Reduction Band Gap Energy of TiO 2 Assembled with Graphene Oxide Nanosheets

This research work aims to reduce the band gap of thin layers of titanium oxide by the incorporation of graphene oxide sheets. Thin layers of the TiO2-GO composites were prepared on a glass substrate by the spin-coating technique from GO and an aqueous solution of TiO2. A significant decrease in optical band gap was observed at the TiO2-GO compound compared to that of pure TiO2. Samples as prepared were characterized using XRD, SEM and UV-visible spectra. XRD analysis revealed the amorphous nature of the deposited layers. Scanning electron microscope reveals the dispersion of graphene nanofiles among titanium oxide nanoparticles distributed at the surface with an almost uniform size distribution. The band gap has been calculated and is around 2 eV after incorporation of Graphene oxide. The chemical bond C-Ti between the titanium oxide and graphene sheets is at the origin of this reduction.


Introduction
The Titania, existing in rutile or anatase phase, is considered an important material for different applications because of its characteristic of photoexcitation phenomenon.Among the applications, the efficiency of photovoltaic solar cells and photocatalytic devices could be improved if the band gap of titanium oxide layers could be reduced [1] [2].Titanium oxide (TiO 2 ) has excellent chemical stability, mechanical hardness and optical transmittance with high refractive index.It has attracted great attention these years and it is widely used in solar cells A. Timoumi DOI: 10.4236/graphene.2018.74004 32 Graphene [3] and other areas.
Originally, the Titania has a band gap more than 3 eV.The lowering of the band gap is essential for optimal use of sunlight and therefore for improving the efficiency of the devices thus produced.A Graphene oxide (GO) is explored for its important effect on the band gap of titanium thin layers.In this context, the composites of GO and TiO 2 are highly promising.There are many reports on the preparation of graphene-TiO 2 composite [4] and its application in the dye-sensitized solar cell [5].In fact, several studies have been reported in the literature [6] [7] [8] in order to reduce the band gap of TiO 2 .
TiO 2 thin films can be prepared by different techniques such as sputter depositions [9], sol-gel process [10], chemical vapour deposition (CVD) [11], and ion beam-assisted processes [12].In this investigation spin coating technique was used for the deposition of TiO 2 thin films.TiO 2 -Graphene oxide composite was successfully prepared via a simple coating approach.Structural, morphological, and optical properties of obtained layers were studied and well discussed in this work.The optical properties give information regarding the band gap Eg, the refractive index n and the extinction coefficient k.

Materials
The Titanium (IV) Isopropoxide (TIP) (99.999%), the graphene oxide in powder form (4% -10% edge-oxidized) and other chemical reagent were purchased from Sigma-Aldrich.All chemicals were of analytical grade and used as-received.

Preparation of TiO2-Graphene Oxide
At room temperature the Titanium isopropoxide (TIP) (precursor) was mixed with acetic acid (stabilizer) and ethanol (solvent) in the molar ratio TIP: ethanol: acetic acid = 1:0.1:9.Then, the resulting solution form was stirred during 2 h.
The reaction mechanism for TiO 2 formation is:

Characterization Methods
A shimadzu type XRD-6000 X-ray diffractometer with a Cu-Kα radiation (λ = 1.5418Å) were used for X-ray diffraction analysis.The morphologies of the samples were examined by scanning electron microscopy (SEM, Shimadzu Supers can SSX-550).A spectrophotometer with a resolution of 0.1 nm (Shimadzu 3150 UV-VIS-NIR) were used for the measurement of the transmittance spectra T (λ) and the reflectance R (λ) of the layers under a normal incidence at room temperature in the spectral range (200 -1800 nm).The thickness layer was determined by a stylus displacement of a Veeco Dektak 150 profilometer.

XRD Analysis
The crystal structure of TiO 2 and TiO 2 -GO samples obtained by XRD is shown in Figure 1.The XRD pattern for the samples showed no detectable peaks, indicating that the samples were amorphous.The possible reason is either to organic solvents which inhibited the formation of the crystalline structure of TiO 2 [13], or to the low calcination temperature given during the growth of TiO 2 thin layers [14] [15].Complete transformation of brookite to anatase was achieved at a calcination temperature of 400˚C [16].No characteristic diffraction peaks for Graphene oxide are observed because it's relatively low diffraction intensity and the low amount used.( )

Optical Measurements
Here, R is the reflectance value, (k = αλ/4π) is the extinction coefficient.The values of the refractive index n, rise in the Ultraviolet spectral range for samples.The n values shifted to longer UV wavelengths when GO is added toTiO 2 .This could be attributed to the fact of the GO that introduced in the solution which may

Conclusion
In this study, TiO 2 -GO composite thin layers were synthesized by a spin coating A. Timoumi DOI: 10.4236/graphene.2018.7400437 Graphene ethod.The dispersion of graphene oxide nanosheets in TiO 2 thin layers, crystallinity, morphology and band gap was evaluated.It was revealed by scanning electron microscopy that the deposited layers are detected some aggregates.The band gap obtained of TiO 2 -GO composite thin layer was 2 eV as compared to titania thin film.This result is significant and encouraging for various applications in different fields, such as dye-sensitive solar cells.
On the other hand the Graphene oxide solution was prepared separately by dispersing graphene oxide (sheets) in powder form in 5 ml of ethanol.After that it is sonicated for 20 minutes.The mass of GO dispersed and mixed with TiO 2 solution is 15 mg.The mixture of TiO 2 and Graphene oxide solutions (5:1) were used and stirred for 30 minutes.Finally, the solution containing TiO 2 -Graphene oxide composite is obtained.A spin coating (Model WS-650MZ-23NPPB) was performed in air by flooding the substrate surface (glass substrate) with spinning at 3500 r/min for 30 s. Thin homogenous layers of TiO 2 -GO with 250 nm thickness were obtained.Graphene

Figure 2
Figure 2 shows the images of as-prepared TiO 2 and TiO 2 -GO samples obtained with scanning electron microscope and scanned with 10,000 magnifications.The titanium oxide product film has homogeneity of the nanoparticles to appreciable dimensions.Agglomerated nanoparticles and pinholes have also been observed on the film.The film also shows a basic morphology of semi-spherical grains with random formation in the shape of a flower.The surface morphology of the

Figure 2 .
Figure 2. SEM patterns of TiO 2 and TiO 2 -GO samples synthesized by spin coating.

Figure 3 (
Figure3(a) depicts the transmission T and the reflection R spectra as a function of wavelength for TiO 2 and TiO 2 -GO samples.These layers exhibited good transparency in the infrared region.A decrease in both R and T values which attributed to GO particles is distributed in the total matrix volume[17] is noted.

Figure 3 (
Figure 3(b)  describes the variation between (αhν)2 and photon energy (eV), which shows that the band gap of pure TiO 2 is about 3.67 eV; value in accordance to the literature[18], whereas the band gap obtained of the TiO 2 -GO composite has been reduced to 2.0 eV.This value is interesting for large spectra photon absorption[19].This, shows that the addition of graphene oxide particles effectively increases the visible light absorption capacity of the titanium dioxide thin layer[8].This can be explained by the presence of acids and oxidizing agents in the synthesis solution.Many groups containing oxygen, such as hydroxyl (C-OH), carboxyl (C-OH) and epoxy (C-O-C) groups become covalently bonded to surfaces of Graphene oxide sheets.So, in the presence of some functional group such as (-OH) and (-COOH) Graphene oxide reacted.Some

Figure 3 (
Figure 3(c) grouped the variation of extinction coefficient and refractive index of samples.The refractive index n, was determined using the reflection, R, values from equation above according to: increase density, leading to an increase of n values.The extinction coefficient, k, indicates that high values are indicated in the zone of the strong absorption or the extrinsic absorption, and decreases in the zone of the weak absorption.The mechanism diagram showing this process is given in Figure 4.Under light irradiation, electrons were excited from the valence band to the conduction band of TiO 2 , leaving positively charged holes in the valence band.In the absence of acceptor, the recombination of electrons and positive charges would take place.A C-Ti bond will be formed participating in the reduce of the TiO 2 band gap.

Figure 4 .
Figure 4. Schematic illustrating the charge transfer in the TiO 2 -GO composite under visible light irradiation with a new energy level E FX .