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Single-crystal cheinically/isotopically pure synthetic diamond operated at low
temperature offers an unusual opportunity for a small transparent optic that may transmit
as much as tens to hundreds of megawatts of light , even in the presence of high peak power in
the light beam. This property stems from the probable very low absorption of light in such
material and the nature of the phonon energy transport at low temperatures.
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Pure diamond has excellent mechanical and infra red properties and would make an
ideal window material were it readily available. Synthetic diamond films can be
grown with good infra red transmission and used as protective coatings. Many
coating requirements can already be met using diamond-like carbon films.
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Boron doped diamond films were deposited onto (100) orientated Si
substrates using a thermal filament CVD method. Boron trioxide was
used as a doping source and samples with boron to carbon (B/C)
ratios of 0, 10, 100, and 1000 ppm were prepared for the optical
measurements. The infrared (IR) results reveal the formation of an
ultrathin SiC layer at the interface between Si and diamond.
Furthermore, the IR data confirm the resistivity data obtained
from electrical measurements. Raman spectroscopy was used to probe
the quality and homogeneity of the diamond films. Upon increasing
B/C ratio the diamond phonon line shifts to lower frequency and is
also broadened revealing a softening of the diamond. In addition,
the optical absorption was found to increase strongly with
increasing B/c ratio.
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The exceptional properties of diamond have stimulated a considerable research effort into the low pressure
synthesis of diamond thin films for a diverse range of applications including:-. tribological coatings,
semiconductor heat sinks and (as in this work) protective optical coatings. Numerous deposition
techniques have been reported in the literature including Microwave Plasma Assisted Chemical Vapour
Deposition (MPACVD). This paper briefly describes the MPAC\'D deposition system used at Plessey
Research Caswell Limited and outlines the effects of important deposition parameters on the growth
morphology of diamond crystallites and thin films. Techniques including SEM, ThM and X-ray
diffraction have been used to study the growth mechanisms of MPACVD diamond.
JR and Raman spectroscopy have been used to characterise the deposited films and an JR reflection
technique is described for studying the infrared properties of the layers. The effect of deposition
parameters on the properties of diamond thin films is discussed with regard to the use of these films for
protecting JR windows and domes.
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Carbon, Carbides, Nitrides, and Phosphides in Optical Coatings
A requirement exists for more durable windows for airborne applications to improve
their survivability under highly erosive conditions. A range of materials show
potential including nitrides, phosphides, carbides and diamond. This paper will
address the phosphide materials system and review the various possibilities
available. Materials such as gallium phosphide show promise for use In the infrared
on the basis of their behaviour in bulk form, with significant lattice
absorption bands only apparent at wavelengths beyond l2jnn. Other known phosphides
include those of Al, B, Si, Mg, In, Zn, Cd, Rb, Ir, Ni, Go, Y, Sc, Ti, Nb, Mo, W, Th
as well as several of the rare earth elements. Ternary systen have also been
examined, largely as bulk materials. Recently the potential of phosphide materials
for infra-red applications has been highlighted by the deinstration of high
durability in amorphous coatings of boron phosphide deposited by plasma assisted
chemcal vapour deposition. The levels of durability obtained have exceeded those
characteristic of diamond-like carbon, whilst allowing simultaneous transmission of
both IR bands and the important 1.O6im wavelength. Here there is significant
evidence of the role of non-stoichiometry, with P/B ratios of as high as 7 being
typical. Some forms of amorphous phosphorus itself have been known to demonstrate
remarkable stability, with samples remaining atomically clean in dry air for
significant periods of time. Various other forms of high phosphorus polyphosphides
are known, such as those containing alkali metals in a bridging configuration
between phosphorus skeletons. These can be produced as thin films and exhibit high
levels of stability and adhesion.
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Diamondlike a-C:H films have been deposited by decomposition of acetylene.
By the combination of Brillouin scattering and the ultralow load
indentation technique, the following mechanical properties of the films
were studied: the microhardness, H, the Young's modulus, E, the shear
modulus, Ii , and the Poisson's ratio, v. From the measured data of mass
density, hydrogen concentration and the ratio of sp3/sp2 bonds the f illing
factors of these films were calculated. The results show that the
hardness,Young's modulus and shear modulus of these films depend stongly
on the volume concentration of voids and are directly proportional to
the filling factor.
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Diamondlike amorphous hydrogenated carbon (a-.C:H) films have found widespread use as
hard coatings for IR optical applications. The refractive index of these films (n=2) allows the
deposition of quarter-wave antireflection coatings on germanium. More complex optical
designs, however, require the extension of the range of the optical constants. For this reason
we studied amorphous hydrogenated carbon-germanium alloys. The corresponding
a-C1 xc3ex H films with 0 < X < 1 were grown by ri-plasma deposition using mixtures of a
hydrocarbon gas and germane or tetramethylgermanium (TMG) as precursors. Film
composition, refractive index and IR absorption spectra were measured. This material system
offers the possibility to adjust. the refractive index between 1 .8 and 4.1 and thus allows the
deposition of multilayer thin film systems for IR optical applications. As a result of numerical
design calculations, a three layer structure with a hard a-C:H top layer is proposed, which acts
as a broadband antireflection coating on germanium substrates for 8-1 2 j.m. We report on the
growth and performance of these hard multilayer AR coatings.
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Deposition and Characterization of Optical Hard Coatings
The fundamental possibifity to synthesize diamond under low pressure from the gas phase as a metastable carbon allotrope is
known nearly as long as the high pressure route to this valuable material. Nevertheless more than twenty years elapsed, befoie
research activities were started world-wide aiming atthe development ofdepositionprocesses meeting the demands of technical
applications. In this review the present state ofthis work will be surveyed, with an emphasis on those topics which are of critical
importance for an eventual success of a diamond technology: Scale-up of deposition processes, low temperature deposition,
heteroepitaxy and control ofnucleation, mechanical adhesion, and electrical properties ofdiamond films.
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Tin was sputtered from a DC planar magiistrcn target in a confined volume , stabilitywas maintained in the reactive
sputtering by controlling the oxygen partial prire throogh observation of this liajit emitted by the oxygen in the -ofthe magnetron. The material deposited on this walls of the chamber was designed to getter this system of
imt, The oxygen coisumption at the set point was a good indication oftlis approach to stoichiometiy of tbo
film. It was observed that trazspazent oonckxting filnis were prepared at the point where this oxygen comaimption
indicated a break from fill izxorporalion into the growing film. Films there had a resistivity of 100 micro
ohm-meters for a 600 ohms per sqisze sheet restance, a thickne ofabont 150 naix>.meters. Tlisse filnis showed
some o1 absorption in the bhis regkm oftho spectziim. Optically clear filnis required preparation in a greater
oxygen rteeane which reckd the rate ofdeposition by a factor c(two. The refractive index was measuied
as2.Oat633nm.
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High quality dielectric films are required today for various interference optical
applications and for planar wave guides in integrated optics. Many inorganic
chemical compounds which were difficult to deposit by conventional techniques in
form of well adherent, dense, hard and stable low-loss films are now routinly synthesized
by reactive gas discharge plasma and energetic ion and/or coating materials
atom processes. A survey over such PVD coating technologies and on the resulting
film properties is given in this paper.
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Silicon nitride films were synthesized in a Balzers BAP 800 coating plant by an
plasma enhanced evaporation process. Transparent, stoichiometric films free of
hydrogen, oxygen, argon, and heavy metals were obtained. The optical properties,
the chemical composition, the microhardness, the structure, and the morphology of
the films were investigated.
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An empirical relationship between the long wavelength edge of the residual ray band in the IRreflectance
of partly ionic compounds and bulk hardness is demonstrated. The group of materials studied
includes alkali halides, semi-conductors and some hard compounds, mostly with cubic structure and a few
with hexagonal. The correlation is shown for the Young modulus, the melting temperature and also to
some extent the indentation hardness. The Young moduli cover a range from 10 to almost 500 GPa and the
melting temperatures vary from 600 to 3000°C.
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There are increasing demands of surface modification of transpar-
ent substrates such as glass and plastics for windows in automobiles as
well as houses in view of adding them fascinating optical properties.
These properties include surface hardening of plastics, infrared re-
flection, ultraviolet absorption, optical switching and birefringence.
This paper reviews recent examples of applications of sophisticated
thin film processes of plasma treatment and Physical Vapour Deposition
(PVD). The novelty of functions by PVD method together with their
durability for practical usage are emphasized as areas where the thin
film process has a significant impact. Characterization of the
modified surface and interface is also included to demonstrate recent
advances in surface chemistry. Finally, future challenges for optical
modification of transparent substrates in the automobile industry are
also discussed.
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Infrared transparent amorphous hydrogenated alloys of
germanium and carbon (germanium carbide) have been deposited
by plasma assisted chemical vapour deposition (PACVD) using
germane (GeH4 ) and butane (C 4Hid as the feedstocks and by
reactive sputtering of germanium with a CH1g-Ar plasma. The effects of varying various deposition conditions have been
assessed on a number of coating properties . Germanium
Carbide has good environmental durability and can be
deposited in thick layers. Using PACVD it can be deposited
with any refractive index in the range 2 to 4 while the
sputtering process is limited to indices in the range 3 to
4 . One advantage of the sputtering process is the high
deposition rates achievable which can be up to '-lOum/h
compared with lum/h for the PACVD process. When used in
conjunction with "diamond-like" carbon (a-'C:H) , germanium
carbide offers the prospect of rnultilayer antireflection
coatings for 8 to 12 urn optics with durabilities which
hitherto have been impossible to achieve. Antireflection
coatings for zinc sulphide windows which are subject to
hostile environmental conditions have been investigated and
the performance of the coatings is presented. The factors
affecting the practical realisation of these coatings on a
production scale are discussed.
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Using a parallel plate reactor we optimized a PECVD process and
coated Si02-films on CR 39 lenses with layer-thicknesses of 2,5 trn to
5 I_tIn. Besides high transmittance in the VIS-range we obtained
refractive indices between n=1.46 and n=1.49 depending on the process
parameters. We achieved deposition rates up to 30 A/s and thickness
uniformities of 10 %. The abrasion resistance of these layers were
tested with different inethodes and gave better results compared with
techniques like lAD or lacquering.
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The inf1ere of simulated space environment on the prcpert ies of the
satel 1 i te temperature-control coat ing --- Optical Sol ar Ref1etor (OSR) is
discussed. I kinds of CSR sample are tested in the simu1at1 space
environment . The simulat ion i tens include vacuum US? irradi at on, electron and
proton i rradiat ion . The surface charge/discharge test is carried out tcx . After
the ecron, proton and UV accelerat ive irradiat ion of total dosage equivalent
to 7 years at the south or north pale of geosyixthrcrx,us satellite, the solar
aI:sorptaire increases from 0 .068 to 0 . 078 for cczxkt ive C , and from 0 . 066 to
0 . 085 for ncn-oonduct ive OSR; the normal ni ttance decreases from 0 .83 to 0.72
for conditive OSR, and from 0.82 to 0.76 for non-conductive OSR. Also, it is
shown from the charge/discharge test that the surface charge potential is only
I5--40 V for conduct ive CSR, and about 1 --1 0 Ky for non-conduct ive CSR.
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The chemical and mechanical stability of tin oxide coated aluminium reflectors have been investigated.
The tin oxide has been applied with the pyrolytic spray technique which results in a hard crystalline
coating. Tin oxide is a wide bandgap semiconductor and is transparent in the visible part of the
spectrum. The visual appearance of tin oxide coated aluminium is therefore similar to the uncoated
metal. Interference effects can give a slightly coloured appearance, and owing to the higher refractive
index and extinction coefficient of the tin oxide the reflectance is lower than for an anodized aluminium
surface. The tin oxide was applied both on electropolished aluminium and on evaporated aluminium
films on glass. In both cases an improved resistance both to alcaline and acid solutions was noted. It
was found that the chemical stability was better than for an anodized surface. The mechanical stability of
the evaporated film was considerably improved. The electropolished samples were also characterized
with respect to film hardness and resistance to erosive and abrasive wear. The hardness of the tin oxide
was found to be higher than that of the anodized layer while the opposite relation applied for the erosive
wear resistance. The abrasive wear resistance was about equal for tin oxide coated and anodized
aluminium.
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