Oxide-based Electric Devices : Flexible Transparent Thin Film Transistors By Yu-Lin Wang Fall 07 A PROPOSAL PRESENTED TO THE GRADUATE COMMITTEE IN PARTIAL FULFILLMENT OF THE REQUIREMENTS OF THE DOCTARAL QUALIFYING EXAM Materials Science and Engineering University of Florida TABLE OF CONTENTS 1.0 Introduction …………………………………………………………………3 1.1 Motivations …………………………………………………………………..3 1.2 Objectives of research ………………………………………….……………4 2.0 Literature review ………………………………………………………………5 2.1 Comparisons of materials for TFTs used in display applications…………5 2.2 Amorphous transparent conducting oxides (ATCOs)….......………………6 2.3 Transparent thin film transistors on flexible substrate (TFTs) …………8 3.0 Research Plan ………………………………………………………………… 9 3.1 Experiments……………………………………………………………….......9 3.1.1 Depletion mode field effect transistors fabricated in a room temperature process by using α-IZO and α-IGZO as the channel layer ….…… 9 3.1.2 Enhance mode field effect transistors fabricated in a room temperature process by using α-IZO and α-IGZO as the channel layer……..…10 3.1.3 Transparent conductive oxide film growth at room temperature…..10 3.1.3.1 N2/O2 gas effect………………………………………………..10 3.1.3.2 SiO2 and IZO co-sputtering ………………………………….11 3.1.4 Gate dielectrics …………………………………………………………12 3.1.5 Surface treatment by O2 plasma and H2 plasma…………………….13 3.1.6 Ring Oscillator…………………………………………………….…….13 3.1.7 Reliability test……………………………………………………….…..13 3.1.8 Device simulation…………………………………………………….....13 3.2 Characterization………………………………………………………….…..13 4.0 Initial Results ………………………………………………………………....14 4.1 Depletion mode IZO thin film transistors…………………………….…….14 4.1.1 Large gate area TFTs…………………………………………………….14 4.1.2 Small gate length FETs and the frequency response………………...15 4.2 Enhance mode IZO thin film transistors…………………………………....17 5.0 Summary ………………………………………………………………………....18 6.0 Timeline……………………………………………………………………..….....19 7.0 References …………………………………………………………………20 2 1.0 Introduction 1.1 Motivations Flexible electronics is emerging rapidly(1,2). Theses devices have the advantages such as low profile, light weight, small size, and better performance. In displays, thin film transistors (TFTs) are used as switching components in the active-matrix over a large area. Currently, liquid crystal displays (LCDs) mostly use amorphous Si as the channel.in TFTs. However, due to the low mobility (<1 cm2/Vs)(40) and high process temperature (350℃)(40), amorphous Si-TFTs are not available for high resolution displays on cheap plastic substrates. Organic TFTs have very low mobility (< 1 cm2/Vs)(40) and may have reliability concerns(40). Oxide-based TFTs have at least 1 order higher mobility (10~50 cm2/Vs)(34,35) than amorphous Si-TFTs and organic TFTs and can be deposited at room temperature. The high mobility of oxide-based TFTs, make them available for high resolution displays and can integrate switching TFTs in the active-matrix and driverintegrated circuits (driver ICs) on the same plastic substrate, which can reduce cost and provide a more compact display. Besides, oxide-based TFTs have other advantages such as room temperature deposition, higher transparency, better smoothness, etc.(31~33). The oxide-based TFTs have a great potential to realize a roll-to-roll display. If this technology can be realized, it may not only replace the current amorphous Si-TFTs for LCDs, but will also create new applications on various sets such as heads-up, windshield, electronic books or light weight computers for soldiers in the battle field and eventually change the whole display industry. 3 1.2 Objectives of research In this study, I propose to fabricate TFTs by sputtering InZnO and InGaZnO on hard (glass) and flexible (plastic) transparent substrates. Depletion mode and enhancement mode field effect transistors will be fabricated. The study will include device designs, materials tuning, process developments, device characterization, device simulation, device reliability test, and device circuit demonstration. The study will cover the whole course of the device development. Transparent conductive oxides (TCOs) were applied in many areas, such as the transparent electrodes used in liquid crystal displays, solar cells, and light emitting diodes because of their high electrical conductivity and high optical transparency(3~5). Oxidebased thin film transistors attract much attention due to their advantages such as high mobility, high electrical conductivity, and high visible transmittance(6~9). Amorphous or nano-crystalline n-type oxide semiconductors such as zinc oxide, zinc tin oxide, indium gallium oxide, and indium gallium zinc tin oxide displays demonstrate surprisingly high carrier mobilities (~10 cm2 /Vs) temperature even for amorphous films deposited at room (9-26) . Many transparent thin film transistors (TTFTs) were reported using crystalline ZnO(27,28), or polycrystalline SnO2(29), and In2O3(30). However, to realize the transparent thin film transistor for flexible electronics, amorphous films are more suitable than crystalline type, because amorphous type oxide films have extra advantages such as low temperature deposition, good film smoothness, low compressive stress, and large area deposition by sputtering(31, 32, 33). An amorphous conductive oxide, InZnO (IZO), with a high carrier mobility (10~50 cm2/Vs)(34,35), was proved a promising TCO due to its good electrical properties and thermal stability, and has been fabricated as TFTs(36,38). A 4 similar material, InGaZnO (IGZO), was also reported as being used as the channel layer in a TFT with a good electrical stability and a high carrier mobility (1~10 cm 2/Vs)(39,31) which may be another choice to replace a-Si in display applications. 2.0 Literature review 2.1 Comparisons of materials for TFTs used in display applications An amorphous or polycrystalline Si:H layer as the channel have been commonly used for most conventional TFTs in display applications. The standard Si-based TFTs have drawbacks such as light sensitivity, light-induced degradation and low field effect mobility (<1 cm2/Vs)(40). Therefore, Si:H TFT devices reduce the efficiency of light transmittance and brightness. Besides, both amorphous and polycrystalline Si:H TFTs require relatively high process temperatures (350℃ and 450℃, respectively)(40) making it difficult to fabricate these TFTs on plastics. One of the methods to increase the efficiency and avoid high temperature is to use amorphous transparent oxides for the channels and electrodes, and fabricate TFTs at room temperature. Table 1 shows the major differences among α-IZO, α-Si, and polycrystalline Si. Obviously, α-IZO has the advantages of high field effect mobility, high transparency, room temperature compatible processing, large area deposition by sputtering, plastics substrate available, and is a cheaper process(40). Table 1. Materials for TFTs used in display applications 5 2.2. Amorphous transparent conducting oxides (ATCOs) TCOs are composed of post-transition metal oxides with outer major quantum number n ≧ 4(39,41). These TCOs exhibit n-type carriers(39,41). Oxygen vacancies dominate the carrier concentration in these TCO films. For these TCOs, the mobility is still close to that of the polycrystalline even in the amorphous material. It is very different fromα-Si, which has a extremely low mobility (<1 cm2/Vs)(40) in amorphous type comparing to the several orders higher mobility in polycrystalline (30~300 cm2/Vs)(40) or crystalline (>1000 cm2/Vs)(40). Table 2 shows some commonly used TCOs have this feature. Although there is more than one mechanism explaining the conduction behavior for these TCOs, the most widely accepted theory of carrier transport is the s orbitals overlapping of these transition metal atoms(39,41). Table 2 Comparisons of various TCOs Among various conductive oxides, the IZO system exhibits many advantages for the flexible transparent TFTs such as high field effect mobility, high transparency, room 6 temperature compatible process, large area deposition by sputtering, plastic substrates available, and is a cheaper process(8,34~36,38). Other conductive oxides may not fit all the requirements for the flexible transparent TFTs. The first requirement is the film has to be transparent in visible region which means the bandgap Eg > 3 eV. CdO-PbO and AgSbO3 systems have a bandgap smaller than this requirement(42,43). The second requirement is the film must be amorphous and conductive as deposited in room temperature. CdOCeO2 is very resistive (resistivity ~1x104 ohm-cm)(44) as deposited if no dopants are added in. In addition, Cd2+ ions is toxic against the environment(39). Amorphous In2O3 looks like a good candidate, however, when the oxygen ratio increases a little bit, it becomes polycrystalline(41,46). ZnO is always polycrystalline as deposited(38). In2O3-ZnO systems have a wide range of amorphous materials in In/Zn ratio and various oxygen partial pressure (37,39). Note that the change in oxygen ratio is very important because the carrier concentration can be adjusted by controlling the oxygen partial pressure or the O2/Ar ratio. α-IZO has a considerable high mobility (10~50 cm2/Vs)(34,38,40) as deposited at room temperature which is at least one order higher than amorphous Si(40). Ga2O3-ZnO (GZO) system has a little bit lower mobility than IZO(38). GaInZnO (GIZO) also has a little bit lower mobility compared to IZO(39). The last candidate is ITO, which is widely used as electrodes in LEDs, solar cells and LCDs(60~62). Compared to ITO, IZO has a higher work function(10,51,57), higher transmittance in the infrared region(58), and lower In concentration than ITO(51). A higher In concentration means higher price(51). Accordingly, the IZO will be used as channels and electrodes to fabricate the flexible transparent TFTs in this research. GIZO-TFTs were reported having a better stability than IZO-TFTs(53). Thus, GIZO-TFTs will also be included in this study. 7 2.3 Transparent thin film transistors on flexible substrates Many groups reported oxide based TFTs using IZO, GZO, ZnO, SnO2, In2O3 as channel layers fabricated on glass(8,29,31,30,34,38, 40). However, few of them are reported on organic flexible transparent substrates. In recent years, α-Si TFTs have been fabricated a lot on organic substrate such as PET (polyethylene terephthalate)(59). Recently, an enhancement mode TTFT using IGZO as the channel layer and Y2O3 as the gate dielectric fabricated on a PET substrate was reported (39,52,53). The TFT has a field effect mobility of 10 cm2/Vs, threshold voltage 1.2V, on-off ratio >106 , subthreshold voltage swing ~0.2V/decade. It shows the TCO type TFTs have great potential to beat theα-Si TFTs (low mobility < 1cm2/Vs, high temperature 350℃ ) and organic TFTs (low mobility < 1 cm2/Vs)(40) not only in electrical properties, but also in optical properties, ease of processing, and cost. Currently, two different technologies are used to fabricate TFTs on plastics. The first one is to deposit films and do processes directly on the plastics(54,59). The other one is to fabricate TFTs on rigid glass first, then etch off the substrate glass and paste the flexible plastics onto the TFTs(55). The second one can avoid high temperature and stress caused by film deposition. However, our IZO and IGZO TFTs are fabricated in a room temperature process, so we can use the direct process approach. 8 3.0 Research Plan 3.1 Experiments 3.1.1 Depletion mode field effect transistors fabricated in a room temperature process by using α-IZO and α-IGZO as the channel layer I plan to fabricate the depletion mode TTFTs as shown in figure 1(a). The gate dielectrics will be SiO2 , SiNx or Sc2O3. Channel layers will be IZO or InGaZnO. Device performance will be compared for different structures. Eventually, a fully transparent TFT will be fabricated on a flexible transparent substrate, PET. (a) (b) Figure 1(a) Schematics of the fully transparent D-Mode TFTs on flexible transparent substrate. (b) D-Mode TFTs on glass. We have already fabricated depletion mode thin film transistors using IZO as the channel layer on glass substrates as depicted in figure 1(b). This is the first report of depletion mode TFTs made of IZO film in channel layer(36). The IZO films were deposited near room temperature by rf magnetron sputtering using 4 inch diameter targets of In2O3 and ZnO(37). The working pressure was varied from 2-15 mTorr in a mixed ambient of O2/Ar. The percentage of O2 in the mixture was varied from 0-3%. At a percentage of 2.5 %, we obtained films with carrier concentration of ~1018 cm-3 and electron mobility of 17 cm2.V-1.s-1 obtained from Hall measurements. The partial pressure of oxygen during the sputter deposition was found to be the dominant factor controlling the conductivity of the films. The sputtering power on the targets was held constant at 9 125W, leading to compositions of the films measured by x-ray fluorescence spectroscopy of In/Zn=0.5 in atomic ratio. The typical thickness of the IZO films deposited was 150 nm, with a root mean square roughness of 0.4 nm measured over a 10x10 μm2 area by Atomic Force Microscopy. The films were amorphous as determined by x-ray diffraction and showed optical transmittance of ~80% in the visible range. 3.1.2 Enhance mode field effect transistors fabricated in a room temperature process by using α-IZO and α-IGZO as the channel layer The enhance mode TFT structure is shown in figure 2(a). Here I also plan to use IZO and IGZO as the channel layers and design structures for the channel. Recently, we successfully fabricated enhance mode thin film transistors using IZO as the channel layer as depicted in figure 2(b). The device has very good performance which will be described in a later chapter. (a) (b) Figure 2(a) Schematics of the fully transparent E-Mode TFTs on flexible transparent substrate. (b) E-Mode TFTs on glass. 3.1.3 Transparent conductive oxide film growth at room temperature 3.1.3.1 N2/O2 gas effect As described in the previous section, the IZO film was deposited in the sputtering machine with two targets, ZnO and In2O3, together with O2 and Ar gas in the chamber. The O2/Ar ratio decides the carrier concentration in the IZO film. Here I plan to use 10 N2/O2/Ar gas mixture to deposit IZO film. The reasons I use N2 is because in the plasma, N2 will convert to N2+, which may replace O and bond with In. This was investigated in forming p-type ZnO(56). We know the carriers in the IZO result from the nonstoichiometry, which means the lack of oxygen allows some In atoms that are not bonded with oxygen atoms to release electrons to the conduction band. That is why when the O2/Ar ratio change during IZO film deposition, the carrier concentration will also change. Higher O2/Ar ratio leads to a decrease in the number of oxygen vacancies, which also means the carrier concentration decreases(37). When removing one oxygen atom from the In, one oxygen vacancy is created. In is a big atom and tends to lose electrons. Oxygen is a small atom and tends to get electrons from the In. ZnO acts as a stabilizer in the In2O3 matrix (38). That’s why IZO and (GaZnO) GZO both have lower sensitivity of O2/Ar ratio to carrier concentration than ZnO (38). Since the oxygen has a higher electronegativity than nitrogen, oxygen can form a strong ionic bond with In. This means when removing or adding a certain amount of oxygen or nitrogen bonded with In, oxygen will produce a larger change in carrier concentration than nitrogen. This means nitrogen can reduce the sensitivity of O2/Ar ratio to carrier concentration. The second reason is, due to the previous reason, nitrogen may improve the device reliability. A reliability issue is one of the reasons why GaInZnO was developed(53). We may provide another view to do the same thing by an easier method. 3.1.3.2 SiO2 and IZO co-sputtering (SIZO) Ga2O3 introduced into the In2O3-ZnO system to form the InGaZnO was reported as providing a better stabilization in TFTs than IZO(53). Ga was chosen because it has an atomic radius close to In(39). The introduction of Ga into the IZO reduces the electron 11 concentration and mobility(39). The highest carrier concentration of IGZO is around ~ 1019 cm-3 (39,41) which is smaller than that of IZO (~1021 cm-3)(35,38). The reduction in carrier concentration is not bad because for the channel layer, 1018 ~1016 cm-3 is enough for both depletion and enhancement mode TFTs. Although carrier concentration in IZO can also be adjusted by O2/Ar ratio, the carrier concentration change in the IZO film is dramatic ranging from 1018 to 1016 cm-3 in a small O2/Ar ratio region(37). Ga not only reduces carrier concentration, but also reduces the sensitivity of the carrier concentration to the O2/Ar ratio(38,39). It is good for controlling the carrier concentration. However, in the mean time, the reduction in mobility is not welcome. It is interesting to introduce another oxide into the IZO system to stabilize the oxide system and the mobility . The idea is to incorporate a smaller atom and in the mean time, oxide formed by this atom has Eg > 3eV. SiO2 fits these requirements. Si can easily bond with oxygen to reduce sensitivity of the carrier concentration to the O2/Ar ratio during film deposition. Also, due to the smaller radius of Si than Ga, In atoms still can keep their s orbitals overlapped. This means the mobility may not be degraded too much. 3.1.4 Gate dielectrics Due to the different interfaces that may form between IZO and various dielectrics, it is necessary to use different dielectrics such as SiO2, SiN, and Sc2O3 as the gate dielectrics in the TFTs and compare the device performance. 3.1.5 Surface treatment by O2 plasma and H2 plasma O2 plasma can obviously decrease the surface carrier concentration of the IZO film due to the annihilation of the oxygen vacancies. This might help to reduce the surface leakage and then improve on/off ratio if the surface leakage dominates the leakage 12 current, especially for the depletion mode FET. H+ was reported to be implanted into the CdO-CeO2 film and act as a shallow donor(44). I believe H2 plasma can also create a donor in IZO film. One very interesting experiment is that if we introduce hydrogen into an IZO film, which had been deposited under a high O2/Ar ratio, will it be easier to control the carrier concentration by hydrogen plasma? Due to the very small size of the hydrogen, it should not reduce the hall mobility of the IZO film because it will not inhibit the overlap of the 5s orbitals of In . 3.1.6 Ring Oscillator After we successfully fabricate the D-mode and E-mode FETs, we can start to make a ring oscillator using these TFTs. 3.1.7 Reliability test The reliability test will include (i) current stress in room temperature and high temperature (ii) thermal shock and bending test. These tests will be applied to the TCO films and devices on both glass and PET. 3.1.8 Device simulation The device will also be measured for the s parameters and be simulated to extract the parasitic parameters of the D-mode and E-mode FETs. We have already performed the simulation for the D-mode IZO TFTs, which will be mentioned in the latter section. TFTs made of IZO, IGZO or SIZO will be compared and discussed. 3.2 Characterization SEM, SIMS, XRD, XPS, AFM, Transmittance, photoluminescence will be used to characterize the films. An Agilent 4156 parameter analyzer and Agilent E8361 network analyzer will be used to characterize the device dc and rf performance, respectively. 13 4.0 Initial Results 4.1 Depletion mode IZO thin film transistors 4.1.1 Large gate area TFTs Top-gate-type TFTs using a-IZO channels and 50 or 95-nm-thick SiO2 gate insulators deposited by plasma enhanced chemical vapor deposition were fabricated as shown schematically in Figure 1(a). Figure 3 shows the top-view of the TFT. The gate dimension is 36 µm × 100 µm. The IZO film deposited in 2.5% O2/Ar ratio has a carrier concentration about 1018 cm-3(37). The whole process was done without heating the substrates, making the entire process consistent with typical continuous-use temperatures of commercial plastic films for electronic devices. Figure 4 shows IDS-VDS characteristics from IZO transistors with 50 nm thick SiO2 gate dielectric. The transistor operates in depletion-mode with an appreciable drain current at zero gate voltage and exhibits excellent drain current saturation. Figure 5 shows IDS and gm as a function of VGS for a device with 50 nm SiO2 gate. The sub-threshold voltage swing was 1.9 V/decade and the device had a threshold voltage of -6.5V.The latter is the gate voltage at the onset of the initial sharp increase in current in a log(ID)-VGS characteristic. The drain current on-to-off ratio was >106. These results are competitive with past results on TFTs using room temperature sputter deposited amorphous InGaZnO4 as the channel material (31). The field-effect mobility was of ~4.5 cm2.V-1.s-1. The gate I-V characteristics from devices with two different gate dielectric thicknesses are shown in Figure 6. The leakage current is very small, in the 10-10A range, for both gate thicknesses and demonstrates that the low temperature deposition process produces acceptable quality SiO2 for TFT applications. The threshold voltage was 14 decreased to -5.5V for the thicker dielectric and the slope of the sub-threshold voltage swing was 0.87V/decade for the 95 nm thick dielectric. Figure 3. Top-view of the TFT Figure 5. IDS, gm, as a function of VGS Figure 4. IDS vs. VDS Figure 6 Gate leakage current 4.1.2 Small gate length FETs and the frequency response Top-gate TFTs using 50 nm of -IZO channels and 12.5 nm-thick SiNx gate insulators deposited by plasma-enhanced chemical vapor deposit ion (PECVD) were fabricated as shown similarly in Figure 1(b). The gate dimension is 1 µm × 200 µm. The SiNx layer was deposited without heating the substrates. In addition, the SiNX gate dielectric provided superior stability of device performance relative to SiO2 deposited under the same conditions(36). Specific contact resistance and sheet resistance from the linear transmission line measurements were 7 × 10-5 Ω.cm2 and 0.9 MΩ/sq, respectively. 15 Figure 7. IDS vs. VDS Figure 8. IDS, gm, as a function of VGS Figure 7 shows typical drain current versus drain voltage, IDS-VDS, characteristics from the IZO transistors. Figure 8 shows drain current, IDS, and transconductance, gm, as a function of VGS for an IZO TFT. An inset plot shows log(IDS), drain current, and log(Ig), gate current, as a function of VGS. A maximum transconductance of 7.5 mS/mm was obtained at IDS=1.35mA ,Vg=0V and Vd=5V. This is the highest transconductance ever reported for IZO based TFTs. The transistor has a low threshold voltage of -2.5V. The drain current on-to-off ratio was >105. The gate leakage is about 10-10A ~10-11A. The field-effect mobility is 14.5 cm2.V-1.s-1. Figure 9. S-parameters Figure 10. h21 and U gain The measured s-parameters, estimated h21 and unilateral power gain of a typical IZO TFT are illustrated in Figure 9 and figure 10 respectively. The TFT was biased at drain 16 and gate voltage of 3V and 0V, respectively during the s-parameter measurements. Unity gain cut-off frequency and maximum frequency of oscillation of 180 and 155 MHz, respectively, were achieved. A simplified equivalent T-model for the IZO TFT, as shown in Figure 11, was used to extract the device parameters. The extracted device parameters are listed in Table 1. The extracted source and drain resistance were consistent with the estimated resistance based on the transmission line measurements and drain I-V characteristics. The simulated intrinsic transconductance was very close to the measured extrinsic transconductance. The low cut-off frequency of the IZO was limited by the fairly long transit time, 16 ps, low transconductance, and high parasitic resistances, which were results of the low mobility and saturation velocity of the -IZO channel layer. However, this MHz-range switching performance is sufficient for many display applications(ref). Figure 11. T-model Table 3. Extracted device parameters 4.2 Enhance mode IZO thin film transistors Recently, enhancement mode top-gate TFTs using 20 nm of a-IZO channels and 100 nm-thick SiO2 gate insulators deposited by plasma-enhanced chemical vapor deposit ion 17 (PECVD) were fabricated. Figure 2(b) shows the cross-section structure of the TFT with a gate dimension of 1 µm × 100 µm. The IZO film was deposited in 3.1% of O2/Ar ratio has a carrier concentration about 1.5x1016 cm-3. The SiO2 layer was deposited without heating the substrates, making the entire process consistent with typical continuous-use temperatures of commercial plastic films for electronic devices.. Figure 12 shows typical drain current versus drain voltage, IDS-VDS, characteristics from the IZO transistors. The transistor operates in enhancement-mode showing excellent pinch-off. Figure 13 shows drain current, IDS, and transconductance, gm, as a function of VGS for an IZO TFT. An inset plot shows log(IDS), drain current, and log(Ig), gate current, as a function of VGS. A transconductance of 10 mS/mm was obtained at drain current of 0.3mA at 0.85V gate voltage and 3V drain voltage. The transistor has a low threshold voltage of 0.5V and an excellent sub-threshold voltage swing of 0.135 V/decade. The drain current on-to-off ratio was ~105. The gate leakage is about 10-10A ~10-9A. Figure 12. IDS vs. VDS Figure 13. IDS, gm, as a function of VGS 5.0 Summary In this proposal, IZO and IGZO will be used as channel layers to fabricate depletion mode and enhancement mode TFTs and ring oscillators on glass and flexible transparent 18 substrate (PET). The SiO2-In2O3-ZnO system and N2 plasma incorporated IZO film will be grown to get a better controllability of the carrier concentration during the film growth. Hydrogen plasma and oxygen plasma effects on the TCO films and the TFTs will be investigated. The device reliability will be tested to compare the effects from different TCO films and process treatments. Devices will be simulated in a device model to extract the parasitic parameters. Devices will be characterized in dc and rf performance. The depletion and enhancement mode TFTs have been fabricated successfully on glass by using IZO films as the channel layers. 6.0 Timeline 19 7. 0. References 1. K. J. Allen, Proceed. IEEE. 93, 1394, (2005). 2. K. Jain, M. Klosner, M. Zemel, S. 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