dental materi als 2 9 ( 2 0 1 3 ) 605617

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Review
A brief history of LED photopolymerization
Klaus D. Jandt
a,b,
, Robin W. Mills
c,
a
Faculty of Physics and Astronomy, Friedrich-Schiller-University Jena, Lbdergraben 32, D-07751 Jena, Germany
b
Jena Center for Soft Matter, Friedrich-Schiller-University Jena, Germany
c
School of Oral and Dental Sciences, University of Bristol, Lower Maudlin Street, Bristol BS1 2LY, United Kingdom
a r t i c l e i n f o
Article history:
Received 26 October 2012
Received in revised form
12 February 2013
Accepted 12 February 2013
Keywords:
LED
Photopolymerization
Light curing
Photocuring
Quartz-tungsten-halogen
Materials science
Clinical aspects
a b s t r a c t
Objectives. The majority of modern resin-based oral restorative biomaterials are cured via
photopolymerization processes. A variety of light sources are available for this light curing
of dental materials, such as composites or ssure sealants. Quartz-tungsten-halogen (QTH)
light curing units (LCUs) have dominated light curing of dental materials for decades and
are now almost entirely replaced by modern light emitting diode light curing units (LED
LCUs). Exactly 50 years ago, visible LEDs were invented. Nevertheless, it was not before the
1990s that LEDs were seriously considered by scientists or manufactures of commercial
LCUs as light sources to photopolymerize dental composites and other dental materials.
The objective of this review paper is to give an overview of the scientic development and
state-of-the-art of LED photopolymerization of oral biomaterials.
Methods. The materials science of LED LCU devices and dental materials photopolymerized
with LEDLCU, as well as advantages and limits of LEDphotopolymerization of oral biomate-
rials, are discussed. This is mainly based on a review of the most frequently cited scientic
papers in international peer reviewed journals. The developments of commercial LED LCUs
as well as aspects of their clinical use are considered in this review.
Results. The development of LED LCUs has progressed in steps and was made possible by
(i) the invention of visible light emitting diodes 50 years ago; (ii) the introduction of high
brightness blue light emitting GaN LEDs in 1994; and (iii) the creation of the rst blue LED
LCUs for the photopolymerization of oral biomaterials. The proof of concept of LED LCUs
had to be demonstrated by the satisfactory performance of resin based restorative dental
materials photopolymerized by these devices, before LED photopolymerization was gener-
ally accepted. Hallmarks of LEDLCUs include a unique light emission spectrum, high curing
efciency, long life, low energy consumption and compact device formfactor.
Signicance. By understanding the physical principles of LEDs, the development of LEDLCUs,
their strengths and limitations and the specic benets of LED photopolymerization will be
better appreciated.
2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Corresponding author at: Faculty of Physics and Astronomy, Friedrich-Schiller-University Jena, Lbdergraben 32, D-07751 Jena, Germany.
Tel.: +49 3641 947730; fax: +49 3641 94 77 32.

Corresponding author.
E-mail addresses: k.Jandt@uni-jena.de (K.D. Jandt), R.W.Mills@bristol.ac.uk (R.W. Mills).
0109-5641/$ see front matter 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.dental.2013.02.003
606 dental materi als 2 9 ( 2 0 1 3 ) 605617
Contents
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
2. Basic physics and technology of LEDs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
3. Materials science of dental materials photopolymerized with LED LCUs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
4. Evolution of commercial LED LCUs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 611
5. Clinical aspects of LED LCUs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 613
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 614
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 614
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 614
All truth passes through three stages. First, it is ridiculed.
Second, it is violently opposed. Third, it is accepted as being
self-evident.
Arthur Schopenhauer
1. Introduction
The introduction of resin-based dental materials near the
middle of the last century was a revolution in restorative den-
tistry. Dental composites are esthetically pleasing since they
possess a tooth-like appearance, are stable within the oral
environment, are relatively easy to handle and set on com-
mand via self curing or light curing.
Today, almost all commercial dental composites utilize
photopolymerization reactions initiated by blue visible light.
Light curing units (LCUs) based on different physical prin-
ciples, such as quartz-tungsten-halogen (QTH) bulbs, laser,
plasma arc lights, and light emitting diodes (LEDs) are avail-
able. Nevertheless, LED LCUs are currently the standard
devices in most modern dental practices.
In many cases, clinicians using LED LCUs on a daily basis
are unaware of the physics and/or history of their develop-
ment. This knowledge, however, is essential so that LED LCUs
can be used to their full potential and are applied appropri-
ately in any particular clinical situation.
In addition, there is currently no scientic review paper
focusing on the LED photopolymerization of available dental
materials. This review, therefore, addresses this need and is
based mainly on peer-reviewed and frequently cited research
articles in international journals available through the Web
of Science. This current paper reviews the history of LED
photopolymerization in the area of oral biomaterials/dental
materials. Withinthis framework, the basic principles of LEDs,
the history and evolution of commercial LED LCUs, the mate-
rials science of dental materials photopolymerized with LED
LCUs, aspects of commercial LED LCUs as well as their clinical
applications are discussed.
2. Basic physics and technology of LEDs
LEDs are a part of our daily lives. LED technology is applied
in modern light sources for room lighting, car headlights
and dashboards, trafc lights, state-of-the-art television at
screens or as LASER LEDs in CD or blue-ray DVD data/video
storage equipment [1]. Compared to conventional light
sources, LEDs are small and energy efcient. Hence, dental
light curing units (LCUs) basedonLEDs are relatively small and
can be battery powered, using high performance nickelmetal
hydride (NiMH) or lithium-ion (Li-ion) batteries [2].
Users of dental LCUs are oftennot fully aware of the physics
of these devices. Because light emission of LED LCUs differs
greatly fromthat of other, more traditional types of LCUs, it is
worth having a closer look at the physical principles of LEDs.
This knowledge may not only help to better understand how
LEDs work, but it may also contribute to the appropriate use
of LED LCUs in clinical practice and to recognize the strengths
and limitations of these devices in daily use.
LEDs are semiconductor-based photonic devices in which
the elementary particles of light (photons) play the key role.
LEDs convert electrical energy into optical radiation [3]. It
has been known for more than one hundred years that light
can be generated if an electric current passes through a
material under bias [3]. This phenomenon is called elec-
troluminescence and was discovered in 1907 in the natural
semiconductor silicon carbide [4].
LEDs emit light under forward biased conditions. To under-
standthis, one has to consider the energy states of electrons in
the semiconductor. Through the quantum mechanical inter-
action of large numbers of atoms (

=10
25
) and electrons in the
solid state, the electronic states may spilt into very closely
spaced electron states called electron energy bands [5]. The
valence energy band is associated with the highest energy,
occupied with electrons at 0K. The band with the next higher
electron energy is called the conduction band and also con-
tains no electrons at 0K. The valence and conduction bands
are separatedby a bandgapinwhichthe Schrdinger equation
has no solution, i.e., no electrons are allowed in this band gap
under normal circumstances. For semiconductors, the typical
band gap energies are generally less than 2eV [5]. Fig. 1 shows
the band structure of an intrinsic semiconductor.
Inintrinsic semiconductors, the electrical behavior is based
on the electronic structure inherent in the pure material,
such as silicon [5]. If impurity atoms are introduced to dic-
tate the electrical behavior of the semiconductor, it is called
anextrinsic (doped) semiconductor. LEDs use both, n-type and
p-type doped extrinsic semiconductors, indicating the major-
ity charge carriers are electrons or holes, respectively. Doping
a semiconductor with atoms of the group VA of the peri-
odic table creates n-type extrinsic semiconductors, whereas
doping with atoms from the group IIIA of the periodic table
creates p-type extrinsic semiconductors [5]. The former leads
to new, so-called electron donor states in the band gap just
belowthe conduction band, whereas the latter leads to accep-
tor states in the band gap just above the valence band.
dental materi als 2 9 ( 2 0 1 3 ) 605617 607
Energy
0
Valence Band
(Filled)
Conducon Band
(Empty)
Band Gap E
g
Fig. 1 Band energy structure of a typical intrinsic
semiconductor at 0K. The valence band is lled with
electrons and the conduction band is empty. Both bands
are separated by a band energy gap (typically <2eV). For
extrinsic (doped) semiconductors there are donor states
just below the bottomof the conduction band (n-type
extrinsic semiconductors) or acceptor states just above the
top of the valence band (p-type extrinsic semiconductors).
As a result, the conductivity of extrinsic semiconductors is
greater than the conductivity of intrinsic semiconductors.
Fifty years ago in 1962, Holonyak and Bevacqua reported
the emission of coherent visible light from GaAsP junctions
[6]. This event can be considered to be the birth of LEDs emit-
ting visible light [7]. The rst visible light LEDs were expensive
(approximately 200 USD per unit) and had very few practi-
cal applications [7]. The rst visible light GaAsP LED emitted
red light and had a luminous efcacy of 1.5 lumens per Watt
of electrical power consumption (lmW
1
) [3]. In the early to
mid-1980s, these types of LEDs were supplemented by green
(GaP:N) and yellow (GaAsP:N) types, respectively.
For materials in which electron and hole conduction exists,
the electrical conductivity is strongly dependent on the num-
ber of electrons and holes [5]. For practical purposes, only
these doped semiconductors are suitable as materials for
LEDs. The LED is a diode having p- and n-doped semi-
conductors that are connected by a junction (pn-junction).
This arrangement ideally allows, under a forward biased con-
dition, an electric current owing from the p-doped side
(anode) to the n-doped side (cathode), whereas no current
(ideally innite resistance) is observed under reverse biased
conditions. This effect is based on interactions of the electri-
cal eld and the different electron and hole concentrations,
respectively, at the pn-junction [3].
In doped semiconductor devices, such as LEDs (Fig. 2), elec-
trons and holes (also called defect electrons) contribute to the
electric current. Under a forward biased condition (electrons
entering the p-doped semiconductor side and exiting through
the n-doped layer), electrons and holes recombine near the
pn-junction of the diode and emit photons: an electron in
the conduction band can spontaneously return to an empty
state in the valence band [3], during which a photon is pro-
duced as well as heat. The frequency of photon emission is
controlled by the chemistry of composition of both the p- and
n-doped materials.
The width of the band gap is xed for a particular semicon-
ductor and determines the emitted photon wavelength and,
thus, the color of light generated, leading to the characteristic
narrow light emission spectrumof LEDs. For example, a rela-
tivelywide bandgapelectrontransitionresults inthe emission
of blue light, whereas a narrow band gap electron transition
results in emission of red light from LEDs. The band gaps in
semiconductors can be either direct or indirect. For LEDs, the
direct band gap is most important, because this value inu-
ences the ability to emit photons through direct conduction
bandvalence band transitions. This ability means that pho-
ton absorption or emission through band transitions is based
on the k-selection rule, where k is the crystal-momentum(k-
vector) [3]. The wave vectors of the valence bandwave function
(k
1
) and of the conduction band wave function (k
2
) must differ
by the amount of the emitted photon wave vector, considering
the physical conservation of momentum[3].
In the early 1990s, the standard LCUs in dental practices
and clinics used incandescent QTH light sources in combina-
tion with a blue light (band-pass) lter to generate blue visible
light. Blue light is necessary to initiate the setting reaction
(photopolymerization) in most light cured dental materials.
For the realization of the radically new approach of LED LCUs
[8,9], at least two prerequisites had to be fullled. The rst
prerequisite was the availability of blue LEDs of proper emis-
sion wavelength, the second was that blue LEDs needed to
have sufcient emitted power to cure dental materials within
a reasonable time (2040s). Although blue LEDs with a suit-
able wavelength emission were available from 1971 [7], their
power emission was much too small to be used for clinically
relevant exposure times. This situation changed in 1994 when
Nakamura at the Nichia Corporation developed high bright-
ness GaN LEDs [10]. Fromthat point in time, the development
and scientic exploration of LED photopolymerization of oral
biomaterials began.
LEDs have a number of intrinsic advantages which make
them ideally suited for the photopolymerization of oral bio-
materials. The typical spectral line width of light for LEDs is
520nm[3]. Compared to the emission spectra fromall other
LCUs, with the exception of narrowband argon-ion lasers, this
is extremely narrow(Fig. 3). This narrowemission range is the
major advantage of LED LCUs compared to light emitted from
LCUs based on different principles, because photo initiators
present in oral biomaterials have light absorption spectra with
distinct maxima. If the wavelength of the LED LCU is chosen
in this range, effective and rapid photopolymerization is the
result.
For oral biomaterials containing more than one photo
initiator with different light absorption spectra, LED LCUs
emitting multiple wavelengths can be employed [11]. These
LED LCUs are sometimes called broad band LED LCUs. This
term, however, is not correct because the LEDemissioncharac-
teristics (see above) apply. Rather than a broad light spectrum,
two or more distinct narrow wavelengths bands are emitted
fromthis collection of different wavelength LEDs, each with a
distinct maximum. Thus, these types of LCUs are more appro-
priately referred to as poly-wave LED LCUs.
Conventional QTH LCUs cannot compete in this respect
with LED LCUs because the emission spectrum of the QTH
lamp emits a relatively broad visible light spectrum[9], much
608 dental materi als 2 9 ( 2 0 1 3 ) 605617
Fig. 2 (a) The energy band diagramof a pn
+
(heavily n-type doped) junction without any bias. Built-in potential V
0
prevents electrons fromdiffusing fromthe n
+
to the p side. (b) The applied bias reduces V
0
and thereby allows electrons to
diffuse or be injected into the p-side. Recombination around the junction and within the diffusion length of the electrons in
the p-side leads to photon emission.
Courtesy of Professor S. Kasap, University of Saskatchewan, Canada.
Fig. 3 Flux and irradiance of a typical QTH LCU and a LED
LCU. The narrow maximumof the light emission of the LED
LCU coincides with the maximumabsorption spectrumthe
camphorquinone photoinitiator present in oral
biomaterials. Much of the light of the QTH LCU is emitted
outside the maximumabsorption spectrumof the
camphorquinone photoinitiator.
Reprinted from[22] with permission fromElsevier.
of which is useless for photopolymerization and is dissipated
as heat. In addition, these lamps require infrared-blocking
blue bandpass lters. These lters can deteriorate over time
due to the substantial heat the lamp produces.
The second major advantage of LEDs for photopolymer-
ization is their efciency. The external quantum efciency is
dened as the number of photons emitted externally divided
by the number of charge carriers passing through the pn-
junction [3]. Due to the internal properties of the pn-junction
and to the differences in refractive indices at interfaces of
the semiconductor and the ambient air, there are losses of
photons (i.e., they are not emitted from the semiconductor).
Three mechanisms reduce the quantity of photons emitted
from the LED: (1) internal absorption, (2) Fresnel loss and (3)
critical angle loss [3]. The Lambertian emission pattern, i.e.,
the angular dependence of light emission is controlled by pla-
nar, hemispherical or parabolic epoxy encapsulates onthe LED
semiconductor [7].
An important measure of a LEDis its luminous efcacy (the
ratio of luminous ux emitted to electrical power consumed)
and is a measure of how well a light source produces visible
light [12]. For LEDs, the luminous efcacy is typically in the
order of 60lmW
1
. LEDluminous efcacies of 150lmW
1
have
been attained [13] for white LEDs whereas typical QTH lamps
present in LCUs, have a luminous efcacy of only 25lmW
1
[14].
When comparing commercially available blue LEDs with
conventional QTH lamps in terms of efciency, the lumi-
nous intensity efciency is the measure that is most easily
obtained from technical data sheets and this is more useful
than the external quantum efciency. The luminous inten-
sity is a photometric measure of the optical radiant intensity
which is weighted by the sensitivity of the human eye, with
the peak at 555nm. The luminous intensity I
v
of a commercial
blue LED with an apex angle of 10

which consumes 6.4mW

electrical power is about 9.3cd [15]. Thus, the luminous inten-
sity efciency for a LED is
LED
=9.3cd/6.4mW=145cdW
1
of
blue light. A 75WQTH lamp with the same apex angle of 10

yields 7500cd [16]. The luminous intensity efciency of a QTH

lamp is, therefore,
QTH
=7500cd/75W=100cdW
1
across the
whole of the visible spectrum.
Another important advantage of LED LCUs is their over-
all energy efciency in terms of energy required for a cure
cycle. A contemporary LED LCU that has one 5WLED chip will
dental materi als 2 9 ( 2 0 1 3 ) 605617 609
operate approximately 25min from a fully charged battery,
which may require 10h at 2.5W to recharge [17]. Assum-
ing a light curing cycle of 20s, 75 curing cycles are possible
froma charged battery and the energy required for this use is
25Wh
1
, corresponding to 0.34Wh
1
per curing cycle.
In contrast, operating a typical 150W QTH lamp based
LCU, equipped with a 75W (12V) QTH source, for the same
time (25min), the energy required would be approximately
62.5Wh
1
. This value corresponds to 0.84Wh
1
per 20s cur-
ing cycle: approximately 2.5 times the energy a LEDLCUneeds
to performthe same task as can be easily calculated.
LEDs can have a typical lifetime of 100,000h or more and
undergo little degradation of light output over this time, if not
over-driven [18]. This level of durability is a distinct advantage
when compared to the characteristics of QTH lamps [9] which
have an effective lifetime of approximately 50h [19].
3. Materials science of dental materials
photopolymerized with LED LCUs
There are several well-known examples in the history of sci-
ence that show that change and new ideas are not always
welcomed enthusiastically [20] and can be even opposed. This
situation can be particularly the case if this change hap-
pens quickly and has the character of a paradigm shift. To
some extent, this circumstance was also the case with the
introduction of LED LCUs to photopolymerization of oral bio-
materials. The authors recall submitting one of their rst
scientic papers reporting the novel concept of LEDs used for
the photopolymerization of oral biomaterials to a renowned
international journal. This manuscript was rejected, based on
a referees comment essentially stating that one cannot cure
dental materials with LEDs.
Inthe early1990s, the most commonLCUs indentistrywere
QTH units. Degradation of the QTH lamp, lter aging, con-
tamination of the light-guide tips, and several other factors,
potentially reduced the light output of these devices over time.
Nevertheless, users of LCUs didgenerally not monitor the light
output of these devices over time and the radiometers needed
to do so were not available in most dental practices.
Against this background, in 1995 Mills wrote a letter to the
British Dental Journal wondering if LEDs could be used as an
alternative light source for the photopolymerization of den-
tal composites [8]. Shortly before this letter was published,
the Nichia CorporationinJapanintroduced highintensity blue
GaN LEDs [10] having an emission peak around 465nm. The
former letter mentioned further a simple photopolymeriza-
tion test of one composite sample [8].
The rst scientic peer-reviewed article published in an
international journal presenting data on photopolymeriza-
tion of three contemporary dental composites with a LED
LCUs was published a few years later [9]. In this paper, the
hypothesis was tested, that a blue LED LCU can produce an
equal composite depth of cure as a QTH LCU adjusted to
give the minimum effective irradiance accepted at that time:
300mWcm
2
. This paper is a milestone in the history of LED
photopolymerization and to date, is the most cited article on
LED photopolymerization of dental composites [9]. The rea-
sons for this acknowledgment are threefold. First, the article
presented a newtechnological approachfor photopolymeriza-
tion of oral biomaterials and for the rst time a new powerful
LED LCU was introduced in a peer reviewed scientic article
[21]. At that time, single blue LED emitters were not strong
enough to emit enough light to polymerize dental compos-
ites satisfactorily andwithina reasonable time. Therefore, this
rst LED LCU used 25 blue LEDs in an array. Second, the paper
presented the rst graph showing simultaneously, the spec-
tral ux and spectral irradiance of a conventional QTH LCU
and a LED array based LCU. In addition, it was also shown
that the light emitted from the LED LCU correlated well with
the peak of the absorption of the camphorquinone photoini-
tiator. Much of the light emitted by the QTH LCU, however,
was not effective for photopolymerizationincomposites using
the camphorquinone photoinitiator. Third, the paper demon-
strated that a LED LCU with an irradiance of 290mWcm
2
was able to cure three popular commercial dental composites
to statistically signicantly greater depths of cure than was a
QTHLCUwhich had a 60%greater irradiance of 455mWcm
2
.
Although the light emission characteristics of QTH LCUs and
the light absorption characteristics of the photoinitiator cam-
phorquinone were already known, this article again raised
awareness of the characteristics of the light emitted from
different LCUs and their effects on the properties of the pho-
topolymerized materials. In addition, this work triggered a
new dynamic of research in the area as is evident from the
highnumber of citations of this paper insubsequent published
research.
In a further study, the depths of cure and compressive
strengths of a dental composite of two different shades,
each polymerized with a QTH LCU or a LED LCU, respec-
tively, were compared [22]. The QTH LCU had an irradiance
of 755mWcm
2
whereas the LEDLCUdelivered 350mWcm
2
emitted from 27 blue LEDs (Fig. 4). In addition, an advanced
characterization of the light of both LCUs was performed.
Both LCUs were able to produce a depth of cure exceeding the
requirements of ISO 4049 and the compressive strength of the
composites did not statistically signicantly differ between
the LCUs, despite that fact the LED LCU had less than half
the irradiance of the QTH LCU. This result was explained
by the light emission spectrum of the LED LCU providing
more radiant energy within the peak spectral range of cam-
phorquinone than that measured from the QTH device. A
later study conrmed that camphorquinone has practically
the highest photopolymerization efciency when irradiated
with blue LEDs compared to other photoinitiators, despite
its rather low polymerization quantum yield [23]. This nd-
ing showed clearly that LED LCUs were more effective in the
photopolymerization of dental composites than were QTH
lights.
Asubsequent larger study using three composites fromdif-
ferent manufacturers and three different shades, conrmed
the ability of LED LCUs for effective composite polymerization
[24]. This study also presented a rst simple physical model
for the curing effectiveness of the dental LED LCU based on
the convolution of the absorption spectrumof the photoinitia-
tor camphorquinone present in composites and the emission
spectra of LCUs. This work also showed that a comparison
of the LCUs total irradiance is not sufcient to anticipate
the performance of LCU in photopolymerization but instead
610 dental materi als 2 9 ( 2 0 1 3 ) 605617
Fig. 4 (Top) An LED LCU research prototype by the authors.
It contains 27 LEDs and uses a tapered optical light guide
with a tip diameter of 6mm(total length of the LED LCU is
27cm). (Bottom) LED array used as light source for the LED
LCU shown containing 27 shaped blue LEDs arranged in
concentric rings. The diameter of the LED array is 15mm.
Reprinted from[22] with permission fromElsevier.
a comparison of the mechanical properties of composites
resulting fromeach type LCUs is more appropriate.
One year later, in 2001, the hardness of a dental composite
photopolymerized with an LED LCU based on six LEDs (irradi-
ance 79mWcm
2
) and a QTH LCU (irradiance 475mWcm
2
)
conrmed the greater curing potential of LEDLCUs [25]. Never-
theless, all samples photopolymerized by the LEDLCUshowed
smaller hardness values compared to the sample cured with
the QTH LCU.
The degree of double bond conversion of composites was
then found to be signicantly inuenced by the light source
type and by the energy level (energy density), in addition to
the parameters of material and depth [26]. This study used
an LED, a QTH and a plasma arc LCU. When the same light
energy was applied, the degree of double bond conversion of
the composites was not different among the different LCUs up
to a depth of 2mm. The differences in degree of double bond
conversion, however, were only signicant at depths >3mm.
By the early 2000s, the rst commercial LED LCUs became
available. Hence, a published report compared the Barcol
hardness and the compressive strength of composites pho-
topolymerized for 20s or 40s with two different LED LCU
prototypes (27 and 54 LEDs), a rst commercial LED LCU (7
LEDs) and a QTH LCU [27]. While composites photopolymer-
ized by the two LED LCU prototypes and the QTH LCU showed
similar hardness and compressive strengths, the correspond-
ing values of composites exposed using the rst commercial
LED LCU were statistically signicantly smaller. The commer-
cial LED LCU lacked the power reserves of the other LCUs,
Fig. 5 Spectral irradiance of the LCUs (lines) used in this
study and the spectral extinction of the photoinitiators
camphorquinone and Lucirin TPO (lines and symbol). The
absorption spectrumof camphorquinone (according to
manufacturer, Rahn Zurich, Switzerland (0.1% in
methanol)) shows the good match with the LED emission
spectra whereas the co-initiator Lucirin TPO (according to
manufacturer, BASF Ludwigshafen, Germany (0.1% in
ethanol)) does not coincide with the emission of the LED
units. The broad emission spectrumof the halogen unit
shows an overlap with the extinction spectrumof the
co-initiator at approximately 375410nm.
Reprinted from[34] with permission fromElsevier.
especially for shorter curing times (20s). At this time (2002),
commercial LED LCUs were obviously still no match for QTH
LCUs in terms of performance. On the other hand, prototype
LED LCUs having larger numbers of LEDs performed as well as
QTH LCUs.
Similar results were found in a later study in 2002, which
compared composite depths of cure withmaterials having dif-
ferent shades, when photopolymerized using commercial LED
LCU (7 LEDs) and an LED LCU prototype (63 LEDs) [28]. This
study also revealed that the commercial LED LCU was pulsed
at 12Hz. In addition, rened spectral power data of the LCUs
were presented.
In the same year, a study was published that investi-
gated the Knoop hardness and depth of cure proles of
four different dental composites photopolymerized using a
QTH LCU adjusted to the same irradiance as a LED LCU
prototype (approximately 570mWcm
2
) a QTH LCU and a
commercial LED LCU, having irradiance values of (1144 and
122mWcm
2
, respectively) [29]. Two of the composites con-
tained co-initiators in addition to camphorquinone (Fig. 5).
Composites photopolymerized with the commercial LED LCU
showed a statistically signicantly lower hardness for all
materials and exposure times, whereas the LEDLCUprototype
performed as well as the QTH LCUs up to a composite depth
of 1.9mm. For greater composite depths of 3.1mm, the QTH
LCUs performed better than the LED LCU prototype in terms
of composite hardness. There were, however, no statistically
signicant differences in compressive strengths of compos-
ites between the QTH LCUs and the LED LCU prototype. This
dental materi als 2 9 ( 2 0 1 3 ) 605617 611
study demonstrated three essentials of the state-of-the-art in
photopolymerization at that time: (i) commercial LED LCUs
were not quite there yet, i.e., the curing potential of com-
mercial LEDLCUs was less thanthat of conventional QTHLCU;
(ii) a laboratory LED LCU prototype performed as well as high
irradiance QTH LCUs for certain composites; (iii) in order to
perform as well as QTH LCUs, the LED LCUs needed several
LEDs, because the irradiance produced by one single LED was
not sufcient for practical use.
Shrinkage strain kinetics, temperature rise and hardness
values were compared among different composites pho-
topolymerized using two LED LCUs (160 and 320mWcm
2
,
respectively) or a QTHLCU(800mWcm
2
) [30]. The LCUs were
operated in continuous or ramped mode. Composite temper-
ature rise during photopolymerization was lower for the LED
LCU compared to the QTH LCU, whereas the latter LCU pro-
duced the fastest increase in polymerization contraction and
the largest shrinkage strains. Ramp curing decreased the con-
traction speed.
The mechanical property data of dental composites cured
using LED LCUs had made it clear that the LEDs were indeed
suitable for photopolymerization of dental composites. Atten-
tion was then focused on other effects of LED LCUs on these
materials, such as the temperature rise of composites during
photopolymerization. This aspect was also of special inter-
est, because from the late 1990s high irradiance plasma arc
LCUs became available that had a signicant potential to
cause high temperature increases during curing. Excessive
heat applied to teeth can cause irreversible pulpal trauma,
when the pulp temperature exceeds 42.4

C [31,32]. In addi-
tion, soft start QTH LCUs entered the market near the year
2000. Therefore, a key milestone study investigated temper-
ature rise and propagation in three different composites of
two different shades that were photocured using two dif-
ferent LEDs or two QTH LCUs [33]. The results showed that
composites shade inuenced temperature increase and that
composites exposed to QTHLCUs reached signicantly higher
temperatures compared to those cured using LED LCUs. An
exception was a composite cured using the soft start mode
of a QTH LCU. Composites of lighter shades reached higher
temperature than those of darker shades when cured with
LED LCUs. For QTH LCUs, the situation was reversed. Further-
more, this study introduced a high-resolution infrared (HRIR)
camera to document heat propagation in composites. These
ndings demonstrated not only that temperatures of compos-
ite cured using LEDs were generally signicantly lower than
in the same composites exposed to QTH LCUs. In addition,
the heat propagation was slower and the heat penetration
lower in composites exposed using LED LCUs, compared to
those cured with QTH LCUs. Because the temperature gra-
dient (T/x) is signicantly smaller in composites exposed
using LED LCUs, the resulting heat ux is smaller when com-
pared with composites cured with QTH LCUs. The more pulp
friendly temperature properties of LED LCU curing, without
having to compromise in the resulting composite mechanical
properties, emphasized the superiority of LED technology and
was attributed to the different light emission characteristics
of LEDs compared to the QTH light.
In addition to the standard photoinitiator cam-
phorquinone, some dental composites contain co-initiators
that absorb light at shorter wavelengths than cam-
phorquinone. To investigate what effect this condition
has on the mechanical properties of composites cured using
QTH or LED LCUs, the photoinitiator-dependent composite
depth of cure and Knoop hardness using these LCUs was
investigated [34] in a milestone study. The depths of cure
did not discriminate between LCUs used for photopolymer-
ization of composites containing photoinitiators in addition
to camphorquinone, but the Knoop hardness tests did. The
study concluded that LED LCUs should be used with caution
when considered for composites containing co-initiators
that absorb light at shorter wavelengths than the LEDs emit.
Furthermore, this study showed that a LED LCU prototype
did cure composites to greater depths than a commercial
LED LCU, indicating that commercial LED LCUs did not have
the power required for challenging clinical situations at that
point in time, whereas the LED LCU prototype did. For the
latter, the LED LCU prototype required 63 blue LEDs arranged
in a sophisticated and compact array. Although this LED
LCU performed well, simpler LED LCU designs seemed more
desirable at that time.
This goal for a simpler LEDunit design need was addressed
through the introduction of second generation LED LCUs [35].
This classication of LEDLCUs is based on a single high power
LED and allows simpler LED LCU form factors. The perfor-
mance of a single LED LCU with an irradiance of 901Wcm
2
was evaluated by measuring the Knoop hardness and depth
of cure of two different dental composites and one ormocer
composite [35]. The single LED LCU achieved a signicantly
greater depth of cure for all materials than did the QTH LCU
which had an irradiance of 860mWcm
2
. There was no dif-
ference in Knoop hardness observed for one composite or
for the ormocer composite, when cured with either LCU. The
other composite showed a signicantly lower Knoop hardness
when polymerized with the LED LCU compared to the QTH
LCU. Two lessons were learned fromthis study: second gener-
ation LED LCUs have the potential to replace QTH LCUs, if the
composite is chosen carefully and the depth of cure does not
discriminate between the LCU performances, whereas Knoop
hardness testing does. The development of single LED LCUs
was, thus, another major milestone inthe advancement of this
technology for dental applications. Althougharrays of discrete
LEDs are no longer normally used in dental LED LCUs, such
arrays may be utilized in the future in LED-based high power
roomlightening systems [36].
As shown previously, some composites that contain co-
initiators in addition to camphorquinone showed lower
hardness when photopolymerized with LED LCU than the
same composites photopolymerized with QTHLCU[34]. Thus,
a test was performed to determine if progressive crosslinking
of the resin phase of such composites after photopolymeriza-
tion (post cure hardening) would eliminate this effect [37]. The
measured increase in post-cure hardening, however, was not
sufcient to compensate for the difference in hardness of the
composites. An interesting additional result of this study was
that the composite Knoop hardness depends on the indenter
load and has the potential to falsify such measurements if not
chosen carefully. These results demonstrated that LED LCUs
had matured and could more than match the performance
provided by QTH LCU technology at that time, however, with
612 dental materi als 2 9 ( 2 0 1 3 ) 605617
a slight restriction of application to certain composites con-
taining co-initiators. The performance of LED LCUs became
clinically satisfactory [38].
Because most manufacturers of direct resin based restor-
ative materials donot provide details about the photoinitiators
contained in their products, it is challenging to choose an
optimal combination of restorative resin and light-curing unit
[39]. Narrow blue LED light spectra emission is ideal for pho-
topolymerization of camphorquinone containing materials,
but when other photoinitiators, such as 1-phenyl-1,2-
propanedione (PPD) are present invery light composite shades
(high color value) used for repair of bleached teeth [40], this
may not be the case. This situation was addressed by manu-
facturing dual-wave (or poly-wave) LEDLCUs, emitting inthe
violet (410nm) and blue (470nm) of the light spectrum [40].
Third generation, poly-wave LEDs are used in these LED LCUs
(see section Evolution of Commercial LED LCUs).
This progress demonstrating the performance of high
power single LED LCUs paved the way for the clinical mass
application of LED LCUs. Nevertheless, more data from com-
posites photopolymerized with LED LCUs were needed to
convince the remaining skeptical minds clinging to the use
of conventional QTH technology LCUs. Thus, distinctions of
the time dependence of composite shrinkage between use of
QTH and LED LCUs was tested [41]. In addition, the reliability
of the light output was tested up to 360min of duty time, for a
prototype LEDLCU, a commercial LEDLCUand a QTHLCU. Dif-
ferent composites showed similar shrinkage behavior when
cured using the LED or QTH LCUs, with one exception [41]. In
the course of this study, the irradiance of the commercial LED
LCU decreased signicantly, whereas the emission spectrum
wavelength characteristics of the QTH LCU changed dramati-
cally. The prototype LEDLCUshowedalmost no change of light
emission spectrumor irradiance over time.
In addition to the power of an LED LCU, further parame-
ters are important for its photopolymerization potential. An
important aspect affecting the LED LCUs irradiance is the
diameter of the light guide tip. At a composites depth of
2mm, a 4mm diameter light guide tip produced a signi-
cantly greater composite hardness than did a 8 or a 10mm
tip [42]. When irradiation times were doubled or tripled for
8mmand 10mmtips, hardness values eventually rose to the
levels of those when using a 4mmtip. In other words, extend-
ing exposure time may compensate for the lower irradiance
found when using larger diameter light guide tips.
It was found later with LED LCUs, that exposing dental
adhesives to a longer time than recommended by the manu-
factures of the adhesives led to a decrease of permeability of
the bonded interfaces [43]. On the other hand, a study inves-
tigating the minimal exposure time of different LED LCUs,
demonstrated that many composites, when incrementally
exposed to LED light, were polymerized sufciently at a maxi-
mumof 20s [44]. This nding underlines that LED LCUs of the
latest generation are not only efcient but are also devices
capable of fast photopolymerization.
At the beginning of the second decade of this current cen-
tury, scientic investigation of LED photopolymerization of
oral biomaterials is still very active. Topics of this research
area include investigations of the inuence of LED LCUs on
the cytotoxicity of dental adhesives [45], evaluation of the
mechanical properties of composites polymerized using LEDs
and with other LCUs [46], curing efciency of high-intensity
LED LCUs [47], depths of cure and gel state-to-glass transition
of composites [48], polymerization efciency of modern LED
LCUs [49], the never-ending quest for the shortest exposure
time possible with LED LCUs [50]. Beyond this, LED lights are
becoming popular in photodynamic therapy in the oral cavity
[51].
4. Evolution of commercial LED LCUs
It was not until 2000 that the rst commercial LEDLCUbecame
available: the LuxOMax LED LCU [46] was a large pen-like
cordless battery-powered design using 7 discrete LEDs. The
device had a tapered fused glass ber light guide to concen-
trate the light output at the tip. The units irradiance measured
116mWcm
2
[8]. The delay in bringing a commercial LEDLCU
into productionwas due to two mainfactors: the power output
of the blue LEDs and their cost. The discrete blue LEDs used
in these early experiments in the 1990s were so-called sin-
gle chip, epoxy-resin encapsulated, through-hole devices of
either the standard T-1 (3mmdiameter LED) or T-1 3/4 (5mm
diameter LED) versions.
In 1995, the 5mm blue LED available from Nichia, had
an optical power output of 1.2mW and cost approximately
50USD [52]. In 2012, Nichia [53] offered 5mm blue LEDs with
a power output of 123mWat an approximate cost of 0.50USD
[54]. This comparison shows how over a period of seventeen
years in one type of LED, its power increased by two orders
of magnitude, while its cost has decreased by two orders of
magnitude. This data translates to approximately a cost of
40USDmW
1
of blue light output in 1995 to 0.004USDmW
1
in 2012. The increase in the external quantum efciency of
LEDs has an advantage for commercial LED LCU designers.
As a greater proportion of the electrical energy driving the
LED is converted into emitted light energy, the heat sinking
requirements of the LEDs become less demanding. This aspect
is important, as smaller heat sinking requirements mean a
potential reduction in the size, weight and cost of commercial
LED LCUs.
The rst generation of LED LCUs on the market in 2000,
such as the previously mentioned LuxOMax LED LCU, was
thus relatively low-powered, compared to their conventional
QTH LCU competitors. This difference led to some disap-
pointing early results, when commercial LED LCUs were
compared with commercial QTH LCUs [28]. In 2002, these
early comparisons of commercial LED LCUs with QTH LCU
sources produced some premature negative predictions for
the future of LED LCUs [55]. Later in 2002, however, it was
demonstrated that an experimental LED LCU could exceed
the performance of a QTH LCU [2].
First generation commercial LED LCUs improved rapidly
and mirrored the advances and efciency achieved in blue
LED semiconductor research and development. In 2001, the
Elipar
TM
FreeLight having 19 discrete LEDs became available,
with an irradiance of 400mWcm
2
[56]. The manufacturer
claimed this output level was equivalent to a conventional
800mWcm
2
QTHLCU, and studies were quoted in their tech-
nical product prole [57]. This more powerful rst generation
dental materi als 2 9 ( 2 0 1 3 ) 605617 613
LED LCU still used a tapered fused glass ber light guide to
further boost the irradiance.
The second generation of LED LCUs is regarded as a move
from devices that employed multiple discrete LEDs to those
that contained the more powerful single LEDs, often specially
designedfor dental curing applications. Examples of these sin-
gle more powerful LED emitters are the Luxeon LXHL-BRD1
in 2004 [58] with an electrical consumption of 1400mW to
provide 140mW of blue light, to the more recent LED Engin
Inc., LZ4-00B200 in 2012 with an electric consumption of
1160mWto give 3800mWof blue light [59]. Thus, in the rst
case 10% of the electrical power is converted into blue light,
while in the second case 30%conversion was attained, a 3-fold
increase in efciency within only a time span of 8 years. An
example of a single LED, second generation LED LCU using
1 LED was the Elipar
TM
FreeLight 2 [60]. The irradiance of
this LED LCU was approximately 1000mWcm
2
and repre-
sented an increase of 2.5 times that of its predecessor: the
Elipar
TM
FreeLight that used 19 discrete LEDs. It should be
noted that a tapered waveguide (the so-called turbo-tip) was
still employed to boost emitted irradiance and nickel metal
hydride batteries were used to supply the operating power
[61]. Even in 2005, another second generation LED LCU, hav-
ing a conventional pistol grip design, the Kerr L. E. Demetron
II, still incorporated a fan, which, considering the efciency
of LEDs, may have indicated a design compromise with the
heat sinking component [62]. The L. E. Demetron II LED LCU,
like others of this era, used the technique of a tapered light
guide to boost irradiance. Other designs of second generation
LED LCUs, such as the Dentsply SmartLite PS did not utilize a
conventional light guide. This unit was a slim, pen-style unit
like the LuxOMax, but had the LED source at the tip of the
unit, adjacent to the tooth [63]. Dentsply also announced in
2012, the imminent launch of a newer version, the SmartLite
Focus having a lens system designed to allow effective cur-
ing for up to 8mm from the composite [64]. This technique
has the advantage of less light loss as there is no light guide
betweenthe light source and the composite. This advantage in
turnresults ina reductioninelectrical power and heat genera-
tion if all other parameters remain the same. This design also
sets out to overcome the two main disadvantages of tapered
light guides: rst the light beam is more divergent. This is
caused by a progressive increase in the angle of total inter-
nal reection as the light propagates through a tapered ber,
resulted in an exaggerated loss of irradiance compared with
a more parallel beam as the LCU tip is moved further away
fromthe tooth. The second is the smaller light tip area which
requires repeated overlapping exposures to adequately cover
the composite area. More recently, a second generation LED
LCU the Elipar
TM
S10 (manufactured by 3M ESPE) having a
10mmdiameter parallel glass ber light guide capable of pro-
ducing an irradiance of 1200mWcm
2
has become available
[65]. This tip delivers not only four times the minimumirradi-
ance of 300mWcm
2
[66,67] required for a conventional QTH
LCU, but it is known that the spectral output froman LED LCU
is more effective than the equivalent QTH LCU of the same
irradiance [68]. This 1200mWcm
2
irradiance over a 10mm
diameter parallel light guide is a remarkable advance made
possible by the increase in power and reduction of cost of
LEDs. An optical power increase of over 50% is required to
achieve the same irradiance over a 10mmdiameter light guide
compared with the standard 8 mmversion.
As mentioned above, these rst and second generation
commercial LED LCUs both consist of blue LEDs designed to
peak in the absorption spectrum of camphorquinone (CQ),
which is the sole photoinitiator in the majority of commercial
composites. The incorporation of other photoinitiators has
led to the development of third generation commercial poly-
wave LED LCUs. The rst of these was the pen-like Ultralume
5 (Ultradent Products Inc., South Jordan, UT, US) in 2003 [69].
This comprised two different LED wavelengths, a central blue
LED surrounded by 4 violet LEDs at the end of the curing tip.
A more sophisticated dual wavelength LED LCU version called
the bluephase 20i (Ivoclar Vivadent AG, Schaan, Principality of
Liechtenstein) has a maximum irradiance of 2200mWcm
2
[70,71]. This LED LCU has 3 blue LED emitter elements and
a shorter violet LED wavelength emitter mounted on a sub-
strate in a square conguration: 1 emitter in each quadrant.
The bluephase 20i has a more traditional gun-shape with a
pistol grip, conventional fused glass ber light guide, and a
cooling fan. Another LED LCU, the VALO (Ultradent Products
Inc., South Jordan, UT, US) sought to improve on this still
further in 2011 by using 4 emitters in a similar square con-
guration to the bluephase 20i. However, in the VALO, there
are two blue emitters (439nm) diagonally opposite to each
other and also two different shorter wavelengthemitters diag-
onally opposite toeachother inthe other quadrants: one violet
(405nm) and another, longer-wavelength blue (460nm) [72].
The VALO, thus, has 3 emitters of different wavelengths incor-
porated. The heat dissipationaspect of this unit is a metal case
machined fromsolid aluminumrather than having a fan. This
design appears to apply the innovative principle of using one
component for two purposes, i.e., the case and the heat sink.
The VALO eliminates the light loss of a light guide by hav-
ing the emitters at the curing tip. This unit has a maximum
claimed irradiance of a remarkable 3200mWcm
2
. Another
third generation LED LCU, the ScanWave (ACTEON Germany
GmbH, Mettmann), uses 4 LED emitters like the bluephase 20i
and the VALO. In this case, however, all 4 emitters have dif-
ferent wavelengths from each other and can be switched in
sequence. The maximumirradiance is 2200mWcm
2
[73]. The
sophisticated programming options of the ScanWave claimto
helpoptimize curing while minimizing heat generationwithin
the target. Some preliminary results fromthis unit have been
described [74]. In this previous study, it is suggested that the
ScanWave couldbe regardedas arst versionof afourthgener-
ationLEDLCUbecause of the sophisticatedcontrol algorithms.
Both the VALO and ScanWave appear to be good examples of
the state-of-the-art of LED LCU evolution at the time of writ-
ing. Fig. 6 shows two examples of contemporary commercial
LED LCUs.
The further evolution of commercial LED LCUs is likely
to be conned to ne tuning the devices to ensure consis-
tent reliable spectral outputs over the lifetime of the device
and uniform irradiances over the whole of the emitting
tip area. Previous work [75] has demonstrated the lack of
homogeneity at the end of the light guide and multiple com-
mercial chip LED sources are imaged at the other end of
the coherent light guide tip resulting in a differential curing
over the target. One possible solution here to achieve more
614 dental materi als 2 9 ( 2 0 1 3 ) 605617
Fig. 6 Two contemporary commercial LED LCUs: (a) is the
SmartLite PS (courtesy of DENTSPLY Ltd., UK) and (b) is the
Elipar
TM
S10 (courtesy of 3M Espe Dental Products). Two
main approaches in LED LCU design are shown here: the
SmartLite PS in which the LED is located at the end of the
LCU which is placed near the tooth and the Elipar
TM
S10 in
which a conventional fused glass ber light guide
transmits the light to the tip that is placed near the tooth.
homogeneity would be to try a non-imaging incoherent light
guide. The higher energy density of lithium-based battery
technologies compared with earlier nickel metal hydride
has allowed commercial portable LED LCUs with enhanced
endurance. Further advances in battery technology would
improve on this aspect. It remains to be seen whether the
third generation of commercial LED LCUs will be sustained
with their more hazardous wavelengths [76]. This factor
together with the more limited penetration of light toward the
UVviolet region [77] resulted in curing wavelengths evolving
into the blue region of the spectrum. It may be that alternative
strategies achieve composites having high color value occur
in the future, without having to accept the disadvantages of
shorter wavelengths of light.
5. Clinical aspects of LED LCUs
When commercial LED LCUs became available to dental prac-
titioners after 2000, they slowly evolved and became serious
contenders to challenge the dominance of QTH LCUs in clini-
cal dentistry. It is natural for clinicians to want more powerful
light-curing devices to reduce the time taken for a given pro-
cedure for patient comfort. LED LCUs can currently achieve
irradiance values in excess of 3200mWcm
2
[72]. This irra-
diance value in isolation is only an approximate guide of the
clinical composites depth of cure. By achieving higher irra-
diance values, the depth of cure can be increased slightly, but
the work by Nomoto et al. reminds clinicians that a doubling of
the irradiance, if all other parameters stay the same, equates
to only an approximate 20% increase in depth of cure [78].
Doubling the irradiance, will however, double the energy deliv-
ered to the tooth of the patient. Higher power means higher
amounts of heat generatedwithinthe toothandpotential pulp
damage [79,80]. It is not only the energy absorbed fromthe LED
LCU that is important but also the exothermic reaction of the
polymerization [33].
Teeth are sensitive to the rate of change of temperature [81]
and can be cooled and warmed slowly within reason without
causing pain. Rapidtemperature changes cancause pain, such
as drinking hot beverages followed immediately by biting into
ice cream. If energy is fed into the dental pulp at a greater
rate than it can be dissipated during curing in a clinical situa-
tion, thena rise intemperature will occur and irreversible pulp
damage is possible [70]. In clinical situations, where a local
anesthetic is used, the protective warning mechanismof pain
is maskedandsothe patient cannot indicate whenthis occurs.
Thus, thermal safety shouldbe of primary considerationwhen
photopolymerizing composites.
The gains obtainedby increasing irradiance tothe very high
levels found in the plasma arc LCUs of the 1990s are often
questioned. To the clinician, the composite may appear hard
when tested with a probe but premature vitrication of the
composite can occur giving the impression that adequate cur-
ing has occurred.
Clinical studies have demonstrated that LED LCUs are as
effective as QTH LCUs when curing composites [82]. This
was also demonstrated in the area of orthodontics [83]. The
drawback for single wavelength LED LCUs is that they cannot
adequately cure composites withphotoinitiators lying outside
the absorption curve of CQ. This issue has been discussed
above and has now been addressed by poly-wave third gen-
eration LED LCUs [84]: units having two or more different
wavelength semiconductor chips [70]. There is a fundamen-
tal exponential correlation between the wavelength of light
and the penetration of the material to be cured. Scattering of
light S is inversely proportional to its wavelength [85]
S

and a signicant factor governing light penetration of a com-

posite [86].
A recent study examined 210 LCUs in government clini-
cal health establishments [87]. One hundred and twenty of
these units were QTH lights and 90 were LED LCUs. Nearly
68% of the QTH LCUs and 15.6% of the LED LCUs were judged
to have failed to reach the minimumacceptable irradiance of
300mWcm
2
for clinical success. This same value was used
for both types of LCU even though it has been demonstrated
that LED LCUs are more effective at the same irradiance when
all other parameters remain equal. It has been suggested
how the clinician can help offset the deterioration in LCUs
in the early stages of declining output by compensating for
this decline [88]. To record the reduction in output of an LED
LCUcontaining more than one wavelength of LEDover time, it
may be necessary to have a more sophisticated radiometer in
a clinical situation in which more than one detector indicates
the reduction of the different wavelength LEDs that comprise
the LCU. Such a radiometer could be constructed by using the
LEDs that comprise the LED LCU used in reverse function as
wavelength-specic detectors [28].
For clinical applications, LED LCUs are the current gold
standard for photopolymerization of resin based dental mate-
rials. Before using LED LCUs clinically, it can be seen that the
dental materi als 2 9 ( 2 0 1 3 ) 605617 615
main tasks are to check the wavelength compatibility with the
composite to be cured and to monitor the output in line with
the manufacturers guidance in combination with the advice
above.
Currently, studies evaluating the clinical performance of
light polymerized dental composites focus almost exclusively
LEDLCUs. The inherent characteristics of LEDs meanthat both
clinicians and patients should be able to rely on the poten-
tial of a consistent and long-lasting light output. This result
will only be true if the LEDs within the LED LCU are heat-
sinked correctly and powered at the recommended voltage
and current ratings of the LED manufacturers datasheets. If
the clinician measures a signicant deterioration in light out-
put over a relatively short period of time in an LED LCU, it
could be an indication that these manufacturing rules have
not been adhered to in the design and construction of the
device. Two main requirements for LCUs in the treatment
of patients are reliability and consistency of performance.
LED LCUs offer clinicians the potential to achieve both of
these.
6. Conclusions
The introduction of LED LCUs has revolutionized the pho-
topolymerization of oral biomaterials. Until the introduction
of LED LCUs, QTH lamp based LCUs were the standard curing
devices in most dental practices. Due to the physical charac-
teristics of the solid-state light emitting diodes, LEDLCUs have
almost entirely replaced QTH LCUs whose inherent problems
include a decay of light output over time, blue light lter degra-
dation, relatively limited time of life of the QTH source, high
energy consumption, bulky construction, a requirement for
a mains electricity supply, and relatively high heat transfer
to the pulp chamber of the tooth during photopolymeriza-
tion. It is, therefore, not surprising that hand-heldpencil-style,
battery powered, compact LED LCUs are now the standard
photopolymerization devices in most dental practices world-
wide.
This paradigm change in photopolymerization develop-
ment was made possible mainly by three factors: (i) the
invention of visible light emitting diodes exactly 50 years
ago; (ii) the introduction of high brightness blue light emit-
ting GaN LEDs in 1994; and (iii) the creation of the rst
blue LED LCUs for photopolymerization of oral biomateri-
als. The physical characterization of these LCUs as well
dental composites photopolymerized with these LCUs and
elucidation of particularities of the LED photopolymeriza-
tion process from 1995 to date have been addressed in this
review.
The LED-based photopolymerization process has become
the gold standard of curing dental composites at the begin-
ning of the 21st century. With efcient high power, single LED
LCUs commercially available, it is likely that this trend will
not change for quite some time, especially if one considers
the energy efciency of LEDs, which are the green way to
produce light. The history of LED photopolymerization of bio-
materials is also a good example of how science works and
progresses.
Acknowledgement
We thank Dipl.-Phys. Matthias M.L. Arras, FSU Jena, for calcu-
lating the luminous intensity values of the LED and the QTH
lamp.
r e f e r e n c e s
[1] http://en.wikipedia.org/wiki/Light-emitting diode
[2] http://en.wikipedia.org/wiki/Dental curing light
[3] Sze SM, Ng KK. Physics of semiconductor devices. 3rd ed.
Hoboken: John Wiley & Sons; 2007. p. 601 ff. 608620.
[4] Round HJ. A note on carborundum. Electrical World
1907;49:309.
[5] Callister WD. Fundamentals of materials science and
engineering. An integrated approach. Hoboken: John Wiley
& Sons; 2005. p. 478ff.
[6] Holonyak Jr N, Bevacqua SF. Coherent (visible) light emission
fromGa(As
1x
P
x
) junctions. Applied Physics Letters
1962;1:823.
[7] Schubert EF. Light-emitting diodes. Cambridge: Cambridge
University Press; 2003. p. 7.
[8] Mills RW. Blue light emitting diodes another method of
light curing? British Dental Journal 1995;178:169.
[9] Mills RW, Jandt KD, Ashworth SH. Dental composite depth of
cure with halogen and blue light emitting diode technology.
British Dental Journal 1999;186:38891.
[10] Nakamura S, Mukai T, Senoh M. Candela-class
high-brightness InGaN/AlGaN double-heterostructure
blue-light-emitting-diodes. Applied Physics Letters
1994;64:1687.
[11] Cao D. Light for use in activating light-activated materials,
the light having a plurality of light emitting semiconductor
chips emitting light of differing peak wavelengths to provide
a wide light spectrumprole. United States Patent US
2002/0190659 A1 (2002), to Cao Group, Inc.
[12] http://en.wikipedia.org/wiki/Luminous efcacy
[13] http://phys.org/news202453100.html
[14] http://techon.nikkeibp.co.jp/english/NEWS EN/20061221/
125713/
[15] Technical data sheet Specications for Nichia Blue LED
Model: NSPB500AS, Nichia Corporation, http://www.nichia.
co.jp/specication/en/product/led/NSPB500AS-E.pdf
[16] Family data sheet OSRAM HALOPAR 30, OsramGmbH;
2013. http://www.osram.com/appsinfo/pdc/pdf.do?cid=
GPS01 1027714&vid=EU ALL eCat&lid=EN
[17] http://www.dentsply.de/
[18] Haitz RH, Craford MG, Weissmann RH. Light emitting diodes.
In: Bass M, editor. Handbook of optics. 2nd ed. New York:
McGraw Hill Inc.; 1995. p. 12.112.39.
[19] Cayless MA, Marsden AM. Tungsten halogen lamps. In:
Lamps and lighting. 3rd ed. London: Edward Arnold Ltd.;
1983. p. 169182.
[20] Gribbin J. Science: a history 15432001. London: Penguin;
2003.
[21] Ferracane JL. A new approach for curing light activated oral
biomaterials. British Dental Journal 1999;186:384.
[22] Jandt KD, Mills RW, Blackwell GB, Ashworth SH. Depth of
cure and compressive strength of composites cured with
blue light emitting diodes (LEDs). Dental Materials
2000;16:417.
[23] Neumann MG, Schmitt CC, Ferreira GC, Correa IC. The
initiating radical yields and the efciency of polymerization
for various dental photoinitiators excited by different light
curing units. Dental Materials 2006;22:57684.
616 dental materi als 2 9 ( 2 0 1 3 ) 605617
[24] Stahl F, Ashworth S, Jandt KD, Mills RW. Light emitting diode
(LED) polymerisation of composites: exural properties and
polymerisation potential. Biomaterials 2000;2:137985.
[25] Kurachi C, Tuboy AM, Magalhaes DV, Bagnato VS. Hardness
evaluation of a dental composite polymerized with
experimental LED-based devices. Dental Materials
2001;17:30915.
[26] Yoon TH, Lee YK, LimBS, KimCW. Degree of polymerization
of resin composites by different light sources. Journal of Oral
Rehabilitation 2002;29:116573.
[27] Mills RW, Uhl A, Blackwell G, Jandt KD. High power light
emitting diode (LED) arrays versus halogen light
polymerisation of oral biomaterials: Barcol hardness,
compressive strength and radiometric properties.
Biomaterials 2002;23:295563.
[28] Mills RW, Uhl A, Jandt KD. Optical power outputs, spectra
and dental composites depths of cure, obtained with blue
light emitting diode (LED) and halogen light curing units
(LCUs). British Dental Journal 2002;193:45963.
[29] Uhl A, Mills RW, Vowles RW, Jandt KD. Knoop hardness
depth proles and compressive strength of selected dental
composites polymerized with halogen and LED light curing
technologies. Journal of Biomedical Materials Research A
2002;63:72938.
[30] Hofmann N, Hugo B, Klaiber B. Effect of irradiation type (LED
or QTH) on photo-activated composite shrinkage strain
kinetics, temperature rise and hardness. European Journal
of Oral Sciences 2002;110:4719.
[31] Pohto M, Scheinin A. Microscopic observation of living
dental pulp. Acta Odontology Scandinavia 1958;16:30327.
[32] Zach L, Cohen G. Pulp response to externally applied heat.
Oral Surgery 1965;19:51530.
[33] Uhl A, Mills RW, Jandt KD. Polymerisation and light-induced
heat of dental composites cured with LED and halogen
technology. Biomaterials 2003;24:180920.
[34] Uhl A, Mills RW, Jandt KD. Photoinitiator dependent
composite depth of cure and Knoop hardness with halogen
and LED light curing units. Biomaterials 2003;24:
178795.
[35] Uhl A, Sigusch BW, Jandt KD. Second generation LEDs for the
polymerization of oral biomaterials. Dental Materials
2004;20:807.
[36] Mills RW, Jandt KD. United States Patent US 7,645,056 B1
(2010), to Koniniklijke Philips Electronics NV.
[37] Uhl A, Michaelis C, Mills RW, Jandt KD. The inuence of
storage and indenter load on the Knoop hardness of dental
composites polymerized with LED and halogen
technologies. Dental Materials 2004;20:218.
[38] Bennett AW, Watts DC. Performance of two blue
Light-emitting-diode dental curing units with distance and
irradiation time. Dental Materials 2004;20:729.
[39] Kameyama A, Hatayama H, Kato J, Haruyama A, Teraoka H,
Takase Y, et al. Spectral characteristics of light-curing units
and dental adhesives. Journal of Photopolymer Science and
Technology 2011;24:4116.
[40] Watts DC. Witness statement (2012) on resin composites
and light curing. London: Witness seminar British Dental
Association; 2012.
[41] Uhl A, Mills RW, Rzanny AE, Jandt KD. Time dependence of
composite shrinkage using halogen and LED light curing.
Dental Materials 2005;21:27886.
[42] Nitta K. Effect of light guide diameter of LED-light curing
unit on polymerization of light-cured composites. Dental
Materials 2005;21:21723.
[43] Breschi L, Cadenarro M, Antoniolli F, Sauro S, Biasotto M,
Prati C, et al. Polymerization kinetics of dental adhesives
cured with LED: correlation between extent of conversion
and permeability. Dental Materials 2007;23:106672.
[44] Schattenberg A, Lichtenberg D, Stender E, Willershausen B,
Erst CP. Minimal exposure time of different LED-curing
devices. Dental Materials 2008;24:10439.
[45] Sigusch BW, PaumT, Volpel A, Schinkel M, Jandt KD. The
inuence of various light curing units on the cytotoxicity of
dental adhesives. Dental Materials 2009;25:
144656.
[46] Topcu FT, Erdemir U, Sahinkesen G, Yildiz E, Uslan I, Acikel
C. Evaluation of microhardness, surface roughness, and
wear behavior of different types of resin composites
polymerized with two different light sources. Journal of
Biomedical Materials Research Part B-Applied Biomaterials
2010;92B:4708.
[47] Rahiotis C, Patsouri K, Silikas N, Kakaboura A. Curing
efciency of high-intensity light-emitting diode (LED)
devices. Journal of Oral Science 2010;52:18795.
[48] Leprince JG, Leveque P, Nystenv B, Gallez B, Devaux J, Leloup
G. New insight into the depth of cure of
dimethacrylate-based dental composites. Dental Materials
2012;28:51220.
[49] Rencz A, Hickel R, Ilie N. Curing efciency of modern LED
units. Clinical Oral Investigations 2012;16:1739.
[50] Busemann I, Lipke C, Schattenberg A, Willershausen B, Ernst
CP. Shortest exposure time possible with LED curing lights.
American Journal of Dentistry 2011;24:3744.
[51] Rios A, He JN, Glickman GN, Spears R, Schneiderman ED,
Honeyman AL. Evaluation of photodynamic therapy using a
light-emitting diode lamp against Enterococcus faecalis in
extracted human teeth. Journal of Endodontics
2011;37:8569.
[52] DCL Components Ltd., 2 Kennet House, 19 High Street,
Hungerford, Berkshire, RG17 0NL, UK.
[53] Nichia Corporation, 491 Oka, Kaminaka-Cho, Anan-Shi,
Tokushima 774-8601, Japan.
[54] Nichia LED Catalogue 2012: p036. Aka, Kaminaka Cho, Anan
Shi, Tokushima 774 8601, Japan.
[55] Christensen GJ. The curing light dilemma. Journal of the
American Dental Association 2002;133:7613.
[56] Elipar
TM
FreeLight Product leaet GD67 2002. 3M ESPE,
Morley Street, Loughborough, Leicestershire LE1 1EP,
UK.
[57] Elipar
TM
FreeLight Technical Product Prole 2002. 3M ESPE,
3M Center, Building 275 2SE-03, St. Paul, MN 55144 1000, US.
[58] Technical Data DS35 Lumileds Lighting U.S., LLC 370 West
Trimble Road San Jose, CA 95131, US.
[59] Data sheet LZ4-00B200 (5.1-09/19/12), 2012. LED Engin, Inc.,
651 River Oaks Parkway, San Jose, CA 95134, US.
[60] Elipar
TM
FreeLight 2 Product brochure (70-2009-3582-6), 2003.
3M ESPE, 3M Center, Building 275 2SE-03, St. Paul, MN 55144
1000, US.
[61] Elipar
TM
FreeLight 2 Technical Product Prole 2002. 3M ESPE,
3M Center, Building 275 2SE-03, St. Paul, MN 55144 1000,
US.
[62] L.E. Demetron II. Kerr Quarterly Promotions 2005 Kerr UK
Limited, 4 Flag Business Exchange, Vicarage FarmRoad,
Peterborough, PE1 5TX, UK.
[63] SmartLite
TM
PS Brochure (ref K103610-02) 2004. DENTSPLY
DeTrey GmbH, De-Trey-Str. 1, 78467 Konstanz, Germany.
[64] SmartLight
TM
Focus 2012. DENTSPLY Limited, Building 1,
Aviator Park, Station Road, Addlestone KT15 2PG, UK.
[65] Elipar
TM
S10 3M ESPE, Morley Street, Loughborough,
Leicestershire LE1 1EP, UK.
[66] Caughman WF, Rueggeberg FA, Curtis Jr JW. Clinical
guidelines for photocuring restorative resins. Journal of the
American Dental Association 1995;126:12806.
[67] Shortall AC, Harrington E. Guidelines for the selection, use,
and maintenance of visible light activation units. British
Dental Journal 1996;181:3837.
dental materi als 2 9 ( 2 0 1 3 ) 605617 617
[68] Fujibayashi K, Ishimaru K, Takahashi N, Kohno A. Newly
developed light curing unit using blue light-emitting diodes.
Dentistry in Japan 1998;34:4953.
[69] Ultralume 5. Ultradent Products Inc., 505 West 10200 South,
South Jordan, UT 84095, US.
[70] Vlkel T. Bluephase

family scientic documentation April

2009. IvoclarVivadent AG, Bendererstr. 2, FL 9494 Schaan,
Principality of Liechtenstein.
[71] Bluephase

20i brochure 627360/0111/e/W. IvoclarVivadent

AG, Bendererstr.2, FL 9494 Schaan, Principality of
Liechtenstein.
[72] Valo LED LCU, 2011. Ultradent Products Inc., 505 West 10200
South, South Jordan, UT 84095, US.
[73] ScanWave product leaet Ref. D05453-W1, 2010. ACTEON
Germany GmbH, Industriestrae 9, D-40822 Mettmann.
[74] Shortall AC, Palin WM, Jacquot B, Pelissier B. Advances in
light-curing units: four generations of LED Lights and
clinical implications for optimizing their use: Part 2. Dental
Update 2012;39:1322.
[75] Price RBT, Rueggeberg FA, Labrie D, Felix CM. Irradiance
uniformity and distribution fromdental light curing units.
Journal of Esthetic and Restorative Dentistry 2010;22:
86103.
[76] HamJr WT, Mueller HA, Ruffolo JJ, Clarke AM. Sensitivity of
the retina to radiation damage as a function of
wavelength. Photochemistry and Photobiology 1979;29:
73543.
[77] Murray GA, Yates JL, Newman SM. Ultraviolet light and
ultraviolet light activated composite resins. Journal of
Prosthetic Dentistry 1981;46:16770.
[78] Nomoto R, Uchida K, Hirasawa T. Effect of light intensity on
polymerization of light-cured composite resins. Dental
Materials Journal 1994;13:198205.
[79] Zach L, Cohen G. Pulp response to externally applied heat.
Oral Surgery, Oral Medicine, Oral Pathology, Oral Radiology
1965;19:51530.
[80] Hannig M, Bott B. In-vitro pulp chamber temperature rise
during composite resin polymerization with various
light-curing sources. Dental Materials 1999;15:27581.
[81] Mumford JM. Toothache and related pain. London, UK:
Churchill Livingstone; 1973.
[82] Yazici AR, Celik C, Ozgunaltay G, Dayangac B. The effects of
different light-curing units on the clinical performance of
nanolled composite resin restorations in non-carious
cervical lesions: 3-year follow-up. Journal of Adhesive
Dentistry 2010;12:2316.
[83] Krishnaswamy NR, Sunitha C. Light-emitting diode vs
halogen light curing of orthodontic brackets: a 15-month
clinical study of bond failures. American Journal of
Orthodontics and Dentofacial Orthopedics 2007;132:
51823.
[84] Santini A, Miletic V, Swift MD, Bradley M. Degree of
conversion and microhardness of TPO containing resin
based composites cured by polywave and monowave LED
units. Journal of Dentistry 2012;40:57784.
[85] Driscoll WG, Vaughan W. Handbook of optics. New York,
USA: McGraw-Hill Book Company; 1978. p. 114.
[86] dos Santos GB, Monte Alto RV, SampaioFilho HR, da Silva
EM, Fellows CE. Light transmission on dental resin
composites. Dental Materials 2008;24:5716.
[87] Al Shaa MM, Maawadh AM, Al Qahtani MQ. Evaluation of
light intensity output of QTH and LED curing devices in
various governmental health institutions. Operative
Dentistry 2011;36:35661.
[88] Rueggeberg FA. State of the art: Dental photocuring A review.
Dental Materials 2011;27:3952.