Infrared-Transmitting Glass-Ceramics
Infrared-Transmitting Glass-Ceramics
Infrared-Transmitting Glass-Ceramics
SPIEDigitalLibrary.org/conference-proceedings-of-spie
Infrared-transmitting glass-ceramics:
a review
John S. McCloy,* Brian J. Riley, David A. Pierce, Bradley R. Johnson, Amy Qiao
Pacific Northwest National Laboratory, 902 Battelle Blvd, Richland, WA, USA 99352
ABSTRACT
A large body of literature was reviewed with the aim of identifying binary and ternary systems for producing long-wave
infrared transmitting glass-ceramics for window applications. Known optical and physical property data was
summarized for many ternary sulfides as well as their constituent binary sulfides. Some phosphide and arsenide
chalcopyrite structures were reviewed as well. Where available, data on the transmission range, energy gap, refractive
index, and hardness were tabulated. Several glass-forming systems were identified containing Ga2S3, GeS2, or As2S3.
1. INTRODUCTION
Over the years materials scientists and engineers have searched for long-wave infrared (LWIR) transmitting materials
for windows and domes with properties superior to chemical vapor deposited (CVD) ZnS.1, 2 ZnS is still the material-
of-choice for combined 8-12 μm transmission, thermal stability, and mechanical strength.3 The primary drivers for
desired improvement are increased transparency (though for most applications multispectral ZnS is more than
adequate), decreased cost, and, most importantly, increased mechanical durability (hardness, toughness, fracture
strength). The latter is driven by harsh environments experienced by military systems including rain and sand erosion,
chemical attack, and shock and vibration. Some of the materials which were not successful replacements for CVD ZnS
include the following. Diamond, while superb in its thermal and mechanical properties, has strong absorption in the
mid-wave infrared (MWIR) and so is not a good multispectral candidate, has very high cost and is difficult to fabricate
into optics. CaLa2S4, a powder-processed ceramic material was considered strongly in the 1980s,4-6 but despite its
improved mechanical hardness and extended transmission window beyond ZnS, it was found to suffer from inferior
thermal properties, higher-then-desirable thermal expansion, and low thermal conductivity. Table 1 shows some
tabulated properties for CVD ZnS,2, 7 multispectral (hot isostatic pressed or HIPped) ZnS,2, 7 and CaLa2S4,8-10 which
allow assessment of LWIR transmission, strength, and thermal shock.1 Other solutions for improving on ZnS have
involved durable coatings of many types,11-14 all of which add additional manufacturing cost and risk. Finally, several
solutions have been proposed for making powder composites of ZnS with diamond15, 16 or Ga2S3,17-19 but the resulting
materials had high optical scattering due to excessive grain sizes and/or large differences in refractive index (Δn)
between the phases.
One other possibility for making durable LWIR transmitting materials that has not yet been widely considered is the use
of a glass-ceramic approach. Glassmaking approaches to fabrication can have advantages over other material
processing methods such as powder-based methods and CVD in terms of scalability. Glass-ceramics can be broadly
defined as polycrystalline materials produced through heat treatment of amorphous glass. Broadly speaking, glass-
ceramics are produced using traditional glass-forming processes (e.g., melting or sol-gel) then are slow cooled or
quenched then heat-treated to nucleate and grow crystals in a controlled way. The resulting material, defined as a glass-
ceramic, has one or more crystalline phases and a range of remaining glass, ranging from the majority phase (essentially
a few crystals in glass) to equal volume fraction (glassy phase(s) plus crystalline phase(s)) to fully ceramic (remaining
glassy phase at grain boundaries). By controlling nucleation and growth, one or more crystalline phases could be
produced which are sufficiently small that transmission of LWIR light is not scattered. Crystals which grow to
*
john.mccloy@pnnl.gov
Window and Dome Technologies and Materials XIII, edited by Randal W. Tustison, Brian J. Zelinski,
Proc. of SPIE Vol. 8708, 87080N · © 2013 SPIE · CCC code: 0277-786X/13/$18 · doi: 10.1117/12.2019142
Multispectral
Property Symbol Units CVD ZnS CaLa2S4
(HIPed) ZnS
Optical Absorption
β cm-1 0.2 0.2 0.1
coefficient, 10.6 μm
2
Mechanical Hardness, Vickers HV Kg/mm 230 150 580
Strength, average σ MPa 103 60-69 86-106
Thermal Conductivity Κ W/(m·K) 16.7 27.2 ~1.6
Coefficient of
α × 10-6/ K 6.8 6.5 14.8
thermal expansion
Elastic Young’s modulus E GPa 74.6 87.6 95.8
Poisson’s ratio ν unitless 0.29 0.32 0.26
In order to achieve strength and transparency comparable to or better than CVD ZnS, a glass-ceramic should have small
grain size (~100 nm) and be fully ceramicized, with only a very minor glassy phase at the grain boundaries. Such glass-
ceramics have not been made in many systems, with the exception of Al2O3-Ln2O3-ZrO2 29 (Ln is a lanthanide rare
earth; e.g., La, Gd, or Y) and possibly Ba-Al-O.30 In the former case, grain sizes were ~100 nm, and in the latter case
500-5000 nm. Many other oxide-based glass-ceramic systems are important commercially, where there exists a
crystalline phase <100 nm in size embedded in a glassy matrix. Important examples are aluminosilicate glasses with
crystalline phases based on β-quartz (e.g. LiAlSiO4 or β-eucryptite), mullite, cordierite, spinel, or oxyfluoride.31-33
Midwave infrared (MWIR) transmitting windows have been proposed based on a glass-ceramic from the BaO-Ga2O3-
GeO2 system,28 where the major crystalline phase is BaGe4O9.27 Similar systems have been proposed substituting S or
Se for O, with the overall glass-forming region decreasing as O→S→Se, but with the infrared transmission cut-off
increasing accordingly.34 Other recent work has explored TeO2-based systems,35 primarily for Raman amplifier, but
these again have transmission only through the MWIR range.
In this review we discuss some possible glass-forming systems which could potentially be used to produce LWIR-
transmitting glass-ceramics by one of the processes described above. This is by no means exhaustive, but represents a
few classes of materials which merit future consideration. Considerable work has been performed by Zhang, Lucas, and
colleagues at the University of Rennes36 for chalcogenide and chalcohalide37 systems. As will be shown, however,
these glass-ceramic materials tend to be mostly glass with some crystals, and so do not strictly fit our criteria for a good
durable glass-ceramic material for ZnS replacement.
This paper starts with a summary of four families of materials for LWIR glass-ceramics: Ga2S3-based glasses, GeS2-
based glasses, As2S3-based glasses, and chalcopyrite glasses. Subsequently we discuss some considerations for
fabricating these materials. Finally, we offer a large set of references for known electronic band-gap, transmission, and
mechanical properties of candidate phases for these systems.
Figure 1 shoows a transmisssion comparisson of measured ZnS (singlee crystal, MTII), CaLa2S4 (R Raytheon), and various
samples of GLS
G glass (So
outhampton an nd Crystran),42 along with coomparisons of literature trannsmission for ZZnGa2S4
(single crystal)43 and GeS2 (glass).44 For GeS2, the larg
ge absorption at ~12.8 μm waas attributed to a Ge-O impurrity band
and not a fuundamental mu ultiphonon bannd.45 For GLS S, the absorptioon band ~8.5 μ
μm is attributeed to oxygen, w
with the
samples con ntaining more oxygen showiing deeper ban nds. These oxxygen impuritiies in GLS alsso lower its reefractive
index.42 Thee commercial sample,
s obtaineed from Crystran Ltd (UK), wwas advertised as 5 mol%La2O3.
11-1
0
-ZnGa25 4 (thkns unkwn) -5%La203-Crystran (^'1 mm)
GeS2
glass
GILS-
o \'' 3LS
lo
ZnGa,S,
o L(-kLeild
3 4 5 9 10 11 12 13 14
Wavelength (pm)
Figure 1: Transmission comparison for Ga2S3 and GeS2 baseed systems
- Ag2S
-CsCI
L7t . ---La2S3
Sulfide-baseed glass-ceram mics reported in i the literaturre have all, too our knowleddge, consistedd of small cryystallites
embedded in n a large amouunt of residual glassy phase. Oftentimes, tthese glass-cerramics are madde inadvertenttly when
exploring a glass-forming region, and sh hould more pro operly be calleed glasses conttaining crystalls or glass com
mposites.
Recently a few studies have h aimed att making sulffide-based glasss-ceramics puurposefully too improve mecchanical
properties. These systemss however are far from fully-ceramized. S Systems investtigated have traaditional chalccogenide
(sulfide) glaasses like Ga-GGe-Sb-S.36 Maany other systeems have beenn explored witth additions off alkali halide, notably
CsCl, which h forms the priimary crystallin m cases: Ge--Sb-S-CsCl,56, 557 Ge-Sb-S-CssCl,21, 58 and G
ne phase in most Ge-Ga-S-
54, 59
CsCl (α
α-Ga2S3 is crysstalline phase). Again, to our
o knowledge no one has ssuccessfully m made a fully-ceeramized
sulfide ceram mic from a glasss process.
The GeS2-Laa2S3 system deserves further comment. A binary b phase diiagram of this system60, 61 shows that that a glass is
formed fromm 50–100 molee% GeS2. Otheer than the end d-members of tthe binary, thee crystalline phhases of interesst in Ge-
La-S are as follows. La2GeSG 5 (2-1-5) iss a monoclinic phase, reporteedly unstable < <600°C but deecomposing intto La2S3
(solid) and GeS
G 2 (vapor) un nless there is a sufficient oveerpressure of GGeS2.62 The othher phase was reported by Saarsikov61
as La2Ge2S7 (2-2-7) but arrgued by Mich helet62 to be La4Ge3S12 (4-3--12). A glass made with, foor example, 555 mole%
GeS2 should d be able to bee crystallized into roughly equale fractionss of La2GeS5 aand La4Ge3S12. Two glassess in this
system are known
k from the literature, 60 0 mole% GeS2 and 92.5 mol% % GeS2.60 Thee first, 60 GeS S2, crystallized β-La2S3
upon heat trreatment wherre the GeS2 an nd residual Laa2S3 likely rem mained in a gllass phase.60 In that study,, sulfide
precursors were
w put into caarbon coated silica
s tubes, evacuated, sealedd, and heated aat 1175°C for 24 hours (60 G GeS2) or
heated to 10 000°C, held fo or 10 hours, th hen heated to 1175°C for 224 hours (92.5 GeS2), follow wed by coolingg in air.
Transmission n electron miccroscopy show wed that the 60 GeS2 was a hhomogenous gglass, while thee 92.5 GeS2 gllass was
phase separaated. Heat treaatment of the 60 GeS2 glass consisted
c of a rramp 10°C/minn in He to 850°°C with 1 minuute hold,
and the resulting material produced
p β-Laa2S3 crystallizeed in the bulk wwhile GeS2 remmained amorphhous. By conttrast, the
heat treated 92.5 GeS2 glasss, ramped 10°°C/min in He to t 700°C with 6 minute holdd, resulted in foormation of Laa4Ge3S12
rhombohedraal crystals,60 ag gain showing thet correctnesss of the modifi fied phase diaggram including the 4-3-12 compound
rather than th
he 2-2-7 compound.
Pure phases,, however show w good promiise for IR transmission, as shhown in Figurre 4. The prouustite Ag3AsS2 data is
measured fro om a single crrystal (Crystran
n), As2S3 is measured comm mercial materiaal, AgAsS2 (sm
mithite) taken ffrom the
literature,71 AgAsGe
A en from the litterature.72 Notee that proustitte shows improoved transmissivity over Ass2S3, but
4 take
shows an absorption ~10 μm,μ probably du ue to an As-O impurity also sseen in the As2S3.
t N
rgion
2\42S
N1,111. no
//
A Ag -As- S minerals
Ag3AsS,
As Ag
Figure 3: Glass-formin
ng regions in thee Ag-As-S in moll%
80
LVA IRwindo.W
70 --.,.--r--
--,,--,...--
7 60 -roo..--''.
s\ nS
c
0 \ qg3AsS
a 50
C
N
C g sS2
40
2 3
30 AgAsGeS
20
10
0
3 4 5 9 10 11 12 13 14 15 16 17
Navelength (um)
ansmission of Ass-S-Ag phases. In
Figure 4: Tra I this figure LW
WIR cut-offs (left to right) are AggAsGeS4, As2S3, A
AgAsS2, Ag3As3, and ZnS
2.4 Chalco
opyrite system
ms
The chalcopyyrite structure is a derivative of the zincblen
nde structure, wwhere ions aree all tetrahedrallly coordinatedd. There
are two maiin types of chaalcopyrites, AIBIIIC2VI (1-3-6 6) chalcopyritees and AIIBIVC2V (2-4-5) chaalcopyrites, whhere the
superscript is
i the valencee of the ion. Chalcopyritess are typicallyy chalcogenidees (sulfides, selenides) or ppnictides
(phosphides,, arsenides). Im
mportant 1-3-6 6 chalcopyrites include photovvoltaics like CCIGS (Cu-In-Gaa-Se) and other related
(Cu,Ag)(In,GGa)(S,Se)2 commpounds. The 1-3-6 chalcopy yrites were nott investigated hhere, but ratherr two exampless of 2-4-
5 chalcopyriites, one a phosphide and one o an arsenid de. These chaalcopyrites aree typically crystalline or am morphous
semiconducttors, and have been consideered as radiatio on detectors.733 Typical phoosphides that hhave been studdied are
(Zn,Cd)(Si,G
Ge)P2 and CdSn nP2. Typical arsenides
a are ZnSiAs2 and CddGeAs2.
As an exam mple of a possiible phosphidee glass-ceramic system, we obtained and measured infr frared transmitttance of
ZnGeP2 (chaalcopyrite struccture) (see Fig G 1 transmisssion of this m
gure 5). Like GaP, material seems w well-suited forr MWIR
applications but not LWIR R applications. It has absorptions at 10 μmm, 11.4 μm, annd is completelly opaque by 112.5 μm.
y, there is a strrong absorptio
Additionally on at 8.9 μm thhat may be inttrinsic by commparison with tthe GaP three phonon
region.1 Thee low transmisssion from 3-7 μm appears to o be due to scaatter, perhaps ddue to a poor ppolishing. Thee overall
low transmitttance may bee due to free carrier
c absorpttion. It shouldd be noted thaat glass-cerammics of the Gee-Ga-P-S
system weree investigated asa dome materrials in the late 1980s.74 Crrystallization inn GeGa0.24P0.2S2 glass was oobserved
and phases of
o Ga-S, Ge-S and Ge-Ga-S were found. Additionally,
A m
materials were made where Z ZnS was addedd to Ge-
Ga-P-S and ZrS3 was addeed to Ge-S. Th he authors conccluded that SiA
AlON-like glasss-ceramic struuctures were foormed in
Ge-Ga-P-S systems,
s but th
hat the measurred thermal exxpansions weree too great to make them a suitable substtitute for
ZnS.74
a
20 -
15
-c
-21
10
Figure 5: Transmission
T off ZnGeP2 crystall and CdGe0.85Ass glass
3. FABRIICATION IS
SSUES
In tailoring the
t transmissio on, it is possible to substitutee Se or Te for S. This helps the starting puurity, since S aas a raw
material (or a metal sulfid
de in general) tends
t to be conntaminated witth O, C-S, andd metal-oxygenn bonds and SO O42- and
2-
SO3 speciees absorb stron ngly in the MWIR and/or LWIR. L Other work has shoown that substtituting In for Ga, for
instance, maay increase the LWIR transmiission, as somee have argued tthat the transm mission cutoff oof GLS glass iss limited
by the Ga2S3 vibrations. Other
O possibilities include sub
bstitution of Srr for Ca, for insstance. In all tthese cases thee heavier
elements wiill provide low wer frequency y vibrations du ue to their weeaker bonds, bbut this can aalso lead to ddegraded
mechanical and
a thermal pro operties.
Fig
gure 6: Transmission of Ge-As--Se-Te glasses
One addition nal consideration in many off these glass sy ystems is the o ccurrence of liiquid-liquid phhase separationn at high
temperature which can ressult in multiplle glass phasess with differennt compositionns when cooled.84 Phase seeparation
resulting in two different glassy phases at room temp perature has allready been m mentioned in thhe context of A Ag-As-S
glasses,69, 85, 86 but it hass also been ob bserved in purre As-S glass,,87, 88 in Cd-G Ge-As glass,89 and in Ge-S glass.46
Potentially, phase
p separation could also be used delibeerately to nuclleate crystallizaation such as hhas been propoosed for
cordierite32 or
o spinel oxidee glass-ceramics.33 This meth hod is likely tto result in a rreasonably low
w total crystal ffraction,
perhaps <50 0 volume%. Furthermore,
F eaach liquid phaase separation will result in a different loccal chemistry aand thus
different cryystalline phasess are likely to precipitate
p he system is fuurther cooled.844, 90
as th
This paper makes an argument for consideration of glass-ceramics as a durable LWIR transmitting window material.
Glass-forming systems based on Ga2S3, GeS2, As2S3, and chalcopyrites are summarized. A large amount of data is
tabulated in the Appendix on binary and ternary sulfide compounds as potential LWIR ceramic phases.
ACKNOWLEDGEMENTS
Thanks to Jarrod Crum who reviewed this manuscript and offered many helpful suggestions. The Pacific Northwest
National Laboratory (PNNL) is a multi-program national laboratory operated by Battelle Memorial Institute for the
United States Department of Energy under DE-AC06-76RLO 1830.
APPENDIX
The following tables are offered as a means of collecting optical and structural data for a wide variety of binary and
ternary sulfides which could be candidate phases for LWIR glass-ceramics. Shown in the table are available data on:
phase name and crystal structure, the energy gap (Eg), the transmission range of a window, the refractive index, the
wavenumber of the longitudinal optical phonon (ωLO, which partially determines the LWIR cutoff), the hardness, the
coefficient of thermal expansion (CTE), and other notes. This is by no means an exhaustive list, but should be taken as
a starting point for further consideration.
Phase E (eV) Transmission Crystal Refractive ωLO Hardness CTE Notes Refs
g
range (μm) structure index (cm-1) (Knoop, (ppm/°C)
(n) kg/mm2)
91, 92
Ag2S 0.92 Monoclinic 60
(acanthite)
Ag2S Cubic
(argentite)
91, 93, 94
As2S3 2.37 0.6 – 11 Monoclinic 120 20
95-99
CaS 4.43 Cubic 2.12 380
(indir) (rocksalt)
100-103
GaS 2.53 hexagonal 2.65, 2.3 336, 359
38, 100,
α-Ga2S3 2.45 hexagonal
104-107
(ICDD 16- (defect
0500) wurtzite) (p61,
p65)
105, 106
α'- Ga2S3 Monoclinic
(Cc, Bb)
100, 106
β- Ga2S3 hexagonal
(wurtzite)
107-109
γ- Ga2S3 cubic (defect 360
(ICDD 43- sphalerite)
0916)
50, 110, 111
α-GeS2 Monoclinic
(Pc)
26, 50, 51,
β- GeS2 Monoclinic
110, 111
(P21/c)
GeS
112
α-La2S3 Orthorhombic
47, 112-114
β-La2S3 2.76 0.5 – 14 Tetragonal Picks up
(I41/acd) oxygen
47, 93, 112-
γ-La2S3 2.0 – 0.5 – 14 Cubic (Th3P4) 240-670 10.8
118
2.7
112, 119,
La3S4 Cubic (Th3P4) 9.8 Too
120
(LaS1.33) conductive
120, 121
La2.7S4 10.7
(LaS1.48)
121, 122
LaS2 Cubic
96, 123, 124
ZnS (CVD) 3.64 0.5 - 12 Cubic 2.35 (0.633 352 250 7-8
(sphalerite) μm)
2.19 (10
μm)
l as Ge2La2S7
148
(Ge,Si,Sn,Ti)(B various
a,Ca,Sr,Pb)2S4
8, 150
(Mg,Zn)(Sc,Yb) spinel
2 S4 structure
8
(Mg,Mn)(Dy,H MnY2S4
o,Er,Tm,Y)2S4 structure
8, 150
Sr(Tb,Dy,Ho,Er CaFe2O4
,Tm,Tb,Y)2S4 structure
8
YbEr2S4 Yb3S4
structure
8, 18, 19, 43, 98,
ZnGa2S4 3.7- 0.3 – 12 Tetragonal 2.33 (0.633 314 367 6.5
104, 151-155
3.8 (defect μm)
stannite)
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