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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 Przisionsblankpressen

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
Keywords: Precision glass molding / MSIP sputtering / Ion plating / diamond-like carbon / DLC / ta-C /
thermo-chemical resistance /

Diamanthnliche 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 prsentierten Ar-
beiten zielen auf die Magnetron-Sputtering-Ion-Plating Abscheidung (MSIP) von ta-C-Beschich-
tungen auf Glasformeinstze ab, die im Przisionsblankpressen 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-
Schlsselwrter: Przisionsblankpressen / MSIP-Sputtern / Ionenplattieren / Diamond-like carbon / DLC /
ta-C / thermo-chemische Bestndigkeit /

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

i 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

662 F. Bernhardt et al. Mat.-wiss. u. Werkstofftech. 2013, 44, No. 8

The present work describes the development of ta-C coatings coating, (2) transfer of the incident particles kinetic energy
for the protection of precision glass molding molds during glass increases the coating density and (3) transition of sp2 to sp3 bonds
pressing using the ubiquitous MSIP deposition process. The by inducing local stresses in the coating [6–7]. However, inducing
coatings must be able to withstand standard loads in precision coating stresses is always at the expense of coating stability, i. e.
glass molding over many molding cycles, especially with regards of the coating-substrate adhesion, increasing with coating thick-
to temperature stability, hardness to withstand typical pressing ness. However, since precision glass molding coating thick-
forces and von Mises stresses or thermo-chemical resistance to nesses are rather <200 nm, unbalanced magnetron sputtering
typical glass types molded by precision glass molding technol- resembles a promising technology for sputtering ta-C coatings.

3 Experimental details
2 Diamond-like carbon (DLC) coatings in the 3.1 Sample preparation
precision glass molding process
Plane samples of binder-free tungsten carbide (Ceratizit
It is generally known that the chemical and mechanical proper- CTN01L) were used as the substrate material. The material is the
ties of diamond-like carbon (DLC) coatings are mainly deter- same used in production tools and is nanoscopically fine-grained
mined by the ratio of sp2/sp3 content, respectively for the graph- so that high surface qualities can be achieved by grinding and
ite and diamond modification of carbon, as well as their hydro- polishing. The samples were polished to a Ra <5 nm, using a con-
gen content. Diamond-like carbon (DLC) ta-C coatings have high ventional Phoenix 4000. The samples were cleaned in an ultra-
sp3-modification content and no hydrogen content [4]. Thus, sonic bath. For ease of analysis, Si wafers were also used as sub-
these types of diamond-like carbon (DLC) coatings have a multi- strates. All sample preparation steps were carried out in clean
tude of advantages over conventional coatings, such as low chem- room environment.
ical reactivity, high, density, high hardness, smooth surface, low The samples were coated in a CemeCon CC800/9 industrial
abrasion rates in tribological contact and low affinity towards sputtering machine, equipped with a graphite target on an
glass sticking. With regards to other diamond-like carbon (DLC) unbalanced magnetron sputtering cathode.
types, the fact that ta-C is hydrogen-free is considered to be the
main advantage for protection of precision glass molding tools in
3.2 Design of experiments
glass contact. Currently, this kind of coatings are often realized
by Ion-Beam Sputtering, Pulsed Laser Deposition or other types Since the ta-C diamond-like carbon (DLC) coating needed to be
of technology using direct bombardment with ionized carbon developed from the concept to practice, at first, different major
particles. By inducing high ion particle energies combined with a process parameter were investigated regarding their influence
good control of the ion energies, high sp3 modification content on the coating quality and on the thermal stability. A full factorial
can be realized. In general, conventional sputtering can induce a experiment has been carried out to identify the strength of influ-
sp3 content of <40%, since the carbon ions do not gain enough ence of the parameters listed and the correlation strength among
energy and deposit with low momentum onto the substrate sur- them. The other process parameters were kept constant, Table 1.
face, often unable to build up sp3 bonds. So, most carbon par-
ticles are cumulating in small grains with graphite modification Table 1: Coating deposition process parameters
[5]. But, some approaches with conventional sputtering were suc- Tabelle 1: Prozessparameter fr die Schichtabscheidung
cessful in producing high-grade carbon coatings with high sp3
content [5–6]. Parameter Value Duration
The fabrication of ta-C coatings with conventional sputtering Setup Target 2 Graphite
is highly desirable due to the high robustness of the coating proc- Heating Heating power 0 – 4000 W 4500 s
ess. Furthermore, magnetron sputtered coatings are highly Etching Heating power 0 – 4000 W
established in various applications, e. g. also for producing noble Argon pressure 500 mPa
metal coatings on precision glass molding molds. Therefore, Bias voltage 650 V, 240 kHz, 60% 900 s
duty cycle
existing equipment could be used, avoiding costly investments Coating Heating power 0 – 4000 W
and significant changes in the process chain regarding the over- Argon pressure 300 – 500 mPa
all industrial precision glass molding process. Nevertheless, ta-C Bias voltage 0 – 200 V, 240 kHz,
coatings have not been produced and assessed with regards to 60% duty cycle
the use for coating precision glass molding tools, so far. Cathode power 0.5 – 1 kW, 50 kHz, varying
90% duty cycle
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- Samples fabricated are then analyzed and evaluated with
strate to induce an ion bombardment also on the sputtered coat- respect to their suitability in precision glass molding. The prop-
ing surface. This effect is widely known as Ion-Plating. The erties of promising samples are refined, whereas samples that
mechanism that associates Ion-Plating with a higher sp3 content show low adhesion, low thermal resistance or other disadvanta-
in the ta-C coating can be described by the following steps: (1) by geous properties for use as protective coatings in precision glass
particle bombardment, C atoms are pressed more deeply into the molding, are excluded from further investigations.

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Mat.-wiss. u. Werkstofftech. 2013, 44, No. 8 Development of a ta-C diamond-like carbon (DLC) coating 663

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
Raman spectroscopy measurements were carried out at
Fraunhofer ICT (He-Ne laser, 633 nm emission wavelength, 10 s Fig. 1: Mean values of deposition rates grouped by process para-
light exposure per spectrum taken, 2 spots measured per sample) meters
and Fraunhofer IWM (Renishaw3000, Ar laser; 514.5 nm emis- Bild 1: Mittelwerte der Depositionsraten, gruppiert nach Prozesspara-
sion wavelength, 60 s per 10 spectrums taken, 3 spots measured metern
per sample) for determining the sp2/sp3 ratio. Using fitting algo-
rithms on the basis of Lorentz fit and the BWT function, the sp2/
(same cathode power and chamber pressure) could indicate that
sp3 ratio was determined. The different ratios of the samples pro-
the deposited carbon coating is more or less dense, due to the
duced were compared during analysis. As a reference and to
variation of the other process parameters (temperature, bias volt-
show the validity of the sp3 determination method, a sample pro-
duced with FCVA, which is known to have very high sp3 content
In Fig. 1, the variation of the deposition rate is displayed for
was added to the analysis (sample no. 1000).
low/high values of the four major process parameters. The
inverse relation between process pressure, bias voltage and depo-
3.4 Annealing tests sition rate could also be verified in the statistical analysis of the
design of experiments. This means that higher pressure or
Annealing tests were carried out by placing the coated samples higher bias voltage is rather opposing the fast built-up of a ta-C
inside the vacuum chamber of the coating machine and anneal- coating. Secondly, the spread in deposition rates is very strong
ing them at elevated temperatures for 8 hours, using three differ- when adjusting the cathode power and the bias voltage. This cor-
ent procedures and analyzing the coatings after each step. At relates with general observations in sputtering. Cathode power
first, all samples they were annealed at 650 8C under vacuum at can be correlated to the degree of ionization and sputtering rate,
2 mPa and without physical contact among them. Secondly, they and bias voltage to the ion-plating efficiency, which can also lead
were annealed together with a glass gob of B270 glass (Schott) at to an etching effect, if impingement energies of the particles are
630 8C, which is the molding temperature of this glass which is too high. Then the diamond-like carbon (DLC) microstructure is
frequently used in precision glass molding. Thirdly, the samples not densified anymore, but re-sputtered by the impinging par-
were annealed at 590 8C, placing a glass gob of Schott P-LASF47 ticles.
at the coating surface. This glass type is known to be chemically Most samples showed good surface quality and adhesion.
aggressive towards different coating types. 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
3.5 Molding tests
voltage and substrate heating, which have led to a higher surface
Molding tests for assessing the performance of the coatings were quality for high bias voltage at adequate heating.
carried out at an industrial Toshiba GPM 211 glass molding However, some coating parameter sets induced failure of the
machine. The lanthanum containing P-LASF47 glass was coatings, Fig. 3.
pressed at 590 8C, under 3 kN pressing force, 0.8 kN holding The samples fabricated at high values for cathode power, bias
force and 100 s pressing time. Roughness measurements and voltage and heating power did not adhere to the substrate, irre-
Raman measurements were carried out to assess the coating per- spective of the process pressure. These coatings were found to be
formance in real precision glass molding processes after 3 and very porous and could be swiped away easily, Fig. 2 (right SEM
10 pressing cycles. For demonstration, a lens wafer was fabri- picture). Also, these coatings could not be analyzed towards their
cated with the most promising coating and used for pressing chemical structure due to their surface quality. Therefore, the
tests. 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
4 Results deamination similar to the phenomenon described before, on
the right hand a sample with porous, highly rough surface. This
The deposition rate ranged from 153 € 15 nm/h to 499 € 45 nm/h. means that a defect-free coating after deposition is not necessa-
The deposition rate is a first indicator of coating density. Variations rily suitable for glass molding and must first be verified under
in the deposition rate under otherwise constant sputter rates glass molding conditions.

i 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

664 F. Bernhardt et al. Mat.-wiss. u. Werkstofftech. 2013, 44, No. 8

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)

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
Fig. 3: Microscopy pictures (65x) of degradated coatings after anneal- 2340 61.5 € 0.7
ing at 650 8C (left: graphitization, right: roughening) 2423-1 63.5 € 1.1
Bild 3: Mikroskopiebild (65fach) von degradierten Beschichtungen
nach Heiztests bei 650 8C (links: Graphitisierung, rechts: Aufrauung)
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.
Fig. 4: Results of the Raman analysis at Fraunhofer CNT Main results from the data analysis can be summarized as fol-
lows: (1) The sp3 content was increased when sputtering with
Bild 4: Ergebnisse der Ramananalyse am Fraunhofer CNT
bias voltage. (2) Among the bias-assisted processes, those with a
lower voltage (<150 V) had higher sp3 content. (3) The coating
Based on the above results, various adjusted coatings were pro- quality can be increased when increasing the cathode power
duced. The results from the Raman analysis at Fraunhofer CNT unless bias voltage is been active, in which case no difference
are shown in Fig. 4. The coating with ID 1000 is a comparison could be observed. (4) While the ID1000 sample showed the
sample from a commercial producer of ta-C coatings in Asia highest sp3 content as expected, some of the coatings produced
using the FCVA process. by MSIP approach this.
The determination of the sp3 content from Raman raw data is The best coatings (ID2323) were used in molding tests of 10
not trivial. The primary G and D-peaks at 1580 cm–1 and 1350 pressing cycles each, after which no relevant roughness change
cm–1 can be easily separated from the measurement data. How- of the coating surface could be observed. That means that the
ever, the secondary peak of Graphite at 1350 cm–1 makes it diffi- coating stays intact for further pressing cycles during the first
cult to interpret the measurement raw data. Deformations in the critical number of cycles. However 10 hours of annealing showed
Raman Shift distribution can occur though clustering in sp2- changes in the Raman spectrum. Finally, lens array mold coated

i 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Mat.-wiss. u. Werkstofftech. 2013, 44, No. 8 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
Fig. 5: Lens mold coated with ta-C thin film after industrial pressing
shown significant process improvements.
tests By using ta-C coatings on wafer molds pressed glass detaches
easier from the mold than with conventional coatings, Fig. 5.
Bild 5: ta-C beschichteter Formeinsatz nach industriellen Glaspress-
tests 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.
with a ta-C coating showed better deforming and low sticking of
glass, compared to state-of-the art Pt-Ir coatings, Fig. 5.
6 Summary and Outlook
5 Discussion of results In total, it could be shown that ta-C coating can be fabricated
using the magnetron sputtering ion plating process (MSIP). The
The micro cracks on the samples with high parameter values for bias voltage has the most significant influence in the sp3 content,
cathode power and bias voltage were caused by high internal but also on the integrity of the coating. Graphitization and
coating stresses. The rise in deposition rate at higher process delamination of the coatings occurs for unsuitable process
pressures is typical for sputtering, since a higher Argon pressure parameters. The proposed model for sp3 bond generation from
leads to a higher ionization density in the plasma and to higher sp2 bonds by Ion-Plating proposed in [8] could be validated in
sputtering rates at the target. In a certain stable coating process general. The influence of coating failure that occurred on some
range, the cathode power is commonly known to directly corre- process parameter sets should be further investigated in order to
late with sputter rate and the bias voltage accelerates ions to the determine the reasons for coating failure or unsatisfactory coat-
substrate, so that stresses can be built up, leading to higher sp3 ing evolution during sputtering. The coatings fabricated in this
ratio. High total energies of the particle deposition and stress work had a thickness in the range of 300 nm. Precision glass
inducing parameters (cathode power and bias voltage) seem to molding diamond-like carbon (DLC) coatings are often below
lead to a breakdown of the coating due to internal stresses, if 200 nm. Reduction of the coating thickness will improve the
these cannot be relieved by thermal annealing mechanisms. So, durability of the coatings by reducing the internal stresses that
similar to metal-based coatings, temperature also seems to are suspected to be responsible for the coating delamination.
release stresses during the diamond-like carbon (DLC) coating Although first molding test have shown good results, the coat-
process, although it might not be the same mechanism of mobi- ing performance should be assessed in long term tests to deter-
lity increase on the assembling coating surface. It can also be mining the end of service lifetime for the ta-C coatings, prefera-
noted that a combination of low pressure and low cathode power bly with a correlation to the sp3 content. The determination of the
produces coatings susceptible to delamination after annealing at sp3 content remains crucial for identifying those correlations.
high temperatures. Since the degraded samples were still stable This is especially challenging, since there is no easy-to-use anal-
at the 450 8C, the critical degradation mechanisms seem to be ysis for determining the degree of diamond hybridization in a
activated above 450 8C. ta-C diamond-like carbon (DLC) coating.
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
7 References
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