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Conductivity changes in ZnO

Zinc Oxide nanoparticles are large band gap semiconductors3.37eVwith large surface-tovolume ratios, rendering surface-interaction effects very significant.
Conductivity of Metal-Oxides
Oxygen vacancies on metal-oxide surfaces are electrically and chemically active. These vacancies
function as n-type donors and often significantly increase the conductivity of the oxide. Upon
adsorption of charge accepting molecules at the vacancy sites, such as NO2 and O2, electrons are
effectively depleted from the conduction band, leading to a reduced conductivity of the n-type
oxide. On the other hand, molecules, such as CO and H2, would react with surface adsorbed
oxygen and consequently remove it, leading to an increases of conductivity. [1]
Conductivity in ZnO
ZnO can be grown with a variety of techniques, which mostly yield ZnO that is highly n-type, with
electrons in the conduction band as the charge carriers. This high level of n-type conductivity is
useful for some applications, but in general it would be desirable to have better control over the
conductivity. In particular, the ability to reduce the n-type background and to achieve p-type
doping would open up many possibilities for applications such as LEDs and lasers (in the UV
The source of this n-type conductivity is still being researched and, because of its prevalence, has
long-since been attributed to native defects. [2]
In particular, zinc interstitials and oxygen vacancies are expected to act as donors, and have
frequently been treated as the source of higher carrier concentrations. A first-principles
investigation revealed, however, that none of the native defects exhibits characteristics
consistent with a high-concentration shallow donor. [4,5]

Transition Levels
Defects and impurities often introduce levels in the band gap, which can be obtained based on
calculated total energies. The transition level (q+1/q) is defined as the Fermi-level positions for
which the formation energies of charge states q+1 and q are equal. The DFT produces band gaps
significantly smaller than experiment. So, when performing calculations, the band-gap error
introduces uncertainty in the position of transition levels. Comparison with the non-linear core
correction (nlcc) approach, with those including full treatment of the 3d states, address this
uncertainty. [3]

Zinc Interstitials and Oxygen Vacancies

Zinc interstitials have high formation energies and low diffusion barriers and unlikely to
incorporate in a stable fashion. Oxygen vacancies, which has the lowest formation energy, has
frequently been thought as the source of n-type conductivity.
We find that oxygen is a negative-U center, implying that (2+/+) lies above (+/0) in the band
gap. As the Fermi level moves upward, the charge-state transition is thus directly from 2+ to the
0 charge state, at an energy about 2.7 eV above the valence band. Thus, the oxygen vacancy
cannot provide electrons to the conduction band in a stable manner. So, to recap, the main
problem is that oxygen vacancies are deep rather than shallow donors. The first principle
calculations from which these results were drawn are based on density functional theory (DFT)
within the local density approximation (LDA) and the pseudo-potential-plane-wave method and
studied Wurtzite (WZ) and zinc-blende (ZB) phases. The computed band gap was found to be
1.81 eV for ZB and 1.91 eV for WZ, smaller than the experimental bang gap of 3.34 eV. [6,7,8]
Clearly, native defects have to be ruled out as a cause for the n-type conductivity and extrinsic
sources now become the next likely factorimpurities that are unintentionally incorporated.
Hydrogen as an Extrinsic Impurity
Hydrogen becomes the candidate extrinsic source: it is ubiquitous and very difficult to remove
from the synthesis environment.
Hydrogen behavior in ZnO is highly unusual. In all other semiconductors studied to date, hydrogen
has been found, both theoretically and experimentally, to act as an amphoteric impurity. So, in ptype materials, hydrogen incorporates as H+, and in n-type material as H-, thus, always
counteracting the conductivity of the material. This behavior prohibits hydrogen from acting as a
dopant (or source of conductivity). However, in ZnO, hydrogen occurs exclusively in the positive
charge state, it always acts as a donor. [3]

Hydrogen Bonding, Doping and Formation Energies

Hydrogen forms a strong bong with oxygen, providing great reason for its incorporation in the
ZnO crystal. The resulting O-H bonding unit can be regarded as a new type of dopant atom
the addition of the proton turning the oxygen into an element behaving more like fluorine, as
will be further discussed shortly. [2]
To more thoroughly analyze the interaction of hydrogen and ZnO, we turn to formation energies,
derived from first-principle calculations. In equilibrium, the formation energy Ef determines the
concentration, c, of the impurity (Hydrogen) in the semiconductor. So
c = Nsitesexp(-Ef/kT)
Where Nsites refer to the number of sites in the lattice where the impurity can be incorporated, k
is the Boltzmann constant, and T is the temperature (?). Thus, the formation energy of a hydrogen
interstitial in charge state q is defined as
Ef(Hq) = Etot(Hq) Etot(bulk) + EZPE H + qEF.
Where Etot(Hq) is the total energy derived from a supercell calculation for the interstitial H
impurity, and Etot(bulk) is the total energy for a supercell containing only bulk ZnO. EZPE is the zeropoint energy (ZPE), obtained from the vibrational mode frequencies of the impurity. H is the
hydrogen chemical potential, the energy of the reservoir with which H atoms are exchanged.
Calculations were then tabulated for the formation energies and lattice relaxations for an
interstitial hydrogen impurity in ZnO (WZ), for various lattice locations and charge states. [3]
Briefly, the following figure describes a ZnO WZ structure, and the sites on which interstitial
hydrogen can incorporate. BC indicates bond-center sites, and AB indicates anti-bonding sites.
After the incorporation of hydrogen
interstitials, lattice relaxations are significant,
especially for the bond-center (BC)
configuration, where the Zn atom moves
outward over a distance equal to 40% of the
bond length. (0.8 A) [2]
Sites for which the total energy surface for
interstitial hydrogen exhibits a local minimum
are depicted. For all charge states (H+, H0,H,H2), the BC configuration is most stable, with
the ABo position slightly higher in energy.
Notably, H0 and H- are never stable. By checking
the nature of the energy level in the band
structure that is occupied with one or two
electrons we can verify this. When H is at the
ABZN site, the corresponding state is indeed
localized near the H atom; but at this site, the energies of H0 and H- are always higher than that
of H+, for all Fermi-level positions. When H is at the BC or Abo sites, the occupied state turns out

to be an extended state. Correct calculations for H0 and H- should therefore not place electrons
in this state and the actual hydrogen-induced energy level occurs higher in the band structure.
When these considerations are taken into account, Abo and BC are found to be even higher in
energy than ABZN for both H0 and H-.
We then note that H+ prefers sites where it can strongly bind to an oxygen atom, forming an O-H
bond with a length of 0.99-1.01 A. Large lattice relaxations occur around the hydrogen interstitial;
in particular, for the BC configuration the Zn atom moves outward over a distance equal to 40%
of the bond length, to a position slightly beyond the plane of its nearest neighbors.
Simultaneously, the O atom moves outward by 11% of the bond length. For the AB configuration,
the relaxation of both Zn and O amount to about 20% of the bond length. [2]
The O-H bond formed, points along the direction of the original O-Zn bond. This indicates, as
mentioned before, that the strength of the O-H bond is the main driving force for stabilization of
this configuration, while details of the orientation and relaxations have only minor effects on the
The figure below illustrates the results more clearly. Showing formation energies of interstitial
hydrogen in ZnO, as a function of Fermi level, obtained from DFT-LDA calculations and referenced
to the energy of a free H2 molecule. For each charge state, only the lowest energy configuration
is shown. Zero-point energies are included. The zero of the Fermi energy is chosen at the top of
the valence band, and both the theoretical (1.91 eV) and experimental band gaps (3.4 eV) are
indicated. The energies for H0 and Hare shown in dashed lines to indicate
they are underestimated in the LDA
calculation; after correction, H+ is the
lowest-energy state throughout the
experimental band gap.

Such large relaxations have also been

verified through calculations for
fluorine in ZnO, a shallow donor,
which agrees with experiment. For
F+, we find a large displacement of
one of the neighboring Zn atoms
away from the F atom, by 25% of the
bond length; the F atom itself moves
outward by 12% of the bond length.
The bond between the F atom and
its Zn neighbors is thus effectively
broken. Such large relaxations are
usually thought of as giving rise to
deep (localized) states, but here we
find that F still behaves as a shallow
donor. [3]

Lowest Energy State

H+ is shown to be the lowest energy state over the entire range of Fermi-level positions within
the theoretical LDA band gap. But does this remain true throughout the experimental band gap?
Inspection of band structures and wave functions indicate that hydrogen does not induce any
defect level in the band gap. Rather, the lowest conduction bands acquire a certain degree of
hydrogen character, indicative of a hydrogen-induced resonance above the conduction-band
minimum. Electrons placed in this resonance, of course, relax to the conduction-band minimum,
where they can be bound to the donor in a hydrogenic state.
Analyses indicated that all relevant conduction-band states shift upwards when the LDA band gap
is adjusted.
The formation energies of H0 and H- (shown in the figure) were obtained by placing electrons in
the next available unoccupied statewhich turns out to be the conduction-band minimum. When
corrections to the LDA band gap are applied, these formation energies will therefore increase
relative to that of H+. The Fermi-level position where the formation energies of H+ and H0 are equal
(i.e. the donor level) will remain at or above the conduction-band minimum, and similar for the
acceptor level.
So in conclusion, H+ is the stable charge state for all Fermi-level positions, which, as mentioned
before, is unlike the situation in other semiconductors. Instead of assuming an amphoteric
behavior, H accommodates an increase in conductivity in ZnO. Only H+ is stable, hence hydrogen
exclusively acts as a donor.
Muonium in ZnO
Recent results by S.F.J. Cox, et al. and K Shimomura, et al. have been obtained with the muon spin
rotation technique. Muonium is a pseudo-isotope of hydrogen and is expected to exhibit all
characteristics of a shallow donor, confirming the model that H acts as a shallow donor. [9,10]
Theoretical evidence has now been presented for the behavior of hydrogen as a shallow donor in
ZnO, where hydrogen, unlike in other semiconductors, occurs exclusively as a donor. It also gives
rises to unusually large lattice relaxations. Controlling the background n-type conductivity of ZnO
thus requires careful control of hydrogen exposure during and after growth, which is the first step
toward achieving p-type doping.

[1] Fan, Z., & Lu, J. G. (January 01, 2005). Zinc oxide nanostructures: synthesis and properties.
Journal of Nanoscience and Nanotechnology, 5, 10, 1561-73.
[2] Van, . W. C. G. (July 01, 2000). Hydrogen as a Cause of Doping in Zinc Oxide. Physical Review
Letters, 85, 5, 1012-1015.
[3] Van, . W. C. G. (January 01, 2001). Defect analysis and engineering in ZnO. Physica B: Physics
of Condensed Matter, 308, 899-903.
[4] A.F. Kohan, G. Ceder, D. Morgan, C.G. Van de Walle, Phys. Rev. B 61 (2000) 15019.
[5] C.G. Van de Walle, unpublished
[6] P. Hohenberg, W. Kohn, Phys. Rev. 136 (1964) B864.
[7] W. Kohn, L.J. Sham, Phys. Rev. 140 (1965) A1133.
[8] M. Bockstedte, et al., Comput. Phys. Commun. 107 (1997) 187.
[9] S.F.J. Cox, et al., Phys. Rev. Lett. 86 (2001) 2601.
[10] K. Shimomura, et al., in these Proceedings (ICDS-21), Physica B 308310 (2001).