Table 6-1 Comparison of IGZO TFTs deposited by non-vacuum process…………100
Figure Captions
Chapter 1 Introduction
Fig. 1-1 A variety of applications of transparent conductive oxide (TCO)……….10 Fig. 1-2 Schematic orbital drawing of electron pathway (conduction band bottom)
in conventional compound semiconductor and ionic oxide semiconductor……….11 Fig. 1-3 The amorphous formation region (right) and the electron mobilities and concentrations evaluated from the Hall effects for the amorphous thin films (left) in the In2O3–Ga2O3–ZnO system……….11 Fig. 1-4 Photographs of some prototype displays using AOS
TFTs……….…..12 Fig. 1-5 Schematic of different kind of plasma sources (a) Transferred arc (b) Cold
plasma torch (c) Corona discharge (d) Dielectric barrier discharge (e) Plasma jet……….……. 13
Chapter 2 Characterizations of Gallium-Doped Zinc Oxide Films
Prepared by AP-PECVD System
path……….27 Fig. 2-2 Optical emission spectra of N2 plasma and N2 incorporated
precursor……….28 Fig. 2-3 SEM images (tilted angle) of GZO with different carrier gas flow rates………28 Fig. 2-4 Thickness and haze factor of GZO with different carrier gas flow
rates………29 Fig. 2-5 SEM images (tilted angle) of GZO with different gap distances between
the nozzle and substrate (a) 5mm (b) 10mm (c) 15mm (d) 20mm……….29 Fig. 2-6 Thickness and haze of GZO deposited at different gap distances……….…30 Fig. 2-7 GIXRD patterns of GZO deposited at different gap distances………….. 30 Fig. 2-8 The resistivity (ρ), carrier concentration (n), and Hall mobility (μ) of GZO thin films deposited at different gap distances………...31 Fig. 2-9 Transmission spectrum of GZO films deposited different gap
distances……….31 Fig. 2-10 The SEM images of GZO deposited at different substrate
temperatures………...32 Fig. 2-11 Thickness and haze of GZO deposited at different substrate
Fig. 2-12 The GIXRD patterns of GZO thin film deposited at different substrate temperatures………...33 Fig. 2-13 The resistivity (ρ), carrier concentration (n), and Hall mobility (μ) of GZO
deposited at different substrate temperatures………...……..33 Fig. 2-14 Transmission spectra of GZO thin film deposited at different substrate temperatures………...34 Fig. 2-15 SEM (tilted angle) and the HRTEM (cross section) images of GZO thin
film with 8at.% Ga doping (a) SEM (b) HRTEM……….……….35 Fig. 2-16 The GIXRD patterns of undoped and different Ga-doped ZnO films
deposited by APPJ at a substrate temperature of 100 oC………36 Fig. 2-17 The resistivity (ρ), carrier concentration (n), and hall mobility (μ) of GZO with different Ga/(Zn+Ga) atomic ratios………37 Fig. 2-18 Transmission spectrum of ZnO films with different Ga concentrations……….37
Chapter 3 Characterizations of Indium-Doped Zinc Oxide Films Prepared by AP-PECVD System
Fig. 3-1 SEM images (tilted angle) of different substrate temperatures (a) 100oC (b)
200oC (c) 300oC……….50
temperatures………...50 Fig. 3-3 The GIXRD pattern of IZO thin film at different substrate
temperatures………...51 Fig. 3-4 Hall measurement of IZO thin film at different substrate
temperatures………..……….51 Fig. 3-5 The transmission spectra of IZO thin film in the visible range at different
substrate temperatures………52 Fig. 3-6 SEM images (tilt angle) of different indium doping concentration from 0 at.% to 10 at.% (a) 0 at.% (Rms=14.7nm)(b) 2 at.% (Rms=12.7nm) (c) 4 at.% (Rms=21.8nm) (d) 6 at.% (Rms=28.5 nm) (e) 8 at.% (Rms=28.5 nm) (f) 10 at% (Rms=34.8nm)………..53 Fig. 3-7 GIXRD patterns of different Indium-doped ZnO films deposited by APPJ
at substrate temperature of 200oC………..………53 Fig. 3-8 (a) The magnified GIXRD patterns of (002) peak (b) crystalline size
estimated along (002) peak with different indium doping concentration………..54 Fig. 3-9 The resistivity (ρ), carrier concentration (n), and Hall mobility (μ) of
different In/(Zn+In) atomic ratios………..…55 Fig. 3-10 Transmission spectrum of IZO films with different indium doping
concentration………...….. 55
Chapter 4 The Effect of Channel Thicknesses and Oxygen Species on the Characteristics of ZnO TFTs Prepared by AP-PECVD system
Fig. 4-1 Schematic structure of the bottom-gate TFT test structure………..70 Fig. 4-2 Grazing incident X-ray patterns of ZnO films prepared with different carrier gases………...……….70 Fig. 4-3 AFM images of ZnO thin films with different carrier gas (a) N2 (b) CDA………...…71 Fig. 4-4 The optical transmission spectra of ZnO films deposited on glass with
different carrier gases………...72 Fig. 4-5 Transfer characteristics of ZnO TFT with different carrier gases………...73 Fig. 4-6 IDS1/2 versus VGS at VD of 80V, used to calculate the threshold voltage and
saturation mobility………..73 Fig. 4-7 Output characteristics (IDVD) of ZnO TFT with different carrier gas (a)
N2 (b) CDA……….74
Fig. 4-8 Transfer characteristics of ZnO TFT with different channel thicknesses……….75 Fig. 4-9 Output characteristics (IDVD) of ZnO TFT with different channel
thicknesses (a) 55nm (b) 110nm (c) 165nm………..….76 Fig. 4-10 GIXRD spectra of ZnO thin films with different oxygen
ratios………...………77 Fig. 4-11 SEM images (tilt angle) of ZnO thin films with different oxygen ratios (a) (0% O2) (b) (0.34% O2)(c) (0.69% O2) (d) (1% O2)………..……77 Fig. 4-12 Optical transmission spectra of ZnO thin film with different oxygen ratios deposited on glass………..….78 Fig. 4-13 PL spectra for ZnO thin films with different oxygen partial pressures……….………78 Fig. 4-14 Transfer characteristics of ZnO TFT with different oxygen
ratios……….…………..79
Chapter 5 The Impacts of Thermal Annealing on the Properties of IGZO TFT Prepared by AP-PECVD
Fig. 5-1 Schematic structure of the bottom-gate TFT test structure……….87 Fig. 5-2 GIXRD spectra of IGZO thin film annealed from 200oC to 500oC in N2 ambient for 30min……….…………..87
Fig. 5-3 High-resolution TEM cross-section image of IGZO thin film annealed at
500 oC for 30min……….88
Fig. 5-4 Top-view SEM images of IGZO thin films (a) as-deposited (b) 200oC (c) 300oC (d) 400oC (e) 500oC………..89 Fig. 5-5 AFM images of IGZO thin films (a) as-deposited (Rms=15.48nm) (b) 200oC (Rms=8.37nm) (c) 300oC (Rms=6.18nm) (d) 400oC (Rms=6.74nm)
(e) 500oC (Rms=6.67nm)………90
Fig. 5-6 Optical transmission spectra of IGZO thin film deposited on glass……….91 Fig. 5-7 Transfer characteristics of IGZO TFTs annealing at various temperatures………91 Fig. 5-8 Output characteristics of IGZO TFT (a) as-deposited (b)
500oC………,……….92
Chapter 6 Characterizations of IGZO TFT Prepared by AP-PECVD Using PE-ALD Al
2O
3Gate Dielectric
Fig. 6-1 A schematic cross view of the bottom-gate/top-contact IGZO TFT………..……..101 Fig. 6-2 Optical transmission spectra and GIXRD patterns of IGZO
Fig. 6-3 High-resolution TEM cross-section image (a) IGZO/Al2O3/n+ Si (b) Al2O3/n+ Si (c) IGZO………102 Fig. 6-4 J-V and C-V (inset graph) characteristics of the Al/Al2O3/n+
capacitors………...103 Fig. 6-5 Transfer characteristics (ID-VG) of the IGZO TFT with PE-ALD Al2O3
gate dielectric………....103 Fig. 6-6 Output characteristics (IDVD) of the IGZO TFT with PE-ALD Al2O3 gate
dielectric………104
Chapter 1 Introduction
1.1 Overview of Transparent Conductive Oxide
Transparent Conductive Oxide (TCO) films has attracted considerable attention due to a wide range of application, such as flat panel display (FPD), touch panels, solar cells, lighting emitting diodes (LED) and other optoelectronic devices [1.1]-[1.4]. Figure 1-1 shows the various applications of TCOs. Nowadays, TCO thin films have been the indispensable component to opto-electrical products. Typically, TCO films must possess a high optical transmittance of more than 80% in the visible region, a low electrical resistivity of less than 1x10-3 Ω.cm and stability in various environments. ZnO, In2O3 and SnO2-based TCOs have been extensively studied in recent few years, because they exhibit high optical transparency and high conductivity that can be control of the non-stoichiometry and doping level [1.5]. Indium tin oxide (ITO) has dominant the TCO market for pass 20 years due to their high transmittance in the visible range and low electrical resistivity. The commercial ITO has been widely used, such as common electrode as well as pixel electrode in FPD application and sensing electrode in touch panels. Recently, smart phone and large-area size
resources. A stable supply of ITO will become a critical issue in the future due to expanding market for optoelectronic devices. As a result, the development of decreasing the usage of indium or an alternative material to ITO films is necessary. In the last few years, ZnO has attracted much attention as a TCO material because of the higher abundance compared to the other TCO materials (about a factor of 1000 more abundant than indium as shown in Table 1.1 [1.6]). Furthermore, ZnO also have good stability in a silane (SiH4) plasma discharge, which is used for preparation of a-Si:H thin film solar cell [1.6]. ZnO is wide band gap (Eg =3.35eV) II-VI semiconductor with hexagonal structure. Un-doped ZnO thin films have n type properties due to intrinsic defects, but un-doped ZnO films have poor thermal stability. In order to increase the conductivity and stability of ZnO films, group-Ⅲ elements (Al, Ga, In) can be used as substitutional dopant for Zn site. ZnO-based thin films can be prepared on several substrates in a number of ways: pulse laser deposition [1.7]-[1.8], ion plating [1.9], RF/DC magnetic sputtering [1.10]-[1.11], metalorganic chemical vapor deposition [1.12], spray pyrolysis [1.13], sol-gel [1.14]-[1.15] and atomic layer deposition [1.16]. Most ZnO-based thin films are deposited using conventional vacuum techniques because vacuum-processed devices exhibit excellent performance and reliability than non-vacuum process. However a non-vacuum process offers competitive advantages, such as low cost, high throughput, and excellent suitability
for large-area applications.
1.2 Overview of Transparent Oxide Semiconductor Based Thin Film Transistors
Amorphous silicon (a-Si) and low-temperature poly-silicon thin film transistors (LTPS TFTs) dominate the active matrix technologies in the flat-panel display industry over the last ten years. However, these silicon-based TFTs have several limitations such as photosensitivity, light degradation, and opacity, etc. Oxide semiconductors are very interesting materials because they combine simultaneously high/low conductivity with high visual transparency via non-stoichiometry and doping
level. Oxide-based semiconductors, such as ZnO [1.17]-[1.18], ZTO [1.9]-[1.20], IZO
[1.21]-[1.22] and IGZO [1.23]-[1.25] have been reported for the active channel layer.
These oxide-based thin film transistors offer good electrical properties and high transparency. Recently, interest has arisen in the possibility of fabricating active electronic devices from transparent oxide semiconductor, because these oxide
semiconductors enable the manufacture of transparent circuit, called “transparent electronics’’. Transparent electronics are nowadays an emerging technology for the
next generation of optoelectronic devices.
Zinc oxide thin-film transistors (ZnO TFTs) have high potential in the active
mobility, low growth temperature and wide bandgap. Because of low growth temperature, devices can be fabricated on inexpensive plastic substrate for flexible electronics applications. The wide bandgap of 3.35eV, which is transparent in the visible region, can also be employed to a channel layer for the transparent TFT (TTFT) application. ZnO TFT offers possibility of increased pixel aspect ratio and intrinsic advantage of insensitivity to visible light. Hence, the ZnO is a good candidate for the transparent electronics.
On the other hand, the transparent amorphous oxide semiconductors (TAOS) have attracted much attention due to high mobility and good uniformity for large-area applications. The ternary oxide system of In2O3, Ga2O3 and ZnO (IGZO) has presented promising performance for TFT channel layer due to superior performance compared with conventional Si-based TFT. Figure 1-2 shows the electron pathway carrier transport path in conventional covalent semiconductor and ionic oxide semiconductor [1.26]. The conduction band of IGZO is composed of metal s-orbitals and carrier transport is almost not affected by the chemical bond distortion. As a result, IGZO thin film shows a high mobility even in amorphous phase. Figure 1-3 depicts amorphous formation region and the electron mobilities and concentrations evaluated from the Hall effects for the amorphous thin films in the IGZO system [1.27]. It is clear that the mobility is primary determined by the fraction of In2O3 content and the
highest value of 40 cm2/V-s is obtained around the samples containing the maximum In2O3 fraction. The IGZO is currently promising AOS materials for mass production with low-temperature process and excellent performance. Several prototype displays using IGZO TFT have been demonstrated as shown in Fig. 1-4 [1.28]
1.3 Background of Atmospheric pressure plasma
Nowadays, the plasma technology is an indispensable technique in various material processes. The advantages of plasma are well known, and the plasma can be well-controlled to generate the high concentration of reactive species that can enhance etching and deposition rate. The most of plasma facilities was operated under vacuum ambient. However, vacuum systems are expensive and maintenance cost is high.
Atmospheric pressure plasmas overcome the drawbacks of vacuum operation.
Atmospheric pressure plasma is used in a variety of materials processes, such as surface modification, etching, and thin film deposition [1.29]-[1.31]. Conventional plasma source includes transferred arcs, plasma torches, corona discharge, dielectric barrier discharges and plasma jet as shown in Figure 1-5 [1.32]. Arc and torch are high gas temperature and not suitable for low-temperature application. A disadvantage of corona discharge and dielectric barrier discharges is that the plasmas are not uniform throughout the volume. On the other hand, non-thermal atmospheric pressure
The non-thermal plasma jet doesn’t be spatially confined by electrodes and is compatible with low process temperature. In this dissertation, non-thermal atmospheric pressure plasma jet (APPJ) was proposed to fabricate ZnO-based TCOs and ZnO/IGZO TFTs.
1.4 Motivation
Recently, APPJ is attracted much attention because this kind of plasma does not require a complicated vacuum system. Non-vacuum system could reduces the cost of processing and enlarge the size limit. Moreover, APPJ is also a low temperature process. The temperature of plasma could be lower than 200oC which could reduce the thermal damage of substrate and even be applied for plastic substrate. In the past, oxide semiconductor was usually fabricated in vacuum system, such as sputtering and evaporation, and MOCVD which would limit the size of substrate and increase the cost of equipment. In this thesis, a novel and innovative APPJ system (also called AP-PECVD system) is proposed to develop TCO and ZnO/IGZO TFTs. Furthermore, an environmentally friendly water-based solution precursor was used.
In order to overcome the shortage of indium, more and more conductive metal oxide materials have been studied such as AZO, GZO, and IZO because of its low cost, high transparency, and favorable conductivity. In this study, APPJ would be utilized to develop GZO and IZO thin film on glass substrate.
On the other hand, for the applications of ZnO TFTs in the flat-panel displays, the off current must be low. The carrier concentration of un-doped ZnO thin films results from the intrinsic defects. Higher carrier concentration generates the external scattering and unexpected leakage current. As a result, the background electron carrier concentration must be reduced while ZnO was used as a channel layer. In order to reduce the intrinsic defects, the oxygen species were incorporated during deposition.
Also, to reduce the leakage current of source to drain current flow, thinner channel layer have been proposed by reducing the conductivity of channel layer.
Moreover, post annealing is usually performed to improve the performance of TFT. As a result, IGZO TFT was developed by APPJ and effect of annealing temperature on the properties of IGZO TFT was discussed. Furthermore, the high-k Al2O3 is a promising gate dielectric because of its low leakage current and excellent compatibility with the IGZO thin film. The plasma-enhanced ALD (PE-ALD)method was assumed to increase reactivity, reduce impurities, widen the process window, and increase the film density compared with conventional ALD. Thus, integration with PE-ALD Al2O3 was expected to achieve a higher performance IGZO TFT.
1.5 Thesis Organization
The organization of this thesis is separated in to seven chapters and organized as
In the first chapter of this dissertation, we briefly give an introduction of the TCOs, oxide-based TFTs and atmospheric-pressure plasma. In the chapter 2 and chapter 3, we use AP-PECVD to deposit GZO and IZO thin films. The structural, optical and electrical properties were discussed. In the chapter 4, we use AP-PECVD to fabricate ZnO TFT at low temperature, and the effect of channel thickness and oxygen species is studied. In the chapter 5, we use AP-PECVD to fabricate IGZO TFTs and discuss the annealing temperature on the characteristic of IGZO TFTs. In the chapter 6, high-k PE-ALD Al2O3 is integrated as a gate dielectric with IGZO TFTs.
Finally, in the chapter 7, the results are summarized and organized. Future work will be presented based on the result of the thesis.
Table 1-1 Properties of ZnO, SnO2 and In2O3 in comparison to that of silicon [1.6].
i-Phone 4S (Apple) i-Pad (Apple )
Flat-panel display (ASUS) E-paper (Eink)
Solar cell (Sharp) Light emitting diode
Fig. 1-1 A variety of applications of transparent conductive oxide (TCO).
Fig. 1-2 Schematic orbital drawing of electron pathway (conduction band bottom) in conventional compound semiconductor and ionic oxide semiconductor [1.26].
Fig. 1-3 The electron mobilities and concentrations evaluated from the Hall effects for the amorphous thin films (left) and the amorphous formation region
Fig. 1-4 Photographs of some prototype displays using AOS TFTs [1.28].
Fig. 1-5 Schematic of different kinds of plasma sources (a) Transferred arc (b) Cold plasma torch (c) Corona discharge (d) Dielectric barrier discharge (e) Plasma jet [1.32].
(a) (b)
(c) (d)
(e)
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