PHOTOINITIATORS IN DENTISTRY:

A REVIEW
ARIO SANTINI BDS, DDS, PHD, FDS RCPS(GLASG), DIPFMED, DGDP, FFGDP(UK), FADM, DIRECTOR
OF BIOMATERIALS RESEARCH, EDINBURGH DENTAL INSTITUTE, THE UNIVERSITY OF EDINBURGH, UK

AND ALSO IRANZIHUATL TORRES GALLEGOS DDS, MSC, PHD,

PHYSICS INSTITUTE AND FACULTY OF DENTISTRY, SAN LUIS POTOSI UNIVERSITY, MEXICO
AND CHRISTOPHER M. FELIX BSC, CHIEF SCIENCE OFFICE, BLUELIGHT ANALYTICS INC., CANADA

ABSTRACT
Polymerization of Resin Based Composites (RBCs) initiated
by a light curing unit activating photoinitiators. Different
RBCs require different light energy levels for proper curing.
Manufacturers are now producing RBCs with more than one
initiator and not all of these will be properly polymerised with
blue LED lights. An added problem is that manufacturers do
not always indicate the type of photoinitiators in their
materials. This review discusses the importance of matching
the spectral output of LCUs to the absorption spectra of RBCs
and the consequences of spectral mismatch.
Resin based composites (RBCs) were first introduced in the
1960s1 and with development of effective and reliable
dentine bonding systems2, have been used routinely as a
filling material for both anterior and posterior teeth. The early
RBCs were either chemically cured two component materials
or photo-initiated materials that used UV initiators in the
beginning and then transitioned to visible light initiators such
as camphorquinine which was introduced in 1978.3 The first
report of a light curing material was of an ultraviolet (UV)
cured fissure sealant.4 However, due to the limited penetration
depth of the UV light and the potential health hazards,
this system was quickly abandoned. The
advancement of science yielded light curing
materials which contributed to a significant
clinical progress over the UV and chemically
cured RBCs.4 Additional advancements to direct
RBC restoration materials included luting agents
for ceramic restorations, pit and fissure sealants
and resin modified glass ionomers.
The amount of activated photo initiator depends on the
concentration of photoinitiator in the material, the number
of photons to which the material is exposed and the energy
of the photons (wavelength), the latter depending on the
curing light.6 The most common photoinitiator in dental
materials today is camphorquinone, which has a peak
activity around 470 nanometres.6
The factors affecting polymerization include filler type,
size and loading, the thickness and shade of the restorative
material, the effectiveness of light transmission (eg. light guide
tips being free from debris and scratches), exposure time,
distance of the light source from the restorative material
and light intensity.7
It is important to note that the photoinitiator activation occurs
at specific wavelengths, in other words, the optimum efficiency
is obtained when the peak absorptivity of the photoinitiator
corresponds with the spectral emission from the LCU.
Commercially available curing units have different light
intensities and light sources, with energy levels in QTH, LED
and other LCUs ranging from 300 to more than 2000 mW/cm.

Polymerization in an RBC is initiated by a light

curing unit (LCU); this technology is based on
the use of photoreactive systems that absorb
light irradiation from the LCUs at appropriate
wavelength. Then the photoinitiators contained
in the RBCs, absorb the incoming photons from
the LCU and the monomers in the molecular
structure become excited and in that active
state, there is a change from monomers into
a polymer network6. The success of this
technology hinges on matching the spectral
emission of the LCU with the requirements of
the photoinitiator system to convert the
monomers into a polymer network.

30 P R I M A R Y D E N TA L J O U R N A L

CQ/tertiary amine
photoinitiator system
Since its invention by Dart and Nemcek
in 19728 the most common photoinitiator
system in RBCs is the camphorquinone/
tertiary amine (CQ/TA). When CQ
absorbs the light (wavelength of maximum
absorbance: 468nm6), it excites and
interacts with the TAs, then forms a photo-
excited complex. In that state, CQ abstracts
a hydrogen atom from the TAs, producing
free radicals both on CQ and TAs. The
formed free radicals attack the C=C bonds
of monomers, resulting in the formation
of new radicals with a much longer chain
than before (propagating radicals). The
same process continues through the chain
reaction until the reaction process
terminates.9 The peak sensitivity of CQ
is near 470 nm in the blue wavelength
range (Figure 1).
Even though CQ/TA systems have
good acceptance, they present some
disadvantages; used in very small amounts
Another major problem is that the α-diketone group, derived from
(ppm), the yellow-colored CQ influences the composite colour10*.
CQ, has peak absorption in the visible range, resulting in fast
photopolymerization under ambient light (fluorescent lamps and
dental lamps) and giving a short therapeutic operation time.11
To solve the problems of CQ/TA, other initiators are now
incorporated in RBCs, for example, phenyl-propanedione (PPD)
and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (TPO)12.
Lucirin TPO and PPD photoinitiator system
TPO is an acyl phosphine oxide. It has been shown that
TPO results in higher degree of conversion (DC) than
5 6
VOL 2 NO 4 OCTOBER 2013
1 Figure 1: Absorption
spectrum of camphorquinone
Figure 2: Absorption
spectrum of Lucirin TPO
Figure 3: Absorption spectrum
of phenylpropanedione (PPD)
Figure 4: Light output form two
2 curing lights: LED (B) conventional
QTH (C) superimposed on the
absorption spectrum of CQ (A)
CQ/TA when is cured with halogen16,
or polywave17 LCUs; in addition, TPO
exhibits greater colour stability compared
to CQ/TA. That is the reason TPO may
3 be especially useful in extra white shades
of RBCs, often required in bleached teeth
since it eliminates the unwanted yellow
effect of CQ/TA18. Its absorption spectrum
extends from 380nm to about 425nm
(Figure 2). Phenyl Propanedione (PPD)
is also a photoinitiator, its absorption
spectrum extends from below 350 nm
to approximately 490 nm. (Figure 3).
4 Spectral mismatching
Different RBCs require different colours of
light for proper curing and this depends on
the photoinitiators present in the materials.
The manufacturers are producing materials
with different initiators and not all of these
materials could be properly polymerized
with blue LED lights. An additional
problem is that manufacturers are not
indicating the type of photoinitiator
incorporated in their materials.
The RBCs that only contain CQ/TA system, only require the blue
spectral range (420-540 nm); however, if the RBCs contain CQ
plus TPO and/or PPD, then light in both the blue (420-540 nm)
and violet (360-420 nm) ranges are required. Not all curing
lights deliver the required colour(s) of light and using a spectrally
mismatched combination of LCU and RBC is possible. QTH LCUs
have a broad spectral range corresponding with the broad
spectral absorption of CQ. (Figure 4) Moreover, its spectral
range extends into the violet range and so it can activate
photoinitiators such as TPO if they were incorporated in the
RBCs. The emission spectrum of commercially available single
Figure 5: Single peaks LCUs
cover the wavelength range
of circa 420 to 515 nm
Figure 6: Dual peak LCUs
cover the wavelength range
of circa 380 to 520 nm
31
 PHOTOINITIATORS IN DENTISTRY:
A REVIEW
peak LCUs
(420-490 nm) is limited
to be effective in activation
CQ/TA19, 20 but not so useful
when TPO type photoinitiators
are present19, 21, 22.
In an attempt to overcome the problem of the
emission-absorption mismatch of TPO and PPD-
containing materials, dual peak LED LCUs (Figure 5) have
been introduced. They have a primary emission peak at around
460 nm to cover the absorption spectrum of the CQ/TA and an
additional peak at around 400 nm to match TPO and PPD.
This should be taken into account when curing bleached shades
of RBCs, even if the manufacturers do not indicate the presence
of TPO in their materials.
Relative photosensitivity
Not all of the photoinitiators have the same sensitivity. Figure 7
illustrates the peak absorption of TPO and CQ/tertiary amines
systems. TPO is about five times more sensitive than CQ.
When the spectral output of both single and dual peak LCUs
are superimposed (Figure 8) on the absorption spectra of CQ
and TPO, the following points become obvious:
• Single peak LCUs deliver light energy mainly in the blue
spectral range
• Dual peak deliver light energy mainly in the blue and
violet spectral range
• Though violet light is delivered, the peak delivery is still
mismatching the peak absorption of TPO and lies in the
wave range where absorption of photons by TPO is low.
This is similar for PPD
Most major dental supply manufacturers market their own
RBCs and LCUs. As they determine the composition of the RBCs
and the light intensities of the LCUs and recommend irradiation
times for both adhesives and RBCs, it may be assumed that the
wavelength or intensity of the curing light matches that of the
RBC. This may not be the case if RBCs and LCUs from different
manufacturers are used by clinicians.
The quality of light produced by a dental light-curing unit
(LCU) has a direct influence on the polymerization of restorative
materials and is highly dependent upon the intensity or strength
of irradiation, the peak wavelength emission, the interactions
between these functions, and their compatibility with the
individual restorative material.
32
Figure 7: Relative
photosensitivity
of CQ and TPO
The darker and more opaque materials generally produce a
shallower depth of cure or need longer curing times because
less light transmits through the increment of RBC reaching the
initiators at the bottom. It is often not possible to polymerize thick
increments reliably unless the material is highly translucent or
contains only a limited amount of light-refracting fillers. The
conventional initiator systems employed in tooth-coloured
materials with enamel-like translucency quickly reach their limits
when they are faced with the demand for a quick and reliable
cure in increments that are thicker than the usual 2mm. This is
due, in part, to the fact that though violet light is delivered, the
peak delivery is still mismatching the peak absorption of TPO and
lies in the wave range where absorption of photons by TPO is low.
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 Figure 8: Spectral
output of single and
dual-peak LCUs
superimposed on the
absorption spectra
of CQ and TPO

Figure 9: Spectra translucency. Figure 9 shows the peak

of single and dual- absorption of Ivocerin which corresponds with
peaked LCUs the peak emission of light in the violet range
superimposed of dual peaked LCUs.
on the absorption
spectra of CQ, Summary
TPO, PPD and The polymerization of RBCs is directly
Ivocerin influenced by the quality of light produced
by the dentist’s LCU, including the strength of
irradiation, peak wavelength emission and the
interaction between that and the constituents
Ivocerin is a new initiator that features a high absorption of the individual RBC. Emission-
coefficient and is therefore highly effective even if used absorption matching of the LCU light
in only small quantities. It is a germanium-based output and photoinitiator light
initiator and complements the current range of absorption is critical to adequate
standard photoinitiators and allows for increased polymerization.
quantum efficiency and is therefore far more
effective than CQ/AT or TPO. Dentists should be aware not only
of the tip irradiance, as stated by
This photoinitiator is said to produce highly reactive manufacturer, of their LCU but also
polymerization and only very small amounts are of the spectral range. Manufacturers
required. Thus photoinitiator colour (compare should also make a clear statement
CQ/TA system) is not a problem and allows it to of the contained photoinitiators in
be used in tooth-coloured materials with enamel like their RBCs.

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