Mat.-wiss. u. Werkstofftech. 2013, 44, No. 8 DOI 10.1002/mawe.

201300171 661

Development of a ta-C diamond-like carbon (DLC) coating by

magnetron sputtering for use in precision glass molding
Entwicklung einer ta-C-Beschichtung mittels Magnetron-Sputtern zur
Anwendung im Pr
zisionsblankpressen

F. Bernhardt1, K. Georgiadis1, L. Dolle1, O. Dambon1, F. Klocke1

Diamond-like carbon (DLC) coatings have become the most versatile class of coatings in various
applications. However, most methods are not practical for industrial fabrication chains. The
work presented here the deposition of ta-C (tetrahedral amorphous carbon = ta-C) coatings on
molding tools for use in precision glass molding by Magnetron Sputtering Ion Plating (MSIP).
The coating properties are analyzed by Scanning Electron Microscopy (SEM), Raman spectro-
scopy and molding tests. By using ion plating, carbon bonds can be induced to change towards
the sp3 form by increasing the internal coating stress. Using this technique, it was possible to
increase the sp3 ratio to about 60%, whereas 40% or less is often reported for conventional
sputtering.
Keywords: Precision glass molding / MSIP sputtering / Ion plating / diamond-like carbon / DLC / ta-C /
thermo-chemical resistance /

Diamant
hnliche Kohlenstoffschichten (Diamond-like-carbon Schichten (DLC)) haben sich zur

vielseitigsten Werkstoffklasse in verschiedensten Anwendungsbereichen entwickelt. Dennoch
sind die meisten Prozesse fr industrielle Fertigungsketten ungeeignet. Die hier pr
sentierten Ar-
beiten zielen auf die Magnetron-Sputtering-Ion-Plating Abscheidung (MSIP) von ta-C-Beschich-
tungen auf Glasformeins
tze ab, die im Pr
zisionsblankpressen eingesetzt werden sollen. Die
Schichteigenschaften wurden mittels Rasterelektronenmikroskopie (REM), Ramanspektrometrie
und Presstests analysiert. Durch das Ionenplattieren werden die Kohlenstoffbindungen ber er-
hhte Filmspannungen zur Bildung hherer sp3-Anteile angeregt. Dadurch war es mglich den
sp3-Anteil auf rund 60% zu steigern, gegenber bisher konventionell erreichten 40% oder weni-
ger.
Schlsselwrter: Pr
zisionsblankpressen / MSIP-Sputtern / Ionenplattieren / Diamond-like carbon / DLC /
ta-C / thermo-chemische Best
ndigkeit /

1 Introduction
Precision glass molding (PGM) of glass is a replicative technol-
ogy for producing high precision lenses for the optical industry
at medium and high volumes. Since the demand for highly com-
plex shaped lenses, e. g. for laser or medical applications, has
increased immensely during the last years, precision glass mold-
ing has become the technology of choice, since direct grinding
and polishing of complex-shaped lenses is neither practical nor
economical [1]. Under vacuum, the upper and lower pressing
molds as well as the glass preform are heated up to a glass spe-
cific temperature (400–800 8C) – therefore the technology is also
known as »isothermal glass molding«. After that, the glass is
1
Fraunhofer Institute for Production Technology, Aachen, Germany
Corresponding author: Frank Bernhardt, Fraunhofer Institute for Pro-
duction Technology, Steinbachstraße 17, 52074 Aachen
E-mail: frank.bernhardt@ipt.fraunhofer.de
molded to the shape of the upper and lower mold die in nitrogen
atmosphere. During cooling, the glass undergoes phase transi-
tions and shrinks to its final shape.
However, the economic viability of the process strongly
depends on the service lifetime of the molding tools. Most critical
failure causes are glass sticking on the mold surface and thermo-
chemical corrosion phenomena after several pressings, which
increase the surface roughness outside the specs. Therefore,
coatings on the optical mold surfaces are used to delay their deg-
radation. Besides noble metal and ceramic coatings, diamond-
like carbon (DLC) coatings are increasingly used as protective
coatings in precision glass molding. Diamond-like carbon (DLC)
is a term that is used to describe a great variety of carbon-based
coatings with sometimes substantially different compositions,
structures and properties [2–3]. So-called ta-C Diamond-like car-
bon (DLC) coatings have shown the most promising results in
the glass molding application, but their deposition requires the
use of specialized processes (FCVA, PLD etc.) that are not com-
mon in the industry.

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662 F. Bernhardt et al.
The present work describes the development of ta-C coatings
for the protection of precision glass molding molds during glass
pressing using the ubiquitous MSIP deposition process. The
coatings must be able to withstand standard loads in precision
glass molding over many molding cycles, especially with regards
to temperature stability, hardness to withstand typical pressing
forces and von Mises stresses or thermo-chemical resistance to
typical glass types molded by precision glass molding technol-
ogy.
2 Diamond-like carbon (DLC) coatings in the
precision glass molding process
It is generally known that the chemical and mechanical proper-
ties of diamond-like carbon (DLC) coatings are mainly deter-
mined by the ratio of sp2/sp3 content, respectively for the graph-
ite and diamond modification of carbon, as well as their hydro-
gen content. Diamond-like carbon (DLC) ta-C coatings have high
sp3-modification content and no hydrogen content [4]. Thus,
these types of diamond-like carbon (DLC) coatings have a multi-
tude of advantages over conventional coatings, such as low chem-
ical reactivity, high, density, high hardness, smooth surface, low
abrasion rates in tribological contact and low affinity towards
glass sticking. With regards to other diamond-like carbon (DLC)
types, the fact that ta-C is hydrogen-free is considered to be the
main advantage for protection of precision glass molding tools in
glass contact. Currently, this kind of coatings are often realized
by Ion-Beam Sputtering, Pulsed Laser Deposition or other types
of technology using direct bombardment with ionized carbon
particles. By inducing high ion particle energies combined with a
good control of the ion energies, high sp3 modification content
can be realized. In general, conventional sputtering can induce a
sp3 content of <40%, since the carbon ions do not gain enough
energy and deposit with low momentum onto the substrate sur-
face, often unable to build up sp3 bonds. So, most carbon par-
ticles are cumulating in small grains with graphite modification
[5]. But, some approaches with conventional sputtering were suc-
cessful in producing high-grade carbon coatings with high sp3
content [5–6].
The fabrication of ta-C coatings with conventional sputtering
is highly desirable due to the high robustness of the coating proc-
ess. Furthermore, magnetron sputtered coatings are highly
established in various applications, e. g. also for producing noble
metal coatings on precision glass molding molds. Therefore,
existing equipment could be used, avoiding costly investments
and significant changes in the process chain regarding the over-
all industrial precision glass molding process. Nevertheless, ta-C
coatings have not been produced and assessed with regards to
the use for coating precision glass molding tools, so far.
Unbalanced magnetron sputtering cathodes that are also used
in this work have stronger magnets than other types, for extend-
ing the magnetic field and the plasma region towards the sub-
strate to induce an ion bombardment also on the sputtered coat-
ing surface. This effect is widely known as Ion-Plating. The
mechanism that associates Ion-Plating with a higher sp3 content
in the ta-C coating can be described by the following steps: (1) by
particle bombardment, C atoms are pressed more deeply into the
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Mat.-wiss. u. Werkstofftech. 2013, 44, No. 8
coating, (2) transfer of the incident particles kinetic energy
increases the coating density and (3) transition of sp2 to sp3 bonds
by inducing local stresses in the coating [6–7]. However, inducing
coating stresses is always at the expense of coating stability, i. e.
of the coating-substrate adhesion, increasing with coating thick-
ness. However, since precision glass molding coating thick-
nesses are rather <200 nm, unbalanced magnetron sputtering
resembles a promising technology for sputtering ta-C coatings.
3 Experimental details
3.1 Sample preparation
Plane samples of binder-free tungsten carbide (Ceratizit
CTN01L) were used as the substrate material. The material is the
same used in production tools and is nanoscopically fine-grained
so that high surface qualities can be achieved by grinding and
polishing. The samples were polished to a Ra <5 nm, using a con-
ventional Phoenix 4000. The samples were cleaned in an ultra-
sonic bath. For ease of analysis, Si wafers were also used as sub-
strates. All sample preparation steps were carried out in clean
room environment.
The samples were coated in a CemeCon CC800/9 industrial
sputtering machine, equipped with a graphite target on an
unbalanced magnetron sputtering cathode.
3.2 Design of experiments
Since the ta-C diamond-like carbon (DLC) coating needed to be
developed from the concept to practice, at first, different major
process parameter were investigated regarding their influence
on the coating quality and on the thermal stability. A full factorial
experiment has been carried out to identify the strength of influ-
ence of the parameters listed and the correlation strength among
them. The other process parameters were kept constant, Table 1.
Table 1: Coating deposition process parameters
Tabelle 1: Prozessparameter fr die Schichtabscheidung
Parameter Value Duration
Setup Target 2 Graphite
Heating Heating power 0 – 4000 W 4500 s
Etching Heating power 0 – 4000 W
Argon pressure 500 mPa
Bias voltage 650 V, 240 kHz, 60% 900 s
duty cycle
Coating Heating power 0 – 4000 W
Argon pressure 300 – 500 mPa
Bias voltage 0 – 200 V, 240 kHz,
60% duty cycle
Cathode power 0.5 – 1 kW, 50 kHz, varying
90% duty cycle
Samples fabricated are then analyzed and evaluated with
respect to their suitability in precision glass molding. The prop-
erties of promising samples are refined, whereas samples that
show low adhesion, low thermal resistance or other disadvanta-
geous properties for use as protective coatings in precision glass
molding, are excluded from further investigations.
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Mat.-wiss. u. Werkstofftech. 2013, 44, No. 8
3.3 Analysis of the coatings
The coating rate was determined by measuring the coating thick-
ness divided by coating time (power on the carbon cathode).
In order to characterize the coatings, light microscopy was
used to make a first level assessment of the coating quality. For
evaluating the coating microstructure, scanning electron micro-
scope pictures were taken with Zeiss Neon 40 EsB. Surface
roughness was measured using the Veeko Wyko NT1100 white
light interferometer in order to detect variations of the surface
roughness.
Raman spectroscopy measurements were carried out at
Fraunhofer ICT (He-Ne laser, 633 nm emission wavelength, 10 s
light exposure per spectrum taken, 2 spots measured per sample)
and Fraunhofer IWM (Renishaw3000, Ar laser; 514.5 nm emis-
sion wavelength, 60 s per 10 spectrums taken, 3 spots measured
per sample) for determining the sp2/sp3 ratio. Using fitting algo-
rithms on the basis of Lorentz fit and the BWT function, the sp2/
sp3 ratio was determined. The different ratios of the samples pro-
duced were compared during analysis. As a reference and to
show the validity of the sp3 determination method, a sample pro-
duced with FCVA, which is known to have very high sp3 content
was added to the analysis (sample no. 1000).
3.4 Annealing tests
Annealing tests were carried out by placing the coated samples
inside the vacuum chamber of the coating machine and anneal-
ing them at elevated temperatures for 8 hours, using three differ-
ent procedures and analyzing the coatings after each step. At
first, all samples they were annealed at 650 8C under vacuum at
2 mPa and without physical contact among them. Secondly, they
were annealed together with a glass gob of B270 glass (Schott) at
630 8C, which is the molding temperature of this glass which is
frequently used in precision glass molding. Thirdly, the samples
were annealed at 590 8C, placing a glass gob of Schott P-LASF47
at the coating surface. This glass type is known to be chemically
aggressive towards different coating types.
3.5 Molding tests
Molding tests for assessing the performance of the coatings were
carried out at an industrial Toshiba GPM 211 glass molding
machine. The lanthanum containing P-LASF47 glass was
pressed at 590 8C, under 3 kN pressing force, 0.8 kN holding
force and 100 s pressing time. Roughness measurements and
Raman measurements were carried out to assess the coating per-
formance in real precision glass molding processes after 3 and
10 pressing cycles. For demonstration, a lens wafer was fabri-
cated with the most promising coating and used for pressing
tests.
4 Results
The deposition rate ranged from 153 € 15 nm/h to 499 € 45 nm/h.
The deposition rate is a first indicator of coating density. Variations
in the deposition rate under otherwise constant sputter rates
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Development of a ta-C diamond-like carbon (DLC) coating 663
Fig. 1: Mean values of deposition rates grouped by process para-
meters
Bild 1: Mittelwerte der Depositionsraten, gruppiert nach Prozesspara-
metern
(same cathode power and chamber pressure) could indicate that
the deposited carbon coating is more or less dense, due to the
variation of the other process parameters (temperature, bias volt-
age).
In Fig. 1, the variation of the deposition rate is displayed for
low/high values of the four major process parameters. The
inverse relation between process pressure, bias voltage and depo-
sition rate could also be verified in the statistical analysis of the
design of experiments. This means that higher pressure or
higher bias voltage is rather opposing the fast built-up of a ta-C
coating. Secondly, the spread in deposition rates is very strong
when adjusting the cathode power and the bias voltage. This cor-
relates with general observations in sputtering. Cathode power
can be correlated to the degree of ionization and sputtering rate,
and bias voltage to the ion-plating efficiency, which can also lead
to an etching effect, if impingement energies of the particles are
too high. Then the diamond-like carbon (DLC) microstructure is
not densified anymore, but re-sputtered by the impinging par-
ticles.
Most samples showed good surface quality and adhesion.
SEM pictures from the remaining samples showed similar
results, Fig. 2 (left and middle SEM picture). One can clearly see
the differences in the microstructure by different settings in bias
voltage and substrate heating, which have led to a higher surface
quality for high bias voltage at adequate heating.
However, some coating parameter sets induced failure of the
coatings, Fig. 3.
The samples fabricated at high values for cathode power, bias
voltage and heating power did not adhere to the substrate, irre-
spective of the process pressure. These coatings were found to be
very porous and could be swiped away easily, Fig. 2 (right SEM
picture). Also, these coatings could not be analyzed towards their
chemical structure due to their surface quality. Therefore, the
actual reason for the detachment remains unknown.
After conducting heating tests with good quality coatings,
some of them degraded, Fig. 3. On the left side, a sample with
deamination similar to the phenomenon described before, on
the right hand a sample with porous, highly rough surface. This
means that a defect-free coating after deposition is not necessa-
rily suitable for glass molding and must first be verified under
glass molding conditions.
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664 F. Bernhardt et al.
Fig. 2: SEM image of ta-C coating on silicon substrate fabricated with (left) and without (middle) bias voltage, but with substrate heating, as
well as without bias voltage and without substrate heating (right)
Bild 2: REM-Aufnahmen der ta-C-Beschichtungen auf Silizium-Subtraten, hergestellt mit (links) und ohne (Mitte) Bias-Spannung, jedoch mit
Subtratheizung, sowie ohne Bias-Spannung und ohne Substratheizung (rechts)
Fig. 3: Microscopy pictures (65x) of degradated coatings after anneal-
ing at 650 8C (left: graphitization, right: roughening)
Bild 3: Mikroskopiebild (65fach) von degradierten Beschichtungen
nach Heiztests bei 650 8C (links: Graphitisierung, rechts: Aufrauung)
Fig. 4: Results of the Raman analysis at Fraunhofer CNT
Bild 4: Ergebnisse der Ramananalyse am Fraunhofer CNT
Based on the above results, various adjusted coatings were pro-
duced. The results from the Raman analysis at Fraunhofer CNT
are shown in Fig. 4. The coating with ID 1000 is a comparison
sample from a commercial producer of ta-C coatings in Asia
using the FCVA process.
The determination of the sp3 content from Raman raw data is
not trivial. The primary G and D-peaks at 1580 cm–1 and 1350
cm–1 can be easily separated from the measurement data. How-
ever, the secondary peak of Graphite at 1350 cm–1 makes it diffi-
cult to interpret the measurement raw data. Deformations in the
Raman Shift distribution can occur though clustering in sp2-
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Mat.-wiss. u. Werkstofftech. 2013, 44, No. 8
Table 2: Raman analysis results at Fraunhofer IWM
Tabelle 2: Ergebnisse der Ramananalyse am Fraunhofer CNT
Coating ID sp3 content [%]
1000 66.7 € 3.4
2325 62.1 € 1.0
2323 62.2 € 1.0
2321 62.1 € 3.7
2332 62.1 € 1.3
2334 61.1 € 2.3
2337 61.9 € 2.2
2340 61.5 € 0.7
2423-1 63.5 € 1.1
bonds, signals from sp2 rings / chains or disorder in bond struc-
tures [8].
Hence, the G-band position and the D/G ratio (right and left
axis) only provide a qualitative indication of the sp3/sp2 ratio, but
no quantitative data. Therefore, reference measurements at
Fraunhofer IWM determined absolute values for the high-sp3-
content samples, Fig. 4, Table 2.
As expected, sample 1000 had the highest sp3 content. All
other samples fabricated at Fraunhofer IPT show lower sp3 con-
tent than sample 1000. However, all samples showed more than
60% sp3 content, which has not been reported for magnetron
sputtering, till now.
Main results from the data analysis can be summarized as fol-
lows: (1) The sp3 content was increased when sputtering with
bias voltage. (2) Among the bias-assisted processes, those with a
lower voltage (<150 V) had higher sp3 content. (3) The coating
quality can be increased when increasing the cathode power
unless bias voltage is been active, in which case no difference
could be observed. (4) While the ID1000 sample showed the
highest sp3 content as expected, some of the coatings produced
by MSIP approach this.
The best coatings (ID2323) were used in molding tests of 10
pressing cycles each, after which no relevant roughness change
of the coating surface could be observed. That means that the
coating stays intact for further pressing cycles during the first
critical number of cycles. However 10 hours of annealing showed
changes in the Raman spectrum. Finally, lens array mold coated
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Mat.-wiss. u. Werkstofftech. 2013, 44, No. 8
Fig. 5: Lens mold coated with ta-C thin film after industrial pressing
tests
Bild 5: ta-C beschichteter Formeinsatz nach industriellen Glaspress-
tests
with a ta-C coating showed better deforming and low sticking of
glass, compared to state-of-the art Pt-Ir coatings, Fig. 5.
5 Discussion of results
The micro cracks on the samples with high parameter values for
cathode power and bias voltage were caused by high internal
coating stresses. The rise in deposition rate at higher process
pressures is typical for sputtering, since a higher Argon pressure
leads to a higher ionization density in the plasma and to higher
sputtering rates at the target. In a certain stable coating process
range, the cathode power is commonly known to directly corre-
late with sputter rate and the bias voltage accelerates ions to the
substrate, so that stresses can be built up, leading to higher sp3
ratio. High total energies of the particle deposition and stress
inducing parameters (cathode power and bias voltage) seem to
lead to a breakdown of the coating due to internal stresses, if
these cannot be relieved by thermal annealing mechanisms. So,
similar to metal-based coatings, temperature also seems to
release stresses during the diamond-like carbon (DLC) coating
process, although it might not be the same mechanism of mobi-
lity increase on the assembling coating surface. It can also be
noted that a combination of low pressure and low cathode power
produces coatings susceptible to delamination after annealing at
high temperatures. Since the degraded samples were still stable
at the 450 8C, the critical degradation mechanisms seem to be
activated above 450 8C.
As assumed from the ion-plating mechanics for diamond-like
carbon (DLC) coatings described in [8], the bias voltage induces a
densifying effect in the fabricated coatings, which leads to an
increase in the sp3 content. Since low bias voltages (50–150 V)
lead to better results in surface quality and coating performance,
these low voltages seem to suffice to cause the ion impingement
to increase sp3 content softly. Deposition, annealing and Ion-Plat-
ing mechanisms are imposing multiple stress patterns to the
coating. If too much load is put on the coating, the inner struc-
ture collapses by means of micro cracks and graphitization of the
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Development of a ta-C diamond-like carbon (DLC) coating 665
coating. A balanced process window needs to be defined that can
withstand thermal and mechanical loads present in the precision
glass molding process.
By analyzing the Raman raw data it could be estimated that sp3
contents >60% could be produced using the described process.
Despite measurement and analysis uncertainties, this represents
a good result for an easy to fabricate ta-C coating. Using an
appropriate adhesion layer between substrate and ta-C coating
the production of coatings with higher internal stresses (and
higher sp3 content) may be possible without the delamination
and graphitization problems. Furthermore, the long-term stabil-
ity of diamond-like carbon (DLC) coatings could be an important
consideration for further investigations, since sp3 content
changes during heating. However, first results on pressing have
shown significant process improvements.
By using ta-C coatings on wafer molds pressed glass detaches
easier from the mold than with conventional coatings, Fig. 5.
This implies a lower tendency to glass breakage and early end of
service life time of the molds, which are the most critical aspects
in wafer lens fabrication by precision glass molding.
6 Summary and Outlook
In total, it could be shown that ta-C coating can be fabricated
using the magnetron sputtering ion plating process (MSIP). The
bias voltage has the most significant influence in the sp3 content,
but also on the integrity of the coating. Graphitization and
delamination of the coatings occurs for unsuitable process
parameters. The proposed model for sp3 bond generation from
sp2 bonds by Ion-Plating proposed in [8] could be validated in
general. The influence of coating failure that occurred on some
process parameter sets should be further investigated in order to
determine the reasons for coating failure or unsatisfactory coat-
ing evolution during sputtering. The coatings fabricated in this
work had a thickness in the range of 300 nm. Precision glass
molding diamond-like carbon (DLC) coatings are often below
200 nm. Reduction of the coating thickness will improve the
durability of the coatings by reducing the internal stresses that
are suspected to be responsible for the coating delamination.
Although first molding test have shown good results, the coat-
ing performance should be assessed in long term tests to deter-
mining the end of service lifetime for the ta-C coatings, prefera-
bly with a correlation to the sp3 content. The determination of the
sp3 content remains crucial for identifying those correlations.
This is especially challenging, since there is no easy-to-use anal-
ysis for determining the degree of diamond hybridization in a
ta-C diamond-like carbon (DLC) coating.
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Received in final form: June 10th 2013 T 171
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