phys. stat. sol. (b) 241, No. 3, 607 611 (2004) / DOI 10.1002/pssb.

200304187

Identification of bound exciton complexes in ZnO

M. Strassburg*, 1, A. Rodina1, M. Dworzak1, U. Haboeck1, I.L. Krestnikov1, A. Hoffmann1,
O. Gelhausen1, 2, M.R. Phillips2, H.R. Alves3, A. Zeuner3, D.M. Hofmann3, and B.K. Meyer3
1

Institute of Solid State Physics, Technical University of Berlin, Hardenbergstrasse 36, 10623 Berlin,
Germany
2
Microstructural Analysis Unit, University of Technology, Sydney, Broadway 2007, Australia
3
I. Physics Institute, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 16, 35392 Giessen, Germany
Received 22 September 2003, revised 26 September 2003, accepted 20 November 2003
Published online 12 February 2004
PACS 71.35.Cc, 71.35.Ji, 71.55.Gs, 71.70.Ej, 78.20.Ls, 78.55.Et
An identification of shallow bound exciton centers in ZnO is presented based on magneto-optical measurements and diffusion experiments. The thermalization behavior of the Zeeman split components confirms that the I4, I6, I8 and I9 exciton lines stem from donor bound exciton complexes. The results are supported by theoretical analysis of shallow bound exciton complexes revealing the 7 symmetry of the upper
valence band. The presence of two-electron satellites related to the respective transitions is further evidence for the donor bound complexes and enabled the determination of donor binding energies. Hydrogen, aluminum, gallium and indium were identified to origin the I4, I6, I8 and I9 lines by doping, diffusion
and annealing experiments combined with photoluminescence and secondary ion mass spectrometry.
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction Due to superior ZnO properties (e.g., a high exciton binding energy combined with a
low lasing threshold density, and a good radiation resistance), it was drawn back into the focus of investigations in the recent years. In order to use ZnO for opto-electronic applications a sufficient high doping
level of some 1018 cm3 needs to be achieved, which can be facilitated by shallow dopants. A comprehensive study of their properties is enabled by the investigation of bound excitons. The near band gap
emission and absorption spectrum of ZnO features a large variety of lines numbered from I0 to I11 [1, 2].
They stem from excitons bound to chemically and structurally different impurity centers. There is still a
controversial discussion about the nature of these shallow bound excitons (BX) in ZnO for several decades [e.g., 15]. In some publications it is claimed that I1 to I5 stem from donor-bound exciton (D0X)
complexes, and the lines I6 to I11 from acceptor-bound excitons (A0X).
In the present work, we report on experimental studies of the magneto-optical properties of shallow
bound excitons in ZnO and doping experiments. First, it will be shown that the emission lines are related
to neutral bound complexes. Thermalization behavior in a magnetic field and the presence of twoelectron satellites (TES) to each transmission line confirm that the investigated lines stem from (D0X).
The identification of their chemical nature is derived from doping, diffusion and annealing experiments.
2 Experimental Both bulk ZnO samples and ZnO epilayers were investigated. The nominally undoped bulk samples stem from Eagle Picher (O-face) whereas the epilayers were grown by chemical
vapor deposition. Furthermore, diffusion experiments with Na, Li, Al, Ga, In and N were performed.
Magneto-optical properties of excitons were examined by polarization-dependent photoluminescence
(PL) and transmission at low temperatures excited by a HeCd laser and by a 450 W XBO lamp, respec*

Corresponding author: e-mail: mstrassburg@gsu.edu, Phone: +1 404 651 2207, Fax: +1 404 651 1427
Present address: Department of Physics and Astronomy, Georgia State University, 29 Peachtree Center Ave, GA-30303
Atlanta, USA
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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tively. The spectral resolution of the detection system was better than 0.15 meV. The measurements were
performed in Faraday (B || c || k) and in Voigt configuration (B c || k) as well as for different angles
between the magnetic field and the c axis of the crystal.
3 Results and discussion At low temperatures, the PL of the samples is dominated by BX emission
lines. Due to their transition energies they were identified with known emission lines numbered I4 to I10.
Furthermore, in the N-doped samples the I2 line was observed. This line is assigned to a charged donor
bound exciton (D+X) revealing the incorporation of acceptors. According to its angular dependent magneto-optical investigations it was shown that the upper valence band of ZnO possesses 7 symmetry [68].
Eexc.= 3.81 eV
T = 4.2 K

PL Intensity (arb. u.)

Bc

3.3580

0T

I9

3.3578

2T

3.3574

6T

Energy [eV]

5T

3.3572

ZnO as grown
3.356

3.357

Energy (eV)

B c, E c
spectral resolution

3.3570
3.3568

I9

3.3566
3.3564
3.3562

(a)

ZnO:N,In

PL ( ) ZnO:N
PL ( ) ZnO:N
Tr ZnO:N
+
PL ( ) ZnO
PL ( ) ZnO

3.3576

3T
4T

B || c || k, E c

3.3560

(b) B = 5 T

T=4K
0

B [Tesla]

(c)

5 0 20 40 60 80

[]

(d)
4

B [Tesla]

Fig. 1 Magnetic field dependence of ZnO (as grown and nitrogen doped) at low temperatures. (a) PL
emission of the I9 for different magnetic fields in Voigt configuration. The background is caused by the
emission of I4 line dominating that sample. The peak position of I9 obtained by transmission and PL is
shown as a function of the magnetic field parallel (b) and perpendicular (d) to the c-axes of the crystal.
The angular dependence at B = 5 T is given in (c).

3.1 Zeeman behavior of bound exciton lines Magneto-optical investigation facilitates the distinction between excitons bound to charged and neutral centers. In Fig. 1 the Zeeman splitting is shown
exemplarily for the I9 line in parallel and perpendicular field and for arbitrary angles between the B field
and the c axis of the crystal. A typical PL dependence is shown in Fig. 1a. In a magnetic field the line
splits into two Zeeman components whereby the energetic distance increases with a stronger magnetic
field. The intensities of both Zeeman split components are nearly the same. The peak positions of the
split components given as a function of the magnetic field in Fig. 1 (b) and (d) were derived by transmission and PL investigations of several samples. The analysis of the angular dependence (Fig. 1 (b)) shows
that an excellent agreement between experimental data and theoretical modeling is achieved if we assume that the hole g factor is smaller than the electron g factor: |gh| < ge [7, 8]. The values of the electron
and hole effective g factors used for the fitting (solid curves) are ge = 1.86, gh = 1.27 and g||h = 0.06 for
the I9. We note that according to the experimental uncertainty the Zeeman behavior of all BX lines from
I4 to I10 is fitted by the same set of parameters confirming both the 7 symmetry of the upper valence
band and that the lines stem from neutral impurity complexes. Nevertheless, the analysis of the thermalization behavior is necessary to distinguish (A0X) and (D0X). The thermalization is revealed, first by the
evolution of the intensity ratio of the Zeeman split components with increasing magnetic field (Fig. 1a),
and by temperature dependent PL (not shown) and transmission measurements (Fig. 2a). Here, we recall
that in the case of (D0X) complexes, the Zeeman splitting of the excited state (D0X) is determined by the
anisotropic hole effective gh factor, while the splitting of the ground state (D0) is given by ge. In the case
of an (A0X) complex the splitting of the excited state (A0X) is determined by ge, while the ground state
(A0) splits according to gh. Since gh of the 7 hole is small, a distinct assignment of the observed transi 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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609

tions either to an (A0X) or to a (D0X) complex in ZnO can be facilitated by thermalization properties in
B c. In transmission, the intensity ratio of the low-energy and the high-energy Zeeman split components decreases with increasing magnetic fields (due to the respective increase of the Zeeman splitting of
the initial D0 state) and increases with increasing temperatures. Therefore, we attribute the I9 line to a
(D0X) complex in excellent agreement with magneto-absorption data of [3].
Bc
B = 2T

ZnO:N,In

TES(I10) TES(I9)

Log PL Intensity (arb. u.)

Transmission (arb. u.)

T = 2.3 K

I9
T = 4.2 K

T = 10 K

T = 35 K

(a)

TES(I5-8)
TES(I4)

I10

I9 I8 I5/6 I4

I2

ZnO

T=4K

x50

(b)

ZnO:Na
T=4K

x500

(c)

3.30 3.31 3.32 3.33

3.355 3.356 3.357 3.358 3.359 3.360

Energy (eV)

3.355 3.360 3.365

Energy (eV)

Fig. 2 Transmission spectra recorded for the I9 line of a ZnO:N sample at B = 2 T as a function of the
temperature (a). Increase of low energy peak confirms the (D0X). Further evidence is given by the presence of two-electron-satellites (TES) (b) and (c). After an annealing procedure above 600 C the I4 line
and the respective TES are vanished (c).
ZnO as grown

Eexc.= 3.81 eV
T=4K

PL Intensity (arb. u.)

I4

10

ZnO:In

SIMS,
(pulses/s)
5

ZnO:Al

10

I6

Zn
In

10

ZnO:Ga

I8

(a)
3.356

3.358

3.360

3.362

Energy (eV)

3.364

10

In cal

(b)

50

100

150

Depth (nm)

Fig. 3 (a) Low temperature PL spectra of undoped, Al and Ga-doped ZnO. I6 and I8 line upon Al and
Ga doping, respectively, dominate the near bandgap emission. (b) SIMS depth profile of indium (115In
ions) in ZnO after doping of the crystals. The dashed line is the calculated diffusion profile according to
Ficks second law [6]. The O and Zn intensities are representative for all samples.

3.2 Identification of donor bound exciton complexes The I4 is known to stem from an exciton bound
to a shallow donor [4, 6, 8, 9]. A strong evidence of the (D0X) complex origin of the I4 line is given by
the observation of TES transitions. Due to the 2s2p splitting, often a doublet of the TES is observed.
The binding energy of the donor is determined to be about 46.1 meV (see also [4, 6, 8, 9] and references
therein). Annealing annihilates this shallow donor. Our zero-field PL measurements for as-grown and
doped ZnO, whose preparation conditions included an annealing process, confirmed this correlation
(Fig. 2b). After annealing above 600 C, neither the I4 line nor the respective TES transition can be ob 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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M. Strassburg et al.: Identification of bound exciton complexes in ZnO

served (Fig. 2c). According to temperature-dependent Hall effect measurements [9] and the magnetic
resonance experiments [10] this particular donor was attributed to Hydrogen. To reveal the origin of the
I6 line a vapor-phase grown nominally undoped sample (Semi-Element Inc.) was investigated. Only one
(D0X) line was observed in its PL (Fig. 3a) exactly at that position where Schilling et al. [11] found an
increase in the I6 recombination upon Al-implantation. We have, therefore, undertaken secondary ion
mass spectrometry (SIMS) in order to provide more information on the impurity content. We found that
Al is the dominant impurity with more than one order of magnitude higher in concentration than other
group-III elements (Ga, In). Group-VII elements (F, Cl, Br) could not be detected. Obviously, Al seems
to be an omnipresent impurity in vapor-phase grown ZnO as already outlined by Gonzales et al. [12]. I8
and I9 were the lines most strongly debated concerning their donor bound origin since in [2] they were
attributed to (A0X). However, for both lines we observed TES (see also Table 1). Furthermore, in Gadoped epitaxial films, the prominent excitonic recombination was I8 (see Fig. 3a). 0.5 meV towards
lower energies compared with a bulk crystal shifts its peak position. Hall-effect measurements revealed a
free carrier concentration (n-type) of 2x1018 cm3 at RT. This is slightly below the Mott transition. We
thus can expect that the observed slight redshift is effected by electronelectron interactions (screening).
In agreement with our findings Ko et al. [13] showed that the exciton bound to neutral Ga-donor recombination occurs at 3.359 eV. I8 is always dominating in our epitaxial films. Additionally, SIMS experiments showed a severe interdiffusion of Ga from the GaN-substrate into the ZnO epitaxial film. Our
assignment of the I9 line to a (D0X) complex is based on the thermalization properties and the observation of TES in nominally undoped and in ZnO:Na and ZnO:Li crystals [4, 6, 15]. Especially Na is believed to cause the I9 line. Therefore, we performed diffusion experiments with Na, Li and In (for a more
detailed description of the diffusion procedure see [6]) on ZnO substrates, which showed no I9 and I10
line. Above diffusion temperatures of 800 C we observed the appearance of the I9 line in In-doped samples. Due to the typically diffusion profile (Fig. 3b) SIMS experiments unambiguous confirmed that In
was introduced. According to [6, 12] we conclude that In was unintentionally incorporated into the
ZnO:N sample (described above) upon implantation and annealing at 900 C.
Table 1 Spectral positions and chemical origin of shallow donor bound exciton lines, and donor binding
energies in ZnO (obtained in this paper). Additionally, detection methods and further references are given.

line
I4

spectral posi- donor

tion (eV)
3.3628
Hydrogen

donor binding
energy (meV)
46.1

I5/6

3.3607

Aluminum

52.0/53.0

I8

3.3598

Gallium

54.6

I9

3.3567

Indium

63.2

methods

references

Magneto-PL, PL, Hall,

ENDOR, IR absorption
Magneto-PL, PL, SIMS,
ODMR
Magneto-PL, PL, SIMS,
Hall, ESR
Magneto-PL, PL, SIMS,
ODMR

46, 810,
14, 15
6, 11, 12
6, 13
4, 6, 12, 15

4 Conclusion The unambiguous identification of the chemical nature of the I4, I6, I8 and I9 exciton
lines in ZnO is presented based on experimental and theoretical confirmation of the 7 symmetry of the
upper valence band, magneto-optical PL and transmission, and doping and diffusion experiments.
Acknowledgements M.S. gratefully acknowledges the fellowship of the Alexander von Humboldt-foundation.

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2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim