Using Flexible Polyimide as a Substrate to Deposit ZnO : Ga Thin Films and Fabricate pi-n α-Si : H Thin-Film Solar Cells

The GZO thin films were deposited on the polyimide (PI) substrates to investigate their properties for the possibly flexible applications.The effects of substrate temperature (from room temperature to 200C) on the surface and cross-sessionmorphologies, X-ray diffraction pattern, optical transmission spectrum, carrier concentration, carrier mobility, and resistivity of the GZO thin films on PI substrates were studied. The measured results showed that the substrate temperature had large effect on the characteristics of the GZO thin films. The cross-section observations really indicated that the GZO thin films deposited at 200C and below had different crystalline structures. The value variations in the films’ optical band gap (E


Introduction
Tin doped indium oxide (ITO) thin films are widely used as a transparent conducting oxide (TCO) electrode in optoelectronic devices because they have high performance in the visible region, including very low resistivity and high transmittance.However, the price of indium is increasing due to the high demand of ITO in the rapid development of flat panel displays (FPDs) industry.In addition, the toxic nature and high cost due to the scarcity of indium have led researchers to seek an alternative candidate for ITO.Recently, impurity doped zinc oxide is a possible alternative to ITO due to its unique electrical and optical properties.Zinc oxide (ZnO) is a novel II-VI compound n-type oxide semiconductor with various electrical, optical, acoustic, and chemical properties because of its wide direct band gap (  ) value of 3.37 eV at room temperature (RT) [1].Because of the good properties of thin films, ZnO-based thin films could be used as a transparent electrode in optoelectronic applications such as solar cells [2], and undoped ZnO thin films could be used as a buffer layer of solar cells [3] and the active layer of transparent thin films transistor [4].Alternatively, the effects of different dopant of In 2 O 3 [5], Al 2 O 3 [6], and Ga 2 O 3 [7] in ZnO films have also been explored and are also regarded as the ideal candidates for replacing ITO as TCO electrodes owing to their promising optical and electrical properties as well as its low cost, nontoxicity, and long-term environmental stability.
Many researchers have reported about the Ga 2 O 3 -doped ZnO thin films according to a different doping concentrations of Ga 2 O 3 [8].The highly conductive and transparent Ga 2 O 3doped ZnO thin films had been deposited at high growth rates by radio frequency magnetron sputtering [9].The thin films processed at room temperature on soda lime glass substrates using a ceramic Ga 2 O 3 -doped ZnO target; a low resistivity of 2.6 × 10 −4 Ω-cm was obtained.In the present paper, a compound of ZnO with 3 wt% Ga 2 O 3 (ZnO : Ga 2 O 3 = 97 : 3 in wt%, GZO) was prepared by solid-state reaction method.For the possibly flexible applications, the polyimides (PI) were used as substrates and the GZO thin films were deposited on them to investigate their physical, optical, and electrical properties.However, there is a still controversy about the effects of substrate temperature of the Ga 2 O 3doped ZnO thin films depositing on PI substrates.For that, the GZO thin films were deposited on PI substrates by changing substrate temperature from RT to 200 ∘ C. We would show that substrate temperature played an important role in nucleation, relatively diffraction intensity of orientations, lattice constant, crystalline size, optical   value, carrier mobility, carrier concentration, and resistivity of the GZO thin films.In the past, GZO thin films were used as the electrodes of the p-i-n -Si:H thin-film solar cells [10], produced in a modified single chamber reactor, and the fabricated solar cells exhibited very good electrical characteristics [11].In the past, the GZO thin films were also deposited on the polyethylene naphthalate (PEN) substrates by RF magnetron sputtering at room temperature [12].In this paper, the GZO thin films were deposited on polyimide (PI) substrates by RF magnetron sputtering under different substrate temperatures (from RT to 200 ∘ C) to investigate their characteristics for the possible applications in flexible photo devices.Finally, the investigated GZO thin films on PI substrates were also used as the transparent electrodes to fabricate the -Si thin-film solar cells.The current-voltage characteristics were measured to determine the effects that substrate temperature of the GZO thin films had on the fabricated -Si solar cells.

Experimental Details
In this work, GZO with the composition of ZnO = 97.0wt% (99.999% purity) and Ga 2 O 3 = 3.0 wt% (99.99% purity) was used to prepare 2-inch (in diameter) target.The weighted composition was mixed, ground, calcined at 1000 ∘ C for 5 h, and sintered at 1400 ∘ C for 4 h to prepare the GZO ceramic target for sputtering process.RF (13.56 MHz) magnetron sputtering process was used, and the used substrate was 33 mm × 33 mm × 2 mm polyimide (abbreviated as PI).Before deposition process was started, base chamber pressure was pumped to less than 1 × 10 −6 Torr; then deposition pressure was controlled at 5 × 10 −2 Torr and the GZO thin films were deposited at different temperatures (from RT to ∼200 ∘ C).In case of the GZO thin films, RF power was controlled as 50 W and substrate temperatures as from room temperature (RT) to 200 ∘ C, and distance between the target and polyimide substrate was 8 cm.Before deposition process was started, base chamber pressure was pumped to 5 × 10 −6 Torr (detected by using MKS Baratron gauge) and substrate temperature was changed from RT to 200 ∘ C; then deposition pressure was controlled at 5 × 10 −3 Torr.During deposition process, only argon was introduced in the chamber; the flow rate of pure argon (99.999%) was 20 sccm.Film thickness of the GZO thin films was determined by averaging five data obtained by FESEM, and deposition rates were calculated from measured thickness of the deposited GZO thin films.Film thickness was measured using a Nano-View SEMF-10 ellipsometer and confirmed by field emission scanning electron microscopy (FESEM); the films' thicknesses were about 260 nm by controlling the deposition time.While the crystalline structure of the GZO thin films was identified by X-ray diffraction (XRD) patterns and the Hall-effect coefficient was measured using a Bio-Rad Hall setup, the optical transmission spectrum was recorded using a Hitachi U-3300 UV-Vis spectrophotometer in the 300-1400 nm wavelength range.Superstrate p-i-n -Si:H thin film solar cells were fabricated using a single-chamber plasmaenhanced chemical vapor deposition unit at 200 ∘ C, with a working pressure of 700×10 −3 Torr and a deposition power of 20 W. The p-type -Si thin films (thickness was about 20 nm) were deposited by controlling the gas flowing rates for H 2 = 100 sccm, SiH 4 = 20 sccm, CH 4 = 10 sccm, and B 2 H 6 = 40 sccm; the i-type -Si thin films (400 nm) were deposited by using H 2 = 100 sccm and SiH 4 = 10 sccm; and the p-type -Si (50 nm) thin films were deposited by using H 2 = 100 sccm, SiH 4 = 20 sccm, and PH 3 = 20 sccm, respectively.The currentvoltage characteristic of the fabricated solar cells was measured under an illumination intensity of 300 mW/cm 2 and an AM 1.5 G spectrum.

Results and Discussion
XRD patterns of the GZO thin films as a function of substrate temperature are shown in Figure 1.Even though all the GZO thin films exhibited the (002) peak, they really had different diffraction results.The RT-and 100 ∘ C-deposited GZO thin films exhibited only a weak (002) peak, and the diffraction intensity of (002) peak had no apparent increase as substrate temperature increased from RT to 100 ∘ C. The 200 ∘ C-deposited GZO thin films exhibited a strong (002) peak and a weak (004) peak, which indicate that the axis is predominantly oriented parallel to the substrate normal.Those results prove that the GZO thin films have different morphologies in the cross-section and they have differently crystalline orientation.The absence of additional peaks in the XRD patterns excludes the possibility of any extra phases and/or large-size precipitates in the GZO thin films.The results in the XRD patterns match the variation in the morphology of the SEM observations that the different morphologies having in the surface (Figure 3) and cross section (Figure 4) of the GZO thin films will lead to different crystallization results.The (002) peaks of the GZO thin films prepared at substrate temperature = RT, 100 ∘ C, and 200 ∘ C were situated at 2 = 34.14∘ , 34.18 ∘ , and 34.36 ∘ , respectively.The lattice constant  was calculated by using the 2 value; the calculated lattice constants () were 0.5249, 0.5243, and 0.5221 as substrate temperatures were RT, 100 ∘ C, and 200 ∘ C, respectively.All the lattice constant  of the GZO thin films being smaller than that of the ZnO thin films is considerable, because the radius of Ga 3+ ions (62 pm) is smaller than that of Zn 2+ ions (72 pm).As substrate temperature is raised from RT to 200 ∘ C, the more Ga 3+ ions will substitute the sites of Zn 2+ ions, because the radius of Ga 3+ ions is shorter than that of  Zn 2+ ions; for that the lattice constant  of the GZO thin films becomes shorter as substrate temperature is raised.As Figure 2 shows, the full widths at half maximum (FWHM) values for the (002) peak of the GZO thin films were 0.412, 0.360, and 0.296 for substrate temperature were RT, 100 ∘ C, and 200 ∘ C, respectively.These results suggest that the GZO thin films deposited at higher temperature have the better crystalline structure.The morphologies of the GZO thin films deposited at different substrate temperatures are shown in Figure 3, which indicates that as deposition temperature is changed, the surface morphologies apparently changed as well.As deposited at room temperature, morphology of the GZO thin films exhibited a roughness surface, which showed the nanocrystalline structure of the GZO grains.As Figure 3 shows, the grain size distributions were around the range of 8∼40 nm, 10∼43 nm, and 15∼55 nm.However, the variations of average crystallization sizes are dependent on substrate temperature and are not easily calculated from the surface observation.We will illustrate the variations of grain sizes from the XRD patterns and the following [13], and the results are also shown in Figure 2: As Figure 2 shows, the average crystallization sizes were 20.2 nm, 23.1 nm, and 28.1 nm as substrate temperatures were RT, 100 ∘ C, and 200 ∘ C, respectively.Even the substrate temperature is raised from RT to 100 ∘ C, only a little increase in the active energy of plasma GZO molecules to improve the crystallinity and grain growth, for that the diffraction intensity of (002) peak has no apparent change and the crystallization size increases slightly; as substrate temperature is raised from 100 ∘ C to 200 ∘ C, the plasma GZO molecules will have enough active energy during deposition process and the chance for growth of the GZO crystallization sizes increases; for that the diffraction intensity of the (002) peak and the crystallization size increases.The number of thin film defects also will decrease and the crystallization of the GZO thin films will be improved; then the crystallization of the GZO thin films is also improved and the FWHM value decreases.From the results in Figures 1-3, as substrate temperature is raised from RT to 200 ∘ C, a smoother surface morphology and a more uniform -axis orientation were obtained in the 200 ∘ C-deposited GZO thin films.Thus, better crystallinity resulting from a stronger axis orientation and smoother surface morphology could be achieved in the 200 ∘ C-deposited GZO thin films prepared on PI substrates.
Figure 4 shows the cross-section observations of the GZO thin films deposited at different substrate temperatures.Calculating the results in Figure 4, thicknesses of both 100 ∘ Cand 200 ∘ C-deposited GZO thin films were about 260 nm.The cross-section observation of the RT-deposited GZO thin films was not shown here because it had the same thickness and the same cross-section morphology as those of the 100 ∘ Cdeposited GZO thin films.As the cross-session micrographs shown in Figure 4 are compared, there are different results as the substrate temperature is changed.As RT (not shown here) and 100 ∘ C were used as substrate temperatures, the GZO thin films grew like an irregular plate with no specific direction.But depositing at 200 ∘ C, the plate-shaped growths were transformed into the nanobar along the up direction.These results prove that the 200 ∘ C-deposited GZO thin films and the 100 ∘ C-deposited GZO thin films have no the highly oriented parallel to the substrate normal.
Figure 5(a) shows the transmission ratios of the GZO thin films plotted against wavelengths in the region of 300-1400 nm, with substrate temperature as the parameter.As substrate temperature was raised from RT to 200 ∘ C, the transmittance ratios of the GZO thin films were almost unchanged.The optical transmission ratios in the visible light region (400-700 nm) were more than 94% for all GZO thin films, regardless of substrate temperature.For the transmission spectra shown in Figure 5(a), as substrate temperature was raised, the optical band edge shifted to a shorter wavelength was observable and a greater sharpness was noticeable in the curves of the absorption edge, which suggest an increase International Journal of Photoenergy in the   values.Also, the GZO thin films deposited on PI substrates had high transmittance ration of over 89.6% in the near-infrared region (750 nm∼1400 nm).
In the past, determination of the optical band gap (  ) was often necessary to develop the electronic band structure of the thin-film materials for investigating them as a transparent electrode of the thin-film solar cells.However, using extrapolation methods, the   values of thin films can be determined from the absorption edge for direct interband transition, which can be calculated using the relation in the following equation: where  is the optical absorption coefficient,  is the constant for direct transition, ℎ is Planck's constant, and ] is the frequency of the incident photon [14].The increase in the optical band is caused by the increase in carrier concentration because of the decreasing of the lattice defects.The improvement in the electrical properties of the GZO thin films (will be shown in Figure 6) will prove the results.Because the E  values of the GZO thin films are larger than the energy of visible light, the high tansmittance ratio in the visible light region is expected.The results of the carrier mobility, carrier concentration, and resistivity shown Figure 6 indicate that the electrical properties of the GZO thin films were dependent on substrate temperature.When plasma molecules are deposited on a glass substrate, many defects result and inhibit electron movement.As different substrate temperatures are used during the deposition process, two factors are believed to cause an increase in the carrier mobility of the GZO thin films.First, higher substrate temperature provides more energy and thus enhances the motion of plasma molecules, which will improve the crystallization and grain size growth of the GZO thin films; also the defects in the thin films will be decreased.Second, as substrate temperature was raised, the defects in the GZO thin films decrease, and that will cause the decrease in the inhibiting of the barriers electron transportation [15].As Figure 7 shows, both the carrier concentration and carrier mobility of the GZO thin films linearly increased with raising substrate temperature and reached the maximum concentration and carrier mobility at 200 ∘ C. The carrier mobility increased from 8.74 cm 2 /V-s to 11.6 cm 2 /V-s and the carrier concentration increased from 14.2 × 10 20 cm −3 to 22.8 × 10 20 cm −3 , respectively, as substrate temperature was raised from RT to 200 ∘ C. The resistivity of the TCO thin films is proportional to the reciprocal of the product of carrier concentration  and mobility : Both the carrier concentration and the carrier mobility contribute to the conductivity.As substrate temperature was raised from RT to 200 ∘ C, the resistivity decreased from 2.44 × 10   Superstrate p-i-n -Si:H thin-film solar cells were fabricated using a single-chamber plasma-enhanced chemical vapor deposition unit at 200 ∘ C to demonstrate the optoelectrical properties of the GZO thin film.Figure 7 shows the structure of the fabricated -Si amorphous silicon thinfilm solar cells; no antireflective coatings were deposited on the cells.Figure 8 shows the measured current-voltage characteristics of the solar cells under illumination.Table 1 lists the values of open-circuit voltage ( oc ), short-circuit current density ( sc ), fill factor (F.F.), and efficiency () for the devices using the developed GZO thin films as the front transparent conductive thin films.However, the  oc value had no apparent change and the  sc value apparently increased as substrate temperature of the GZO thin films increased from 100 ∘ C to 200 ∘ C. The efficiency of the solar cells increased from 4.15% to 4.20% as substrate temperature of the GZO thin films increased from RT to 100 ∘ C.Moreover, the efficiency was raised to 4.65% as the GZO thin film was deposited at 200 ∘ C. The efficiency of the fabricated solar cells apparently depends on substrate temperature of the GZO thin films.Many reasons will cause the improvement in the efficiency of the -Si:H thin-film solar cells.In this study, the greater efficiency is mainly ascribable to the results in Figures 2, 5, and 6.From the cross-section (Figure 2) of the GZO thin films, the nanobar along the up direction will have the more optical waveguide function than the irregular plate with no specific direction, which may scatter the photons in any direction.As 200 ∘ C-deposited GZO thin films are used as the electrodes, more photons will reach the solar cells' optical absorption layer to generate more electron-hole pairs and improve the efficiency of the solar cells.As the GZO thin films have the higher transmittance ratio (Figure 5), also the more photons will improve the efficiency of the solar cells.The third reason from Figure 6 is that the smaller value of resistivity of the contact electrodes (GZO thin films) can cause the fabricated solar cells having more short-circuit current density; then the efficiency of the fabricated solar cells increases.This is proved by the - curves shown in Figure 8 and Table 1, where the  sc value increases with decreasing in the resistivity of the GZO thin films.

Conclusion
In this study, the GZO thin films were deposited on flexible PI substrates and their properties were well developed.As substrate temperatures increased from RT to 200 ∘ C, the FWHM values for the (002) peak of the GZO thin films decreased from 0.412 to 0.296; the crystallization sizes increased from 20.2 nm to 28.1 nm; the carrier mobility 8.74 cm 2 /V-s to 11.6 cm 2 /V-s; the carrier concentration increased from 14.2 × 10 20 cm −3 to 22.8 × 10 20 cm −3 ; and the resistivity decreased from 2.44 × 10 −3 Ω-cm to 0.65 × 10 −3 Ω-cm, respectively.The Burstein-Moss shift theorem was used to prove that as substrate temperatures increased from RT to 200 ∘ C, the   value shifting from 3.524 eV to 3.599 eV was caused by the increase of carrier concentration increasing from 14.2 × 10 20 cm −3 to 22.8 × 10 20 cm −3 .Finally, the -Si thin-film solar cells were successfully fabricated on the GZO-deposited PI substrates.As substrate temperatures increased from RT to 200 ∘ C, the  sc value increased from 9.11 mA/cm 2 to 10.13 mA/cm 2 and the  value increased from 4.15 to 4.65, respectively.

Figure 1 :
Figure 1: XRD patterns of the GZO thin films as a function of substrate temperature.

FWHMFigure 2 :
Figure 2: FWHM value and crystalline size of the GZO thin films as a function of substrate temperature.

Figure 3 :Figure 4 :
Figure 3: Surface observations of the GZO thin films as a function of substrate temperature.

Figure 5 (
b) plots (ℎ])2 against ℎ] (photo energy) in accordance with(2), and the   values can be found by extrapolating a straight line at (ℎ]) 2 = 0; the calculated   values of the GZO thin films are shown.The linear dependence of (ℎ]) 2 on ℎ] indicates that GZO thin films are direct transition type semiconductors.As the substrate temperature increases from RT to 200 ∘ C, the   values increase from 3.524 eV to 3.595 eV.Many factors will affect the transmission spectra of the GZO thin films.

Figure 6 :Figure 7 :
Figure 6: Carrier mobility, carrier concentration, and resistivity of the GZO thin films as a function of substrate temperature.

Figure 8 :
Figure 8: Current-voltage characteristics of the p-i-n -Si:H thinfilm solar cells under illumination.