Optical and Photonic Glasses

Lecture 1:
Intro to Glass and the Glass Transition

Professor Rui Almeida

International Materials Institute

For New Functionality in Glass
Lehigh University

Spring 2005 Lecture 1 Rui M. Almeida

 Program
• Glass and amorphous materials
- What is glass
- Composition and preparation
- Structure
- Properties
• Optical glass: fabrication and optical properties
- Traditional optical glasses
- New optical glasses
- Abnormal dispersion glasses
- Transparent glass ceramics
• Photonic glasses
- Gradient index glass and fiberoptic glasses
- Photosensitive glasses
- Acousto-optical and magneto-optical glasses
- Laser glasses
- Non-linear optical glasses
Spring 2005 Lecture 1 Rui M. Almeida
Detailed course syllabus

What is glass: definition, glass formation, Tg, regions of glass formation, theories of
glass formation.
Glass composition and preparation: glass formers, modifiers and intermediates;
preparation of oxide glasses (melting, sol-gel, CVD, …); flat glass, hollow glass,
fiber glass.
Glass structure: structure of network oxide glasses; X-ray diffraction analysis;
structure of modified oxide glasses (silicates, borates, aluminosilicates, phosphates,
…), fraction of NBO atom species; glass-in-glass phase separation, Vycor glass;
glass-ceramics.
Basic glass properties: density; mechanical behavior; viscosity; thermal expansion.

Traditional optical glasses: composition and fabrication; optical properties (refractive

index, reflection, scattering, absorption - electronic, vibrational, Raman scattering).
New optical glasses: preparation of non-oxide glasses (fluorides and chalcogenides);
specific properties (mechanical behavior, viscosity, Tg, IR transmission).
Abnormal dispersion glasses: abnormal dispersion in phosphate based glasses;
athermal glasses.
Transparent glass ceramics: Pr-doped oxyfluoride glass ceramics; other transparent
GC’s doped with Er, Yb, Tm and Eu.
Spring 2005 Lecture 1 Rui M. Almeida
Gradient index glass and fiberoptic glasses: GRIN glasses by ion exchange and sol-
gel; guided wave optical glasses; glass fiberoptics; integrated optical glass waveguides.
Photosensitive glasses: photochromic glasses; permanent refractive index changes in
germania containing glasses; Bragg gratings; photoinduced effects in chalcogenide
glasses (photocontraction, photoexpansion, …).

Acousto-optical and magneto-optical glasses: acousto-optical and delay line glasses;

Faraday rotation in glass; paramagnetic glasses; optical isolators.

Laser glasses: rare-earth doped glasses (Nd, Er, Yb, Tm, Pr, …); photoluminescence of
rare-earth ions in glass; laser effect in glass; optical amplification in glass; glass fiber
lasers and fiber amplifiers; glass waveguide lasers and amplifiers.

Non-linear optical glasses: fundamentals of NLO; non-resonant optical non-linearity;

non-linear refractive index; resonant optical non-linearity; semiconductor-doped glasses
(strong confinement case, photodarkening, weak confinement case); metal-doped
glasses; NLO properties of metal-doped glasses (electric field enhancement and
quantum confinement effects).

Spring 2005 Lecture 1 Rui M. Almeida

Relevant books

T.S. Izumitani, Optical Glass, American Institute of Physics Translation Series (New
York, 1986).

Masayuki Yamane and Yoshiyuki Asahara, Glasses for Photonics, Cambridge

University Press (Cambridge, U.K., 2000).

K. Booth and S. Hill, The essence of optoelectronics, Prentice Hall (London, 1998).

R. Tilley, Colour and the optical properties of materials, John Wiley (New York,
2000).

J.H. Simmons and K.S. Potter, Optical Materials, Academic Press (New York, 2000).

M. Fox, Optical properties of solids, Oxford University Press (Oxford, UK, 2001).

A.K. Varshneya, Fundamentals of Inorganic Glasses, Academic Press (New York,

1994).

James E. Shelby, Introduction to Glass Science and Technology, The Royal Society
of Chemistry (Cambridge, U.K., 1997).
Spring 2005 Lecture 1 Rui M. Almeida
 Glass and amorphous materials

What is glass?

A glass, whether in bulk, fiber or film form, is a non-crystalline solid (NCS). In

principle, any substance can be vitrified by quenching it from the liquid state,
while preventing crystallization, into a solid glass. A glass is, therefore, a non-
crystalline (or amorphous) solid.

Most commercially available glasses, are prepared by melting and quenching.

But deposition from a vapor or a liquid solution are alternative methods to obtain
glasses, usually in thin film form, some of which may otherwise be rather
difficult to prepare from the melt.

Glass formation, although in principle a property of any material, is in practice

limited to a relatively small number of substances. And most commercial
glasses, available in large bulk shapes, are silicates of one type or another, i.e.,
materials based on silica, the oxide SiO2.

Spring 2005 Lecture 1 Rui M. Almeida

 The structural transformation of silica from crystal to glass

β - Quartz v - SiO2

Spring 2005 Lecture 1 Rui M. Almeida

 Glass forming systems
P raticam en te q u alq u er m aterial é cap az d e fo rm ar vid ro s:
Below
o únicoare someento
requerim of the most
é que representative
o m aterial glass-forming
seja arrefecido a partir do
líquido a um a v elocidade suficientem ente elev ada para que a
substances knownnão
estrutura cristalina to date.
tenha tem po de se desenv olv er.

, TeO2

4
ssa

(Adapted from: The science and design of engineering materials. J.P. Schaffer et al., McGraw-Hill, 1999)

Spring 2005 Lecture 1 Rui M. Almeida

 One of the best experimental tools to distinguish a glass (or NCS) from a crystalline material
is X-ray diffraction (XRD). In the case of silica, one has the following XRD patterns:

(Adapted from: The science and design of engineering materials, J.P. Schaffer et al.,
McGraw-Hill, 1999)

SiO

SiO

The patterns of silica glass are a very broadened and smeared version of those of the high
temperature crystalline form, crystoballite. This is also a strong indication that the atomic
scale short range order is the same in the glassy and crystalline forms of solid silica.

Spring 2005 Lecture 1 Rui M. Almeida

 It is important to realize that some materials which have a very strong glassy
appearance under the naked eye, or even under a laser beam (such as the He-Ne
red light @ 633 nm), may actually contain a fine dispersion of very minute crystals
with dimensions well below 100 nm, i.e., nanocrystals.

Such nanocomposite materials may be very difficult to differentiate from a

100% glassy material, even using XRD. However, their nanocrystalline nature
may be identified by means of a microscopic method such as Transmission
Electron Microscopy (TEM), after suitable (and often time-consuming) sample
preparation.

Spring 2005 Lecture 1 Rui M. Almeida

 Glass transition temperature

Most commercially available glasses are NCS obtained by rapid solidification

of a viscous liquid below a given “freezing” temperature, designated by Glass
Transition Temperature, Tg. We shall see that Tg is often ~ 2/3 of the melting
(or the liquidus) temperature, Tm.

The liquid of rapidly increasing viscosity which is obtained between Tm and Tg

is called a supercooled liquid. Tg marks, therefore, the transformation from
the supercooled liquid into the solid glass.

The preparation of glasses by melting and quenching may be understood by

plotting the volume (or the enthalpy), or their corresponding derivatives,
the thermal expansion coefficient, αT (or the specific heat, cp), as functions
of temperature.
Spring 2005 Lecture 1 Rui M. Almeida
 (Tg))h (Tg)g

(Adapted from: Fundamentals of inorganic glasses, A.K. Varshneya, Academic Press, 1994)
Spring 2005 Lecture 1 Rui M. Almeida
 or
liquid

scl
glass

crystal

or

Spring 2005 Lecture 1 Rui M. Almeida

 Important points to bear in mind about the nature of the
temperature range designated as Tg:

Unlike Tm, which represents a first order thermodynamic transition, accompanied by a

discontinuity in the specific volume, v, Tg is not a well defined temperature, but rather a
temperature range. The faster the quenching of the liquid, the higher the Tg value of the
glass obtained. Tg, therefore, depends on the actual rate of cooling of the supercooled
liquid. Tg also represents the highest useful temperature for the utilization of a glass.

The appearance of the temperature range around Tg, where cp (the first derivative of the
enthalpy, (∂H/∂T)p), has a pronounced drop (or an apparent discontinuity) can be
considered as a kinetic necessity, in order to avoid a violation of the third principle
of thermodynamics. This is, in essence, the reasoning associated with the Kauzmann
paradox.

Spring 2005 Lecture 1 Rui M. Almeida

 Fig. com Kauzman par., onde esta????
~

SsclT1 – SxtalT1 = ∫ToT1 (Cpscl – Cpxtal) dT/T

Kauzmann paradox: if there were no sudden drop in cp at Tg, the entropy of the scl
would eventually fall below that of the crystal, being negative at 0 Kelvin, when the
third law requires Sxtal = 0. (The glass has a positive residual entropy at 0 Kelvin).
To → lowest limit of Tg, for infinitely slow cooling.
(VFT equation: η = ηo exp Q/(T-To) T → To => η → ∞ and Vf → 0)
Spring 2005 Lecture 1 Rui M. Almeida
The value of Tg for a given glass can be obtained, for example, from a measurement of
its thermal expansion coefficient, as we shall see later.
Tg can also be routinely measured by means of DSC (or DTA) scans, which also
provide the temperature of onset of glass crystallization, Tx, as well as estimates of the
solidus and liquidus temperatures of the system (which may vary with the scan rate).

Spring 2005 Lecture 1 Rui M. Almeida

 Sakka and Mackenzie (1971) have established the so-called “two
thirds” rule, which expresses the fact that, for most good glass-forming
substances (or systems), the ratio between Tg and the melting (or
liquidus) temperatures is of the order of “two thirds”:

Tg / Tm ~ 2/3

when the temperatures are expressed in Kelvin.

(For poor glass-forming systems, this ratio is often close to 0.60 or
0.70, rather than 0.66).

Spring 2005 Lecture 1 Rui M. Almeida