PREPARATION OF ZnO NANOWIRES BY ELECTROCHEMICAL DEPOSITIONPREPARATION OF ZnO NANOWIRES BY ELECTROCHEMICAL DEPOSITION

Samples A B C D

Conditions Flowing air

Flowing air and lower H2O2

concentration

Lower H2O2 concentration;

Magnetic stirrer

Higher H2O2 concentration; Magnetic stirrer

Thickness 2.0 µm 2.5 µm 1.5 µm 2.0 µm

Central Laboratory of Solar Energy and New Energy Sources

Bulgarian Academy of Sciences

ZnO nanostructured films were deposited by the electrochemical process from acid aqueous solution of ZnCl2 (5. 10-3 M) and KCl (0.1 M) with pH = 4.0 at a temperature of 600C in flowing air and/or

addition of H2O2 as precursors using a three-electrode electrochemical cell and saturated calomel

electrodes (SCE) as reference electrodes. SnO2 doped with F coated glass substrates and on the surface

of the carbon tissue (for bio-medical application) were used as working electrode. Spectrally pure graphite electrode was used as an anode. The solution was stirred either by air bubbling or by magnetic stirrer. The deposition was carried out by varying the redox potential of the system. Since the potential of Zn in the electrolyte is -1.05 V vs. SCE the deposition process of ZnO was carried out at -0.9V vs. The results of the study of the morphology of electrochemically prepared ZnO layers show that the synthesis in these conditions results in deposition of ZnO layers with large grains and the orientation of the wires different from only perpendicular to the substrate. Growing of ZnO in the conditions with addition of H2O2 in the lower concentration and without flowing air results in larger grain formation. Possibly the conditions of higher oxidation during the electrochemical deposition of ZnO slow down the growth rate of the nanowires. The ZnO layers demonstrated higher diffuse reflection in the near IR and visible range than SnO2:F. Typical Raman bands for ZnO at 437 cm-1 (E2), 407 cm-1 (E1), 574 cm-1 (A1) are observed.

Crystalline nanostructures such as nanowires have received increasing attention due to potential applications in solar cells, nanoscale electronics, optical and sensing devices, etc. Different physical and chemical methods have been applied for the synthesis of nanowires. Since, however, the preparation conditions determine to a great extent the properties of the nanowires, their fabrication with predetermined size and perfect morphology is still a challenging task. In this work preliminary results on the preparation of ZnO nanostructred films by electrodeposition on glass substrate coated with SnO2 doped with F (SnO2:F) are reported. The influence of

some technological parameters such as increasing of the conditions for oxidation on the structural properties of the obtained ZnO films was studied by electron optical imaging, Raman spectroscopy, diffuse reflection measurements.

Motivation Motivation ExperimentalExperimental Results and Discussions Results and Discussions

H. Nichev, P. Andreev, M. Sendova-Vassileva, D. Dimova-Malinovska, K. Starbova a Central Laboratory of Solar Energy and New Energy Sources, Bulgarian Academy of Sciences, Sofia, Bulgaria

a Central Laboratory for Photoprocesses, Bulg. Acad. Sci., Sofia, Bulgaria

ConclusionsConclusions

The work has been funded by the Bulgarian National Science Fund under contract, DO02-207-2008 The work has been funded by the Bulgarian National Science Fund under contract, DO02-207-2008 Human Resources Human Resources Development Programme, under the contract BG 051PO001/07/3.3-02/58/ 17.06.2008Development Programme, under the contract BG 051PO001/07/3.3-02/58/ 17.06.2008

•The ZnO nanostructured films were deposited by electrochemical method on SnO2:F coated glass substrates and on the surface of the

carbon tissue (for bio-medical application) .•The surface morphology and the structure of the ZnO nanostructured films depend on the deposition conditions: ZnO films with larger grain size were obtained in the conditions providing a lower oxidation of Zn ions. •The ZnO layers demonstrated high diffuse reflection in the near IR and visible range of the spectrum.• ZnO layers with such surface morphology could be applied as a back contact for increased light trapping in thin film solar cells.

a b Fig. 3. SEM image of the surface (a) and cross section (b) of the ZnO nanostructured film deposited in the condition with lower H2O2 concentration with flowing air (sample B).

a bFig. 4. SEM image of the surface (a) and the cross section (b) of the ZnO nanostructured film deposited in the condition with lower H2O2 concentration without flowing air (sample C).

a bFig. 5. SEM image of the surface (a) and the cross section (b) of ZnO film deposited in the conditions with higher H2O2 concentration and without flowing air (sample D).

Table 1. The deposition conditions and the thickness of different samples.

400 500 600

Ram

an In

ten

sity

[a.

u.]

Raman Shift [cm-1]

substrate

A

B

C

D

400 600 800 1000 1200 1400

10

20

30

substrate

Dif

fuse

Ref

lect

ion

[%

]

Wavelength [nm]

A

B

C

D

Fig. 6. Raman spectra of the SnO2:F substrate and the four ZnO samples as indicated in the figure.

Fig. 7. Diffuse reflection spectra of the SnO2:F substrate and the four ZnO samples as indicated in the figure.

Fig. 1. SEM image of the surface of SnO2:F film deposited on glass

substrate.

a bFig.2. SEM image of the surface (a) and cross section (b) of

the ZnO nanostructured film deposited on SnO2:F coated glass substrate in the conditions with flowing air only (sample

A) .

Fig. 8 SEM of ZnO nanonopilars on a carbon tissue surface. Note the different magnification in two pictures.