopting a bottom-contact field effect
transistor (FET) configuration. Through systematic experiments we aim to quantify
the improvements (or detriments) in electrical properties and to understand the underlying
mechanisms driving these changes. We propose optimal doping concentrations and methods
to achieve the desired electrical characteristics.
2. Materials and Methods
2.1 Preparation of the Zn Precursor Solution:
Zinc acetate dihydrate was dissolved in 2-methoxyethanol to achieve a concentration
of 0.8M. The solution was prepared using 5mL of 2-methoxyethanol as the solvent. Subsequently,
ethanolamine, serving as a stabilizer, was introduced to the solution in quantities
equimolar with the Zn ions. The resulting mixture was then stirred at 75°C for a duration
of 2 hours. The completely dissolved solution underwent filtration using a polytetrafluoroethylene
(PTFE) syringe filter with a pore size of 0.2μm. Following filtration, the solution
was allowed to age in ambient air for a period of 48 hours.
2.2 Lithium Doping Process
Lithium acetate dihydrate was added to the Zn precursor solution to achieve Li doping
concentrations of 0.25, 0.50, and 0.75 mol%. After thorough mixing, the solution was
stirred at room temperature for 2 hours. The homogenized mixture was then subjected
to filtration through a 0.2μm pore PTFE syringe filter. All of the containers utilized
during this procedure had been meticulously cleaned with acetone, methanol, and deionized
(DI) water.
2.3 Substrate Preparation
A highly doped silicon (Si) substrate, featuring a 200nm thick SiO2 layer, was cleaned using a sequential sonication process in acetone, methanol, and
DI water, each for 10 minutes. This was followed by a UV-ozone treatment for 5 minutes.
Subsequently, the cleaned substrate was spin-coated with the prepared solution at
3000 rpm for 30 seconds. Patterning of the coated film was carried out, followed by
a soft annealing process on a hot plate set to 250°C for 5 minutes, facilitating the
evaporation of any residual solvents.
2.4 Oxidation Process
The precursor-coated film underwent an oxidation process for 1 hour via the rapid
thermal annealing (RTA) method. Both the oxidation temperature and the oxygen partial
pressure were maintained at constant values during the RTA process. The final thickness
of the oxidized film was approximately 60 nm.
2.5 Device Fabrication, and Electrical/Structural Characterizations
For the final device assembly, aluminum (Al) electrodes with a thickness of 100 nm
were thermally evaporated onto the oxidized film. This facilitated the fabrication
of a field-effect transistor (FET) with defined channel dimensions: a length of 60
μm and a width of 6 mm. FET characteristic curves were measured using HP4145B in an
Ar-filled glovebox. The surface morphology and structural characteristics of the ZnO
films were investigated by scanning electron microscopy (SEM) and X-ray diffraction
(XRD) using CuKa radiation (λ=1.54178 Å). Photoluminescence (PL) measurements were
conducted at room temperature, utilizing the He–Cd laser line at 325 nm.
3. Results and Discussion
Figure 1(a) presents an SEM image of a ZnO film deposited via spin-coating on a SiO2 substrate. Notably, void spaces are discernible between individual ZnO grains following
the drying process. To explore charge transport in proximity to the gate dielectric
under carrier accumulation conditions, we intentionally limited the film thickness
to approximately 60 nm in the bottom-contact FET configuration. Figures 1(b), 1(c), and 1(d) depict the optical absorption data for the ZnO and LZO films. With increasing Li
content, a slight increase in the band gap was observed, shifting from 3.217 eV (in
non-doped ZnO) to 3.232 eV (in 0.5mol% LZO). This rise can be attributed to the Burstein-Moss
effect, which results from the occupation of lower energy states in the conduction
band by surplus carriers, causing an apparent shift in the absorption edge toward
higher energies [25, 26]. The electrical properties of ZnO were measured using FET devices in which source
and drain Al (100nm) electrodes were deposited on the ZnO layer. In the FET structure,
the drain current (ID) arises due to the movement of charge carriers, either electrons (in n-type FETs)
or holes (in p-type FETs), between the source and drain electrodes, modulated by the gate voltage
(VG) . The behavior of the drain current is typically characterized by two regimes: the
linear regime and the saturation regime. Here we measured the FET mobility and the
threshold voltage (VT) in the linear regime. The magnitude of the drain current (ID) is determined by the mobility (μ) and carrier concentration (n=Ci(VG-VT)/q), as given in the equation,
, where L, Z, and Ci represent the channel width, length, and the capacity of the gate dielectric respectively.
The threshold voltage (VT) is the gate voltage (VG) used to induce mobile carriers in the channel, a measure of electron carrier concentration.
We systematically examined the impact of oxidation temperature, under constant oxygen
pressure, on the Field-Effect Transistor (FET) mobility and the threshold voltage
of the undoped ZnO, as illustrated in Figure 2.
The FET structure (depicted in Figure 2(a)) showed n-channel FET behavior, with the drain current increasing alongside rising gate voltage
(VG), as depicted in the VG-ID curve in Figure 2(b).
Notably, with increasing oxidation temperature, the ID-VG curve displayed an augmented slope within the linear region, indicating an enhancement
in FET mobility. These variations in FET mobility and threshold voltage in relation
to oxidation temperature are illustrated in Figure 2(c). As oxidation temperature increased, FET mobility exhibited a corresponding rise
in threshold voltage (indicating electron concentration) decreasing (increasing electron
carrier concentration) from -19 V (400°C) to -36 V (600°C). This increase in FET mobility
and electron concentration is attributed to improved crystalline quality, grain growth,
and a reduction in defect density, factors that will be discussed in detail later.
Li doping introduces an additional layer of complexity into the system. Figure 3 illustrates the variations in mobility according to Li content in ZnO under different
oxygen pressures and oxidation temperatures.
Notably, in non-doped ZnO, reducing oxygen pressure from 0.4 torr to 0.1 torr resulted
in a remarkable increase in mobility as marked in Figure 3(a). For sample 3, the FET mobility increased from 0.07 to 1.23 cm2/Vs. This phenomenon is attributed to the formation of oxygen vacancies (Vo) in ZnO, acting as donor defects that contribute free electrons to the conduction
band, thereby enabling n-type conductivity [27, 28].
Reducing oxygen pressure during growth enhances oxygen vacancy formation, subsequently
raising the electron carrier concentration. While increased electron concentration
may appear advantageous for conductivity, it can also introduce elevated electron-electron
scattering, which often leads to reduced mobility. However, if the rise in free electrons
is within a certain range or if alternative scattering mechanisms (e.g., phonon scattering
or defect scattering) are mitigated at lower oxygen pressures, an overall mobility
enhancement is observed. Another potential factor contributing to increased mobility
is the improved crystalline quality of the ZnO film due to reduced oxygen pressure.
Enhanced crystallinity translates to fewer grain boundaries and defects, minimizing
scattering events and thus promoting higher mobility. Notably, our XRD results did
not detect significant changes in (002) peak intensity in relation to these effects.
The dramatic increase in mobility at reduced oxygen pressure suggests that, in this
pressure range, the benefits (increased free carriers and possibly improved crystallinity)
outweigh the potential downsides (increased electron-electron scattering) associated
with a reduced oxygen environment. At a very low oxygen pressure of 0.05 torr, the
mobility of the LZO was very low, at 500℃, with the Li content between 0 and 0.75
mol%, as clearly seen in Figure 3(b) (semi-logarithmic plot of Figure 3(a)), independent of Li content. At very low oxygen pressures, the formation of oxygen
vacancies becomes predominant. These vacancies act as shallow donors in ZnO and can
trap electrons, thus increasing scattering events and reducing electron mobility.
While the concentration of electrons (carrier concentration) is increased by oxygen
vacancies, this does not guarantee increased mobility. Oxygen vacancies can act as
scattering centers for conduction electrons, leading to a higher frequency of electron
scattering events, reducing overall mobility [29, 30].
At low Li doping concentrations, specifically up to 0.5 mol%, the trend in mobility
variations was similar for doped and non-doped ZnO. However, a noteworthy transition
occurred when Li was introduced in higher concentrations, particularly from 0.5 mol%
to 0.75 mol%. During this transition, a significant drop in the FET mobility was observed
in samples 3 and 4.
When Li substitutes for zinc (LiZn), it assumes the role of an acceptor in the ZnO lattice. Consequently, LiZn can effectively capture some of the free electrons, thus mitigating the overall increase
in electron concentration stemming from oxygen vacancies (VO) [31, 32]. This introduces a competitive dynamic: while VO introduces electrons, LiZn has the capacity to capture some of these electrons. Furthermore, it's worth noting
that Li can also act as a shallow donor, similar in function to VO.
Figures 4(a) and 4(b) show the transistor output (0.5 mol% LZO) and transfer characteristic curves for
sample 2, respectively. In the optimized condition (sample 2), mobility significantly
outperformed other samples (samples 1, 3, 4, and 5) and exhibited a consistent increase
with rising Li concentration. A noteworthy observation was the shift in the threshold
voltage to a more positive value (increase), indicating a concurrent reduction in
electron carrier concentration, as depicted in Figure 4(c). In essence, mobility was enhanced at the same time the electron carrier concentration
decreased, signifying an improvement in the electronic properties of ZnO.
This improvement could be attributed to several factors, including the reduction in
the number of scattering centers within the lattice, and enhancements in crystallinity
or grain boundary structure [30, 33]. Significantly, Figure 5(a) illustrates the emergence of the (002) peak as Li content increased from 0.25 to
0.5 mol% Li doping, indicating a pronounced preference for c-axis orientation. Consequently,
the persistent increase in FET mobility with Li content, even in the face of declining
carrier concentration, can be attributed to heightened crystallinity. Therefore, in
the optimized condition of sample 2, mobility changes appeared to be sensitive to
crystallinity. This is supported by the fact that the mobility remained the same while
Li concentration increased from 0 to 0.25 mol%, and no improvements in crystallinity
were observed when Li content increased from 0 to 0.25 mol%, as shown in Figure 5.
It's crucial to highlight that the concentration of oxygen vacancy defects remained
consistent across different Li concentrations, as evidenced by the PL measurements
in Figure 5(b), which show there were no significant changes in the intensity of the green emission
at 520 nm as Li concentration increased. This green emission is typically associated
with oxygen vacancy defects [30, 34]. Hence, it's clear that alterations in mobility related to varying Li content were
unrelated to oxygen vacancy defects. Additionally, we did not observe substantial
changes in surface morphology with different Li content.
In contrast to the optimized condition (sample 2), where mobility consistently increased
with Li concentration, samples 3 and 4 exhibited a trend of mobility peaking at a
certain Li concentration and then subsequently declining, despite a continuous rise
in carrier concentration. This behavior underscores the intricate interplay of doping
mechanisms, defect interactions, and microstructural alterations within the ZnO matrix.
More specifically, the incorporation of Li into the ZnO matrix involves distinct site
preferences: Li, when replacing zinc (LiZn), acts as an acceptor, resulting in carrier depletion [35]. Conversely, Li residing in interstitial sites (Lii) acts as a donor, facilitating
carrier contribution [36,21]. At lower doping levels, these effects might balance, resulting in higher mobility.
However, at higher doping levels, other factors, such as the clustering of Li or the
formation of complex defects, may dominate [37]. As Li concentration increases, especially beyond optimal levels, some introduced
Li atoms might serve as compensating centers. In this capacity, they introduce carriers
while simultaneously capturing or neutralizing other carriers, thus increasing carrier
concentration without a corresponding increase in mobility. Additionally, overdoping
or clustering of Li can create deep-level traps, which can impede carrier movement
and lower mobility.
An upward trend in the FET mobility for undoped ZnO in Figure 2 was observed with increasing oxidation temperature, suggesting enhanced electronic
transport properties. At higher temperatures, the equilibrium concentration of oxygen
vacancies (VO) in ZnO increases [28]. This is because higher temperatures provide more thermal energy to promote the
formation of vacancies in the crystal lattice. As the concentration of oxygen vacancies
rises, it can introduce more free electrons into the crystal, thereby increasing the
carrier concentration, consistent with the negative shift of the threshold voltage
in an n-channel FET. These vacancies can introduce additional free electrons into the crystal,
increasing carrier concentration. As electrons from these vacancies fill other trap
sites, the life-times of electrons increase, resulting in enhanced mobility. An increase
in carrier concentration, if not offset by other factors like increased scattering
mechanisms, leads to higher electrical mobility. The increase in electrical mobility
in undoped ZnO with higher oxidation temperature can be explained, at least in part,
by the higher equilibrium concentration of oxygen vacancies at elevated temperatures.
4. Conclusion
In this study, we systematically investigated the influence of oxidation temperature,
oxygen pressure, and lithium doping on FET mobility and the threshold voltage of ZnO
films. Most of all we directly investigated the ZnO film close to the gate dielectric,
using a thin ZnO film. A notable elevation in mobility was identified when the oxygen
pressure was reduced from 0.4 torr to 0.1 torr for undoped ZnO. Oxygen vacancies,
serving as donor defects in ZnO, are amplified under diminished oxygen pressure, enhancing
the electron carrier concentration. However, increased carrier concentration can also
augment electron-electron scattering, potentially impeding mobility. The sharp increase
in mobility suggests that the advantages of elevated free carriers, potentially coupled
with heightened crystallinity, overcomes the limitations imposed by increased scattering
at these oxygen pressures. Intriguingly, at an extremely low oxygen pressure of 0.05
torr, mobility dwindled considerably, possibly due to excessive oxygen vacancies acting
as electron traps and scattering sites.
LZO exhibited intriguing behavior. Up to 0.5 mol% of Li doping, the mobility patterns
mirrored those of undoped ZnO. Yet, a stark decline in mobility was observed as the
doping was increased to 0.75 mol%. Lithium, when substituting zinc, behaves as an
acceptor in ZnO, capturing some free electrons and thus potentially opposing the electron-boosting
effect of oxygen vacancies. This intricate interplay governs the observed mobility
trends.
In optimized conditions at 0.5 mol% Li doping, an increase in Li content was concomitant
with an upswing in mobility. Concurrently, a positive shift in the threshold voltage
indicated a reduction in electron carrier concentration. These observations hint at
a synergistic effect, where Li doping helps to minimize certain scattering centers
and perhaps refine crystalline properties. Indeed, XRD data corroborated this by revealing
a preferential c-axis orientation at this doping level.
In conclusion, the results underscore the delicate balance and interplay between defect
engineering, crystalline quality, and external parameters like oxidation temperature
and oxygen pressure in modulating the electronic properties of ZnO. Li doping offers
a potent tool to fine-tune these properties, with implications for enhancing the performance
of ZnO-based electronic devices. The precise tuning of Li-doping levels, combined
with controlled annealing processes, is crucial to optimize both carrier concentration
and mobility in LZO. Further investigations using techniques like transmission electron
microscopy (TEM) for structural analysis or deep level transient spectroscopy for
defect state characterization might provide more insights into the observed trends.