Controlled growth of ZnO nanorod arrays and their PL

properties
Minqiang Wang，Zhuo Xu, Zhiguang Wang, Yaohui Xue, Jiefei Zhu

Electronic Materials Research Laboratory, Key Laboratory of Education Ministry,

Xi’an Jiaotong University, Xi’an 710049, China

Abstract

Using chemical bath deposition(CBD) method we fabricated hexagonally, vertical aligned ZnO nanorod

arrays on glass. XRD pattern of the sample shows only (002) diffraction peaks were observed, indicating excellent

(001) orientation and well vertical alignment of the ZnO arrays. SEM results of samples fabricated under different

condition show that we can control the diameter of the nanorods by using growing solution with different

concentration. To attain the desired length, we ushered a novel multi-growth method, with which we obtained ZnO

nanorod arrays thicker than 10μm. PL spectra of the sample shows strong UV emission.

Key words: ZnO nanorod array, CBD, diameter control, length control, PL

1.Introduction

Among these various band gap materials, ZnO has received much attention over the past few years, mainly for

two reasons: firstly, ZnO can be easily grown in many different nanoscale forms, including highly ordered

nanowire arrays[1], tower-like structures, nanorods[2], nanobelts[3], nanosprings, nanocombs, and nanoneedles[4],

etc. on different substrates with different methods; secondly, ZnO has a wide range of properties that depend on

doping, including wide-bandgap semiconductivity, a range of conductivity(including n-type, p-type conductivity),

piezoelectricity, chemical-sensing effects and so on[5].

In this report, we systematically investigated the growth and control of size and aspect ratio of ZnO

Micro (MEMS) and Nanotechnologies for Space, Defense, and Security II

edited by Thomas George, Zhongyang Cheng, Proc. of SPIE Vol. 6959, 695905, (2008)
0277-786X/08/$18 · doi: 10.1117/12.781919

Proc. of SPIE Vol. 6959 695905-1

nanorod(NR) arrays with solution based low temperature and low cost CBD methods and studied their

photoluminescence (PL) properties.

2. Experimental procedure

2.1 Preparation of seed-coated substrates

A layer of ZnO thin film was deposited on glass substrates. Firstly, ZnO coating precursor solution was

prepared, in which equal molar Zn(CH3COO)2 · 2H2O(0.75mol/L) and monoethanolamine were solved in

2-methoxyethanol with stirring at 60 ℃ for 0.5h to yield a homogeneous solution. Subsequently, the precursor

solution was dropped on the selected clean substrate, spun at 500r/min for 9s then spun at 4000r/min for 20s. Then

the substrate was dried in air and heated to 500℃ at 2℃/min and held at 500℃ for 1h to obtain a dense and

transparent ZnO seed layer on the substrate.

2.2 Multi-growth of ZnO NR arrays

Using the methods reported in the literature [6], growing precursor solution for chemical bath deposition was

prepared by dissolving same molar zinc nitrate hydrate (Zn(NO3)2) and hexamethylenetetramine ((CH2)6N4) in

deionized water to form 0.05mol/L and 0.1mol/L(zinc and amine concentration) solutions. Then, the substrates

were suspended in the precursor solutions at 90℃ for 5h and then change the growing solution and repeat the

above mentioned procedure for several times to prolong the length of the ZnO NRs. Subsequently, the resultant

films were washed with deionized water and heated at 400℃ for 1h to remove any residual materials.

2.3 Characterization

The morphologies of as-synthesized samples were characterized using scanning electron microscopy (SEM, JSM

6700F). X-ray diffraction (XRD) was recorded by Rigaku D/max-3C(30kV, 20mA) with copper targets(λ

=0.154065nm). Thickness of the ZnO NRs was measured by JASCO V-570 UV–Vis spectrometer at room

temperature and PL property was measured using Nd:YAG laser（355nm） as the excitation source.

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3. Results and discussion

a b

Fig.1 SEM of samples grown in solutions with different concentration（a）0.05mol/L,(b) 0.1mol/L。

The ZnO seed layer on glass substrate consists of densely packed assemblies of nanocrystalline grains which serve

to nucleate the subsequent growth of c-axis oriented ZnO NR arrays. Fig.1 is the plan-view and the

cross-section (Fig.1a, inset) SEM images of the samples grown in 0.05mol/L and 0.1mol/L precursor solutions for

5h. As expected, fairly well-aligned flat-top hexagonal ZnO NRs were grown vertically onto the surface of the

ZnO-coated glass and highly c-axis orientation of these ZnO NRs was confirmed by the following XRD analysis

(Fig.2). It can be found that with increasing the precursor solution from 0.05mol/L to 0.1mol/L, the mean diameter

of the ZnO NR arrays increased from about 100 nm to 400 nm. The possible process of nanocrystal growth

reaction in the precursor solution is supposed as follows:

(CH2)6N4+6H2O ↔ 6HCHO+4NH3 (1)

NH3+H2O ↔ NH4++OH- (2)

2OH-+Zn 2+ → ZnO(s)+H2O (3)

The reason for c-axis orientation growth is that (0001) basal plane of hexagonal rod is polar and has

relatively high surface energy. As a result the growth rates(R) of the ZnO crystal planes is
−
R (0001) > R(1010) > R(1000) [7].

XRD measurements were used to study the oriented growth property of as-prepared samples, as shown in Fig.2.

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Strong and single (002) diffraction peaks were observed in the XRD pattern of samples grown in solution with

different concentration, and no other peaks were observed which indicated highly oriented c-axis growth.

(002)

c
Intensity(a.u.)

a
10 20 30 40 50 60 70
2θ (degree)

Fig.2 XRD analysis of samples grown in different growing solutions (a)0.025 mol/L,(b)0.05mol/L, (c)0.1mol/L.

High aspect ratio is very important in some application fields of ZnO NR arrays. Building on the

understanding that both diameter and length of ZnO NRs will decide the aspect ratio of ZnO NR arrays, we used

multi-growth method to increase the length of ZnO NRs. Fig.3 is the reflection measurement curves and with its

surge structure we can calculate the thickness of ZnO NR arrays.

λ1 × λ2
1 p 1 p
d= • = • • •104 [um]
2 n − sin φ λ1 − λ2 1000 2 n − sin φ r1 − r2
2 2 2 2

λ1，λ2 are the wavelength of peaks or troughs（nm）, n is the refractive index of ZnO material. φ is the

incidence angle, r1, r2 are wave numbers（cm-1）, p is the number of interference waves betweenλ1andλ2.

And the calculated thicknesses of samples grown for 1, 4 and 7 times are 2.743, 8.183 and 10.747μm respectively.

Proc. of SPIE Vol. 6959 695905-4

Matt Law et al [8] used polyethylenimine (PEI) to increase the aspect ratio of ZnO NRs and our experiment

proves that without the use of expensive surfactant we can also prolong the length of ZnO NRs with simple

multi-growth methods.

b
%R

0 200 400 600 800 1000 1200 1400 1600 1800 2000
Wavelength (nm)

Fig.3 Reflection measurement of samples growing for: a 1, b 4, and c 7 times.

Photoluminescence spectra of ZnO NR arrays with different diameters are shown in Fig.4. Strong emission at

~390nm was observed for all ZnO NRs with different diameters, corresponding to the near band-edge

emission(bandgap 3.37eV at room temperature). No green emission was observed which is commonly referred to

as deep-level or trap-state emission[9] This result indicates relatively good crystallization and offers great

application potential in the fabrication of UV LED or laser fields.

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 Intensity(a.u.)

360 380 400 420 440 460 480 500

Wavelength(nm)

Fig.4 PL spectra of ZnO NRs grown in a,0.05mol/L and b,0.1mol/L precursor solutions.

4.Conclusion

In sum, ZnO NR arrays with different diameters have been grown on glass substrates with a low cost

solution-based CBD method. We also managed to prolong the length of the arrays to increase their surface to

volume ratio which will enhance their potential applications. Finally, PL spectra of the samples show strong UV

emission and no green emission is observed.

Acknowledgements

This work was supported by the Ministry of Sciences and Technology of china through 973-project under

grant 2002CB613305, the Science and Technology Developing Project of Shaanxi Province (2006K06-G15) and

Xi’an Science and Technology Developing Project (GG5040).

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