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Vol 1 | Issue 2 | Summer Edition | June 2013 | Pp 45-49 | ISSN 2279 0381

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Methods Of Preparation Of Anti Reflective Mgf2 Nano Coating


On Glass Substrate A Comparative Survey
V. Radhikaa*, Dr. V. Annamalaib
a
Asst. Prof of Physics, PKR Arts college for women, Gobichettipalayam, India.
b
Asso. Prof of Physics, Chikkanna Govt. Arts college, Tirupur, India.
*email: radhikaviswanath@gmail.com

Keywords: MgF2 thin films, Anti reflective coating, quarter of the wavelength (/4) of interest has
Sol-gel method, Spin coating, Ion-Beam Sputtering, been used as an AR coating. Ideally, such a single-
Evaporation
layer /4 anti-reflection (AR) coating should have
a refractive index, n /4, as given by,
Abstract. An anti-reflection nano coating (AR
n /4(nsubstrate _ nair).
coating) is a dielectric thin-film coating applied to
an optical surface in order to reduce the optical If no suitable medium for a single-layer
reflectivity of that surface in a certain wavelength coating can be found, multi-layer AR coatings
range. Ideally, an antireflection coating should having three or more layers can be furnished. This
have a refractive index equal to the square root of can also be used for anti-reflective properties
the index of the glass substrate. The most common which are required for a very broad wavelength
material for a single-layer coating is MgF2, which range.
has a relatively low index of about 1.38 at visible Hakuzo Tani[6] showed in his work that
wavelengths. MgF2 is a dielectric material with a the three layer AR coating includes an outer layer
wide transmission range and a low refractive (first) consists of material selected from a group
index. So it can be used as anti-reflective nano comprising MgF2, LaF2, Na3(AlF4) and SiO2
coating to reduce the loss of light in lenses or (n=1.38) with an optical thickness of /4. The 2nd
mirrors. There are various methods of preparing layer is a mixture of oxides of titanium and Al2O3
AR nano coating on glass substrates. The methods (n=2) with an optical thickness of /2. Finally, the
discussed here are sol-gel process (chemical third layer from a group comprising Al2O3, CeF3,
method by spin coating), evaporation process Y2O3, Gd2O3 and MgO.
(PVD) and ion-beam sputtering method.

Material Refractive Optical


Introduction Index Thickness
An anti-reflection thin-film nano coating
I layer MgF2 1.385 0.251
designed for normal incidence consists of a single
quarter-wave layer of a material the refractive II layer Mixture of 2.05 0.501
index of which is close to the geometric mean ZrO2 and
value of the refractive indices of the two adjacent TiO2
media. Here, two reflections of equal magnitude III layer MgO 1.70 0.632
arise at the two interfaces, and these cancel each
other by destructive interference. It is not always IV layer Mixture of 2.05 0.035
possible to find a coating material with suitable ZrO2 and
TiO2
refractive index, particularly in cases where the
bulk medium has a relatively low refractive index. Substrate Glass 1.62
A single-layer coating works only in a limited
bandwidth (wavelength range). A single-layer
coating with optical thickness equal to one-
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Journal of NanoScience and NanoTechnology | Vol 1 | Issue 2 | Summer Edition | ISSN 2279 0381

Experimental deposited on silicon or glass substrates using spin-


or dip-coating. After a moderate thermal
(i) Sol-Gel Method: treatment (100 C300 C), transparent and
In this chemical procedure, the 'sol' (or strongly adhering MgF2-films are obtained. This
solution) gradually evolves towards the formation coating process is very simple and cheap in
of a gel-like diphasic system containing both a comparison to the common, very complex PVD-
liquid phase and solid phase whose morphologies methods and corrosive gases such as HF and F2
range from discrete particles to continuous are not needed. Because the calcination
polymer networks. In the case of the colloid, the temperature of the coatings can be below 150 C,
volume fraction of particles (or particle density) this method is suitable for temperature-sensitive
may be so low that a significant amount of fluid substrates like organic polymers and therefore
may need to be removed initially for the gel-like facilitates other fields of application.
properties to be recognized. This can be
Spin Coating
accomplished in any number of ways. The
simplest method is to allow time for sedimentation This is a method of applying solution-
to occur, and then pour off the remaining liquid. based AR coatings. In this case, the substrate is
Centrifugation can also be used to accelerate the mounted horizontally on a rotating platform. The
process of phase separation. substrate then spins very rapidly and the coating
solution is dispensed onto it. The high-speed
The precursor sol can be either deposited
rotation throws off most of the solution, leaving
on a substrate to form a nano film (e.g., by dip
behind a thin, uniform coating. Coating thickness
coating or spin coating), cast into a suitable
is precisely controlled by the rotational speed of
container with the desired shape (e.g., to obtain
the substrate. Faster rotation results in a thinner
monolithic ceramics, glasses, fibers, membranes,
coating layer. A nano thin film coating is
aerogels), or used to synthesize powders. The sol-
preferably expected to be within the thickness
gel approach is a cheap and low-temperature
range of 100nm. Benefits of spin coating include
technique that allows for the fine control of the
fast process time (only a few seconds per coating)
products chemical composition. Even small
and high uniformity over the surface of curved
quantities of dopants, such as organic dyes and
parts.
rare earth elements, can be introduced in the sol
and end up uniformly dispersed in the final
product.

Hannes Krger[15] et.al., showed that the


solgel synthesis method for metal fluorides
Lenses with varying curvatures may be coated
allows for the preparation of MgF2-films at low
evenly and uniformly with minimal thickness
temperatures. The MgF2-sol obtained by this
variation or edge effects. However, spin coating
method are prepared from a suspension of
can only be performed on one part at a time, in
magnesium methoxide in methanol and a non-
contrast to dip coating in which many parts may
aqueous HF solution in methanol. The molar ratio
be processed simultaneously.
of magnesium alkoxide and HF is kept at 1:2 and
the sol concentration can be adjusted by altering Ishizawa et.al.,[9] showed that the optical
the amount of solvent used. This MgF2-sol can be element comprising a substrate, a multilayered

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Journal of NanoScience and NanoTechnology | Vol 1 | Issue 2 | Summer Edition | ISSN 2279 0381

AR film which is formed on the substrate and spin-coated. A Spin-Coater KW-4a from Chemat
which is constructed of a stack of at least 3 types Technology was used for this process. The coatings
of layers having different refractive indices were prepared at 5000 rpm for 40s. After each
respectively. The uppermost layer makes contact coating step, the substrates were dried for 30 min
with MgF2 optical thin film, which has the at 100C. The number of coating/drying cycles is
refractive index of not more than 1.30 and the described in Table 1. The final calcinations were
remaining layers other than the uppermost layer carried out for 2 h at temperatures of 100 C or
may be constructed by stacking a layer having a 300 C in air.
refractive index of not less than 2. In this case, the
incident angle characteristic is remarkably (ii) Ion Beam Sputtering:
improved. The reflectance (shown in graph) can be Ion-beam sputtering (IBS) is a method in
suppressed to be low with respect to the light which the target is external to the ion source. A
beam allowed and over a wide wavelength range. source can work without any magnetic field like in
It has been revealed that the film can be formed to a hot filament ionization gauge. In a Kaufman
have the uniform thickness on the surface having source ions are generated by collisions with
the small radius of curvature even in the case of electrons that are confined by a magnetic field as
the spin coat, unlike the general vacuum vapor in a magnetron. They are then accelerated by the
deposition method. electric field emanating from a grid toward a
target. As the ions leave the source they are
H. Krger et al.,[15]s Table 1
neutralized by electrons from a second external
Dependence of the thickness of the MgF2-layers on filament. IBS has an advantage in that the energy
the number of coating steps and the concentration and flux of ions can be controlled independently.
of the MgF2-sols Since the flux that strikes the target is composed
of neutral atoms, either insulating or conducting
Concentration Number Film targets can be sputtered. A pressure gradient
of the sols of thickness between the ion source and the sample chamber is
[mol/l] coating [nm] generated by placing the gas inlet at the source
steps and shooting through a tube into the sample
chamber. This saves gas and reduces
contamination in UHV applications.
1 40
0.15 Juan I. Larruquert et.al.,[14] explained that
the IBS system was equipped with a 3-cm
3 83
Kauffman ion gun that focused an Ar beam onto a
water-cooled target placed at about 45 to the ion
0.3 6 196
beam. An Ar flow of 7.0 sccm was maintained. The
ions sputtered target atoms that impinged
0.6 1 63
perpendicularly onto a water-cooled, float glass or
MgF2 crystal substrate placed 10 cm away from
3 182
the target. A 101.6-mm diameter, 99.997% purity
MgF2 sputtering target was used.
6 435
The base pressures in the sputtering and
evaporation chambers were 4106 and 106 Pa,
H. Krger et al.,[15] showed that the MgF2
respectively. Typical total pressures during
precursor solution are prepared from a suspension
deposition were 4102 Pa in the sputtering
of magnesium methoxide in methanol and a non-
chamber, and 105 Pa in the evaporation chamber.
aqueous HF solution in methanol. The molar ratio
The deposition rates of evaporated materials were
of magnesium alkoxide and HF is maintained at
20 nm/s for Al, and 23 nm/s for MgF2, and it
1:2. The concentration of magnesium methoxide in
was0.15 nm/s for sputtered MgF2. The layer
the precursor solution was varied as indicated in
thickness was measured with a quartz crystal
Table 1. The Si substrates were cleaned in an
thickness monitor that was 94nm. A slightly
ultrasonic bath and etched with the RCA method,
higher transparency at the 121.6-nm, H Lyman, a
they were then wetted with the MgF2-sol and
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Journal of NanoScience and NanoTechnology | Vol 1 | Issue 2 | Summer Edition | ISSN 2279 0381

line was obtained for IBS MgF2 films compared to Hajime Ichikawa[7] proved that in the
films deposited by evaporation, which makes IBS electron beam evaporation process, when the
MgF2 a promising protective material for Al intensiy of electron ray or evaporation rate is
reflective coatings. large, cracks are apt to occur in the evaporated
coating, during the taking out of the coating from
the chamber into atmosphere. Further, the
coating is apt to cause tape-peeling even in the
adhesion test.

The transparency of MgF2 films deposited


by evaporation is continuously enhanced when the
substrate is held at increasing temperatures up to
670K during deposition due to the increase in the
film crystallinity. In spite of the enhanced
transparency, no significant change in the FUV
reflectance of MgF2 over coated Al films was
obtained for films deposited on a substrate heated
up to 370K, whereas a lower reflectance was
obtained when deposited on a substrate heated at
Evaporation:
420 K and above. Richard A. Hoffman[8] in his
Martin Bischoff[5] et al., fabricated MgF2, work used a disk of single-crystal NaCl2, 1.5
LaF3 and AlF3 thin films with a thickness of 150 inches in diameter and 5mm thick, which was
nm 200 nm by metal boat and electron beam placed on one face in a bell jar along with CaF2
evaporation gun (supply voltage 6 kV) in a (refractive index = 1.282) at 10 m in an
Leybold SYRUSpro 1110 deposition chamber electrically-heated tungsten boat.
equipped with turbo molecular pumps. The
background pressure was less than 10-6 mbar, the Results and discussion
substrate temperature 150C, and the deposition (i) The results show that MgF2 layers with
rate 0.2nm/s. As starting material, highly pure qualified optical properties can be deposited by
and high-quality low-oxide MgF2, LaF3 and AlF3 this solgel synthesis on planar surfaces. Further
(Merck) was used. Fused silica (dia. 1" and optimisation of this process may allow the
thickness 2 mm) with an rms roughness (AFM) of preparation of thin films with defined thicknesses
0.7 nm, single-crystal CaF2 (dia. 1" and thickness for use in optical multilayer systems. Low
2 mm) with an rms roughness of less than 0.2 nm, calcination temperatures during the post-
and silicon wafers were used as substrate treatment of the layers permit the deposition of
materials. heat sensitive substrate materials. In combination
The densification of the thin films was with high refractive index metal fluorides like
performed by a Leybold LION ion beam source. As PbF2 which are also available by this solgel
working gas, a mixture of argon and fluorine was synthesis, alternatives for optical multilayers with
chosen, whereas the flow of the gases was improved properties in the UV compared to oxides
adjustable, respectively. That means 100% argon emerge. The formation of high refracting metal
and 100% fluorine can be used for the ion fluoride coatings with the same optical quality
assistance of the metal fluorides as well. therefore is in the focus of present activities.
Transmission and reflection spectra were obtained
by a Lambda 850 (Perkin Elmer) in the range of (ii) IBS MgF2 films were shown to have
180 nm 300 nm, whereas the measuring device FUV optical properties close to those of MgF2
was purged continuously with N2 gas to avoid deposited by evaporation. The main differences
photo absorption of oxygen, moisture and organic were that IBS films were slightly more
contamination. IR spectra were measured with a transparent at the important H 121.6-nm, Lyman
FT-IR spectrometer (Varian 3100). The mass line, but the radiation losses for IBS-MgF2 were
density and surface roughness was measured by larger at longer wavelengths. Due to the enhanced
grazing incidence X-ray diffraction (GI-XRD). transparency at 121.6 nm, Al films that were
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Journal of NanoScience and NanoTechnology | Vol 1 | Issue 2 | Summer Edition | ISSN 2279 0381

protected first with a thin MgF2 film deposited by References and links
evaporation followed by an IBS MgF2 film to
1. R. Thomas, D.C. Dube, Jpn. J. Appl. Phys., Part 1
produce a combined 25-nm thick protective film
39 (2000) 1771.
showed a reflectance at 121.6 nm that was higher
2. F.K. Shan, G.X. Liu, W.J. Lee, G.H. Lee, I.S. Kim,
by about 0.03 than that of a standard Al film
B.C. Shin, Y.C. Kim, J. Cryst. Growth 277 (2005)
protected with an all-evaporated MgF2 film. 284.
However, at 143.6 nm and above a standard Al 3. P. Ericsson, S. Bengtsson, U. Sdervall, J. Appl.
film protected with an all-evaporatedMgF2 film Phys. 78 (1995) 3472.
had a higher reflectance based on the higher 4. M. Heyde, K. Rademann, B. Capella, M. Geuss, H.
transparency at long wavelengths of MgF2 Sturm, T. Spangenberg, H. Niehus, Rev. Sci.
deposited by evaporation. The highest reflectance Instrum. 72 (2001) 136.
measured at 121.6 nm for samples with IBS MgF2 5. Martin Bischoff, Maik Sode,et.al., Metal fluoride
was 0.866. coatings prepared by ion-assisted deposition Proc.
of SPIE Vol. 7101 71010L-1.
(iii) An obvious disadvantage of the
6. U.S.Patent Document :4,387,960-6/1983 Hakuzo
application of ion beams in general is the added
Tani
expense and complexity of the coating process.
7. U.S. Patent Document :4,599,272-7/1986 Hajime
However, neither of these is severe. Another one is Ichikawa
that it is more difficult to scale the ion beam 8. U.S. Patent Document :3,883,214-3/1975 Richard A.
sputter process compared to magnetron or some Hoffman
other sputter process. Geometrics of the ion beam 9. U.S. Patent Document:0058261A1-3/2012, Hitoshi
sputter arrangement must sometimes be small in Ishizawa et.al.,
order to provide reasonable deposition rates, and 10. John R. McNeil et al., Ion Beam Deposition,
this might be a problem. Also, a large amount of Jinghong vacuum Thin film co. Ltd.,
maintenance required to keep the ion source 11. Harper, J. M. E., Thin Film Processes (J. L. Vossen
and W. Kern, eds.), pp. 175 206, Academic Press,
operating.
New York (1978).
(iv) Martin Bischoff et. al.,[5] observed that 12. Wilson, R. G., and Brewer, G. R., Ion Beams with
the optical constants of the MgF2 single layer Applications to Ion Implantation, Wiley, New York
prepared by electron beam evaporation are good. (1973).
Though it is like that, H. Krger et al.,[15] showed 13. Denis Bade, Optical & Electronic Properties of
Magnesium Fluoride Layers, yearbook 2004, DIT,
that the optical constants of the solgel MgF2-
School of Physics.
films determined by ellipsometry are in good
14. Juan I. Larruquert, Ritva A.M. Keski-Kuha, Far
agreement with literature values of bulk-MgF2.
ultraviolet optical properties of MgF2 films
The film indices of refraction are smaller than deposited by ion-beam sputtering and their
those of the bulk phase due to a lower density of application as protective coatings for Al Elsevier,
the MgF2-films as compared to the bulk material. Nov 2002.
The absorption of the MgF2-layers in the UV 15. Hannes Krger, Erhard Kemnitz, Andreas Hertwig,
appears to be higher than literature data suggest. Uwe Beck, Transparent MgF2-films by solgel
coating: Synthesis and optical properties, Elsevier
Conclusion Nov 2007, Thin Solid Films 516 (2008) 41754177.
It was found that the sol-gel process, also
known as chemical solution deposition, a wet-
chemical technique widely used in the fields of
materials science and ceramic engineering has
more advantages. This is an easy-to-use method,
which is used primarily for the fabrication of
materials (typically a metal oxide) starting from a
chemical solution which acts as the precursor for
an integrated network (or gel) of either discrete
particles. The advantages offered by the sol gel
process are, it uses relatively low temperature, it
can create very fine powder and it produces
compositions not possible by solid-state fusion.
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