A TiO2 nanotubes film with excellent antireflective and near-perfect self-cleaning performances

doi:10.1016/j.jmst.2021.01.080

Abstract

Abstract:

SiO₂/TiO₂ composite films have been frequently used to realize the functions of self-cleaning and antireflection. Increasing the TiO₂ volume ratio in SiO₂/TiO₂ composite film is beneficial to enhance the self-cleaning effect, while high TiO₂ content leads to a strong Rayleigh scattering and depresses the antireflective performance, resulting in a bottleneck problem for the dual-functional application. Here, we have achieved a high-quality TiO₂ nanotubes film with excellent antireflective and near-perfect self-cleaning performances. Ultrasound assisted pickling method has been developed to effectively prepare the well-dispersed protonated titanate nanotubes colloid. After spin-coating and annealing treatment, glass substrate coated with double-side TiO₂ nanotubes film has a peak transmittance of 99.2 % and average transmittance of 97.4 % at 400-800 nm. Ultra-high porosity of TiO₂ nanotubes film (80 %) and ultra-fine size of TiO₂ nanotubes (8.6 nm in outer diameter) lead to excellent antireflective performance. With high UV absorptivity (80 % at 254 nm) and formal quantum efficiency of stearic acid (10.9 × 10^-3), TiO₂ nanotubes film shows near-perfect self-cleaning performance. A persistent anti-fogging ability is also presented. This study demonstrates the feasibility to fabricate pure TiO₂ antireflective coating for glass substrate, extends application field of the classic TiO₂ nanotubes, and sheds lights on the practical applications of high-powered TiO₂ nanotube-based multi-functional films.

Key words: TiO₂ nanotubes, Antireflective, Self-cleaning, Anti-fogging, Multi-functional films

Kaibin Li, Ming Li, Chang Xu, Zengyan Du, Jiawang Chen, Fengxia Zou, Chongwen Zou, Sichao Xu, Guanghai Li. A TiO₂ nanotubes film with excellent antireflective and near-perfect self-cleaning performances[J]. J. Mater. Sci. Technol., 2021, 88: 11-20.

Figures/Tables 8

Fig. 1. (a) Low- and (b) high-resolution TEM images of as-prepared sodium titanate nanotubes. (c)-(e) are the size statistical results of inner diameter, outer diameter and length of sodium titanate nanotubes.

Fig. 2. (a) Tyndall phenomena, (b) FT-IR spectra, (c) Raman spectra and (d) high-resolution N 1s XPS spectra of the samples with different treatments. (e) N atomic ratio with different treatments according to the peak areas in (d).

Fig. 3. (a) Schematic preparation process of TiO2 nanotubes film by hydrothermal synthesis, ultrasound assisted pickling method, spin coating and annealing treatment. (b) XRD patterns of the samples with different treatments. (c) High-resolution TEM image of TiO2 nanotubes after pickling and annealing treatment. SEM images of (d) front and (e) cross section of TiO2 nanotubes film. The inset in (d) is magnified SEM image of TiO2 nanotubes film front section.

Fig. 4. (a) Transmittance and (b) reflectance spectra of glass substrate without coating and with different kinds of coatings. (c) Photograph of glass substrate without coating, with double-side TiO2 sol-gel film and TiO2 nanotubes film. (d) Wavelength dependence of refractive index of TiO2 sol-gel film, TiO2 nanotubes film, glass substrate and ideal antireflective coating.

Table 1 Optical parameters of glass substrate without coating and with different kinds of coatings.

Wavelength 400-800 nm	Transmittance (%)		Reflectance (%)		Refractive index at 550 nm
Wavelength 400-800 nm	Max.	average	Min.	Average	Refractive index at 550 nm
glass substrate	91.3	90.5	7.3	7.6	1.5
single-side TSF	85.8	77.4	12.0	19.0	2.1
double-side TSF	83.8	69.9	14.3	26.3	2.1
single-side TNF	95.3	94.1	4.3	4.6	1.31
double-side TNF	99.2	97.4	0.8	1.5	1.31

Fig. 5. (a) Simulated absorptivity spectra of an ideal single-side SiO2/TiO2 porous antireflective coating with different values of νtitania at 200-400?nm according to Eq. S9 in the Supporting Information. The black line represents the absorptivity of an ideal single-side SiO2/TiO2 porous antireflective coating at 254?nm according to Eq. S10 in the Supporting Information. Time evolution of IR absorption spectrum of the glass substrate (b) without coating, (c) with single-side TSF and (d) with single-side TiO2 nanotubes film attached by a layer of SA. (e) Integrated areas of IR absorption peaks of blank glass substrate, TiO2 sol-gel film and TiO2 nanotubes film over the range 2700-3000?cm-1. The inset in (e) is an enlarged integrated area for glass substrate with single-side TiO2 nanotubes film. Transmittance, reflectance and absorptivity spectra of quartz substrate (f) with single-side TiO2 sol-gel film and (g) with single-side TiO2 nanotubes film at 200-400?nm.

Table 2 Calculated FQE(SA) and FA under irradiation at 254?nma.

Sample types	TSF	TNF	Common SiO₂/TiO₂ ARC [14,15]
Rate of initial SA disappearance (× 10¹³ molecules cm^-2 s^-1)	0.7	5.0	/
Incident light intensity (mW cm^-2)	4.5	4.5	/
Absorptivity (%)	84	80	<< 80 %
Rate of light absorption (× 10¹⁵ photons cm^-2 s^-1)	4.9	4.6	/
FQE(SA) (× 10^-3)	1.4	10.9	< 10.9
FA (× 10^-3)	1.2	8.7	<< 8.7

Fig. 6. (a) Time evolution of water contact angle of glass substrate without and with different freshly prepared coatings. (b) Photographs of water droplet on glass substrate without and with different freshly prepared coatings at 500?ms. (c) Corresponding photograph of samples on the top of beakers containing hot water. (d) Time evolution of water contact angle of glass substrate without and with different coatings stored in the darkness for 2 months. (e) Photographs of water droplet on glass substrate without and with different coatings stored in the darkness for 2 months at 500?ms. (f) Corresponding photograph of samples on the top of beakers containing hot water. (g)-(h) AFM images of TiO2 sol-gel film and TiO2 nanotubes film, respectively, at the scanning area of 2?μm?×?2?μm.

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A TiO₂ nanotubes film with excellent antireflective and near-perfect self-cleaning performances

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