materials

Review
Radiation-Induced Defects and Effects in Germanate
and Tellurite Glasses
Mikko Hongisto 1,2, * , Alexander Veber 1 , Yannick Petit 2 , Thierry Cardinal 2 , Sylvain Danto 2 ,
Veronique Jubera 2 and Laeticia Petit 1
1 Photonics Laboratory, Tampere University, Korkeakoulunkatu 3, 33720 Tampere, Finland;
[email protected] (A.V.); [email protected] (L.P.)
2 CNRS, University of Bordeaux, Bordeaux INP, ICMCB, UMR 5026, F-33600 Pessac, France;
[email protected] (Y.P.); [email protected] (T.C.); [email protected] (S.D.);
[email protected] (V.J.)
* Correspondence: [email protected]




Received: 29 July 2020; Accepted: 25 August 2020; Published: 31 August 2020


Abstract: This review focuses on the radiation-induced changes in germanate and tellurite glasses.
These glasses have been of great interest due to their remarkable potential for photonics, in terms of
extended transmission window in the mid-infrared, ability of rare-earth loading suitable with
a laser, and amplification in the near- and mid-infrared or high nonlinear optical properties.
Here, we summarize information about possible radiation-induced defects, mechanisms of their
formation, and the influence of the glass composition on this process. Special attention is paid to
laser-induced structural modification of these glasses, including possible mechanisms of the laser-glass
interaction, laser-induced crystallization, and waveguide writing. It is shown that these methods can
be used for photostructuring of the glass and have great potential for practical applications.

Keywords: germanate glass; tellurite glass; radiation treatment; defects; structuring

1. Introduction
Glasses play a key role in many areas of modern life. The fundamental understanding
of the photoresponse of the glass to radiation has allowed the development of novel glasses
with tailored photoresponse as, for example, radiation-hardened optical fibers based on glassy
silica [1]. High-energy radiation can induce multiple physical and chemical modifications in
materials. It includes among other modifications in crystallinity [2,3] and bond structure [4],
lattice defects [5], optical properties [5], spectroscopic properties [6], electrical properties [2], and surface
and interface morphology. These modifications are a consequence of lattice defect creation, migration,
and recombination, the kind and extent of defects depending mostly on the substrate material, radiation
type, dose, and energy fluence. Although the photoresponse has been widely investigated for silica [7,8],
chalcogenide [4,9], and phosphate glasses [10,11], fewer studies have been reported on the radiation
treatment of heavy metal oxide (HMO) based glasses. These are often described as glasses containing
TeO2 , Sb2 O3 , GeO2 , Ga2 O3 , and/or Bi2 O3 glass formers, to cite a few.
The objective of this review is to provide details on the defect formation mechanism and the
radiation-induced variation of properties in tellurite and germanate glasses, such as their optical and
structural properties. Besides creating point defects and modification of the glass network, radiation
treatment can induce crystallization or bubble formation [10]. In the selected papers, the glasses were
irradiated using different sources ranging from the ionizing (alpha, beta, gamma, and X-rays) to the
near-infrared ultra-short pulse laser radiations [12]. With laser radiation treatment, the energy is
controlled and focused, and thus has been used extensively to write structures, such as active [13] and

Materials 2020, 13, 3846; doi:10.3390/ma13173846 www.mdpi.com/journal/materials

Materials 2020, 13, 3846 2 of 21

passive [14] waveguides in glasses, for example. Another objective is to propose strategy to engineer
radiation-tolerant HMO glass photonic devices and/or to mitigate their damages (ex: annealing) [11].
This review is organized as follows: at first (Section 2), a general introduction to HMO glasses
and to their physical, chemical, optical, and structural properties is presented. After (Section 3),
the mechanisms of energy deposition, structural relaxation, and the different defect generation
processes are introduced. Finally (Section 4), the use of radiation treatment to locally structure the
glasses is described.

2. Description of the Tellurite and Germanate Glasses

Heavy metal oxide (HMO) based glasses have been popular choices for applications in the telecoms
and mid IR bands (up to around 5 µm), since the most common silicate glasses cannot be used in this
spectral region [15]. Since the discovery of several HMO glasses, the tellurite and germanate glasses
have demonstrated growing interest, as these glasses possess wide transmission region, good corrosion
resistance, low phonon energy, and high linear and nonlinear refractive index [16]. As opposed to silica
glass, these glasses are transparent beyond 2 µm, where silica glass become opaque. They are also good
hosts for rare-earth (RE) ions as they can also incorporate a large amount of rare-earth ions without
clustering [17–19]. These HMO glasses are especially good hosts for mid-infrared emitting optical
centers, e.g., Er3+ emitting at 2.7 µm, having potential applications in surgery, remote atmospheric
sensing, and eye-safe laser radar because of their spectral overlap with regions associated with strong
water absorption [20].
Tellurite and germanate HMO glasses have been identified as good glass hosts also for metal or
semiconductor nanoparticles (NPs) with the objective to enhance their optical properties provided
by the surface plasmon resonance (SPR) mechanism [21,22]. Applications have been found for
these nanoparticle/glass structures in photothermal therapy [23], medical sensing of antibodies [24],
and Raman spectroscopy [25], just to cite several examples. Metallic NPs containing HMO glasses are
also promising materials for use in nonlinear optical devices, as the NPs can also be used to enhance
the linear and nonlinear properties of the glasses [26,27]. The introduction of silver has appeared as
the most efficient and fruitful route toward the functionalization of glasses with distinctive properties.
Since the first reported study on the nucleation of silver in germanate (PbO-GeO2 ) and in tellurite
glasses in [28] and in [29], respectively, precipitation of Ag nanoparticles in germanate and tellurite
glasses has been of great interest. For example, considering tellurite glasses [30] have synthesized
the Er3+ /Yb3+ codoped tellurite glasses with silver NPs through melt-quenching method, and a large
enhancement in visible upconversion emissions (539, 557, and 675 nm), the near-infrared emission
(1.5 µm) along with the mid-infrared emission (2.7 µm) was found with the precipitation of silver
NPs. In [31], it has been reported the surface-enhanced Raman scattering and plasmon-enhanced
emission by silver NPs in Er3+ -doped zinc-tellurite glasses. An enhancement by about 10 times in
Raman signal and up to three times in upconversion emissions (520, 550, and 650 nm) of Er3+ was
demonstrated. In germano-bismuthate glasses, a significant enhancement of the Tm3+ fluorescence
intensity at 1.47 µm in Ag0 NPs embedded glasses could be obtained [32]. Similar enhancement was
also obtained in Er3+ /Yb3+ doped glasses [33]. All the aforementioned fluorescence enhancement of
doped rare-earth ions is mainly attributed to the local field enhanced effect of metallic NPs. The deep
understanding of the formation mechanisms of silver nanoparticles in host matrix is essential to achieve
new silver species with proper size and shape, inter-particle distances, and volume concentration. Gold
insertion was also considered as a luminescence sensitizer of rare-earth ions, such as in the Er3+ -doped
TeO2 -ZnO system by [34]. These metallic nanoparticles were found to enhance the photoluminescence
due to presence of the RE ions in the proximity of an array of silver nanoparticles.

2.1. Elaboration Methods of HMO Glasses

HMO glasses are generally obtained by a standard melt-casting method under different
atmospheric conditions, the most commonly employed crucibles being platinum (Pt), gold (Au),
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melted. For example,

or corundum (Al2 O3 ).the
Bothtellurite glasses tend
the atmosphere to the
and dissolve Pt from
crucible depend crucible
on theasglass
Pt iscomposition
not inert when in
to be
contact
melted. with TeO2 [35].the
For example, The glass batches
tellurite glassescan
tendbetomelted
dissolvein Pt
different atmospheres.
from crucible as Pt isAn
notatmosphere
inert when of in
pure oxygen at ambient pressure would avoid reduction of TeO during the
contact with TeO2 [35]. The glass batches can be melted in different atmospheres. An atmosphere of
2 melting [36]. A review
on the
pure preparation
oxygen of tellurite
at ambient pressureglasses was recently
would avoid reduction published
of TeO2 duringand canthebe found[36].
melting in [37]. Sol–gel
A review on
technique has been
the preparation also used
of tellurite forwas
glasses the recently
preparation of HMO
published and glasses. The main
can be found in [37].advantages of this
Sol–gel technique
technique
has been alsocompared
used forto the
the melting–quenching
preparation of HMO method
glasses.areThe
(1) the
mainlow processingoftemperature,
advantages this technique (2)
the control to
compared of the
the melting–quenching
purity and homogeneity of the
method areglass, and
(1) the low(3)processing
the flexibility of the glass(2)
temperature, composition.
the control
Recently, aerodynamic levitation technique (ADL) has been reported to be a suitable
of the purity and homogeneity of the glass, and (3) the flexibility of the glass composition. Recently, technique to
prepare HMO glasses [38]. In ADL technique, the melt is levitated by a gas flow
aerodynamic levitation technique (ADL) has been reported to be a suitable technique to prepare HMO without the use of
crucible before
glasses [38]. beingtechnique,
In ADL solidified.the This technique
melt is often
is levitated by a gasused
flowto without
preparethe glasses
use ofwith low before
crucible glass-
forming ability to vitrify in bulk form, especially when preparing glasses with
being solidified. This technique is often used to prepare glasses with low glass-forming ability large amount of RE
to
ions.
vitrify in bulk form, especially when preparing glasses with large amount of RE ions.

2.2. Glass
Glass Network
Network Structure of HMO Glasses
It isiswell
wellknown
known thatthat
the the various
various properties
properties of theof the glasses
glasses are dictated
are dictated by their Therefore,
by their structure. structure.
Therefore,
it is crucialitto is crucial to understand
understand how the
how the atoms areatoms are bonded
bonded to formto form
the the network.
network. Tellurite
Tellurite glassesglasses
have
have been under
been under investigation
investigation sincediscovery
since their their discovery by Stanworth
by Stanworth in 1952 in 1952
[39]. The[39].
main The main
glass glass
network
network is constituted
is constituted of tellurium
of tellurium ad oxygen ad oxygen
atoms,atoms, belonging
belonging to thetogroup
the group
VIA VIA in the
in the periodic
periodic table
table of
of elements
elements [16].
[16]. Thenetwork
The networkcan canbebeformed
formedby byTeO
TeO4 4(trigonal
(trigonalbipyramid),
bipyramid), TeO
TeO33 (trigonal pyramid),
pyramid),
and the intermediate TeO TeO3+1
3+1 polyhedron.
polyhedron.Each Eachunitunitcarries
carriesaalone
lone pair
pair electron
electron (LPE)
(LPE) [40],
[40], which is
thought to tocontribute
contributetotothe the large
large linear
linear andand nonlinear
nonlinear refractive
refractive indexindex
of theof the tellurite
tellurite glasses.glasses.
As shown As
shown
in Figure in 1,
Figure 1, the
the four four oxygens
oxygens in the TeO in4the TeO
units 4 units
are are coordinated
coordinated to one tellurium
to one tellurium atom
atom to form to form
a trigonal
abipyramid
trigonal bipyramid
(tbp). (tbp).

Schematic of
Figure 1. Schematic of the
the structural
structural units in tellurite glasses, modified from [41].

The two
The two equatorial
equatorial and and two
two apical
apical oxygen
oxygen sites
sites are
are bridging oxygens (BO),
bridging oxygens (BO), while
while the
the third
third
equatorial site
equatorial site isis occupied
occupiedby bythe
theLPEs
LPEsinin the
the valence
valence band
band of tellurium.
of tellurium. In TeO
In the the 3TeO 3 structure,
structure, two
two oxygens are bridging oxygen and one oxygen is one non-bridging oxygen
oxygens are bridging oxygen and one oxygen is one non-bridging oxygen (NBO) double bonded with (NBO) double bonded
with a tellurium
a tellurium atomatom(Te =(Te=O).
O). During During the formation
the formation of the
of the glass
glass network,
network, the the
sitesite
for for an oxide
an oxide ionion
andand
an
an LPE can interchange mutually with four bridging oxygen sites leading
LPE can interchange mutually with four bridging oxygen sites leading to bond deformation and to bond deformation and
packing
packing of structural units,
of structural units, which
which isis aa unique
unique characteristic
characteristic of
of tellurite
tellurite glasses. Others have
glasses. Others have described
described
the structure n
the structure in in terms
terms ofof QQm units as
mn units as represented
represented in in Figure
Figure 2.
2. NN is
is the
the number
number of of bridging
bridging oxygen
oxygen
bonded to the central atom and m is the coordination number, as of oxygen
bonded to the central atom and m is the coordination number, as of oxygen around tellurium, whicharound tellurium, which is
three or four [42]. The addition of modifier cation was reported to lead to the transformation
is three or four [42]. The addition of modifier cation was reported to lead to the transformation of the of the
Q4444to
Q toQQ443 3(TeO
(TeO4 4totoTeO
TeO3+13+1 ) [43].
) [43].
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2020,13,
13,x xFOR
FORPEER
PEERREVIEW
REVIEW 4 4ofof2222

Figure
Figure 2.2.2.
Figure Schematic
Schematic
Schematic ofof
of the
the
the Qmnm
QQm n nunits in the tellurite glasses, modified
units in the tellurite glasses, modifiedfrom
from[42].
[42].

The
Theglass
The glass formation
glass formation
formation and
andstructural
and structuralanalysis
structural analysis
analysis of tellurite glasses
ofoftellurite
tellurite have been
glasses
glasses have
haveintensively
been studiedstudied
beenintensively
intensively [44,45].
studied
A review
[44,45]. on the structural properties of tellurite glasses with different
[44,45]. A review on the structural properties of tellurite glasses with different compositionscan
A review on the structural properties of tellurite glasses with compositions
different can
compositions be found
canbe be
in [41]. inin[41].
found
found [41].
The
Thenetwork
The networkof
network ofofpure
puregermanate
pure germanateglass
germanate glassisisisformed
glass formedby
formed byGeO
by GeO
GeO44 units
unitswhich
4units whichshare
which sharetheir
share theircorners,
their corners,the
corners, theGe
the Ge
Ge
atom
atom being
being covalently
covalently bonded
bonded to
to four
four bridging
bridging oxygens.
oxygens. The structural units,
atom being covalently bonded to four bridging oxygens. The structural units, along with tetrahedra, along with tetrahedra,
can
canbe
can betrigonal
be trigonalbipyramids
trigonal bipyramidsand
bipyramids andoctahedra,
and octahedra,where
octahedra, wherethe
where thecentral
the centralatom
central atomis
atom isisgermanium,
germanium,surrounded
germanium, surroundedby
surrounded bybyfive
five
five
or
ororsix
six oxygen
oxygen atoms,
atoms, respectively,
respectively, as
asdepicted
depicted
six oxygen atoms, respectively, as depicted in Figure 3. ininFigure
Figure 3.3.

Figure
Figure 3. Schematic of the structural units in germanate glasses, modified from [46].
Figure3.3.Schematic
Schematicofofthe
thestructural
structuralunits
unitsiningermanate
germanateglasses,
glasses,modified
modifiedfrom
from[46].
[46].
As opposed to silica glass, the physical properties of germanate glass exhibit extrema depending
As
Asopposed
opposedtotosilica silicaglass,
glass,thethephysical
physicalproperties
propertiesofofgermanate
germanateglass glassexhibit
exhibitextrema
extremadepending
depending
on the alkali oxide content. This phenomenon is known as the “germanate anomaly effect” which was
on
on the alkali oxide content. This phenomenon is known as the “germanate anomaly effect”which
the alkali oxide content. This phenomenon is known as the “germanate anomaly effect” which
first reported in 1962 [47]. The first model to explain this anomaly effect was proposed in 1964 [48].
was
wasfirst
firstreported
reportedinin1962 1962[47].
[47].TheThefirst
firstmodel
modeltotoexplain
explainthisthisanomaly
anomalyeffect
effectwas wasproposed
proposedinin1964 1964
Murthy et al. suggested that the coordination of Ge gradually changes from GeO4 to GeO6 and
[48]. Murthy et al. suggested that the coordination of Ge gradually changes
[48]. Murthy et al. suggested that the coordination of Ge gradually changes from GeO4 to GeO6 and from GeO 4 to GeO 6 and
then from GeO6 to GeO4 with the progressive introduction of alkali oxide. This change in the Ge
then
thenfromfromGeOGeO6 6totoGeO GeO4 4with
withthe theprogressive
progressiveintroduction
introductionofofalkalialkalioxide.
oxide.This Thischange
changeininthe theGeGe
coordination was confirmed using X-ray, neutron scattering [49,50], and also using extended X-ray
coordination
coordinationwas wasconfirmed
confirmedusing usingX-ray,
X-ray,neutron
neutronscattering
scattering[49,50],
[49,50],andandalso
alsousing
usingextended
extendedX-ray X-ray
absorption fine structure (EXAFS) [51,52]. However, the presence of GeO5 or GeO6 in the germanate
absorption
absorptionfine finestructure
structure(EXAFS)
(EXAFS)[51,52].
[51,52].However,
However,the thepresence
presenceofofGeO GeO5 5ororGeO
GeO6 6ininthethegermanate
germanate
network is still uncertain as these characterization tools cannot distinguish between fivefold and
network
networkisisstill stilluncertain
uncertainasasthese thesecharacterization
characterizationtools toolscannot
cannotdistinguish
distinguishbetweenbetweenfivefoldfivefoldandand
sixfold coordination of Ge. According to molecular dynamics study [53] and neutron diffraction
sixfold
sixfoldcoordination
coordinationofofGe. Ge.According
Accordingtotomolecular
moleculardynamics
dynamicsstudy study[53]
[53]and
andneutron
neutrondiffraction
diffractionwith with
with high real-space resolution [54], the higher Ge coordination is suspected to be GeO5 . However,
high
highreal-space
real-spaceresolution
resolution[54],[54],thethehigher
higherGe Gecoordination
coordinationisissuspected
suspectedtotobe beGeO
GeO5.5.However,
However,others others
others reported that non-bridging oxygen (NBO) atoms would occur when the alkali oxide content is
reported
reportedthat thatnon-bridging
non-bridgingoxygen oxygen(NBO) (NBO)atoms
atomswould
wouldoccur
occurwhen
whenthe thealkali
alkalioxide
oxidecontent
contentisisbelow
below
below 10 mol%. The germanate anomaly phenomenon would then be related to the transformation of
10
10 mol%. The germanate anomaly phenomenon would then be related to the transformationofof
mol%. The germanate anomaly phenomenon would then be related to the transformation
different member rings [55,56]. In this model, the addition of alkali oxide is suspected to lead to the
different
differentmember
memberrings rings[55,56].
[55,56].InInthis
thismodel,
model,thetheaddition
additionofofalkali
alkalioxide
oxideisissuspected
suspectedtotolead leadtotothe
the
formation of a three-membered ring which converts to a four-membered ring generating non-bridging
formation
formation ofof aa three-membered
three-membered ring ring which
which converts
converts toto aa four-membered
four-membered ring ring generating
generating non- non-
oxygen with further addition of alkali oxide. Recently, a new insight into the mechanism of germanate
bridging
bridgingoxygen
oxygenwith withfurther
furtheraddition
additionofofalkali
alkalioxide.
oxide.Recently,
Recently,aanewnewinsight
insightintointothethemechanism
mechanismofof
anomaly was reported in [57]. Three Ge structural units (fourfold, fivefold, and sixfold) were found
germanate
germanateanomalyanomalywas wasreported
reportedinin[57]. [57].Three
ThreeGe Gestructural
structuralunits
units(fourfold,
(fourfold,fivefold,
fivefold,and andsixfold)
sixfold)
in the K2 O-GeO2 glass system with a K2 O content between 11 and 20 mol%, whereas the network
were
werefound
foundininthe theKK2O-GeO
2O-GeO 2 2glass
glasssystem
systemwithwithaaKK2O 2Ocontent
contentbetween
between11 11and
and20 20mol%,
mol%,whereaswhereasthe the
contains only two Ge species (fourfold and sixfold) when the K2 O content is larger than 20 mol%.
network contains only two Ge species (fourfold and sixfold) when the
network contains only two Ge species (fourfold and sixfold) when the K2O content is larger than 20K 2 O content is larger than 20
The main structural modification process for the content of K2 O > 0.25 is the depolymerization of
mol%.
mol%.The Themain
mainstructural
structuralmodification
modificationprocess processforforthe
thecontent
contentofofKK2O 2O>>0.25
0.25isisthe
thedepolymerization
depolymerization
the germanate network through NBO formation in various Qn species. For more information about
ofofthe
thegermanate
germanatenetworknetworkthrough
throughNBO NBOformation
formationininvarious
variousQQn nspecies.
species.ForFormore
moreinformation
informationabout about
germanate anomaly, the reader is referred to [58]. Additional element as RE added in the glass network
germanate anomaly, the reader is referred to [58]. Additional element
germanate anomaly, the reader is referred to [58]. Additional element as RE added in the glass as RE added in the glass
could also influence the local structure of germanate glasses. If variation of RE concentration does not
network
networkcould couldalsoalsoinfluence
influencethe thelocal
localstructure
structureofofgermanate
germanateglasses.
glasses.IfIfvariation
variationofofRE REconcentration
concentration
modify the molecular vibrational part of the Raman response, which indicates that no specific new site
does
does not modify the molecular vibrational part of the Raman response, which indicatesthat
not modify the molecular vibrational part of the Raman response, which indicates thatno no
specific
specificnewnewsitesiteisisstabilized,
stabilized,these
thesedoping
dopingelements
elementsimpact
impactthe thenon-bridging
non-bridginganions anionsinintheirtheirvicinity.
vicinity.
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Materials 2020, 13, x FOR PEER REVIEW 5 of 22

isThis results these

stabilized, in a variation of the boson
doping elements intensity
impact peak which anions
the non-bridging has been in described in [59].
their vicinity. ThisTuning
resultsof
inthe
a
glass transition
variation and intensity
of the boson crystallization temperature
peak which has beencould also inbe[59].
described managed
Tuning by controlling
of the the RE
glass transition
concentration
and [3]. temperature could also be managed by controlling the RE concentration [3].
crystallization

3.3.Defects
DefectsFormation
FormationininGermanate
Germanateand
andTellurite
TelluriteGlass
GlassDue
DuetotoRadiation
RadiationTreatment
Treatment
ItIthas
hasbeen
beenknown
knownthat thationizing
ionizingradiation
radiationaffects
affectsthe
theglass
glassnetwork
networkby bycreating
creatingdefects,
defects,whichwhichinin
turn
turnaffect
affectthe properties
the properties of of
glasses with
glasses withchanges
changesin the optical
in the properties
optical receiving
properties the most
receiving the mostinterest [5].
interest
These defects can, for example, be used for radiation measurement in sensing,
[5]. These defects can, for example, be used for radiation measurement in sensing, cause absorptioncause absorption
losses
lossesininfibers
fibers[60],
[60],ororact
actasasluminescent
luminescentcenters
centersand
andreplace
replacephosphorescent
phosphorescentcompounds
compoundsininlighting
lighting
applications
applications[61].[61].To
Tobetter
betterunderstand
understandthe theglasses’
glasses’performance
performanceininthese
theseapplications,
applications,ititisistherefore
therefore
imperative
imperativetotounderstand
understandthe thedefects
defectsand
andhow
howthey
theyare
areformed.
formed.

3.1.
3.1.Types
TypesofofDefects
Defectsand
andTheir
TheirCharacterization
Characterization
The
Thetypes
typesofofdefects
defectsthat
thathave
havebeen
beendiscovered
discoveredinintellurite
telluriteglasses
glassesare
areshown
shownininFigure
Figure4.4.

Figure 4. Defects in tellurite glasses.

Figure 4. Defects in tellurite glasses.
The Te-NOBHC is a central Te atom linked to three bridging oxygens and one oxygen being
The Te-NOBHC is a central Te atom linked to three bridging oxygens and one oxygen being a
a non-bridging one with positive charge indicating a trapped hole. The TeEC and V0 defects have
non-bridging one with positive charge indicating a trapped hole. The TeEC and V0 defects have been
been attributed to an electron and a hole trapped in an oxygen vacancy, respectively, while the Te
attributed to an electron and a hole trapped in an oxygen vacancy, respectively, while the Te is
is connected to three oxygens [62]. A schematic of different defects formation is shown in Figure 5.
connected to three oxygens [62]. A schematic of different defects formation is shown in Figure 5. A
A modifier-related trap is observed when an electron is trapped near a modifier atom. The TeOHC is
modifier-related trap is observed when an electron is trapped near a modifier atom. The TeOHC is
deemed to be an intrinsic defect consisting of a hole trapped in the bridging oxygen [63].
deemed to be an intrinsic defect consisting of a hole trapped in the bridging oxygen [63].
While the effects of various types of radiation on tellurite glasses have been studied in detail [64,65],
the characterization of the formed defects have received significantly less attention. The existing
defect-related studies are sparse and focused mainly on the EPR measurements [62,63,66]. No direct
attributions of optical absorption bands to specific defects have yet been made. However, there exists
research results describing absorption caused by radiation-induced defects [64]. Table 1 shows the
defects and their respective electron paramagnetic resonance (EPR) g-values.

Table 1. Defects found in tellurite glasses and their EPR values.

Defect EPR g-Value

Te-NBOHC 1.9960 [62]
TeEC/VO 1.9705 [66]
Modifier related trap 2.0010 [63]
TeOHC 2.0747 [63]

Various defects have been observed in germanate glasses. The defects can be classified as
intrinsic or extrinsic. Intrinsic defects are formed during the preparation of the glass, whereas the
extrinsic defects are due to ionizing radiation breaking bonds or changing the valency of modifier
ions. The defects are further classified based on their structure, whether the defect is formed with a
positive hole, i.e., absence of electron, or a trapped excess electron. Formation and photoresponse
depends on the structure and type of the defect [67]. Upon prolonged exposure to irradiation, more and
more extrinsic defects are formed, and the number of intrinsic defects decreases. This causes a
Materials 2020, 13, 3846 6 of 21

reduction in the defect-induced absorption band in a process known as bleaching [68]. The structures
of germanium-related defects usually encountered are presented in Figure 6.
Materials 2020, 13, x FOR PEER REVIEW 6 of 22

Materials 2020, 13, x FOR PEER REVIEW 7 of 22

Figure 5. Formation of some defects. (a) Alkali oxide M2O and a BO react and form a pair of NBOs.
5. Formation of some
and Figure
more extrinsic defects are defects.
formed,(a)and
Alkali
theoxide
number M2 Oofand a BO react
intrinsic and decreases.
defects form a pair of NBOs.
This causes a
(b) The reaction
(b) Theinreaction is partially reversed
is partially reversed and a
and a VV 0 defect forms. (c) Further irradiation results in electron
reduction the defect-induced absorption 0 defect
band in aforms.
process(c) known
Further as
irradiation
bleachingresults
[68].in
Theelectron
structures
transferand
transfer andformation
formationofofan anTe-NBOHC
Te-NBOHC andand aa TeEC
TeEC defects.
defects. Reproduced
Reproduced from [62]. Copyrights
of germanium-related
Elsevier 2010.
defects usually encountered are presented in Figurefrom6. [62]. Copyrights
Elsevier 2010.

While the effects of various types of radiation on tellurite glasses have been studied in detail
[64,65], the characterization of the formed defects have received significantly less attention. The
existing defect-related studies are sparse and focused mainly on the EPR measurements [62,63,66].
No direct attributions of optical absorption bands to specific defects have yet been made. However,
there exists research results describing absorption caused by radiation-induced defects [64]. Table 1
shows the defects and their respective electron paramagnetic resonance (EPR) g-values.

Table 1. Defects found in tellurite glasses and their EPR values.

Defect EPR g-Value

Te-NBOHC 1.9960 [62]
TeEC/VO 1.9705 [66]
Modifier related trap 2.0010 [63]
TeOHC 2.0747 [63]

Various
Figure
Figure
defects
6.6. Various
Various have been
germanate
germanate
observed
defects
defects with
in germanate
withvalues
values ofαα and
of
glasses.
and FWHM
FWHM The defects
provided
provided foreach
for
can
each be correspond
center
center
classified as
correspond
intrinsic
to
or
toposition
extrinsic.
positionofofthe
Intrinsic
themaximum
maximumand
defects
andfull
are
width
full
formed
at at
width half
during
maximum
half maximum
the preparation
of the absorption
of the
of the glass,
peakpeak
absorption
whereas
associated
the
withwith
associated the
extrinsic
defect.
defects
Modified
are due to
fromfrom
ionizing
[61,69].
radiation breaking bonds or changing the valency of modifier
the defect. Modified [61,69].
ions. The defects are further classified based on their structure, whether the defect is formed with a
positive hole,
Intrinsic i.e., absence
germanate of electron,
defects or a trapped
are expected to formexcess electron.
at the glass Formation
preparation and[67].
stage photoresponse
These defects
depends on the structure and type of the defect [67]. Upon prolonged exposure to irradiation, more
are classified as neutral oxygen monovacancy and divacancy color centers, NOMV and NODV,
respectively (see Figure 6). These linked Ge atoms are precursors to further extrinsic defects caused
by irradiation [69].
Materials 2020, 13, 3846 7 of 21

Intrinsic germanate defects are expected to form at the glass preparation stage [67]. These defects
are classified as neutral oxygen monovacancy and divacancy color centers, NOMV and NODV,
respectively (see Figure 6). These linked Ge atoms are precursors to further extrinsic defects caused by
irradiation [69].
The germanium related lone-pair center (GLPC) is comprised of a germanium atom linked to
two oxygens and a lone pair of electrons. The entire system has a positive charge, resulting in a
(GLPC)+ defect. Germanium electron trapped center (GEC) is a fully coordinated Ge atom with an
extra electron trapped at the center. The Ge E0 (E0 (Ge) in some texts) is a neutral color center defect
where a Ge is linked to three oxygens and the fourth link is replaced by a lone pair of electrons.
The germanium-related non-bridging oxygen hole center (Ge-NBOHC) consists of a central Ge atom
linked to four oxygens. One of the oxygens is an NBO atom and has a positive charge due to a
missing electron. The GeO3 + defect is a counterpart to a Ge E0 defect, a Ge linked to three oxygens,
and a residual positive charge. The structures of these defects and the proposed mechanisms of their
formation are presented in Figure 7.
Materials 2020, 13, x FOR PEER REVIEW 8 of 22

Figure 7. Proposed formation mechanisms of germanate defects. One-photon process (a), two-photon
process
Figure (b), and balance
7. Proposed reaction
formation of one- andoftwo-photon
mechanisms germanate processes (c). Modified
defects. One-photon from (a),
process [69].two-photon
process (b), and balance reaction of one- and two-photon processes (c). Modified from [69].
It is proposed that the extrinsic defects are formed via two different processes: one- and two-photon
reactions.
It is In the one-photon
proposed that the process,
extrinsicindefects
Figure are
7a, aformed
UV photon (243different
via two nm/5.1 eV) forms anone-
processes: electron and
and two-
pair of Ge E0 and GeO + defects. This is the result of a NOMV Ge-Ge bond breaking. NODVs do not
photon reactions. In the 3 one-photon process, in Figure 7a, a UV photon (243 nm/5.1 eV) forms an
break
electron and pair of Ge E’ rather,
under UV irradiation; and GeO the3center relaxes
+ defects. Thisfrom theresult
is the excited
of state through
a NOMV photoluminescence.
Ge-Ge bond breaking.
In the two-photon
NODVs reaction,
do not break it UV
under is proposed thatrather,
irradiation; the NOMV is changed
the center relaxesinto
fromtwothe E0 defects
Geexcited asthrough
state shown
in Figure 5b. NODV and normal
photoluminescence. In the two-photon GeO 2 units
reaction, it is proposed that the NOMV is changed intoGEC
can also react and form a mix of NOMV, GLPC, and two
defects
Ge E’ defects as shown in Figure 5b. NODV and normal GeO2 units can also react and form a mixan
through an intermediate state as shown in Figure 5c [69]. However, it should be noted that of
NOMV, GLPC, and GEC defects through an intermediate state as shown in Figure 5c [69]. However,
it should be noted that an alternate model for the two-photon reaction has been proposed by [70].
This model does not contain NODVs, present in Figure 7c, but rather, it assumes that GeO2 and
neutral GLPC react to form a pair of GEC and (GLPC)+ defects.
The various defects are usually referred to as color centers, meaning they absorb light in the UV-
Materials 2020, 13, 3846 8 of 21

alternate model for the two-photon reaction has been proposed by [70]. This model does not contain
NODVs, present in Figure 7c, but rather, it assumes that GeO2 and neutral GLPC react to form a pair of
GEC and (GLPC)+ defects.
The various defects are usually referred to as color centers, meaning they absorb light in the
UV-visible range. Although some defects are optically inactive, most have bands in the UV with some
in the visible range. Therefore, a UV-Vis absorption measurement offers an easy and effective way
to study various optically active defects [8]. Another common technique used to complement the
absorption measurements is the electron paramagnetic resonance spectroscopy (EPR). It is especially
useful in cases where the defect is optically inactive or the absorption band of one type of defect
overlaps with another defect’s band. Other techniques such as photo- and thermoluminescence,
PL and TL respectively, have been reported in some papers [71,72] and can be used together with
absorption and EPR measurements. Table 2 shows the EPR g-values and corresponding absorption
peak parameters for different defects.

Table 2. Common defects found in germanate glasses, their EPR values, and absorption bands.

Defect EPR g-Value Abs. Wavelength nm [eV] PL Wavelength nm [eV]

(GLPC)+ 1.9866 [70] 225 [5.5] [69] 400 [3.1] [71] 1
GEC 1.9933 [70] 261 [4.75] [69] and 315 [3.9] [72] -
Ge E0 2.0011 [73] 197 [6.3] [68] 590 [2.1] [61] 2
Ge-NBOHC 2.0076 [74] 375 [3.3] [72] 590 [2.1] [61] 2 650 [1.9] [71] 1
GeO3 + 2.008 [73] - -
1 Excited at 325 nm; 2 excited at various wavelengths between 250–400 nm.

3.2. Impact of Glass Composition on Defects Formation

The sensitivity of HMO glasses and the type of defects induced due to irradiation of the material,
depends on the chemical composition. It is clear for instance that formation of Te-related defect is
impossible in Te-free glass. At the same time, different types of defects can be induced in presence of
several network formers.
Irradiation of pure GeO2 glass results in formation of Ge E0 and oxygen excess centers: Ge-NBOHC
and Ge-O3 + [75]. Gradual introduction of GeO2 in other glass systems, e.g., in gallate glass, also results
in formation of Ge-related defects upon the irradiation, as it was demonstrated for 3CaO-2Ga2 O3 -xGeO2
glasses (x = 0, 3, 4) upon γ, X-ray, and UV irradiation [76]. At the same time, the number of the induced
centers depends on the pre-existing units in the glass network. A detailed investigation on number of
Ge-E0 and Ge-NBOHC induced under irradiation was done for xNa2 O-(1-x)GeO2 , where x = 0–0.35
glasses [77]. The EPR center density was investigated as a function of the modifier content (Figure 8).
It can be seen that the number of both defects increases coherently with the modifier content up to
~5 mol% (region I); that at higher concentrations up to 20 mol.%, the concentration of Ge-NBOHC
continues to increase while amount of Ge-E0 decreases (region II); and that finally, a further increase of
Na2 O results in saturation or even slow decrease in Ge-NBOHC centers (region III).
Apparently, at low modifier levels, only slight changes in the glass network occur, and the
following mechanism is responsible for the formation of the defect pairs:

≡ Ge − O − Ge ≡ + hν → ≡ Ge − O• + • Ge ≡ (1)

In their original work, Azzoni et al. explained the higher yield of the reaction with increasing
Na2 O content in region I by network densification, without detailed investigation of its microscopic
origin [77]. One may note that this reaction is identical to the one proposed for silicate glasses, where it
was found that the number of defects induced is proportional to number of strained bonds in silica
network, which are associated in particular with presence of threefold rings [78]. Investigation of
Na2 O-GeO2 glasses by means of Raman spectroscopy revealed that number of three-membered GeO4
 also results in formation of Ge-related defects upon the irradiation, as it was demonstrated for 3CaO-
2Ga2O3-xGeO2 glasses (x = 0, 3, 4) upon γ, X-ray, and UV irradiation [76]. At the same time, the
number of the induced centers depends on the pre-existing units in the glass network. A detailed
investigation on number of Ge-E’ and Ge-NBOHC induced under irradiation was done for xNa2O-
(1-x)GeO
Materials 2, where
2020, 13, 3846 x = 0–0.35 glasses [77]. The EPR center density was investigated as a function 9 ofof
21the
modifier content (Figure 8). It can be seen that the number of both defects increases coherently with
the modifier content up to ~5 mol% (region I); that at higher concentrations up to 20 mol.%, the
rings increases upoftoGe-NBOHC
concentration ~10 mol% of the modifier
continues contentwhile
to increase [79], amount
allowingoftoGe-E’
assume that the(region
decreases increasing
II); and
amount of defects in region I of both the types associated with low-membered rings occurs
that finally, a further increase of Na2O results in saturation or even slow decrease in Ge-NBOHC in the same
manner,
centers as(region
it happensIII). in silicate glasses.

Figure
Figure 8. EPR
8. EPR center
center density
density in2Na
in Na 2O-GeO
O-GeO 2 glasses
2 glasses as aasfunction
a function of Na2O
of the the Nacontent.
2O content.
TheThe hollow
hollow
circles
circles referrefer
to Ge-E 0 signals
to Ge-E’ signals before
before X-ray
X-ray irradiation,
irradiation, the the filled
filled circles
circles referrefer 0 signals
to Ge-E’
to Ge-E signals after
after X-ray
X-ray
irradiation,
irradiation, the the filled
filled triangles
triangles refer
refer to Ge-NBOHC
to Ge-NBOHC signals
signals after
after X-ray
X-ray irradiation,
irradiation, andand
the the hollow
hollow
squares
squares referrefer
to thetog =the
2.21g signal
= 2.21(unidentified).
signal (unidentified). Thedrawn
The lines are lines as
are drawn
a guide foras
theaeye.
guide for the eye.
Reproduced
fromReproduced from [77].
[77]. Copyrights Copyrights
Elsevier 2000. Elsevier 2000.

Further increaseatinlow
Apparently, Na2 O contentlevels,
modifier leads to formation
only of significant
slight changes in theamount of NBOsoccur,
glass network in the glass
and the
network and the following reaction is prevalent in regions II and III:
following mechanism is responsible for the formation of the defect pairs:
● ●
≡≡
Ge − − − + +≡hν
O − Na +ℎ→ →≡ ≡ −• + •+
Ge − O Na ≡ (2)(1)
In their original work, Azzoni et al. explained the higher yield of the reaction with increasing
Maximal
Na2O content yield
in of the Ge-NBOHC
region I by network is densification,
observed in the range 15–25
without mol%
detailed of Na2 O, which
investigation matches
of its microscopic
with the region of the maximal strain in the glass network [79]. Despite an even larger amount
origin [77]. One may note that this reaction is identical to the one proposed for silicate glasses, of NBOs
where
at Na 2 O concentration beyond 25 mol%, the defects formation yield does not change significantly,
it was found that the number of defects induced is proportional to number of strained bonds in silica
which can bewhich
network, explained by relief of in
are associated theparticular
bonds strain
with[79].
presence of threefold rings [78]. Investigation of
The higher yield of defects upon irradiation in the glasses with larger amount of modifier seems
to also be valid for Te-glasses [62] as well as for Si-glasses [78]. Thus, the amount of preexisting NBOs
in the glass network before the irradiation could be one of the key factors influencing the overall
defect yield and should be also valid for other glass systems. However, many HMO glasses still
need to be investigated experimentally. Another important factor is strain of the bonds in the glass
network, which also can be assessed by modification of the glass chemistry and often can be related to
glass density.
However, it is possible to partially control the generation of color centers and improve radiation
hardness of HMO glasses without significant changes in its structure. This can be achieved by low level
doping with an additional element. It was found that introduction of Tb, Pr, and Ce can significantly
decrease amount of the defects induced upon irradiation of GeO2 -Gd2O3 -BaO glasses (Figure 9),
while low levels of the dopants should not significantly change the glass network [80].
The addition of cerium is known to increase the radiation hardness of different glasses,
including germanate [80,81] and tellurite glasses [82]. Usually, two forms of cerium are stabilized
simultaneously in glass, namely Ce3+ and Ce4+ ions. It has been found that Ce3+ and Ce4+ are capable
of trapping electrons and holes induced upon irradiation of glass as follows [83,84]:

Ce3+ + hole+ → 3+ +
h Ce i
Ce4+ + e− → Ce4+ ·e−

The irradiation results in the formation of Ce-related defects, rather than electron or holes centers
associated with the glass network, such as Ge-EC and Ge-NBOHC in the case of germanate glasses.
 significantly, which can be explained by relief of the bonds strain [79].
The higher yield of defects upon irradiation in the glasses with larger amount of modifier seems
to also be valid for Te-glasses [62] as well as for Si-glasses [78]. Thus, the amount of preexisting NBOs
in the glass network before the irradiation could be one of the key factors influencing the overall
defect 2020,
Materials yield13,and
3846should be also valid for other glass systems. However, many HMO glasses still 10 need
of 21
to be investigated experimentally. Another important factor is strain of the bonds in the glass
network, which also can be assessed by modification of the glass chemistry and often can be related
The Ce-related
to glass density.defect centers do not have absorption bands in visible and NIR ranges of optical
spectrum, consequently
However, addition
it is possible of Ce helps
to partially to minimize
control photodarkening
the generation effects
of color centers andinimprove
glass. Moreover,
radiation
ithardness
is shownofthat newly formed 3++
Ce significant 4+
and [Ce changes−
·e ] centers
HMO glasses without in itscan quicklyThis
structure. transform
can be back to original
achieved by low
Ce-states, even at ambient conditions [84,85]. Thus, Ce-doping results in the permanent
level doping with an additional element. It was found that introduction of Tb, Pr, and Ce can enhancement
ofsignificantly
glass radiation hardness.
decrease This of
amount is used in commercial
the defects inducedfiber
uponlasers to protect
irradiation of against defects
GeO2-Gd2O formed
3-BaO by
glasses
the laser itself.
(Figure Thelow
9), while defect would
levels absorb
of the pump
dopants light and
should therefore reduce
not significantly laserthe
change power
glassover time [85,86].
network [80].

Figure9.9.Radiation-induced
Figure Radiation-inducedcolor
colorcenter
centerdistribution
distributionininall
allglasses
glassesafter
afterthe
thehighest
highestirradiation
irradiationdose.
dose.
Inset:
Inset:radiation-induced
radiation-inducedabsorption
absorption bands
bands“removed”
“removed”by bythe
thetrivalent
trivalentdoping
dopingand
andthe
theGaussian
Gaussianfitfit
curves
curvesrelated
relatedtototerbium
terbiumdoped
dopedglass
glass(dashed
(dashedlines).
lines).Reproduced
Reproducedfromfrom[80].
[80].Copyrights
CopyrightsTaylor
Taylor&&
Francis 2003.
Francis 2003.

An
Theincrease
additionofof
the glass radiation
cerium is known hardness
to increase was
thealso observed
radiation on codoping
hardness of HMO
of different glasses
glasses, with
including
other polyvalent
germanate elements
[80,81] such as Tb,
and tellurite Pr, Ni,[82].
glasses and Sn [80–82,87].
Usually, two Significant
forms of influence
cerium are of rare-earth
stabilized
elements (REE) on the defect formation mechanism in HMO glasses can be also
simultaneously in glass, namely Ce and Ce ions. It has been found that Ce and Ce are capable
3+ 4+ detected
3+ by
4+ variation
ofoftheir thermoluminescence
trapping electrons and holes(TL)induced
properties.
uponIt was shown of
irradiation that the as
glass doping of tellurite
follows [83,84]: glasses by REE
can strongly modify their TL induced under+γ ℎirradiation → [22]. The dependence of glass properties
on used REE dopant can be explained by difference + → the efficiency
in ∙ of the defect trapping and their
releaseTheduring heating afterwards among the elements [22,88].
irradiation results in the formation of Ce-related defects, rather than electron or holes centers
However,
associated withinthecontrast to Ce, such
glass network, theseaselements
Ge-EC and often require in
Ge-NBOHC higher doping
the case concentrations;
of germanate glasses.
possess optical bands in Vis-NIR optical ranges; and have different effects, depending on the matrix
glass composition or glass redox, which makes Ce the most common dopant used to improve resistance
of glass against irradiation. In particular, it has been found that Ce codoping can be an effective way to
reduce photodarkening in HMO glasses—this approach has been already widely used for prevention
of photodarkening in active Yb/Er doped silicate glasses [21,89].
Changes induced in glasses under irradiation are often reversible and the initial glass state can be
restored by annealing of the irradiated material at elevated temperatures [16]. At sufficiently high
temperatures, the defects can overcome the trapping energy barrier and escape the trap, which is
increasing mobility of the defects and their recombination rate. Partial recombination of the defects
and recovery of the glasses can happen even at room temperature. In particular, it was shown
that TL-response of γ-irradiated REE-doped Te-glasses decreases for up to 15% in two months [22],
i.e., a considerable decrease of the trapped defects with time is observed. Moreover, fading of the TL
with time was found to depend on the REE dopant and Dy-doped glass being the most stable from
this point of view [22]. This implies that use of different dopants can allow controlling stability of the
radiation-induced defects in glasses and tailor properties of the material for a specific application—for
instance, glasses with long-term defect stability can be used for dosimetry purposes [25].
Materials 2020, 13, 3846 11 of 21

In addition to temperature, visible light has been used to reverse the defect formation. In a
germanosilicate fiber preform containing intrinsic defects, 3.5 eV/330 nm UV radiation was used to
bleach luminescence caused by the defects. Here, the absorbing center, presumably related to the
Ge-NBOHC, absorbs the bleaching photon and transfers the energy internally to destroy a defect with
much higher absorption band [90].

4. Local Changes in the Glasses Due to Radiation Treatment Using Short Pulsed Lasers
In the following section, the use of ultra-short pulses radiation treatment to locally structure
the glasses is described. In recent decades, ultra-short pulsed lasers have been of great interest
due to their unique advantages in three-dimensional processing of materials. Femtosecond
laser-induced photochemistry has been intensively investigated in a large variety of glass
matrices, including silicates [91], aluminosilicates [91], aluminoborates [92], chalcogenides [93],
and silver-activated phosphates [12]. Indeed, focused femtosecond laser pulses with energies of a
few hundreds of nanojoules have become a key tool to modify the physical properties of glass in
three dimensions (3D). Because of the nonlinear behavior of the interaction, the energy deposited by a
focused femtosecond pulse is confined inside the focal volume. The high repetition rate femtosecond
laser irradiation promotes not only the generation of defects or photodarkening of glass but also
Materials 2020, 13,
microstructure x FOR PEER REVIEW
rearrangement 12 of 22
associated with density changes, ion migration, or phase transition [92].

StructuralStructural
4.1. Laser-Induced modifications are often observed upon high-intensity ultra-short pulsed laser
Modifications
irradiation of HMO glasses. The effect of the laser irradiation depends on the glass composition as
Structural modifications are often observed upon high-intensity ultra-short pulsed laser irradiation
well as on the laser beam parameters used during the irradiation, such as average energy, pulse
of HMO glasses. The effect of the laser irradiation depends on the glass composition as well as on
duration, pulse repetition frequency, and beam focusing.
the laser beam parameters used during the irradiation, such as average energy, pulse duration,
In tellurite glasses, fs-laser irradiation can cause transformation of trigonal bipyramids to
pulse repetition frequency, and beam focusing.
trigonal pyramids Te-units. The latter are characterized by the shortening of Te-O bond lengths and
In tellurite glasses, fs-laser irradiation can cause transformation of trigonal bipyramids to trigonal
result in the local increase of glass density and refractive index [94]. Migration of elements is another
pyramids Te-units. The latter are characterized by the shortening of Te-O bond lengths and result in
effect observed in tellurite glasses upon laser irradiation [94,95]. For instance, redistribution of Te and
the local increase of glass density and refractive index [94]. Migration of elements is another effect
Na was observed in 50TeO2-20P2O5-20Na2O-5ZnO-5ZnF2 glass (Figure 10). The migration direction
observed in tellurite glasses upon laser irradiation [94,95]. For instance, redistribution of Te and Na
of elements is found to depend on the laser fluence [94] and laser intensity distribution [96], which
was observed in 50TeO2 -20P2 O5 -20Na2 O-5ZnO-5ZnF2 glass (Figure 10). The migration direction of
shows that ion diffusion mechanisms are rather complex and still require further investigation.
elements is found to depend on the laser fluence [94] and laser intensity distribution [96], which shows
that ion diffusion mechanisms are rather complex and still require further investigation.

Figure 10. Line scans showing ion migration in 50TeO2-20P2O5-20Na2O-5ZnO-5ZnF2 (λ = 1040 nm,
400-fs, 39 nJ)
Figure 10.(a) andscans
Line the corresponding secondaryinelectron
showing ion migration image. (b) Modified from [94]: Copyrights
50TeO2-20P2O5-20Na2O-5ZnO-5ZnF2 (λ = 1040 nm,
OSA 2014.
400-fs, 39 nJ) (a) and the corresponding secondary electron image. (b) Modified from [94]: Copyrights
OSA 2014.
In germanate glasses, it was found that single 150 fs pulses with energies up to 600 nJ (λ = 800 nm)
do not change Ge-coordination but cause an increase in the number of three-membered rings of
In germanate glasses, it was found that single 150 fs pulses with energies up to 600 nJ (λ = 800
nm) do not change Ge-coordination but cause an increase in the number of three-membered rings of
(GeO)3. By comparing a permanently densified Ge-glass (see Figure 11) and amorphous GeO2 with
different thermal history, it was established that the densification mechanism is prevalent under this
irradiation regime and the degree of this modification is proportional to the laser power [97]. At the
same time, if the pulses are too close to each other in space, the glass crystallizes in a hexagonal GeO2
Materials 2020, 13, 3846 12 of 21

(GeO)3 . By comparing a permanently densified Ge-glass (see Figure 11) and amorphous GeO2 with
different thermal history, it was established that the densification mechanism is prevalent under this
irradiation regime and the degree of this modification is proportional to the laser power [97]. At the
same time, if the pulses are too close to each other in space, the glass crystallizes in a hexagonal
GeO2 form and no presence of the high-pressure tetragonal GeO2 can be detected. This highlights
the high local temperature accumulation in the sample, which causes devitrification of the material.
This effect was explained by a local decrease of the thermal diffusivity and hence accumulation of
the heat in the laser modified area [98]. Similar changes were observed for 15Na2 O-85GeO2 (mol%)
glass [99], which allows to suggest that these mechanisms also remain dominant in modified Ge-glasses.
Nevertheless, higher fluence laser irradiation can also cause Ge and O ions separation with the
formation of the molecular O2 species inside the glass [100] or the migration and redistribution of the
elements in the
Materials 2020, 13, xglass network
FOR PEER [101–103].
REVIEW 13 of 22

Figure11.
Figure 11. (a)
(a)AnAnoptical
opticalimage
imageofofa aGeO
GeO 2 region
2 region modified
modified byby single
single pulses
pulses of 300
of 300 nJ/pulse
nJ/pulse energy
energy (at
(at the
the entrance
entrance of microscope),
of microscope), 800 nm 800 nm wavelength,
wavelength, and
and 150 150 fsduration
fs pulse pulse duration
focused focused
at 10 µmat 10 µm
depth. (b)depth.
Map
(b)the
of Map of the
region region
boxed in boxed in (a)
(a) at the 520atcm −1 520
the cm−1 D2-band,
D2-band, which corresponds
which corresponds to three-membered
to three-membered (GeO)3
rings. 3 rings.
(GeO)(c) Raman (c) Raman
spectra spectra
of laser of laser irradiated
irradiated regions regions at different
at different pulse energies
pulse energies 200, 300,200,
and300,
400and 400
nJ and
at
nJdifferent hydrostatic
and at different pressures,pressures,
hydrostatic measuredmeasured
using 532 using
and 633532nm wavelength
and illumination.
633 nm wavelength Arrows in
illumination.
(c) showsinthe(c)observed
Arrows shows thetendencies
observed with increasingwith
tendencies pulseincreasing
energy and/or
pulsepressure. Wavelengths
energy and/or pressure.of
laser irradiation
Wavelengths of for Raman
laser measurements
irradiation for Raman are denoted in the legend
measurements of (c). Reproduced
are denoted in the legend fromof[97].
(c).
Copyrights
ReproducedOSA from2011.
[97]. Copyrights OSA 2011.

4.2.
4.2. Photostructuring
Photostructuring
Sophisticated
Sophisticated localized
localized structures
structures cancan be
be written
written inin glasses
glasses using
using high-repetition
high-repetition raterate ultrafast
ultrafast
lasers in a controlled manner.
lasers in a controlled manner.
For
Forexample,
example,laser irradiation
laser irradiation can can
be used to produce
be used waveguides
to produce suitable suitable
waveguides for amplifiers, couplers,
for amplifiers,
splitters,
couplers,and sensors.
splitters, andDepending on the laser
sensors. Depending on and the glass,
the laser the glass,
and the radiation
the treatment can lead to
radiation treatment a
can
refractive index change, a birefringent refractive index modification, or voids due to
lead to a refractive index change, a birefringent refractive index modification, or voids due to micro- micro-explosions.
The first waveguide
explosions. The firstamplifier
waveguide in tellurite
amplifier glass was reported
in tellurite in 2014
glass was [94]. The
reported increase
in 2014 [94].in theincrease
The refractive
in
index was related
the refractive indexto the
wasmigration
related toofthetellurium towards
migration the irradiated
of tellurium towardsregion. The sodium
the irradiated migrates
region. The
to the tellurium
sodium migratesdeficient zone anddeficient
to the tellurium forms a zone
relatively low index
and forms change low
a relatively region.
indexRefractive index
change region.
dots with lower
Refractive index refractive index refractive
dots with lower were alsoindex
generated in tellurite
were also glasses
generated in the glasses
in tellurite TeO2 -Na in2 O-Al 2 O32-,
the TeO
TeO 2 -Na 2 O-GeO 2 and TeO 2 -Na 2 O-TiO glass systems due to the direct heating
Na2O-Al2O3, TeO2-Na2O-GeO2 and TeO2-Na2O-TiO glass systems due to the direct heating of the glass of the glass with the
laser beam spot [104]. The pattern of the refractive index dots was almost equivalent
with the laser beam spot [104]. The pattern of the refractive index dots was almost equivalent to the to the beam size.
beam size.
D.M. Da Silva et al. reported on the inscription of single-line active waveguides in Er3+-doped
germanate glass in the GeO2-PbO-Ga2O3 system using a femtosecond laser delivering pulses of 80 fs
duration at 1 kHz repetition rate [13,105]. In this case, the modification of the material causes a
refractive index increase, leading to light confinement and guiding. Alternatively, the demonstration
Materials 2020, 13, 3846 13 of 21

D.M. Da Silva et al. reported on the inscription of single-line active waveguides in Er3+ -doped
germanate glass in the GeO2 -PbO-Ga2 O3 system using a femtosecond laser delivering pulses of 80 fs
duration at 1 kHz repetition rate [13,105]. In this case, the modification of the material causes a
refractive index increase, leading to light confinement and guiding. Alternatively, the demonstration
of waveguiding by the double-line approach was provided in germanate (GeO2 -PbO) and tellurite
(TeO2 -ZnO) glasses [106]. In this case, the fs-laser process leads to a stress-induced negative refractive
index changes in the laser focal region, the light being guided in between the written lines.
Material structuring has been achieved not only with laser irradiation but also with ion beam
irradiation. For example, a high-energy nitrogen ion beam was found to be also a suitable to fabricate
waveguide. Berneschi et al. reported on the successful fabrication of such a channel waveguide in
an active sodium-tungsten-tellurite glass [107]. The light confinement was achieved due to localized
increase of the refractive index in the ion-implanted channel. The 2D light confinement was achieved
due to localized increase of the refractive index in the ion-implanted channel. Nevertheless, due to
their widespread accessibility, ease of operation and control, and high reproducibility, pulsed lasers are
much more commonly used for fabrication of waveguide in glasses.
Beyond laser-induced structural modifications and associated density changes for integrated
waveguides, as well as for NP precipitation for rare-earth emission enhancement, HMO can also
undergo laser-induced dielectric crystallite phase transition. Indeed, the LaBGeO5 system is a model
system, as it is one of the few oxides that easily forms glass as well as shows a congruent ferroelectric
stillwellite crystal structure with large nonlinear optical properties [108]. Transparent ferroelectric
crystallites can be obtained by thermal treatment for the LaBGeO5 system [108] or for other congruent
systems langasite-type La3 Ga5 GeO14 –Ba3 Ga2 Ge4 O14 [109] Such crystallization can be obtained by
continuous wave (cw) laser irradiation and local heating by resonant absorption of a doping rare-earth
element such as Nd3+ ions in Nd0.2 La0.8 BGeO5 glasses with a cw 800 nm Ti:sapphire laser [110] or
Sm3+ in Sm0.5 La0.5 BGeO5 Glass with a cw 1064 nm Nd:YAG laser [111]. It can even occur without any
absorbing dopant by multi-photon absorption of high repetition rate femtosecond Ti:sapphire amplified
lasers [112]. The optimal irradiation parameters and scanning speeds of these stoichiometric systems
have allowed for the creation of single crystal precipitation [111], requiring the ideal management of
thermal gradients at the voxel by the in-depth multi-plane management of spherical aberrations [113].
Moreover, directionally controlled 3D ferroelectric single crystals have been grown, showing a bended
single crystal where the orientation of the ferroelectric c-axis follows the laser scanning direction [112].
Crystal-in-glass functionalities such as waveguiding and efficient nonlinear second harmonic generation
have been demonstrated [111,114]. Three-dimensional crystal-in-glass architectures have thus been
achieved, including integrated crystal Y-junctions compatible with a Mach–Zehnder geometry with
losses no higher than 2.64 dB/cm at 1530 nm [112].
Moreover, it is demonstrated that the RE elements not only facilitate the laser-induced
crystallization process, but also can enter the formed crystal lattice, which was investigated in
detail for neodymium- and erbium-doped LaBGeO5 glass [110,115]. Finally, recent work brought a
new understanding of the laser-induced crystallization process of LaBGeO5 glass and how to optimally
manage heat deposition during laser irradiation in order to grow single-crystal waveguides in the
glass of quasi-stoichiometric or even in non-congruent matrix compositions [116]. The results on
laser-induced crystallization of LaBGeO5 glass demonstrate that this approach can be used for the
implementation of crystal-in-glass photonic architectures and possess applicative perspectives in
terms of fabrication of functional photonic circuits inside bulk glass materials or at the surface of
ribbon-shaped fibers [117].
During laser irradiation, glasses can also undergo spinodal decomposition which leads to
a three-dimensional interconnected texture. This interconnected texture of amorphous phases is
produced by the heating and cooling cycle of the pulses. Spinodal decomposition was successfully
obtained in tellurite glasses using an excimer laser (248 nm) [118]. These irradiated glasses could find
Materials 2020, 13, 3846 14 of 21

various vital applications such as membranes and sensors—for example, if one of the phases can be
selectively etched.
Radiation treatment can also be used to form bubble-like structures, which has been observed
in several glass types, especially in silica glass [119]. As bubbles can be used to generate periodic
structures, interest in controlled generation of these bubbles has grown recently [120]. Generation
of bubbles in the glass with the composition of 85GeO2 -15Na2 O (mol.%) has been reported in [121].
The irradiation under a high repetition rate femtosecond laser creates a local melting and a migration
of matter within the glass matrix. The spatial separation of Ge and O ions and the micro-explosion
inside the glass melt are thought to be responsible for the generation of bubbles. Mobility of the bubble
is followed by confocal Raman spectroscopy which highlights the thermal gravity convection and the
viscous drag force effect during the process. Air-bubble-containing tellurite glass microspheres were
successfully prepared by local heat treatment of tellurite glass cullets placed on a substrate using a
cw-Ti:sapphire laser at the wavelength of 810 nm. This allowed for the selective formation of a bubble
at a certain place in the microsphere [122]. Such micrometer-size spheres could find applications in
micro-optical system for microlasers and microamplifiers, for example. Despite few studies on bubble
generation in glasses, the origin of the bubble formation during radiation treatment is still unclear.
The combination of metallic nanoparticles with rare-earth ions in HMO-doped glasses, in order to
enhance their luminescent properties as well as their nonlinear optical properties, has been of great
interest during the past decades as discussed in the previous section. The formation of NPs during
the radiation treatment was demonstrated for Bi-containing germanate glass using a 1030 nm, 370 fs,
500 kHz laser. Bi atoms were reported to migrate perpendicular to the laser irradiation direction inside
the glass, and the observed Bi-enriched regions were associated with the formation of Bi nanoparticles
inside the glass [103]. Despite the fact that various metallic particles can be precipitated in the glass,
precipitation of Ag or Au NPs is highly desirable, as these are known to enhance the emission properties
of REE ions in glasses. Local laser-induced precipitation of these particles was demonstrated and
carefully studied for example in phosphate glasses [123] and few articles report similar behavior of
laser-induced precipitation of Ag NPs or Au NPs in HMO glasses [124].
Recently, we initiated a study of silver-containing glasses in the TeO2 -Na2 O-ZnO-Ag2 O system.
We irradiated these glasses with an Ytterbium femtosecond oscillator (1030 nm central wavelength,
9.8 MHz repetition rate, 390 fs pulse direction (FWHM) with a 20x − NA = 0.75 microscope objective).
We found that due to the glass matrix UV cutoff being located at larger wavelengths than the
excitation bands of the embedded silver ions, silver chemistry did not seem to take place, contrarily to
silver-containing phosphates. Nevertheless, glass modifications led to refractive index modifications
compatible with waveguiding ability by means of the double-track approach. Indeed, a He-Ne beam
at 632.8 nm was injected in such double-track modifications. The associated output beam profile is
displayed in Figure 12a, revealing distinct waveguiding behaviors generated by two tracks separated
by 10, 20, 30, and 40 µm, respectively.
Horizontal cross-sections of CCD images of the near-field output profiles for track separation
of 10 and 20 µm and for track separation of 30 and 40 µm are provided in Figure 12b,c. The 10 µm
separation shows a lossy mode with a non-confined profile outside of the two tracks. Larger separation
distances of 30 and 40 µm show a poor spatial quality resulting both from the multi-mode waveguiding
behavior and from the associated laser injection. For the ideal track separation of 20 µm, the induced
structure behaves much more as a single-mode waveguide at wavelength of 632.8 nm, as generally
demanded for integrated photonic applications. This result, in agreement with [14,107], confirms that,
despite silver doping, the two-line “depressed cladding” configuration is favored in this system.
excitation bands of the embedded silver ions, silver chemistry did not seem to take place, contrarily
to silver-containing phosphates. Nevertheless, glass modifications led to refractive index
modifications compatible with waveguiding ability by means of the double-track approach. Indeed,
a He-Ne beam at 632.8 nm was injected in such double-track modifications. The associated output
beam profile
Materials 2020, 13,is3846
displayed in Figure 12a, revealing distinct waveguiding behaviors generated by15two
of 21
tracks separated by 10, 20, 30, and 40 µm, respectively.

Figure 12.
Figure 12. (a) Near-field helium-neon
helium-neon beam beam profile
profileat
atthe
theoutput
outputofofwaveguides
waveguidesgenerated
generatedbybytwo
two
tracks separated by 10 µm (1), 20 µm (2), 30 µm (3), and 40 µm (4). Scale bar 20 µm,
tracks separated by 10 µm (1), 20 µm (2), 30 µm (3), and 40 µm (4). Scale bar 20 µm, and white rectangles and white
rectangles
locate locate the structure.
the double-track double-track
(b,c)structure.
Horizontal(b,c) Horizontal
cross-sections cross-sections
of CCD of CCD for
for track separations track
of 10 and
separations
20 µm, and for of 10 andseparations
track 20 µm, andof for30track
and 40separations of 30 and(unpublished
µm, respectively 40 µm, respectively
results).(unpublished
Dashed lines
results). the
indicate Dashed lines indicate
respective theofrespective
positions positions
the double-track of the double-track structures.
structures.

5. Conclusions
Horizontaland Future Opportunities
cross-sections of CCD images of the near-field output profiles for track separation of
10 and 20 µm and for track separation of 30 and 40inµm
The studies on radiation-induced defects/effects are provided
germanate in Figure
and tellurite 12b,c.
glasses Thereviewed
were 10 µm
separation
in this paper.shows a lossya mode
Although with a non-confined
large number of studies on profile
radiationoutside of the
of silicate andtwo tracks. Larger
phosphate can be
found in the literature, radiation treatment of tellurite and germanate glasses has not yetmulti-mode
separation distances of 30 and 40 µm show a poor spatial quality resulting both from the been deeply
waveguiding Radiation
investigated. behavior and from the
treatment of associated laser
these glasses injection.
using For sources
different the idealwas
track separation
found to lead of
to 20
the
µm, the induced structure behaves much more as a single-mode waveguide at wavelength of 632.8
formation of defects as well as structural modifications. The latter occurs due to three competitive
nm, as generally demanded for integrated photonic applications. This result, in agreement with [107]
processes: an effect of heat/temperature; effect of pressure; or induced local variation in chemical
and [14], confirms that, despite silver doping, the two-line “depressed cladding” configuration is
composition. However, the data on the origin of the structural changes induced by the radiation
favored in this system.
treatment are still fragmented and not well investigated. Nonetheless, this lack of the fundamental
understanding has not hampered the practical use of the HMO glass structural modifications.
5. Conclusions and Future Opportunities
To summarize, the radiation treatment can lead to thermal and ionization effects. The thermal
effectsThe
can studies
include: on radiation-induced
(i) crystallization defects/effects
or spinodal in germanate
decomposition and due
which occurs tellurite glassesheating;
to localized were
reviewed in this paper. Although a large number of studies on radiation of silicate
(ii) bubble formation due to the plasma formation which decomposes oxygen from glass matrix or due and phosphate
can
to behigh
the found in the literature,
temperature radiation
liberating treatment
dissolved ofand
gases; tellurite andmigration.
(iii) ion germanate Theglasses has not effects
ionization yet beenare
(i) point defects due to the formation of free electron—hole pairs and (ii) generation of metallic NPs.
With this review, we clearly show that radiation treatment is capable to modify macroscopic properties
of HMO glasses, and these modifications can be controlled spatially, especially if made with use of
high-intensity ultra-short pulsed laser radiation sources. At the same time, we would like to emphasize
that the photoresponse of these materials should be investigated more, as a deeper understanding
is required for fabricating materials with enhanced radiation resistance or enhanced sensitivity to
radiation based on HMO glasses. Such knowledge would contribute to guiding the industries to
manufacture new commercial mid-infrared transparent glasses with tailored photoresponse for use in
the radiation environment.

Author Contributions: This paper has been written in close collaboration with all authors, with HMO glass
description and structure mostly by L.P., defect formation and types by M.H., radiation impact of composition on
defects and induced structural modifications by A.V., and photostructuring by Y.P., T.C., S.D., and V.J. All authors
have read and agreed to the published version of the manuscript.
Funding: Academy of Finland (Flagship Programme, Photonics Research and Innovation PREIN-320165 and
Academy Project−326418), the French National Research Agency (ANR) in the frame of “the investments for the
future” Programme IdEx Bordeaux–LAPHIA (ANR-10-IDEX-03-02) and project ANR-19-CE08-0021-01, and the
Région Nouvelle-Aquitaine (Projects n◦ 2019-1R1MO1 and AAPR2020-2019-8193110) are greatly acknowledged
for the financial support.
Conflicts of Interest: The authors declare no conflict of interest.
Materials 2020, 13, 3846 16 of 21

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