Tuning the peak position of subwavelength silica nanosphere broadband antireflection coatings
© Tao et al.; licensee Springer. 2014
Received: 21 April 2014
Accepted: 9 July 2014
Published: 19 July 2014
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© Tao et al.; licensee Springer. 2014
Received: 21 April 2014
Accepted: 9 July 2014
Published: 19 July 2014
Subwavelength nanostructures are considered as promising building blocks for antireflection and light trapping applications. In this study, we demonstrate excellent broadband antireflection effect from thin films of monolayer silica nanospheres with a diameter of 100 nm prepared by Langmuir-Blodgett method on glass substrates. With a single layer of compact silica nanosphere thin film coated on both sides of a glass, we achieved maximum transmittance of 99% at 560 nm. Furthermore, the optical transmission peak of the nanosphere thin films can be tuned over the UV-visible range by changing processing parameters during Langmuir-Blodgett deposition. The tunable optical transmission peaks of the Langmuir-Blodgett films were correlated with deposition parameters such as surface pressure, surfactant concentration, ageing of suspensions and annealing effect. Such peak-tunable broadband antireflection coating has wide applications in diversified industries such as solar cells, windows, displays and lenses.
Antireflection coatings (ARCs) have important roles in a wide range of industrial applications such as solar cells, buildings, smartphone displays and camera lenses. Current ARC technology, which based on destructive interference mechanism, usually requires costly vacuum deposition techniques such as sputtering or chemical vapour deposition. Recently, subwavelength nanostructures, such as nanowires, nanospheres and nanorods, resulting in a graded refractive index, emerged as ideal optical structures for ARC application. Among these, silica spheres with controllable diameter ranging from 50 nm to 2 µm prepared by Stober method have been the most studied [1–5]. Silica nanospheres could be used as etching mask [6, 7] to create graded refractive index nanowire/nanodome structures, or nanospheres themselves could be used as antireflection coatings directly [8, 9]. Optimized refractive index of single AR film was given by the equation , where na and ns are the refractive index of the air and the substrate, respectively. Commercial borosilicate glass substrate typically has a refractive index approximately 1.51, which means that a material with a refractive index approximately 1.23 is required in order to get the AR effect between air and glass. Given the fact that no material with such low refractive index has been discovered, most researchers have adopted mesoporous or hollow silica spheres to get the desired low refractive index [4, 10, 11]. Few attention were paid to the solid silica nanospheres. It is questionable whether thin films composing solid silica spheres, in particular for monolayer of silica nanospheres, could lead to remarkable AR effects.
Several methods have been employed to deposit nanosphere films on various substrates, including continuous assembly , convective assembly [5, 13], layer by layer method (LbL) [3, 4], printing  and Langmuir-Blodgett method [15, 16]. Among them, Langmuir-Blodgett (LB) method is the most convenient and effective approach for controllable deposition of ordered nanospheres. It has been commonly used to make two-dimensional (2D) and three-dimensional (3D) photonic crystal structures. Bardosova et al. reviewed the monolayer and multilayer deposition of silica spheres by LB method . Although the mechanism behind LB deposition and self-ordering thin film has been discussed for a number of years [17–19], it is unclear how the LB deposition parameters could affect the AR performance of deposited nanosphere thin films.
In this study, we focused on 2D solid silica sphere film made by LB technique and its superior antireflection effect. A parametric study of deposition conditions is conducted and correlated to the resulting film morphology and optical properties. We demonstrated that the thin films of single-layer solid silica nanospheres with a diameter of approximately 100 nm could offer comparable AR effect with respect to the mesoporous counterparts. Furthermore, the transmission peak of the nanosphere silica AR coating can be controlled by varying the LB deposition parameters. To our best knowledge, no such peak-tunable property has been reported before, although spectral shift due to the thickness of mesoporous silica spheres’ thin film has been observed in previous works [4, 5, 9, 10]. The deposition parameters which determine the peak transmission wavelength are extracted. Three variables, namely deposition pressure, surfactant concentration and solution ageing, were found to strongly correlate with the maximum transmission position. Film density and aggregations of nanospheres resulting from the above variables are considered as principal determining factor behind this shift. The ability of achieving broadband transmission and simultaneously being able to determine the position of maximum transmission (>99%) opens the possibility of many application-specific solutions. For photovoltaics, for instance, it is possible to match the absorption peak of absorber materials by tuning the transmission peak of glass. For displays, it can reduce reflection and glare, while transmitting more of the display light, thereby requiring lower intensity light and reducing energy consumption.
All chemicals were used as received, without any further purification. Aqueous suspension of silica spheres (50 mg/ml, polydispersity index <0.2, diameter 100 nm) were purchased from Kisker Biotech GmbH & Co, Steinfurt, Germany. The silica sphere suspension was diluted down to 10 mg/ml with pure ethanol (ACS reagent, ≥99.5%, absolute, Sigma-Aldrich, St. Louis, MO, USA) and then mixed with hexadecyltrimethylammonium bromide (CTAB; ≥98%, Sigma-Aldrich). CTAB was used to change the hydrophilic/hydrophobic nature of the silica spheres. The final diluted suspension with CTAB was ultrasonicated for 30 min each time before deposition.
Microscope glass slides (Agar Scientific, Essex, UK, 76 mm × 26 mm) were cleaned in acetone, IPA and DI water subsequently in an ultrasonic bath for 10 min at each step. After cleaning, glass slides were treated with oxygen plasma (Philips RIE, New York, USA). Both sides of the slides were treated by 100-W O 2 plasma for 5 min at a pressure of 150 mbar. Monolayer of silica nanospheres were deposited onto plain glass slides using a Langmuir-Blodgett trough (NIMA Technology model 612D, Coventry, UK). The deposition process and mechanism has been discussed by many previous reports [17–19]. After deposition, the samples were washed in ethanol for 10 min twice in order to remove the residual CTAB. Finally, the samples were blow-dried with nitrogen gas.
Optical transmission measurements were made using a Thermoelectron Corporation UV/VIS Spectrometer UV2 double beam spectrophotometer (Waltham, MA, USA). All transmission measurements here shown are with respect to air reference. Spatial arrangement of the silica spheres was characterized by scanning electron microscope (SEM; Zeiss EVO 50, Oberkochen, Germany). Finite-difference time-domain (FDTD) simulation (FDTD solutions, Lumerical Solutions, Inc., Vancouver, Canada) was used to verify the experimental results. The simulation software is a 3D computer-based Maxwell solver. Transmittance spectra of SiO 2 nanosphere array with cubic arrangement on single side and double sides of glass were simulated. Details of simulation parameters are shown in Additional files 1, 2, 3 and 4.
To further control the transmission peak position of the glass with AR coatings, we studied several key LB deposition parameters, including deposition pressure, concentration of CTAB, compression-relaxation cycles and dipper speed. The annealing effect on the thin films and the effect of ageing the sphere-CTAB suspension were also studied.
It is noted that in our experiments the arrangement was not perfect close-packed but amorphous alike. This is due to the high polydispersity (<20%) of the silica nanospheres. Jiang et al. found that in their work when samples with slightly broader size distributions (>8%) are deposited, grain boundaries in the plane parallel to the substrate are observed . It is believed that the monodispersity of the colloids, rather than the deposition process itself, is responsible for their long-range ordering. Agod et al. investigated the effect of polydispersity on the anisotropy and the fluctuation of the surface pressure tensor in Langmuir films during uniaxial compression . They found that domain-structured films can form only below 7% to 8% polydispersity; beyond this limit, the particulate films have rather amorphous structure. As a result, we conclude that the non-perfect close-packed arrangement was a result of the high polydispersity index of the silica spheres. Nevertheless, the subwavelength structure showed excellent antireflection performance.
In addition, isotherm of the fresh and ageing suspension was also found to be different. Isotherm of ageing suspension gave much higher collapse pressure, which may indicate that the surface tension of water with monolayer nanospheres γ was further decreased by aggregated CTAB molecules and nanospheres. These results show that the shift of the transmission peak is strongly influenced by the aggregations introduced by CTAB. This is in agreement to the report by Yang et al.  who found that the concentration of CTAB in gold colloids is critical for self-assembling linear chain-like aggregates with different interconnecting particle number and network-like aggregates. In light of this phenomenon, we believe it is possible to control the transmission peak position via controlling the aggregation rate and size of the nanospheres. Another three variables including compression-relaxation cycles, dipper speed and annealing effect were found to have a weak correlation with peak position. Although increasing the number of compression-relaxation cycles of the spheres in water is known to produce a more compact film , transmission spectra of samples deposited with or without using compression-relaxation cycles were hard to distinguish (see Additional file 3). Situations of the other two parameters are similar. Given the fact that these three parameters have no effect on the formation of aggregations, it is consistent with our previous analysis that aggregation rate and size are the main factors determining the peak position.
According to the analysis above, deposition pressure, surfactant concentration and solution ageing have a strong correlation with the position of peak transmittance of the resulting coating. By varying these parameters, it was possible to tune the transmission peak position from 468 nm to beyond 800 nm, covering most of the visible spectrum.
In summary, antireflection (AR) films were deposited on glass substrates using 100-nm silica nanospheres by Langmuir-Blodgett method. Double-side subwavelength nanosphere films showed excellent broadband AR effect which improved sample transmittance to higher than 95% in the whole visible spectrum, with transmittance peak higher than 99%. Furthermore, the spectral position of transmission peak can be tuned by controlling three key deposition parameters (deposition pressure, surfactant concentration, ageing of suspension). It is possible to tune the transmission spectral peak widely across the whole visible spectrum. Aggregations of nanospheres were ascribed to be the cause for this peak-tunable property according to our investigation. Transmission peak shifts to longer wavelength as the size and rate of aggregation increases. We believe that such peak-tunable broadband antireflection effect has huge potential for many application areas, such as solar cells, LED and displays.
The support from the CU Centre for Advanced Photonics and Electronics (CAPE) under the Strategic Research Initiative and the Nokia-Cambridge Strategic Alliance in Nanoscience and Nanotechnology as part of the Mobile Energy Programme is gratefully acknowledged. Hang Zhou would like to acknowledge the support from the National Natural Science Foundation of China (61204077) and the Shenzhen Science and Technology Innovation Commission (JCYJ20120614150521967). Yong Wang would like to thank the support from the Shenzhen Strategic Emerging Industries Project (JCYJ201206141509581, CXZZ20130322142615483).
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