ELSEVIER Surfaceand Coatings Technology82 (1996) 110-113

Optical transmittance of antireflective diamond-like coatings on ZnS

substrates
G.F. Zhang, X. Zheng
Department of Materials Science and Engineering, Northwestern Polytechnical University, Xian 710072, People’s Republic of China
Received 10 May 1995; accepted in final form 31 July 1995

Abstract

Diamond-like carbon films were prepared from C,H, and Ar by r.f. plasma chemical vapor deposition. The hydrogen content
and ratio of sp3 to sp’ bonds in the deposited films were investigated as a function of negative d.c. bias voltage. The deposited
films were characterized by spectroscopic ellipsometry and IR spectrophotometry. The results show that the ratio of sps to sp2
bonds and the hydrogen content of the deposited films increase with increasing bias voltage VB. The percentage of sp’ carbon sites
decreases with V, and disappears when V, reaches 700 V. The optimum condition for depositing antireflective diamond-like carbon
coatings onto the II-VI compound zinc sulfide was achieved by optimizing the deposition process. The peak IR transmission of
the zinc sulfide substrate coated with DLC films on both sides reached 95.8% at a wavelength of 2.5 lun, and the reproducibility
of the results is excellent. The change in IR transmittance of the DLC coated zinc sulfide substrate after annealing in atmosphere
for 2 h at temperatures up to 300 “C shows that the film is thermally stable.

Keywords: Diamond-like carbon Urns; Bonding; Hydrogen content; IR antireflection; Zinc sulphide

1. Introduction However, this material is soft and often degradeswhen

Diamond-like carbon (DLC) films have a number of
properties which make them suitable for antireflection
and scratch protective coatings on IR optics and for
wear-resistant coatings for tools, etc. These properties
include good IR transparency, high hardness, chemical
inertness and impermeability to moisture [1,2]. Up to
the present, numerous studies have been conducted on
the preparation, properties and application of DLC
films. Previous experiments have shown that there exist
different kinds of carbon bonds, i.e. sp3,sp* and sp’, as
well as various C-H bonding configurations [ 31. The
properties of DLC films depend strongly on the ratio of
sp3-to-sp* bonds and the hydrogen content [4]. The
experimental laws governing the change in the sp3-to-
sp* ratio and the hydrogen content with deposition
parameters, however, are not exactly identical even for
the samedeposition method. Therefore, it is very impor-
tant to investigate deposition parameter-structure-prop-
erty relationships in order to obtain an insight into the
applications of DLC films for mechanical and optical
industries.
Zinc sulfide (ZnS) is often used as an optical window,
owing to its high transmittance at IR wavelengths.
subjected to a particle-impacting environment. DLC
films have been evaluated as protective coatings for ZnS
IR transmitting windows exposedto particle erosion. In
our previous work, it was reported how a DLC film was
deposited directly onto a ZnS substrate with excellent
adhesion to protect the ZnS from corrosion and scratch-
ing, and the maximum value of IR transmission of ZnS
coated with DLC on both sideswas 90% [5].
In the present study, we investigated the relationship
between the deposition parameters and the sp3-to-sp*
ratio and hydrogen content, which provided a scientific
basisfor optimizing the deposition process.An optimum
deposition technology for DLC antireflection coatings
is obtained on the basis of our investigations. The
thermostability of DLC films was also investigated.
2. Experimental details
DLC films were synthesized using an r-f. plasma
chemical vapor deposition (CVD) systemwith parallel
electrodes, as reported in previous work [S]. A 20-60
vol.% acetylene in argon gas mixture was admitted to
the reactor at a total flow rate of 7.2 standard cm3
 G.F. Zhang, X. Zheng/Surface
mm-l, controlled with two mass flow meters, with a
reactor pressure of 5-12 Pa maintained by throttling the
mechanical pump valve during tYm deposition. The r.f.
power was kept constant at 55 W in all experiments.
The negative d.c. bias voltage was changed continuously
from 300 to 1000 v. The temperature of the substrate
materials did not exceed 80 “C during the deposition
process.
ZnS and Si substrates were used to deposit DLC films
for optical applications. Before the deposition, the sub-
strates were cleaned in acetone, methanol and trichlore-
tylene ultrasonic baths and bombarded in situ with
argon plasma (7 min, acceleration voltage 1 kV) at a
pressure of 4 Pa.
The refractive index and thickness of the DLC films
were measured at 0.6328 urn using a laser ellipsometer
and also an interferoscope for measurement of the film
thickness. The IR transmittance in the range
4000-400 cm-l was measured using a GOSXR Fourier
transform IR (FTIR) spectrometer. The spectra were
recorded at a resolution of 4 cm-l and averaged over
32 scans. The sp3 : sp2: spl ratio was calculated from the
integrated absorption of the C-H stretch vibrational
bands in the range 2780-3060 cm-’ [6]. The hydrogen
content was determined by combustion analysis.
3. Results and Discussion
3.1. Relationship of the bias voltage with bonding and
hydrogen content
Different kinds of bonding configuration and their
relative concentrations in DLC films were obtained from
IR absorbance spectra. The relationship between the
negative bias voltage and the percentage of sp3, sp2 and
spl carbon sites is shown in Fig. 1. The ratio of sp3 to
sp2 bonds increases with increasing negative bias voltage,
and the percentage of sp’ bonds reduces and vanishes
when the bias voltage exceeds 700 v. It is known that
the addition of argon or hydrogen or oxygen to the
hydrocarbon source gas results in sputtering out of the
g Go-
$ 40-
8 SPZ
20-N
0 2
E SP’
h
300 500 700
BIAS VOLTAGE (V)
Fig. 1. Percentage of sp3, sp2 and sp’ carbon sites as a function of
negative bias voltage.
and Coatings Technology 82 (1996) 110-113 111
weakly bonded graphitic phases from the growing films
[7-lo]. The d.c. bias between the plasma and the
electrode influences Ari acceleration across the sheath
space, and hence the sputter efficiency. Therefore a
higher proportion of Ar atoms in the chamber will be
ionized with increasing d.c. bias voltage. In this case, the
result is an increase in the sp3-to-sp2 ratio, and hence
the hardness, refractive index and other diamond-like
characteristics, which is in good agreement with the
results of Koidl et al. for a-C : H films deposited from a
benzene discharge and previous results reported by
us [ 11,121.
The relationship between the hydrogen content and
negative bias voltage is shown in Fig. 2. It can be seen
that the hydrogen content varied within 15-30 at.%
with variation of the bias voltage within 500-900 V. The
experimental result is not in agreement with the results
of Wood and others [ 11,13,14]. The conticting results
should reflect the different deposition conditions.
However, our experimental observations confirmed the
theoretical prediction of Angus and Hayman [ 151 and
the results of Kleber and coworkers [ 16,171, where an
increase in the H-to-C ratio leads to an increase in the
sp3-to-sp2 bond ratio. Generally, high sp3-to-sp2 ratios
and hydrogen contents lead to high hardness, internal
stress, and refractive index. However, a decrease in
hardness and internal stress with increasing sp3-to-sp2
ratio and hydrogen content was found by Zhou et al.
[3] for C,H,-based films. One possible explanation for
these differences is the presence of voids in the amor-
phous network so that the void concentration determines
the mechanical properties rather than the sp3-to-sp2
ratio or the hydrogen content. In our experiment, the
concentration of argon gas is up to 70%. Therefore, the
effect of voids on the properties is not dominant.
3.2. Antirejective DLC coating on ZnS
The refractive index of zinc sulfide is about 2.3 at a
wavelength of 2.5 urn, resulting in a reflection of 15.5%
from a single surface and of 27% for a slab allowing for
multiple reflection. The refractive index of DLC films
varies from 1.5 to 2.9 depending on the deposition
methods and conditions. In our laboratory, the refractive
g‘_;.:/i,
l
2
8 .
r\ 25
0”
20 .
c
900 8&
vx 15
500 600 700 800 90(
BIAS VOLTAGE (V)
Fig. 2. Effect of bias voltage on the hydrogen content.
112 G.F. Zhang, X. Zheng/Surjace and Coatings Technology 82 (1996) 110-113
index of the films deposited onto ZnS increased from
1.7 to 1.95 when the bias voltage was changed from 300
to 900 V. Therefore, the theoretical maximum values of
IR transmittance of ZnS with single-layer DLC films on
both sidesare 88%-97%. A previous paper has already
shown that the deposition parameters which influence
the optical and mechanical properties of DLC films are
interrelated, which implies that identical values of refrac-
tive index can be obtained from different process
parameters.
The IR transmittance spectra of ZnS substrateswith
DLC films obtained at acetylene percentages of
lo%-60% for the higher bias voltage (e.g. 1000V) were
very similar. It was not until an acetyleneconcentration
of 100% that the transmittance changed dramatically.
From the relationship betweenthe transmittance spectra
and the acetylene flow, the following information was
obtained: with rising C2H2 gascontent (a) the IR absorp-
tion peaks near 2900 cm-l of CH2 and CH, groups
decrease,(b) the IR transmittance at %/4remained nearly
constant (except for 100% C,H,), and (c) the peak
transmittance shifted gradually to lower frequencies.The
above-mentioned results led to the conclusion that the
growth rate is susceptible,while the refractive index is
not susceptible, to changes in the acetylene content
under high bias voltage. On the contrary, the influence
of the C2H, content on the refractive index is obvious
under lower bias voltage, as shown in Fig. 3, where
curves A and B are for films deposited onto both sides
of the ZnS substratesfrom 35% and 45% CzHzrespec-
tively. Fig. 4 shows the relationship between the IR
transmittance of ZnS substrates with DLC films on a
single surface deposited from 60% C,H, with bias
voltage. It is clear that either a lower or higher bias
voltage results in a decrease in the IR transmittance.
The crest value of transmittance was found at 500 or
700 V bias voltage in the region 2.5-12 pm.
In summary,in order to enhancethe IR transmittance
of ZnS substratesa lower bias voltage should be adopted;
4000 2666 1666
, LJI
1000 333
WAVENUMBER (cm-‘)
Fig. 3. IR transmittance spectra of ZnS substrates with DLC films on
both sides, acetylene content 35% (A), 45% (B,C); deposition time
70 min (A,B), 90 min (C).
I I
400 500 600 700 800 900
BIAS VOLTAGE(V)
Fig. 4. IR transmittance spectra as a function of bias voltage.
the decreasedeffect of sputtering out the weakly bonded
graphitic phasescan be remedied by increasing the Ar
concentration. Optimum deposition conditions are as
follows: 500-800 v (but not 600 v) bias voltage and
30%-50% CzH2 concentration. The IR transmittance
spectra of the films synthesized under the optimum
conditions for 70 (curve B) and 90 (curve C) min
respectively are shown in Fig. 3. It can be seenthat the
IR transmission is significantly improved in the wave-
length region 2.5-12 ltm. The peak transmission of a
ZnS substrate with DLC films on both sides reaches
95.8% in the 2.5 pm wavelength band, which is close to
the theoretical prediction. It can also be seenfrom Fig. 3
that the experimental results have very good repeatabil-
ity but the growth rate is much slower compared than
that reported previously [ 121. The peak of the transmis-
sion shifts slightly to a longer wavelength when the
deposition time is increased from 70 min to 90 min.
Therefore, the wavelengths at which the optical thickness
of the DLC films corresponds to Iti/4 are moved to
8-12 pm.
Owing to its good abrasive resistance,DLC film is a
candidate material for protective optical dome and
window coating. Moreover, the wide range of refractive
index values achievable offers the possibility of adjust-
ment with a single-layer antireflection coating. Many
experimental results have shown that direct preparation
of DLC films on ZnS substratesto act as both protective
and antireflective coatings is difficult [ 18-201. Firstly,
the considerable absorption losses and high internal
stressof the layers prevent the preparation of coatings
thicker than 1 pm, which would be necessaryto protect
the substratesagainst dust and rain erosion. Secondly,
there is a general problem concerning the adhesion of
DLC films to ZnS substrates.Moreover, to improve the
effectiveness of the antireflection, the thickness of a
single-layer DLC film is restricted to less than 1 pm,
typically only 0.357 pm for the deposited films in this
report. An effectual measure to solve the contradiction
between protection and antireflection is to adopt multi-
layer coatings including boron phosphide or GeC alloys
and DLC films.
 G.F. Zhang, X. ZhenglSurface and Coatings Technology 82 (1996) 110-113
IV”
!2
E 40-
4000 2666 1666 1000 333
WAVENUMBER (cm-‘)
Fig. 5. IR transmittance spectra from as-deposited DLC Urn and
annealed DLC 6lms.
3.3. Temperature effect of DLCjilms on ZnS
The thermal stability of the DLC coated ZnS substrate
was tested by heating in atmosphere at 100, 200, 300
and 400 “C respectively for 2 h. Fig. 5 shows the spectra
of DLC/ZnS as a function of the annealing temperature.
It can be observed that the high frequency transmittance
decreases below 200 “C. The intensity of the absorption
peaks centered around 2900 cm-l, 1450 cm-l, and
1370 cm-l, indicating the C-H asymmetry stretch vibra-
tion, C-CH, asymmetric and symmetric deformations
respectively [9], decreases with the annealing temper-
ature. At 400 “C, the peak at around 2900 cm-l disap-
pears, and an spl C-H stretch and an sp2 C-C stretching
mode appear at around 3200 cm-’ and 1600 cm-’
respectively. These observations indicate that (1) the
films starts to lose hydrogen above 300 “C, (2) the
conversion of amorphous carbon to microcrystalline
graphite has occurred, and (3) a small amount of hydro-
carbon polymer starts to form during annealing for
temperatures up to 400 “C. No C=O bond centered
around 1714 cm-l [21] was observed, i.e. the DLC film
was not oxidized under annealing at 400 “C in
atmosphere.
4. Conclusions
Our investigations reveal that the sp3-to-sp2 bond
ratio and hydrogen concentration in the deposited films
increase with negative bias voltage. An excellent antire-
flection DLC film on ZnS substrate can be obtained at
500 V bias voltage and 30%-50% acetylene concen-
tration. The IR transmittance of ZnS coated on both
surfaces with DLC in the wave band between 2.5 and
12 pm is greatly enhanced and the peak IR transmittance
113
at 2.5 pm has reached 95.8%, which is close to the
theoretical value. Annealing at temperatures lower than
300 “C has no appreciable effect on the IR transmittance
of DLC-coated ZnS substrates.
Acknowledgments
The authors wish to thank the Chinese Aeronautics
and Astronautics Establishment and Hong Kong Chiang
Industrial Charity Foundation for their support under
grant No. RC92119.
References
Cl1 F. Richter, K. Bewilogua, H. Kupfer, I. Miihling, B. Rau,
B. Rother and D. Schumacher, Thin Solid Films, 212 (1992) 245.
PI N. Mutsukura, S. Inoue and Y. Machi, J. Appl. Phys., 72(l)
(1992) 43.
[31 J.W. Zou, K. Schmidt, K. Reichelt and B. Dischler, J. Appl.
Phys., 67 (1990) 487.
c41 X. Jiang, K., Reichelt and B. Stritzker, J. Appl. Phys., 68(3)
(1990) 1018.
[51 G.F. Zhang, L.J. Guo, Z.T. Liu and X. Zheng, Opt. Eng., 33(4)
(1994) 1330.
C61 D.R. He, X.Y. Ji, R.B. Wang, Q.H. Liu, W.D. Wang, M.L. Liu,
W.Z. Chen, Z.Y. Liu, W.X. Ji and R.J. Zhang, J. Mater. Sci.
Lett., 9 (1990) 1371.
c71 G. Amaratunga, A. Putnis, K. Clay and W. Milne, Appl. Phys.
Lett., 55(7) (1989) 634.
PI Y. Suefuji, Y. Nakamura, Y. Watanabe, S. Hirayama and
K. Tamaki, Thin Solid Films, 236 (1993) 77.
[91 5. Seth, R. Padiyath and S.V. Babu, J. Vat. Sci. Technol. A,
10(2) (1992) 284.
Cl01 W. Zhang and Y. Catherine, SUI$ Coat. Technol., 47 (1991) 69.
Cl11 P. Koidl, Ch. Wild, B. Dischler, J. Wanger and M. Ramsteiner,
Mater. Sci. Forum, 52-53 (1989) 41.
[121 G.F. Zhang, X. Zheng, L.J. Guo, Z.T. Liu and N.K. Xiu, Su$
Coat. Technol., 64 (1994) 127.
El31 P. Wood, T. Wydeven and 0. Tsuji, Surf. Coat. Technol., 49
(1991) 399.
Cl41 C. Serra, E. Pascual, F. Maass and J. Esteve, Surf. Coat.
Technol., 47 (1991) 89.
Cl51 J.C. Angus and CC. Hayman, Science, 241 (1988) 913.
[K R. Kleber, W. Dworschak, J. Gerber, A. Krtiger, K. Jung,
H. Ehrhardt, S. Schulze, I. Mtihling, S. Deutschmann, W. Scharff,
F. Engelke and H. Metz, Mater. Sci. Eng. A, 140 (1991) 775.
Cl71 M. Weiler, S. Sattel, K. Jung, H. Ehrhardt and VS. Veerasamy,
Diamond Relat. Mater., 3 (1994) 608.
Cl81 M.J. Mirtich, D. Nir, D. Swec and B.A. Banks, J. Vat. Sci.
Technol. A, 4 (1986) 2680.
[I91 D.M. Swec, M.J. Mirtich, D. Nir and B.A. Banks, J. Vat. Sci.
Technol. A, 4 (1986) 3030.
PO1 F. Davanloo, T.J. Lee, H. Park, J.H. You and C.B. Collins,
J. Mater. Res., 8( 12) (1993) 3090.
PI D.S. Kim, T.E. Fischer and B. Gallois, SurjI Coat. Technol., 49
(1991) 537.