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OPTICAL PROPERTIES

3.1 INTRODUCTION:

If one were to list the major technological developments that have added to the

comforts of living, glass lenses as an aid to failing vision, glass windows to bring day

light into houses structures while providing protection from the harsh elements of nature,

glass in the light bulb to provide a similar function after dark and glass fibers for

enhanced communication capabilities would perhaps rank it very high.

For the glass window and the glass bulb to function, the optical transmission

property is important. The correction for the failing vision and glass fiber communication

is based upon the refractive, optical dispersion and transmission properties of glass.

Beside these, there are many more technological advances where the optical properties of

glass play a pivotal role [19]. The most obvious optical property of ordinary silicate

glasses is their very high transparency to visible light [20].

The optical properties of glass depend on its chemical composition of constituent

elements and thermal history etc.

Valuable information about the structure of glasses can be obtained from their

optical properties. Optical transitions of electrons in atoms are characterized by line

spectra and in molecules the rotation and vibration cause the electrons to form band

spectra where as in solid amorphous materials like glasses. The optical transitions are

characterized by continuous bands invariably make up of number of sub bands [21].


When light travels through a medium, a part of it is reflected from the surface, a

part is absorbed and the balance is transmitted. [20].

3.2 OPTICAL PROPERTIES:

3.2.1 ABSORPTION:

Absorption is the transformation of energy radiation into different forms of energy

in a medium. The nature of this process depends on the frequency of the radiation and on

the substance involved. [22].

The most direct and perhaps simplest method for probing the band structure of

material is to measure the absorption spectrum. In the absorption process, a photon of a

known energy excites an electron from a lower to higher energy state.

Absorption is expressed in terms of a coefficient , which is defined as the

relative rate of decrease in light intensity along its propagation path. The

measurement of optical absorption coefficient particularly near the fundamental

absorption edge, provides a standard method for the investigation of optically induced

electronic transitions and give some idea about the band structure and energy gaps in both

the crystalline and non-crystalline materials.

Basically two types of optical transitions can occur at the fundamental edge i.e.

direct and indirect optical transitions. In direct optical transition the wave vector of

electron remains unchanged. However the wave vector must change in indirect transition.

The fundamental absorption edge in the most disordered materials usually follows the

Urback rule [23,24],


() = A exp(h) / E) (3.1)

Where () is the absorption coefficient at an angular frequency and E is

the width of tail of localized states in the band gap of the amorphous materials,

E = Ec - Ea

Mott and Davis [25] suggested the following expression for the optical transitions

independent of temperature and free from electron-hole interactions

() = A (h) - Eopt)n / h (3.2)

Where n = 1/2 or 3/2 for direct transition depending on whether the transition is

allowed or forbidden in quantum mechanical sense. In case of indirect transition n = 2

stands for allowed and n = 3 for forbidden transitons.

In non-crystalline materials absorption can arise from the inter band transitions

involving the tails of the localized states. The absorption in many amorphous materials is

suggested to be associated with indirect transitions, which obey the above eq. [26].

Optical absorption in amorphous materials is classified it four different mechanisms.

3.2.1.1 INTER BOND ABSORPTION:

In amorphous semi conducting materials, inert band absorption which

corresponds to the high energy spectrum region is dominant. The absorption coefficient

() rises very sharply at a spectral region called the absorption edge. The corresponding

photon energy for this absorption edge provides the optical gap of the material.

It is an important [27] assumption that the mobility gap is equal to twice the

activation energy for electrical conduction of amorphous semiconductors.


3.2.12. INTRA BAND ABSORPTION [FREE CARRIER

ABSORPTION]:

The transition between the states within a single band is known as intra band

transition. When a free electron (or a hole) absorbs a photon it excited to another state in

the same band, this type of absorption is known as the intra band absorption.

3.2.1.3. ABSORPTION

INVOLVING STATES IN THE GAP:

It is the absorption on the low energy side of the fundamental absorption edge and

is associated with the transitions from or to impurity or defect levels in the gap. Another

absorption process in amorphous materials is also observed at very low frequencies due

to electronic hopping between the localized states at the fermi energy.

3.2.1.4. LATTICE [PHONON] ABSORPTION:

In infrared region of spectrum viberational modes of atoms in solids and liquids

give rise to absorption. In amorphous material the lattice absorption process are retained

to a degree, which depends on the materials, but the fine structure presents in the

crystalline spectra is diffused in the corresponding amorphous spectra.

3.2.2 TRANSMITTANCE:

Transmission is the passage of radiation through the material without any

frequency change the nature of this process depend on the frequency of the radiation and

on the nature of substance involved [22].


The transmission coefficient is defined as the extent to which a body transmits

incident light or other electromagnetic radiation, equal to the ratio of the flux. The

transmittance depends on the path length of the radiation and on its wave length [28].

When a beam of radiation passes through a material, the amount of transmitted

radiatons depends not only upon the absorbed but also on the amount of reflected

radiation at the interfaces. It is also possible that diffused transmission may occur, that is

transmission in which the laws of refraction are not obeyed on the microscopic scale and

part of the radiation is scattered and lost form the beam without being absorbed.

Transmission measurement is undoubtedly the most common type of the optical

measurements made. They may be made easily, conveniently and with moderately good

accuracy and the results are easy to interpret.

3.2.3 REFLECTANCE:

The process in which the incident radiation on the surface of the material bounces

back into the original medium without any change in its frequency rather than passing

into the second medium is called reflection [22]. Reflection depends upon the frequency

of radiation and on the surface nature of the substance.

The reflectance is defined as the ratio of reflected luminous flux to the incident

flux.

The reflectance can be calculated from the relation [19].

R+A+T=1 (3.3)

R = Reflectance.

A = Absorbance.
T = Transmittance.

3.3 PHYSICAL PROPERTIES:

3.3.1 DENSITY:

Density is a commonly measured property of materials. It describes the amount of

material in a unit volume and is usually an additive property. However, the structure

developed after the reaction of constituents determines the value of density in a system

such as glass. The calculation of density are therefore, based on assumptions about the

structure of glass. The structure of glass is determined by the interatomic for ces between

glass forming contains (like Ge+2 , B+3, Si+4, P+5) and surrounding oxygen anions.

In pure silica glasses, each oxygen bridges two silicon while other silicate glasses

contains both bridging and non-bridging oxygen atoms. The ratio of bridging to non-

bridging oxygen determines the nature the closeness of packing [29].

The addition of intermediates and modifiers in glass forming oxides cause

changes in the density of glass. These changes may be due to the differences in densities

of the additive oxides and their arrangements in the final structure.

Density is an important parameter used for explaining the structure of glass,

physical and electrical behavior of glasses.

3.3.1.1. PARAMETERS DETERMINED FROM DENSITY:

Parameters determined from density are oxygen packing density and molar

volume which are described as under.


3.1.1.1 MOLAR VOLUME:

The molar volume of binary and ternary phosphate glasses have been estimated

by the relation,

Molar volume = M/ (3.4)

Where,

M = molecular weight of glass composition

= measured density of the glass sample

Molar volume is an important parameter which can be used to explain the density,

modulus of rigidity, coefficient of thermal expansion and transition temperature data. [51,

52, 53],

3.3.1.1 OXYGEN PACKING DENSITY:

The oxygen packing density was calculated by using the following expression as

given in; [30]

Oxygen packing density = {1000 |O|} /M (3.5)

Where M is molecular weight of the glass composition, [O] is the number of

oxygen atoms in the composition and the density of the glass sample.

Oxygen packing density is an important parameter in explaining the structure of

glass. [31].
4.1 REVIEW ON OPTICAL PROPERTIES OF

PHOSPHATE GLASSES

In recent years the optical band gap of some binary and ternary phosphate glasses

has been studied [58-61]. A large amount of experimental data on the optical properties of

oxide glasses has been reviewed by Mott and Davis [35].

Austin and Garbet [40] describe that the absorption coefficient shows an

exponential behaviour in vanadium phosphate glasses with Ni, Co, Cu, ions but tails in

the absorption have been reported by Nunoshita et. A1 [41] Hogarth and Gharuri [42]

also reported similar results on cadmium phosphate and cadmium-zinc phosphate glasses.

These tails were suspected to be due to the presence of impurities, structural defects or

other kind of in homogeneity. It is accepted that in most cases the d.c photoconduction

measurements follow the optical absorption gap, which in some cases yield mobility gap

only indirectly in some amorphous semiconductors. [35]

Hogarth and Hosseni [24], Khawaja etal. [73], Kutub et.al. [74], and Siddiqi

et.al [75] studied the absorption edges of some binary and ternary phosphate glasses

having colorant centers i.e transition element oxides that have been used as modifiers.

The fundamental absorption edges [43] of the vanadium phosphate and vanadium-

Tellurium phosphate glasses in the short wave length part of the visible region are

measured by Hogarth and Hosseini. It was found that the fundamental absorption of

these glasses is dependent on composition and arises from direct forbidden transition and
occurs at photon energy in the range 1.9--2.6ev depending upon the composition. They

concluded that the carrier concentration in the localized levels ( band tails) depends upon

the total number of available sites which in the case of vanadium-phosphate glasses are

different for V4+ and V5+ ions.

In their research publication [43] they suggested that in transition metal oxide

glasses a photon with a certain energy range could be absorbed by transition metal ions

present in the glass by two different process.

i. The absorption may be due to a transfer of an electron from a neighboring

atom to the transition metal ion and vice versa.

ii. The absorption may be due to the internal transition between the d-shell

electrons.

Khawaja et al [73], studied the copper-sodium-phosphate glass system. They concluded

that optical absorption may be attributed to the change in the ratio of concentration of Cu +

and Cu++ ions in the glasses as a consequence of changing the sodium content. Siddiqi et.

al. [76,75]. Studied the optical properties of manganese phosphate and cadmium

manganese phosphate glasses. They observed that, at zero field, band gaps were

dependent on manganese concentration. In the presence of electromagnetic field, optical

band gap decreases with the increase of applied field in binary MnO-P 2O5 glasses but in

ternary MnO-CdO-P2O5 glasses the deduced values of band gaps were found to be almost

independent of the applied field.


Garden [44] made the optical measurements of the fundamental edge and broad

absorption tail of vanadium phosphate glasses in the range 3850-3000 cm-1. The band

gaps were determined to be 2.71-2.82eV under different conditions. The concentration of

reduced V+4 ions was concluded to be largely responsible for the variation of E g and of

the absorption tail.

The Band gap in cadmiun zinc phosphate glasses by absorption and photo

conduction measurements was determined by Ghauri et. al [45]. The two values of the

band gaps are nearly same within the experimental error. The photoconduction band gap

shows a slow decrease with an increase in the applied field. The results have been

discussed in terms of energy band model for non-crystalline solids.

Tauc [46] believes that the variation of absorption coefficient with photon energy

is due to the electronic transition between the localized states. Where as, Mott and Daivs

[35] were uncertain about the explanation because the slopes of the observed exponential

behaviour do not change for a great variety of materials. Redfied and Afromawitaz [62]

suggested that this region of absorption edge is related to imperfection in the material.

While Vasilyev et. al [47] suggested that the spectral dependence can be related to a

distribution of density of meta-stable states with in the gap.

Ilograth and Ghauri [48] worked on cadmium-zinc phosphate glasses and

reported that the optical absorption is due to forbidden indirect transition. They reported

the basic measurements on the cadmium-zinc phosphate glass and made some

suggestions about the energy band gaps.


The fundamental absorption edge of cadmium phosphate and cadmium zinc

phosphate glasses has been measured in the UV-visible spectral region by photo

absorption method.

Hogarth and Ghauri [63], Ghauri et al. [64], Nazar & Ghauri [65], Ahmad &

Hogarth [66] and Hikmat Shoar et al [67] had suggested that optical absorption in these

glasses were due to indirect electronic transition. It was found that optical band gaps of

these glasses were composition dependent, which is known as zero field optical band gap.

Ghuari et al [68] had also verified that non-crystalline materials like semi

conducing oxide glasses obey the phenomena of photoconduction in the presence of

applied electric field.

Nadeem et al. [69], Bilal et al. [70], Chaudhry et al [71,72] had studied the

optical absorption spectra of some binary cadmium phosphate, zinc phosphate and

ternary cadmium-zinc phosphate glasses. It was found that absorption edges lie in the

UV- region of the spectra and optical band gaps of these glasses were.
4.2 PURPOSE OF THE PRESENT WORK:

There are many technical and biological applications of Phosphate glasses. The

phosphate glasses can be used as semiconductor and dielectrics. Due to the potential

application for transmission and detection of optical data and also in laser technology, the

phosphate glasses containing high concentration of rare earth ions are of interest.

Phosphate glass containers are used to store radioactive waste material. From the

Biological aspect phosphate glass ceramics are used for artificial bones. Thin Films of

phosphate glasses are employed in various detectors.

The Purpose of the present review on optical properties of phosphate glasses was

to make an assessment of the kind of work which can be carried out with various

composition of phosphate glasses with special emphasis on their applications.

For the present work, Binary and Ternary systems of some phosphate glasses were

selected with composition

60%ZnO+40%P2O5

50%ZnO+50%P2O5

40%ZnO+60%P2O5

30%ZnO+70%P2O5

10%B2O3+30%ZnO+60%P205
20%B2O3+30%ZnO+50P2O5

30%B2O3+30%ZnO+40%P2O5

40%B2O3+30%ZnO+30%P2O5

Because no work to our knowledge on the optical properties of such composition

has been carried out so far. We studied the binary systems of zinc phosphate glasses in

order to make a comparison with already published data [82] and also with ternary

phosphate glasses examined in the present work.


5.1 SAMPLE PREPRATION

The phosphate glasses of various composition were prepared in the laboratory.

The detail of each composition as given in chapter 4.

For the preparation of all these binary and ternary phosphate glasses the relevant

amounts of the constituents were calculated for 10 gm samples, using the molecular

weight formula of required glass system. After weighing required amounts for each

composition, they were thoroughly mixed and then put in a platinum crucible. Which was

then kept in an electrically pre-heated furnace at 300C0 for half an hour to avoid the

fuming effect of P2O5. The crucible was then kept in electrically pre-heated furnace at

500C0 for further half an hour .Then it was at 1350C 0 for two or one hour to homogenized

melt. The molten form of the materials then casted in stainless steal discs of diameter 20

mm each.

Then samples were annealed at 200C for an hour to remove the mechanical and

thermal stresses produced in the samples during casting.

5.2 SAMPLE POLISHING

After annealing, the discs shaped glass samples of binary and ternary systems

have been polished by grinding them on Silicon Carbide paper of different grades. For

Fine polishing the silicon carbide papers of grades 320 to 1000 were used. To achieve the
best optical transparency the samples were finally polished on micron grade polishing

paper.

5.3 OPTICALMEASUR EMENT

The optical absorption and transmittance for all samples of glass were obtained in

UV/visible/near infrared region (from 190 nm up to 1100nm) by means of Hitachi U-

2001 UV/visible double beam Spectrophotometer with air as reference. The

measurements were done in wavelength scanning mode under the following parametric

conditions.

1. At room temperature

2. Incident is normal to the surface.

3. Reference is air.

The optical system of the model UV-2001 Spectrophotometer is

illustrated in fig-5.1.
Figure 5.1

A block diagram of Hitachi U2001 Spectrophotometer


5.4 DENSITY MEASUREMENT;

The density was measured by using Pyknometric Method. For this purpose

sartorious balance was used. In this method, at first a gravity bottle is weighed, then

gravity bottle with sample is weighed, then gravity bottle with toluene is weighed, finally

the gravity bottle with toluene and with sample is weighed. Then density is calculated by

the following formula,

- mass of sample * d

mass of liquid of equivalent vol. Of the sample

= [w2 w1 / (w3 w1) - (W4 - W2) / *d

where,

W1 = weight of empty bottle .

w2 = weight of empty bottle +sample.

W3 = weight of empty bottle +liquid.

W4 = weight of empty bottle +liquid +sample.

d = density of liquid used


Figure 5.2

Sartarious balance to measure the density of glass sample by pyknometeric method.


The phosphate glasses of different composition as shown in Tables [1,2] were

prepared by using the melt-quench method under the same parametric conditions. The

density and optical band gap are the main concern of this study. The results related to

these properties have been discussed in this chapter.

6.1 DENSITY

For various composition of binary and ternary glasses the results of the

measurements of density are listed in tables [3,4] .The same results related to these

glasses has been plotted with ZnO concentration in Fig.-6.1. From the graph it can be

seen that the variations of density is such that it decreases with decreasing amount of

ZnO. We know that density of ZnO is 5.47gm/cm3, P2O5 is 2.39gm/cm3.

In these binary glasses P2O5 is replaced by an equal amount of ZnO which may

cause the decrease of density with decrease of ZnO as shown in Fig -6.1.

At 60% ZnO white spots in glass has been observed .which are related to the

imperfectness of the glass and caused by the unavailability of the temperature due to

furnace limitations.

We know that the density of B2O3 is 1.84 gm/cm3 It is observed that the density of

ternary phosphate glasses [B2O3-ZnO-P2O5] increases as the amount of B2O3 increases

keeping the ZnO constant at 30 mole percent as shown in Fig -6.2.


Table 1:

Composition of Binary Phosphate Glasses.

Sr.No. Composition in moles.

1 60% H3BO3 + 30% PbO + 10%SrO

2 60% H3BO3 + 28% PbO + 12%SrO

3 60% H3BO3 + 26% PbO + 14%SrO

4 60% H3BO3 + 24% PbO + 16%SrO

5 60% H3BO3 + 22% PbO + 18%SrO

6 60% H3BO3 + 20% PbO + 20%SrO


Table 2:

Composition without doping.

Sr.No. Composition in moles.

1 60% H3BO3 + 40% PbO + 0%SrO

6
Table 3:

Measured Density of Binary Phosphate Glasses

Sr.No. Composition in moles. Density gm/cm3

1 60% H3BO3 + 30% PbO + 10%SrO

2 60% H3BO3 + 28% PbO + 12%SrO

3 60% H3BO3 + 26% PbO + 14%SrO

4 60% H3BO3 + 24% PbO + 16%SrO

5 60% H3BO3 + 22% PbO + 18%SrO

6 60% H3BO3 + 20% PbO + 20%SrO


This increase may be due to some structural changes, which might have occurred

during glass preparation. B2O3 is the glass former with highest bond strength. When we

are replacing P2O5 with B2O3 i.e low bond with high bond strength material may contract

the structure of the material which may cause the decrease in molar volume of glass and

hence increase the density of glass.

6.2 OPTICAL PROPERTIES:

The optical property such as the absorbency was measured by using the Hitachi

U-2001 UV/visible double beam spectrophotometer. The results of these measurements

are given below.

6.2.1 OPTICAL BAND GAP:

For various composition of binary and ternary phosphate glasses, the optical

absorption spectra have been recorded in UV-visible range.

The data obtained are shown in Fig-6.2.1 to Fig-6.2.8. There is no sharp

absorption edge, which may refer the characteristic to the glassy state. The absorption

values for different wavelengths for different glass composition are calculated from these

graphs. The experimental values of absorption coefficient a near the fundamental

absorption edge are calculated by using the relation,

= 2.303 A/D
Which has been derived from Lambard Beer's law|54|.

I = Io e-d

I / Io = e -d

Io / I = ed

log Io / I = log ed

A = d loge

A = d 0.4343

= A / 0.4343d

= 2.303A/d

Where,

A = (log Io / I ) is normalized optical absorption

d = thickness of the sample. Theoretical formula for given by Mott and Davis is

() = A (h - Eopt)2 / h

() h = A (h - Eopt)2

Where,

h = incident photon energy

Eopt = Optical band gap of the material.

Now above equation can be written as,


Eopt= [h - (h / A)l/2]

For various binary and ternary glass compositions, the observed data related to

above equation are given in Tables [5-12]. These data are plotted to determine the optical

band gap of these samples. The straight portion of these graphs shown in Fig- 6.2.9 to

Fig- 6.2.16.were extrapolated to meet x-axis at zero values of (h) 1/2. The values of

h at that point yield a direct measure of optical band gap energy. The values of

optical band gap for different composition of ZnO-P2O5 are lies 2.7-3.35eV while the

values of optical band gap for different composition of B2O3-ZnO-P2O5 lie between 2.4-

3eV in which the amount of ZnO is fix.

The results of measurement of optical band gap are listed in Table [13-14] .For

binary phosphate glasses (ZnO-P2O5) the optical band gap data has been depicted in Fig-

6.2.17, as a function of ZnO composition expressed in mole percent. It can be seen that

variation of optical band gap is such that at first it increases, then decreases and again

increases with decreasing amount of ZnO in binary ZnO-P2O5 glasses. This may be due

to the fact that ZnO acts both as a modifier and as an intermediate. At low values of ZnO

it may work as a modifier, while at higher concentrations it acts as an intermediate,

thereby becoming a part of the glass forming network.

If it does not enter into the glass forming network and only acts as an impurity or

structural defect it causes the band tailing and have reduces the band gap energy.

However if it does enter into the network, it increases the band gap as described in fig-

6.2.17 [55],
At 60% ZnO white spots in glass has been observed , which are related to the

imperfectness of the glass and caused by the unavailability of the temperature due to

furnace limitation, which may cause to decrease in the optical band gap.

In the ternary phosphate glasses (B2O3-ZnO-P2O5) the optical band gap data has

been depicted in figure (6.2.18) as a function of B2O3 composition expressed in mole %.

The variation of band gap is such that at first it increases with increases amount of

B2O3 and then it decrease with increasing amount of B2O3 keeping the amount of ZnO

constant as shown in figure [6.2.18]. This may be due to certain structural change

occurring in the material with changing composition.


Table No: 5

OBSERBED DATA FOR ABSORBANCE AND CALCULATED VALUES OF

PHOTON ENERGY, ABSORPTION COEFFICIENT AND (h)1/2 FOR THE

DETERMINATION OF BAND GAP OF 60% ZnO+40% P2O5 GLASS.

Thickness of Sample =. 172cm

Where h = 6.63 x 10-34 J-sec.

= 2.303A hw = hc /
A (hw)1/2
(nm) (cm-1) d (ev)

300 .229 3.0662 4.1437 3.5644

290 .275 3.6821 4.2866 3.9728

280 .321 4.2980 4.4397 4.3682

270 .373 4.9942 4.6041 4.7951

260 .429 5.7441 4.7812 5.2405

250 .479 6.4137 4.9725 5.6472


240 .544 7.2839 5.1796 6.1422
230 .625 8.3684 5.4048 6.7252
220 .737 9.8680 5.6505 7.4672
210 .876 11.7292 5.9196 8.3325
200 1.305 17.4733 6.2156 10.4214
190 2.554 13.1968 6.5427 14.9579