CHIN. PHYS. LETT. Vol. 29, No.

11 (2012) 117101

Tunable UV Absorption and Mobility of Yttrium-Doped ZnO using First-Principles Calculations *

BAI Li-Na()1,2 , SUN Hai-Ming()1 , LIAN Jian-She()1** , JIANG Qing()1
1

The Key Lab of Automobile Materials (Ministry of Education), College of Materials Science and Engineering, Jilin University, Changchun 130025 2 The Key Laboratory of Photonic and Electric Bandgap Materials (Ministry of Education), School of Physics and Electronic Engineering, Harbin Normal University, Harbin 150025

(Received 5 July 2012)

The electronic structures and optical properties of Y-doped ZnO are calculated using first-principles calculations. It is found that the replacement of Zn by the rare-earth element Y presents a shallow donor, and the Fermi level moves into the conduction band (CB). The high dispersion and s-type character of CB is expected to result in an increase in conductivity. Moreover, the absorption spectrum of the Y-doped ZnO system exhibits a slight blue shift with an increase of Y concentration, and a higher transparency in visible light is expected. Therefore, the Y-doping in ZnO would enhance the mobility and hence increase the electrical conductivity without sacrificing the optical transparency, which is essential for the improvement of ZnOs behavior and its performance in extension applications.

PACS: 71.15.Mb, 71.20.b, 71.20.Nr

DOI: 10.1088/0256-307X/29/11/117101 (GGA).[12] A plane wave cutoff of 480 eV and a 333 -point mesh are found to give sufficient convergence. The spin-polarized calculation is performed. A supercell containing 108 atoms with 54 zinc atoms and 54 oxygen atoms is used as the simulation model. To investigate the doping of rare-earth atoms, six probable models are designed, as shown in Fig. 1. In order to enable the Zn0.963 Y0.037 O configuration to converge to a stable conformation, four doped models are selected with the symmetry. The model 1 ( = 25) represent various possible symmetries of Zn0.963 Y0.037 O, 1 (12 site), 8 (13 site), 36 (14 site), 156 (15 site) symmetries, respectively. Among them the preferred site of Y in Zn0.963 Y0.037 O configurations is the 1 4 site after geometry optimization. Accordingly, the structural and electronic properties of Zn0.963 Y0.037 O for the 14 site will be discussed in the following. The band gap is estimated after a self-consistent calculation that can generate a high quality charge density with an optimized geometrical structure. For Zn1 Y O alloys, the calculated equilibrium lattice constants of or are a function of Y concentration (0 0.037). As the ionic radius of Y3+ (0.89 ) is larger than that of Zn2+ (0.74 ), the replacement of Zn by Y should cause a lattice expansion, for example, lattice constant increases from 5.274 of ZnO to 5.329 of Zn0.963 Y0.037 O, which is similar to the experimentally reported increase.[13] Additionally, the lattice parameters of / and show a slight decrease based on the theoretical calculation. For the ideal wurtzite structure, the lattice parameters of / and are 1.633 and 0.375, respectively.

Transparent conducting oxides (TCO) are used in photovoltaic devices, sensors, solar cells and smart windows. ZnO is a prototypical n-type TCO with wide band gap and large exciton binding energy.[1] Doped zinc oxide thin films have been extensively investigated in recent years.[25] Additionally, rareearth doped semiconductors have been the focus of numerous investigations because of their unique optical properties and high mobility. Ce-doping in ZnO could blue shift the onset of optical absorption[6] and La-doped ZnO shows high relative photonic efficiencies and high photocatalytic activity for the degradation of MCP.[7] It was experimentally reported that Y-doping in ZnO can induce an evidence increase of UV emission.[8] However, the key requirement for improved zinc oxide thin films is to develop high mobility materials to increase their electrical conductivity without sacrificing their optical transparency. Such an improvement in ZnO material behavior would enhance its performance in relative applications. In this Letter, we investigate the structural, electronic, and optical properties of rare-earth element Y doping in a ZnO lattice using first-principles ultrasoft pseudopotential calculations, in order to find the possible advantages in optical and electric properties as compared to commercial indium-tin-oxide (ITO). Theoretical calculations are performed on the Cambridge serial total energy package (CASTEP) code,[911] which are based on the density functional theory (DFT) using the ultrasoft pseudopotential method. Exchange and correlation effects are described by the generalized gradient approximation

* Supported by the National Basic Research Program of China (No 2010CB631001), the National Natural Science Foundation of China (No 50871046), the Programs of Science and Technology Department of Heilongjiang Province (No QC2011C026), and the Program for Changjiang Scholars and Innovative Research Team in University. ** Corresponding author. Email: lianjs@jlu.edu.cn 2012 Chinese Physical Society and IOP Publishing Ltd

117101-1

CHIN. PHYS. LETT. Vol. 29, No. 11 (2012) 117101

For Zn1 Y O alloys with Y concentration = 0.037, the calculated / ratio (1.605 0.0035) and internal parameter (0.379 0.002) indicate a homogeneous expansion of the hexagonal wurtzite lattice due to the doping of Y, which agrees well with the experimental result.[8,1316] The band structure (along high symmetry lines in the Brillouin zone) and partial density of states (PDOS) for pure ZnO are shown in Fig. 2(a). Our results show a direct band gap value of 0.761 eV for ZnO, this value is typically underestimated by the GGA in comparison with the experimental optical band gap of 3.27 eV.[17] Similarly, the calculated values are much smaller than the previously simulated value of 3.219 eV by the generalized gradient approximation with introducing the on-site Coulomb interaction parameter (GGA+ ).[18] However, we focus on the relative change of the band gap between different undoped and doped systems. Thus, we expect the GGA band gap error is largely cancelled between different doped systems and the variation value in band gap is reasonable. The partial density of states (PDOS) of ZnO shows that the Zn 3 and O 2 states mainly contribute to

the top of the valence band (VB), and the Zn 4 states hybridized with O 2 states form the bottom of the conduction band (CB).
(a) (b)

z y x

Fig. 1. The supercell structures (a) of wurtzite structure ZnO are depicted with possible configurations of Y-doped ZnO by 16 sites in a ball and stick representation (1st site of Y substitute Zn for Zn0.9815 Y0.0185 O, and 1 ( = 2 5) are disubstituted configurations of different symmetry for Zn0.963 Y0.037 O, and the 6th site of the possible interstitial position for ZnY0.0185 O); (b) of ZnY0.0185 O alloy. Red spheres represent O atoms, gray spheres represent Zn atoms, and blue spheres represent Y atoms.

4
Energy (eV)

2 0

ZnO

(a)

4 2 0 -2

Zn0.9815Y0.0185O

(b)

-2 -4 4
G A H K G M L H Zn0.963Y0.037O (c)

-4 G 20 40 60 80 100 4 2 0 -2 -4 20 40 60 80 100
PDOS (1/eV)

H K

M LH

20 40 60 80 100
ZnY0.0185O (d)

Energy (eV)

2 0

-2 -4
G A H K G M L H

G A

H K

L H

20 40 60 80 100
PDOS (1/eV)

Fig. 2. The calculated band structures and partial density of states for a supercell containing 108 atoms of wurtzite structure of (a) ZnO, (b) Zn0.9815 Y0.0185 O, (c) Zn0.963 Y0.037 O, and (d) for a supercell containing 109 atoms of wurtzite structure of ZnY0.0185 O. The band energies are referenced to the top of the valence band. The Fermi levels at 0 eV, 2.034 eV, 1.746 eV, and 1.767 eV, respectively, are indicated by a horizontal dotted line.

The band structure (along high symmetry lines in the Brillouin zone) and PDOS for Y-doped ZnO with Y concentrations from 1.85at% to 3.70at% are presented in Figs. 2(b) and 2(c), respectively. The Zn1 Y O (0 < 0.037) alloys are still direct band gap semiconductors for all stable wurtzite structures, with both the top of the valence band and the bottom of the conduction band are located at the (0,0,0) point. The doping of Y induces an slightly increase

or blue-shift of band gap from 0.761 eV of ZnO to 0.782 eV of Zn0.963 Y0.037 O (if calculated by GGA+ approach,[18] the band gap increase from 3.219 eV to 3.229 eV, which is in agreement with the reported increase in the band gap of Y doped ZnO,[8] and the increase of band gap (3.2193.229 eV) is comparable to the calculated result (0.7610.782 eV) without the + approach). Because the band gap of cubic Y2 O3 is much larger than that of wurtzite ZnO, a small pro-

117101-2

CHIN. PHYS. LETT. Vol. 29, No. 11 (2012) 117101

portion of Y-doping, can evidently increase the band gap of ZnO. Compared with the band structure of ZnO, one can observe that the features of flat topmost VB and the high dispersion CB are conserved. In addition, three variations in the partial density of states can be observed: (1) the Fermi level has risen into the conduction band due to the extra n-type charge carriers because the Y atom has more valence electrons than the zinc atom, which is comparable to the cases of the system of trivalent metal ions doped ZnO,[19,20] (ii) doping of Y induces the splits in the conduction and valence bands due to the breaking of symmetry of the ZnO lattice by Y doping and (iii) the single states of Zn and Y character the very bottom of the conduction band, i.e., the high dispersion of the conduction band and the single states are observed, which could result in high conductivity due to the high mobility of these states compared to the ITO films.[2123] Indeed, a lower electrical resistivity in Y doped ZnO has been experimentally reported.[13] The PDOS of Zn1 Y O alloys shows that the top of VB is predominated by Zn 3 and O 2 states and their strong hybridization. The bottom of the conduction band consists of the hybrid states of Zn 4 and Y 5.

2(

2.0

ZnO Zn0.9815Y0.0185O Zn0.963Y0.037O

Dielectric function

1.5

1.0

The peak at 1.79 eV should mainly be caused by optical transitions between the O 2 state in the highest valence band and the Zn 4 state in the lowest conduction band. The peak at 6.02 eV can be attributed to the optical transition between the Zn 3 and O 2 states, and the weak peak at 9.94 eV is mainly derived from the optical transition between the Zn 3 and O 2 states. The calculated values agree well with other first-principles evaluations.[24] The 2 ( ) values of Zn1 Y O alloys have been affected by Y incorporation. As the Y concentration increases, the optical transition spectrum shifts to the high energy direction, indicating the increasing direct band gap with Y doping. Simultaneously, to reflect on the influence of Y doping induced defects on the visible light absorption, we present the calculated results of absorption spectra of ZnO and Zn1 Y O alloys in the wavelength range from 250 nm to 500 nm with light polarized perpendicular to the axis ( ), as shown in Fig. 4. As the calculated band gap of ZnO is much smaller than the experimental band gap, the scissor operator with a revised value of 2.5 eV is used to fit the absorption edge to the experimental data. It is seen that the absorption edge of Zn1 Y O alloys shifts evidently to the high energy range with increasing Y concentration compared to that of pure ZnO, which is consistent with the previous experimental results.[8] In the visible light range, high optical transparency is observed for Y-doped ZnO. Accordingly, Y-doping in ZnO can increase the electrical conductivity without sacrificing its optical transparency.
50000

)
0.5

Absorption (1/cm )

40000 30000 20000 10000 0 250

ZnO Zn0.9815Y0.0185O Zn0.963Y0.037O ZnY0.0185O

0.0 0

10

12

Frequency (eV)

Fig. 3. The imaginary part of the dielectric function (2 ( )) of ZnO, Zn0.9815 Y0.0185 O, and Zn0.963 Y0.037 O alloys for the lowest energy structure corresponding to the polarization vectors perpendicular to the axis ( ) in a wide energy range (013 eV).

The imaginary part 2 ( ) of the dielectric constant is calculated by CASTEP, which can be regarded as detailing the real transitions between the occupied and unoccupied electronic states, 2 ( ^ , ) 2 2 2 = | | | | ( ). 0
,,

300

Wavelength (nm)

350

400

450

500

Fig. 4. The absorption spectra of ZnO, Zn0.9815 Y0.0185 O, Zn0.963 Y0.037 O, and ZnY0.0185 O alloys in UV and visible light spectra with absorption polarized perpendicular to the axis.

(1)

The real part 1 ( ) of the dielectric function can be obtained from the imaginary part with the Kramers Kroning relations. Then the optical spectra, i.e. the absorption coefficient ( ) can be obtained from 1 ( ) and 2 ( ). The 2 ( ) to the polarization vectors perpendicular to the axis ( ) are shown in Fig. 3.

We also examined the structure of Y in interstitial sites in the ZnO lattice (Y3+ ). Interstitial Y favors the site of the nearest zinc atom and can push it noticeably outward in relaxation, as shown in Fig. 1(b). The band structure and PDOS of Y interstitial doped configurations of ZnY0.0185 O are shown in Fig. 2(d) with the comparative analysis of electronic structure change. The interstitial defects of cation Y3+ lead to the splitting of the conduction band into a second gap, because

117101-3

CHIN. PHYS. LETT. Vol. 29, No. 11 (2012) 117101

Y occupies a deep level located at high energies close to the CBM. The transitions from the occupied part of the highly dispersed band to the unoccupied part can lead to the decrease of optical transparency in visible light. Compared with the PDOS of Zn1 Y O, the VB characters are conserved, but the interstitial Y in ZnO causes the hybridization between states of the metal cation and states of the oxygen anion in the bottom of the conduction band. It is clearly seen that Y defects cause an increase of absorption in the visible light range in Fig. 4, which may be beneficial to the photocatalytic activity if ZnO is used as the photocatalytic material. Thus, the experimentally observed wide visible light emission and absorption may be attributed to the introduction of various crystalline defects due to high concentration doping of Y. In summary, we have modeled the structural and electronic properties of Y-doped ZnO with the DFT method. It has been found that replacement of Zn by Y should generate a shallow donor. The Fermi level is moved into the conduction band due to the Y doping. The high dispersion and s-type character is expected to result in an increased conductivity in Y-doped ZnO. Moreover, a high optical transparency of Y-doped ZnO is obtained in the visible light spectrum. Thus, Y-doped in ZnO would be a material with enhanced mobility and hence improve electrical conductivity without sacrificing optical transparency. This is essential to improve the behavior of the material and its performance in extension applications.

References
[1] zgr Alivov Y I, Liu C, Teke A, Reshchikov M A, Doan S, Avrutin V, Cho S J and Morkoc H 2005 J. Appl. Phys. 98 041301 [2] Xu X G, Yang H L, Wu Y, Zhang D L and Jiang Y 2012

Chin. Phys. B 21 047504 [3] Peng L P, Fang L, Wu W D, Wang X M and Li L 2012 Chin. Phys. B 21 047305 [4] Chen X C, Zhou J P, Wang H Y, Xu P S and Pan G Q 2011 Chin. Phys. B 20 096102 [5] Weng Z Z, Zhang J M, Huang Z G and Lin W X 2011 Chin. Phys. B 20 027103 [6] Yang J H, Gao M, Yang L L, Zhang Y J, Lang J H, Wang D D, Wang Y X, Liu H L and Fan H G 2008 Appl. Surf. Sci. 255 2646 [7] Anandan S, Vinu A, Sheeja K L P, Gokulakrishnan N, Srinivasu P, Mori T, Murugesan V, Sivamurugan V and Ariga K 2007 J. Mol. Catalysis A 266 149 [8] Zheng J H, Song J L, Jiang Q and Lian J S 2012 Appl. Surf. Sci. 258 6735 [9] Segall M D, Lindan P J D, Probert M J, Pickard C J, Hasnip P J, Clark S J and Payne M C 2002 J. Phys.: Condens. Matter 14 2717 [10] Vanderbilt D 1990 Phys. Rev. B 41 7892 [11] Troullier N and Martins J L 1991 Phys. Rev. B 43 1993 [12] Perdew J P, Chevary J A, Vosko S H, Jackson K A, Pederson M R, Singh D J and Fiolhais C 1992 Phys. Rev. B 46 6671 [13] Yu Q J, Fu W Y, Yu C L, Yang H B et al 2007 J. Phys. D: Appl. Phys. 40 5592 [14] Lin C C, Young S L, Kung C Y, Jhang M C, Kao M C, Chen H Z and Shih Y T 2010 J. Supercond. Nov. Magn. 23 1201 [15] Jia T K, Wang W M, Long F, Fu Z Y, Wang H and Zhang Q J 2009 Mater. Sci. Eng. B 162 179 [16] Yang J H, Wang R, Yang L L, Lang J H, Wei M B et al 2011 J. Alloys Compd. 509 3606 [17] Zheng B J, Lian J S, Zhao L and Jiang Q 2011 Appl. Surf. Sci. 257 5657 [18] Bai L N, Zheng B J, Lian J S and Jiang Q 2012 Solid State Sci. 14 698 [19] Palacios P, S nchez K and P Wahnn 2009 Thin Solid Films 517 2448 [20] Jang M S, Ryu M K, Yoon M H, Lee S H, Kim H K, Onodrea A and Kojima S 2009 Curr. Appl. Phys. 9 651 [21] Mryasov O N and Freeman A J 2001 Phys. Rev. B 64 233111 [22] Robertson J 2008 Phys. Status Solidi B 245 1026 [23] Rosen J and Warschkow O 2009 Phys. Rev. B 80 115215 [24] Zhang X D, Guo M L, Li W X and Liu C L 2008 J. Appl. Phys. 103 63721

117101-4