Mater. Res. Soc. Symp. Proc. Vol.

829 2005 Materials Research Society

B2.23.1

Defect structures in undoped and doped ZnO films studied by solid state diffusion Haruki Ryoken,1,2 Isao Sakaguchi,1 Takeshi Ohgaki,1 Naoki Ohashi,1 Yutaka Adachi,1 and Hajime Haneda1 National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan 2 Kyushu University, 6-1 Kasuga-kouen, Kasuga, Fukuoka, 816-8580, Japan ABSTRACT Defect structures in ZnO thin films were studied to clarify the mechanism of charge compensation and crystallinity degradation induced by alloying. Regarding the undoped ZnO films, it was indicated that the degree of non-equilibrium behavior in the films deposited by PLD was much less than in the films prepared by the other two methods, i.e., MBE and sputtering, and, moreover, the solid-state diffusion behavior in the PLD-grown undoped ZnO was close to that of bulk ZnO. The heavily Al-doped films and alloy films with high concentrations of MgO exhibited significant non-equilibrium behavior, even for those prepared by PLD. It was indicated that the high concentration of extrinsic elements, e.g., Al and Mg, introduces non-equilibrium defects into ZnO films and those defects are the cause of the crystallinity degradation and thermal instability of the films. INTRODUCTION Zinc oxide (ZnO) is a candidate material for transparent semiconductor electronics, such as transparent field effect transistors [1,2]. To achieve high-performance transparent devices, the quality of ZnO films and control of defects, particularly in regard to defects for charge compensation, are of great importance. Undoped ZnO usually exhibits n-type conduction, and the electrons are thought to be injected from oxygen vacancies or interstitial zinc. However, theoreticians [3] have recently claimed that such native defects are not the origin of n-type conduction in ZnO. Thus, the defect chemistry of ZnO has likely returned to the starting point, where we have to think again about the origin of its intrinsic n-type conduction as well as its mechanism of charge compensation. There are several experimental techniques for characterizing the structures and properties of defects in solids. For example, electron paramagnetic resonance (EPR) has high sensitivity, and it makes it possible to do structural analyses [4]. However, the applicability of EPR is principally limited to magnetic defects. The Hall effect can only be exploited to analyze defects injecting the major carrier, and dielectric methods, such as evaluating the relationship between applied bias and capacitance at a Schottky junction, are sometimes difficult to employ because of problems with the electrodes stability [5] . Among these techniques, solid-state diffusion is characterized by its sensitivity to compensated defects, particularly compensated deep defects. In fact, the self-diffusion coefficient is proportional to the concentration of responsible defects. In the present study, we investigated both cation and anion diffusion in ZnO thin films prepared by pulsed laser deposition (PLD). We paid attention to two aspects: the process dependence of defect formation, particularly the role of oxidation assist, and the effect of doping or substitution on the defect structures in ZnO. We usually have to dope ZnO with large amounts
1

B2.23.2

of group IIIa elements to obtain a high electrical conductivity and have to add a large amount of MgO to expand the band gap. Thus, we focused on solid-state diffusion in ZnO. EXPERIMENTS ZnO thin film samples were prepared with the PLD method [6] using ceramic oxide targets. For the ablation, the fourth harmonic generation of a Nd:YAG laser (repetition rate of 1 Hz) was irradiated on the ceramic targets. Four kinds of target were employed: undoped ZnO, ZnO doped with 0.1 mol % Al, ZnO mixed with 15 mol% MgO, and ZnO mixed with both 15mol% MgO and 0.1mol% Al. To clarify the effect of oxidation activity on the defect structures, we examined two kinds of oxidation agent: supplying pure oxygen gas and irradiation of oxygen radicals generated by an r.f. plasma source. For both cases, the total pressure in the growth chamber was kept at 2 x 10-3 Pa. We used two kinds of substrate: single crystalline ZnO with c-face and single crystalline sapphire with A-face. The obtained films were characterized by using the Hall effect to obtain the electron concentration, by x-ray diffraction (XRD) to evaluate crystallinity and lattice parameters, transmission electron microscopy to evaluate morphology, and photoluminescence (PL) and optical transmittance to evaluate band-gap energy. The anion diffusion was evaluated by using the so-called gas-solid exchange method[7]. The detailed methodology for evaluating the oxygen diffusion coefficients in ZnO has been described elsewhere [8,9]. The deposited films were heated in pure isotope oxygen gas (18O2) to introduce isotope tracer into the ZnO films. For cation diffusion, we selected cobalt as the tracer, because cobalt oxide is known to form a solid solution with ZnO and its ionic charge is the same as zincs [10]. The cobalt metal films were deposited by vacuum evaporation on the film surface, and the films with a Co coating layer on the surface were heated in oxygen gas ambient to induce diffusion. After these diffusion processes, we measured the depth profile of the elemental and isotope distribution using secondary ion mass spectroscopy (SIMS). We used the primary beam of Cs+ for anion analyses and the O2+ ion beam for cation analyses. The resultant depth profiles were fit to the solution of the diffusion equation to evaluate the diffusion coefficient. RESULTS and DISCUSSION The obtained films were of a single phase with a wurtzite structure, and no trace of secondary phase was found in our XRD analyses. Figure 1 shows the relationship between substrate temperature during deposition and electron concentration of the undoped ZnO films evaluated by the Hall effect at room temperature. The result for the ZnO films grown by molecular beam epitaxy [11] (MBE) is also plotted. The most interesting feature is that the carrier concentrations of PLD-grown films show the completely opposite tendency to the films grown by MBE. For bulk ZnO, an increase in temperature and a decrease in oxygen partial pressure during the heat treatment cause the electron concentration to increase [12]. The behavior of the PLD-grown thin film was similar to that of bulk ZnO. In contrast, the films grown by MBE exhibited a steep decrease in electron concentration with increasing substrate temperature. In our previous study, this behavior was also observed in the films deposited by sputtering [13]. The tendency of films grown by MBE and sputtering is likely due to the non-equilibrium behavior of the system, whereas the films grown by PLD were likely close to the equilibrium state.

B2.23.3

Figure 1 Growth temperature dependence of electron concentration in ZnO films. The open and closed circles are for ZnO films grown by PLD with oxygen radical irradiation and pure O2 gas supply, respectively, and the closed squares indicate ZnO films grown by MBE in ref. 11

Figure 2 Electron concentration in Al(1000 ppm) doped ZnO grown by PLD. The open and closed triangles indicate the films deposited under oxygen radical irradiation and pure O2 gas supply, respectively.

Figure 1 also indicates the role of the oxygen assists on ZnO deposited by PLD. As seen in this figure, the carrier concentration in the PLD-grown film did not depend on the method of oxidation (pure O2 gas or oxygen radicals). This indicates that the PLD-grown films were likely oxidized enough with the pure oxygen gas supply. However, this result is not evidence that the oxygen radical irradiation has nothing to do with the stoichiometry in ZnO. The effect of oxygen radical irradiation will be discussed later, along with the result for Al-doped ZnO films. Figure 2 shows electron concentration, ne, in Al-doped ZnO prepared with or without oxygen radical irradiation. In contrast to the undoped ZnO films, the properties of the Al-doped ZnO were obviously changed by oxygen radical irradiation, and the electron concentration decreased with increasing growth temperature. The growth temperature dependence of electron concentration in Al-doped ZnO was likely similar to that observed in undoped ZnO prepared by MBE. This implies that non-equilibrium defects were formed in the Al-doped film grown by PLD. As for the oxidation agent dependence, the defect reaction in Al-doped ZnO can be expressed as Eq. 1.

1 Al 2O 3 2AlZn +2OO +2e'+ O 2 2 Al 2O 3 2 AlZn +VZn' '+3OO

(O2 gas) (O radicals)

1.a 1.b

It is plausible that electrons introduced by doping with Al were compensated by the formation of zinc vacancy in the film prepared under oxygen radical irradiation. Thus, it is presumable that the films with extrinsic donors are strongly affected by the oxidation activity. However, the oxygen diffusion results for Al-doped ZnO films cannot be understood with the simple model of Eqs. 1. The most notable characteristic is very the high oxygen diffusion

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Figure 3 Oxygen diffusion coefficient of ZnO films. The open and closed triangles indicate the Al-doped films deposited with oxygen radical irradiation and pure O2 gas supply, respectively, and the closed circles indicate undoped ZnO films deposited with pure O2 gas supply. The solid line is cited from ref. 14.

coefficient of the Al-doped ZnO regardless of the oxidation agent, as seen in Fig. 3. This means that the oxygen defect concentration of ZnO was not determined by the oxidation activity of the ambient, and suggests that the oxygen defects detected by the diffusion study do not cause changes in the electron concentration. In fact, the electron concentration of Al-doped ZnO varied with oxidation agent, whereas the oxygen diffusion coefficient was unchanged. Thus, charge compensation in Al-doped ZnO cannot be expressed by using Eq. 1. In contrast to the Al-doped films, the oxygen diffusion coefficient of undoped ZnO was consistent with the results of the Hall measurements. In fact, the oxygen diffusion coefficients in this case were not affected by the oxidation agent, and their absolute values were in good agreement with those reported for bulk ZnO [14]. These results confirmed that the undoped ZnO film grown by PLD is close to the equilibrium state. Table I lists the carrier concentration and lattice parameters of (Zn,Mg)O films prepared by PLD. In general, it is reasonable that the carrier concentration increased after doping with Al and lattice parameters changed after alloying with Mg. Regarding the Al-doped (Zn,Mg)O films, the electron concentration in the film deposited with oxygen radical irradiation decreased like the Al-doped ZnO. As for undoped (Zn,Mg)O alloy, a slight change in electron concentration was caused by changing the oxidation agent, whereas the electron concentration of undoped ZnO was insensitive to the oxidation agent. It seems that the use of oxygen radical irradiation slightly decreased the electron concentration in (Zn,Mg)O .

Table I Lattice parameters (c0) and carrier concentration (n) in undoped and Al-doped (Zn,Mg)O alloy films prepared by PLD Composition* ZnO (Zn0.85Mg0.15)O (Zn0.85Mg0.15)O (Zn0.85Mg0.15)O:Al(1000ppm) (Zn0.85Mg0.15)O:Al(1000ppm) *Composition of target. Oxidation O2 gas O2 gas Oxygen radical O2 gas Oxygen radical Growth temp. / oC 600 600 600 600 600 c0 / nm 0.5212 0.5158 0.5158 0.5164 0.5161 n / cm-3 3.6x1016 5.1x1016 2.7x1015 2.0x1018 1.0x1017

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Figure 4 Oxygen (a) and cobalt (b) diffusion coefficients in ZnO and (Mg,Zn)O films. Closed circles, open squares, and close triangles indicate undoped ZnO, undoped (Zn,Mg)O, and Al-doped (Zn,Mg)O, respectively. All the films were grown with pure O2 gas supply. The broken and solid line for oxygen diffusion (a) was cited from ref. 13 and 14 and the solid line for Co diffusion (b) was cited from ref. 15

From the viewpoint of charge compensation, no defects can be expected after substitution of Mg ions for Zn ions, as in Eq. 2.

MgO MgZn +OO

(2)

However, the diffusion study revealed that both oxygen and cation diffusion in the films were enhanced by about one to two orders of magnitude after alloying with MgO. Since the carrier concentration was nearly unchanged by alloying, the oxygen and cation defects causing the enhanced diffusion in (Zn,Mg)O alloy were nearly perfectly compensated. This means we have to assume a defect equation like Eq. 3
' null = VZn ' +VO

(3)

This defect reaction indicates that a non-equilibrium defect complex was caused by addition of a large amount of MgO. In fact, the solid solution limit of MgO in wurtzite ZnO is reported to be 4% [16], and the Mg concentration in the present sample was nominally 15%. The dependency of the electron concentration in (Zn,Mg)O on the oxidation agent shown in Table I was likely due to the change in the degree of non-equilibrium behavior. Comparing the oxygen diffusion coefficients of (Zn,Mg)O with those of undoped ZnO deposited by sputtering, it was indicated that the concentration of non-equilibrium oxygen defects was much higher in the (Zn,Mg)O alloy prepared by PLD. The diffusion coefficient of Co in undoped ZnO was also larger than that in bulk ZnO. This implies that undoped ZnO contains compensated defect complexes, although it seemed to be close to the equilibrium state from the viewpoint of oxygen diffusion and electron concentration. The large carrier concentration and the large zinc diffusion coefficient of the Al-doped (Zn,Mg)O film can be also explained by Eq. 1. Namely, electrons in Al-doped film were

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partially compensated by the formation of zinc vacancies. However, the behavior of oxygen diffusion in Al-doped (Zn,Mg)O alloy cannot be explained with only that equation. Both the Al-doped ZnO and Al-doped (Zn,Mg)O had large oxygen diffusion coefficients. Therefore, the reason for the large oxygen diffusion coefficient of Al-doped ZnO is likely the same as the one for the large oxygen diffusion coefficient of Al-doped (Zn,Mg)O and undoped (Zn,Mg)O. Thus, ' it is obvious that non-equilibrium defects, e.g., [VZn ' ,VO ] pair, were formed because of the high concentration of Al and Mg exceeding their solid-solution limits. SUMMARY

Defects on PLD grown films were studied from the viewpoint of solid-state diffusion. It was indicated that the undoped ZnO films prepared by PLD in this study were relatively closer to chemical equilibrium than the ZnO films prepared by MBE and sputtering in our previous study. In contrast, Al-doped films and alloy films of (Zn,Mg)O had large amounts non-equilibrium defects. Those non-equilibrium defects were found to be compensated by forming both cationic and anionic defects simultaneously. From these results, we propose firstly that the diffusion coefficient is a useful probe to analyze the defects in solids and secondly that passivation and/or elimination of these non-equilibrium defects should be a key issue for development of optoelectronic applications using ZnO technology.
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