CHAPTER 3

ELECTRICAL CONDUCTIVITY MEASUREMENTS IN

BISMUTH, ANTIMONY, BISMUTH OXIDE AND
ANTIMONY OXIDE THIN FILMS

3.1 lntroductiorl

The electrical conductivity studies in bismuth, antimony, bismuth oxide and

anlirnony oxide thin films are made. Both bismuth and antimony undergo

semimetal-semiconductor transition. The kinetic properties such as the electrical

resistivity and Hall effect measurements of vacuum evaporated bismuth [I-81and

iir~tirnony[9-13lhave been reported in its thin film form. Bismuth and antimony thin

tilrns exhibit "ordinary size effect" [14-171 and "quantum size effect" [18-211. The

electrical resistivity studies made earlier on bismuth and antimony films have large
Inconsistencies [22].This inconsistency is attributed to different parameters of

evaporation and annealing. The electrical conductivity studies in metal oxides has

beell studied to deterll~inethe dc controlling mechanism. Because of the difficulties

in preparing bismuth oxide filrns by vacuum evaporation comparatively few

investigations have been made on their electrical properties. There has been an

increasing interest in the studies on the dielectric properties of thin solid films of

Ki203 for use in the fabrication of miniaturized electronic and optical devices [23].

Antimony oxide films are very attractive materials for spectroscopic studies, solar

energy applications and other industrial purposes [24]. According to the character

of rlon stochiometry, the antimony oxide behaves as an n type or p type

serniconductor.

3.2 Theory

The thickness dependence on electrical transport properties and thermal

1ran:;port coefficients of thin films of Bi and S b have been discussed according to

theories developed for thin metal films by Fuchs [25], Sondeimer [26] and Mayadas

and Shatzkes [27].Investigations on bulk samples have shown that the electrical and

Lhel~naltransport coefficients can satisfactorily be interpreted by means of a two

0a11tlrnodel [28]. In the temperatu~erange 80 to 400 K bismuth with its small band

ovc:rlap is within the transient range between degeneration and non-degeneration.

The band structure of monocrystalline Bi and Sb samples can be described by the

Ferrlli surfaces at the extrerna of the conduction and valence bands. This has lead to

anisotropy of the transport coefficients.

The energy-niomentum study of charge carriers in crystalline bismuth is an

involved problenl. According to the rlonparabolic ellipsoidal model [18, 29, 301,

electrons in bismuth assume the following energy spectrum

~vherc.E, = 15.3meV is the energy gap between the conduction band and valence

ba~lcl,In bismuth, the n elements form the inverse effective mass tensor, and the

subscripts 1,2 and 3 refer to the binary, bisetrix and trigonal axes, respectively. The

electron energy E, is measured from the bottom of the conduction band and p's are

the momentum components. There are three electron ellipsoids in the conduction

banti. There is only one hole ellipsoid in the valence band that overlaps the

conduction band. The hole energy measured from the top of the valence band takes

the form.

where MI=M, indicating the rotational symmetry of the ellipsoid.

 In thin films of bismuth, the separations between subbands are well

pronounced and the charge carriers in each of the subbands can be treated as a

two-dimensional system. The conductivity of bismuth film would then be the sum of

the inclividual contributions of the subbands. The electron conductivity o, and the

hole conductivity o,, are given by

o, = 312 e2 re N, [1+2EriE,l ' [a,, + ( ~ , - ~ ( 22~a33)1

3 ....3.3

2
oh = e T~ NhM ~ " ....3.4

where EF is the Ferrni energy, z, and zh are the relaxation times of electrons and

holes, N, and Nhare the number densities of electrons and holes respectively.

Thin film data are generally analysed using the Fuch's size effect theory [25]

in which a spherical Fermi surface arid an isotropic mean free path are assumed and

the ordinary scattering mechanism which operates in the bulk is taken to be valid in

the films. The litnitation of the electron mean free path at the film surface is taken

into account and the ratio of the resistivity p~ of a thin film to the resistivity pn of the

bullt is given by [31],

where y is the ratio of the film thickness t to the electron mean free path I in the

bc~llc,p is the spclcularity parameter and a = lIcos0, where 0 is the angle which

the electron mean free path makes with the normal to the film.
 The limiting value is given by

pFipl3 = 1 + 318y (1-p) for y > I ....3.6

Lqnation 3.6 indicates that plot of p,- Vs lit is a straight line, ps can be obtained

from the intercept of the plot and slope will give the value of l(1-p).

In practice, the structure of a thin film does not approximate to a single

cryslal parallel to slab but rather consists of an array of randomly oriented

polycrystallites. The crystal structure is often columnar, with individual crystallites

growing roughly vertically from the substrate to the upper surface of the film, and

the grain boundaries lie parallel or perpendicular to the applied electric field. The

linear dimensions of the crystallites in the plane of the film are often comparable

with the electron mean free path and hence the contribution from electron scattering

at the crystallite boundaries should also be taken into account. Mayadas and

Sl~alzkes [27] proposed grain boundary scattering in polycrystalline films and

analysed it by considering the resistivity due to the scattering of conduction electrons

at the grain boundaries together with the normal bulk ground scattering from the

delects and phonons.

'I'lle Mayadas ancl Shatzkes expression for the resistivity is

P F ~ P B= 41 ( ~ ~ $ if1 (at)
where, f (a') = 3 1113 - ti12 i- tr" - t i 3 / In ( I + llcc')} .... 3.7
I
ar~tlt z = IRID(1-R)and @(p,y]is given by equation 3.5,where y = yi/f(n),

P) is the grain size and R is the coefficient of reflection at the grain boundary.

111 a serr~iconductorthe conductivity can be written as

 o = (ne p, + pe J-L~) .... 3.8

where n and 11, are the carrier concentrations and mobility of the electrons and p

a r ~ dit,, are the corresponding quantities for the holes. In an intrinsic semiconductor

the number of electrons is equal to the number of holes. If we assume that the

varialion of mobility of electrons and holes in the electric field with temperature is

small, the electrical conductivity has the variation of the form.

o = oo exp (-A!3kBT) ....3.9

where o, is a constant, AE is the activation energy and kB is the Boltzmann

constant.

3.3 Bismuth

Thin films of bismuth are prepared by thermal evaporation technique using

Flint1 H~vaccoating unit described in chapter 2 (section 2.7). Spectroscopically pure

bismuth (99.999 % of purity) ingots procured from SlSCO is used as the source

material. This ingot is evaporated from a molybdenum boat. Initially the vacuum

chamber is evacuated to a base pressure of torr. Ultrasonically cleaned glass

slides are used as substrates. A calibrated chromel-alumel thermocouple is used for

the substrate temperature measurement. The substrates are subjected to ionic

bonlbardment for 5 minutes in tile vacuum chamber before the film deposition. The

substrate temperature is varied using a substrate heater. The rate of evaporation is

within the range 10-15nrdmin.

cc~r~trolled
 The thickness of the film is measured and controlled using the quartz crystal

thiclcr~essmonitor and counterchecked by Tolansky's multiple beam interference

technique. The electrical conductivity and sheet resistance are measured in a

condl~ctivity cell using a lCei[hley 1~rogrammableelectrometer (Model No: 617).

Conductivity is also nieasured using a four probe set-up (Model No: DFP - 02). Pre

evaporated silver electrodes and silver epoxy are used as ohmic contacts.

Figure 3.1 shows the variation of sheet resistance Rsh with thickness of

film deposited at different substrate temperatures (Ts) 30, 75, 100, 150,
bis~~nuth

200. and 250°C. The film with Ts = 30°C has a sheet resistance of 68 Q/o for film

thickness of 100 nm. For a film of thickness 550 nm, the measured sheet resistance

it; 10.2 I2In at the same substrate terrrperature. In the case of Ts = 100°C, Rsh for a

filrrl of thickness 100 nm is 5 6 Q / o . For the thickness 550 nm, the sheet resistance

obtained is 8.7i21o. Increase in substrate temperature and increase in thickness of

the film at same substrate temperature considerably lowers the sheet resistance.

Sheet resistance of 35, 15.2, 9.7 and 4.6 Cl/o are obtained for thicknesses 100, 200,

300 and 600 nm respectively for the films deposited at 250°C.

The variation of conductivity for Bi thin film as a function of temperature is

shown in figure 3.2 for the film of thicknesses 135 nm and 550 nm. The conductivity

of the film increases with increase in temperature. Das and Soundararajan [32] has

observed that resistivity of Bi film decreases with increase in temperature. The

resistivity of the film during cooling cycle is lower than the heating cycle for all the

lihr~s,indicating that the thermally unstable defects incorporated in the film during its
Fig. 3.1 P l o t of sheet resistance Rsh Vs thickness
f o r b i s m u t h t h i n f i l m deposited a t different
Substrate t e m p e r a t u r e s .
 0-0 135 nm. Heating
Q
E
Q
- Cooling
=
** 550 nm. Heating
ooooo Cooling

, ~ l t l l l ~ ~ ~ ~ l l ~ ~ i I lI l l l l l l
100.0 200.0 300.0
Temperature OC

Fig. 3 . 2 Plot of conductivity Vs temperature f o ~

Bi thin film.
growth have been removed during the heating. It has been suggested [I41 that the

semiconductor like behaviour observed in bismuth film is due to the uncrossing of

the conduction and valence bands.

A typical plot of loy o Vs lOOO/T for Bi film for thicknesses 135 nm and 550

nln are shown in figure 3.3. From the slope of the graph the activation energy can

be determined using ttie equation (3.9).The values of activation energy for Bi thin

film for different thicknesses are reported in table 3.1. It is found that the activation

eriergy increases with increase in the thickness,

'l'itl~lc3.1 V:ui;~tionol activation cnc~gyfor bisn~uththin lilm as a function of thickness

'I'llickncss niii. Activation encrgy n~eV

I

Figures 3.4, 3.5 and 3.6 show the temperature dependence of dc electrical

conductivity of bismuth thin film of thickness 180 nm deposited at substrate

temperatures, 75,100 and 250 "C respectively. From these figures it can be seen

t l ~ d il~ilially
l the co~itluctivityincreases with temperature and then decreases during

the heating cycle. Here the film shows the semiconducting as well as metallic nature

in the different temperature regions. Figures 3.7 and 3.8 give the second and third

heating cycles for bismuth thin film. Das and Jagadeesh (331 have made the
Fig. 3.3 Plot of log r Vs 1000/T for bismuth
thin f i l m deposited a t 30°C
Fig. 3.4 Plot of conductivity Vs temperature for
bismuth thin film deposited a t 7 5 O C .
Fig. 3.5 Plot of corilluctivity Vs teriiperatoure for
b i s m u t h thirl film deposited a t 100 C.
Fig. 3.6 Plot of conductivity Vs temperature for
bismuth t h i n f i l m deposited a t 250°C.
Fig. 3.7 Plot of condiictivity Vs t e m p e r a t ~ r e f o r
b i s m u t h t h i n f i l m deposited a t 100 C.
(second heating)
Fig. 3.8 Plot of conductivity Vs temperature f o r
b i s m u t h thin f i l m deposited a t 1 0 0 ° C .
(third heating)
resistance measurennents with temperature variation on BiSb alloy thin films and

analy;!ed the results by classifying the different regions as: region 1 where, resistance

decrease with decrease in temperature, region 2 where, resistance increases slowly

with the fall of temperature, region 3 where, resistance increases rapidly with

temperature decrease and region 4 where, resistance is temperature independent.

Figure 3.9 gives the typical plot of log a vs lOOOrT for Bi thin film deposited

at substrate temperatures, 75, 100 and 250°C. The slopes of the graph can be used

to calculate the activation energy using equation 3.9. Table 3.2 reports the

activation energy as a function of substrate temperature for Bi thin film. The

activation energy decreases as we increase the substrate temperature. Thin film

consists of indiviclual islands which have many of the characteristics of the liquid

'l'ablc 3.2 Variation of activalion ciiergy Sor bis~rluththin film as a fu~lctionof

substrate temperature.

- ~~ -- - ~

Substrate celnpcralul-e 'C Activation energy ~neV

75 14.19

100 9.03

150 7.91

droplets. As the substrate temperature increases, the contact angle between droplet

and substrate decreases and the droplet grows in size. Thus a given amount of
Fig. 3.9 Plot of l o g a Vs 1000/T f o r bismuth t h i n
f i l m deposited n t d i f f e r e n t s u b s t r a t e t e m p e r a t u r e s .
matel-ial deposited on a substrate at a low temperature may be enough to form a

continuous film, whereas the same amount of material deposited on a hotter

substrate will result in an island structure. Similar results have been observed [34]

when gold films were deposited on Zinc sulfide substrates.

3.4 Antimony

Thin films of antimony is prepared by vacuum evaporation by resistive

heatit ~gfroin a molybdenum boat using vacuum coating unit as described in chapter

2 (section 2.7). Spectroscopically pure antimony (99.999% of purity) procured from

FIIZIDIZL is used as the source material. The substrate temperature is varied using the

substrate heater and the temperature is measured using a chrornel-alumel

therll~ocoupleplaced over the substrate. The rate of evaporation is 10-15 n d m i n .

The tl~icknessof the sample is controlled using the quartz crystal thickness monitor.

It is counter checked using Tolansky's interference technique described in chapter 2.

The ohmic contacts are made by pre-evaporated silver electrodes. The sheet

resistance is measured using four-probe set-up (model No: DFP - 02) and electrical

concluctivity is measured using Keithley electrometer (model No: 617) and

conductivity cell. The temperature of the sample during the conductivity study is

measured using a chromel-alumel thermocouple. The conductivity measurements

are [lone both in vacuum and in air,

Figure 3.10 gives the plot of sheet resistance Rsh Vs thickness for antimony

t h i ~ ltilrns deposited at substrate temperatures 30, 75, 100, 150 and 200 "C. For the

lihn of thickness 80 nrn deposited at a substrate temperature of 150°C, the sheet

 0 To 30 Oc
x 0
.=* 75OC
0 ~ 1Q0 o 0 c
+..*= 150°C
0 0 0 0 20o0c

- ~ " ' I i " " " "

200.0 400.0 6(
Thickness nm

Fig. 3.10 Plot of sheet resistance Vs thickness f o r

a n t i m o n y thin film deposited a t different
substrate temperature.
resistance obtained is 30i21~1which is higher than the sheet resistance 25RIo of the

fib11 cleposited at 200°C. At substrate temperatures 100, 75 and 30°C, the sheet

resistances are 35, 38 and 40l2/o respectively.

The temperature dependence of conductivity of antimony thin films of

thickness 200 nm deposited at 30, 75 and 200°C is shown in figures 3.11, 3.12 and

3.13 respectively. The decrease in conductivity with annealing temperature is

observed by Kotlinska and Subotowicz [lo] for S b films. In practice collisions

between the conduclion electrons and the grain boundaries often contribute more to

film resistivity than does surface scattering.

Saha [35]observed that the initial resistance of the antimony films decreased

irreversibly as the films were heated uniforn2ly. The maximum value of lattice

distortion energy function varied from 6 x 1 0 ~ to

~ 30x10.~ c 4 e V . At higher

temperatures, as the annealing effect increases the fall in resistance due to the

removal of defects become greater than the increase due to the lattice vibrations

and hence a net fall in resistance is observed. Jensen et al [36]studied the electrical

]>ropertiesof amorphous antimony films. Below a critical temperature T, = 350 K,

the conductance of amorphous antimony is thermally activated. When T, is

~ 2.2
reached, the conductance suddenly jumps from 2.8 x 1 0 to ~ x S. The

~naynitudeof this jurnp is attributed to the crystallization of the sample. Volklein and

Kessler [37] have studied the electrical and thermal properties of antimony films and

reported that these films can be used as thermoelectric sensors.

 -0 Cooling
CX~
=
.=
*=.
In air Heating
Cooling

Fig. 3.1 1 Plot of conductivity Vs ternperfture f o r

nntimony thin filrn deposited a t 30 C.
Fig. 3.12 Plot of conductivity Vs temperature for
nntimony thin filrn deposited a t 75'C
 0-5 in v a c . Heating
o x + Cooling

.=-
= in air Heating
Cooling

0.01
0.0 100.0 200.0
~~~~~~I 300.0
Temperature O C

i 5.13 Plot of condl~ctivityVs temperature for

thin filiri deposiked n t %OO0C.
clntir~ir~nv
3.5 Bismuth Oxide

Bismuth oxide filrns car) be prepared by different techniques such as thermal

evaporation [38],reactive evaporation, activated reactive evaporation [39] and by

tliet.~nalsublimation of metallic bismutli followed by oxidation of the film in air [40].

We have used the thermal sublimation of metallic bismuth followed by oxidation.

Pure bismuth is used as the source material. This material is evaporated onto glass

substrates by resistive heating method from a molybdenum boat to obtain thin films,

using a Hind Hivac coating unit. The pressure of the system is kept at 1 0 torr.
~ ~The

substrate temperature is varied using the substrate heater. The temperature of the

substrate is measured using a chromel-alumel thermocouple placed on the

substrates. The rate of evaporation is 10-15nmlmin. The thickness of the films are

11nonitoredusing quartz crystal thickness monitor. The thickness is counter checked

by the multiple beam interference technique. The bismuth films thus obtained are

then annealed in air to obtain bismuth oxide. Annealing of the bismuth film are

done in a furnace at a temperature of 200°C for 48-60 hours.

Figure 3.14 shows the variation in electrical conductivity of Bi203 thin film as

a function of ambient air pressure. The conductivity is found to increase as the

pressure increases. The decrease in conductivity is 4.5 times when we decrease the

pressure from atrnospheric pressure to 1 0 " m bar. Figures 3.15, 3.16 and 3.17 give

the temperature dependence of electrical conductivity of bismuth oxide films

deposited at substrate temperatures (Ts) 30 and 250 " C , both for heating and

coolilq cycles. At a Ts of 200°C the conductivity obtained at room temperature is

 .;,oo ---
-
~ - .

-
-
-
-
-
E "00 -
.
.
\ -
0 -
L -
E -
-
-
X .
.
>
e2.00 - -

.e
- -
-
0 -
3
u -

L -
0
0 l .oo -:
-

-
-
+-
-
-
-
-
0.00- T T l l l m ~ r m m i 1 lmml l l m m i IN-l 11'11"1 I W

0.00001 0.1 1000

Ambient P r e s s u r e (m b a r )

Fig. 3.14 Plot of conductivity Vs a m b i e n t pressure

f o r bismuth oxide t h i n film.
 0-0 in air Heating
Q 3 9 Cooling
.=. in vac. Heating
Cooling

Fig. 3.15 Plot of conductivit Vs 1000/T for bismuth

Y
oxide thin film deposi ed a t r o o m temperature.
Fig. 3.1 6 Plot of conductivit Vs 1000/T f o r bismuth
Y
oxide thin film deposi ed a t 250°C.
Fig. 3.17 Plot of conductivit Vs 1000/T f o r bismuth
Y
oxide thin film deposi ed a t 250°C.
0.07 rnho/m in vacuum and 0.16 rrlho/rn in air. At Ts = 250°C, it is increased to

0.085 mho/~nin vacuum and 0.17 mho/m in air respectively. The conductivity value

at 90°C in air is 2.2 times that in vacuum. The corresponding increase at 250°C is

nine fold for the film coated at 200°C. The plot of log G Vs lOOO/T is shown in figure

3.18,~uhichis used to determine the activation energy and the values are reported in

table 3.3.

'l'i~hlc1.3 Variation of activation erlcrgy lor bismuth oxide thin film deposited at different
suhstr;ltc tempcr;itures.

Substrate ternpera(urc "C Activation energy eV

30 0.3 1

75 0.29
100 0.28

150 0.27

200 0.25

250 0.25

Vidadi et al [40] have observed that at relatively high temperatures (T > 310

K) the temperature dependence of conductivity in Bi203 is exponential. At these

Leniperatures a thermal activation of charge carriers outside the penetration

threshold takes place. At low temperatures (T < 310 K) the angular slope of the

curve continuously decreases with decreasing temperature. They have determined

x 1 0 Rlcm.
the pre exponential factor as ~ " = 1 . 2 ~ ~ It is found that the activation
Fig. 5.18 Plot of log ff Vs 1000/T for bismuth oxide
film f o r d i f f e r e n t substrate temperatures.
energy decreases with increase in substrate temperature. It is known that the

conductive disordering structures can have both tails of the energy bands and a

non-zero density of states in the energy gap. Witti the final density of states near the

Fern~ilevel, N(E,),
the localized charge carriers can move in a small energy region,

near EFdue to tunnel transitions activated by phonons. Such a charge transfer is

characterized by activation energy decreasing with decrease of temperature [41].

Agasiev et a1 1421 have studied the effect of structural and impurity defects on

conductivity and measured the activation energy at different annealing temperatures

and obtained the values as 0.59 eV, 0.65 eV and 0.99 eV for annealing

temperatures of 200. 300 and 400°C respectively. A strong annealing temperature

dependence of resistivity and activation energy may be attributed to varying

concentrations of oxygen vacancies or interstitial Bi atoms in Bi,03 films. It should

be [luted that [43] the illumination of Bi203 film in vacuum leads to an increase of

dark conductivity and photosensitivity which can be explained by the effect of loss

of oxygen atoms. With increase in illumination intensity, the activation energy

dt:c~-easesfrom 0.19 - 0.15eV. The activation energy for dark conductivity is

obtained as 0.25 eV. Vidadi et al [40] have obtained the activation energy as 0.6

t?V.

Steam is passed through the experimental chamber and the conductivity of

bismuth oxide thin film with time is measured. As the steam is passed, temperature

of the system rises up to 70°C. Figure 3.19 shows the change in conductivity when
Fig. 3.19 Plot of conductivity Vs time for bismuth
oxide t h i n film at the onset of s t e a m .
 2
steam is passed. lrnrnediately after passing the steam the conductivity increases 10

to 10:' times. Initially, tlhe conductivity increases as we inject the steam into the

system and reaches a saturated value. After the removal of the steam, the

concl~~ctivity
decreases and reaches a steady value. This is shown in figure 3.20.

This steady state value is 3 to 4 times smaller than the saturated value. This property

of bismuth oxide is used in humidity sensors. Suzuoki et a1 [44] reported that Bi203

thin film can be used as humidity sensors. The reproducibility in conductivity and

adhesivity of the films on glass substrates make it a good candidate for the use in

humidity sensors.

3.6 Antimony Oxide

Thin films of antimony oxide are prepared by thermal evaporation as

described in chapter 2 (section 2.7). Spectroscopically pure Sb2O3powder (99.99%

of purity) is used as the source rnaterial. The films are evaporated from a

molybdenum boat in a Hind Hivac coating unit. Glass slides have been used as the

substrates. The rate of evaporation is 10-20 nm/min. The thickness of the films is

monitored by quartz crystal thickness monitor. The thickness is counter checked by

ihe ~riultiplebearn interference technique. The electrical conductivity is measured

u s i ~ ~Lhe
g Keithley electro~rleter (Model No.617) in the conductivity cell and is

~)erfo~.med
in vacuum and in air.

Figure 3.21 shows the conductivity Vs ambient pressure for Sb2O3 thin film
deposited at room temperature. The conductivity is found to increase with increase
Fig. 3.20 Plot of conductivity Vs time for bismuth
oxide t h i n f i l m a f t e r t h e r e m o v a l of s t e a m .
 3,(JL, . ~ ~~ ~ . . ~ - ~
---~-
-
-

.
-

E -
-
\
rj ?.on -
1.

t .
-
.
>\
.
-w
- -
>
.*
- -
-
0 -
3 -
7
0
I .oo -
.
-
0 -
-
-
-
-
-

-
0.00 - - - r r m r r l ~mml~ 1 11111111 1 1 llllnl Tmlllll l mml
0.00001 0.1 1000
A m b i e n t Pressure ( m b a r )

Fig. 3.21 Plot of conductivity Vs ambient pressure

f o r antimony oxide t h ~ nfilm.
In ariibient pressure. Figure 3.22 shows the temperature dependence of dc electrical
contluctivity of antirr~ony oxide film of thickness 280 nm deposited at room
temperature. The electrical conductivity in air is greater than that in vacuum. The
conductivity at 50°C is 1.2 times that in vacuum and the corresponding increase at
270°C is four fold for a film thickness of 280 nm. In the case of a film of thickness
230 nm, the conductivity values in air is 2.9 times that in vacuum. The plot of log a

Vs lOOO/T is given in figure 3.23 for films having different thicknesses. From the
slope of the graph,the activation energy is calculated using the equation (3.9).The
activation energy for different film thicknesses for antimony oxide is given in table
3.4. It is found that the activation energy decreases with decrease in thickness.
Stearn is passed through the chamber and the conductivity of Sb203 film is noted
tI11r11igand after passing the stea~n.The response of the film with time is given in
figures 3.24 and 3.25 respectively.

'l';lhlc 3.4 Variatio~iof activation energy with thickness for antimony oxide thin l'il~n.

'Thickness nnl. Activation energy eV

280 0.10

230 0.07

200 0.07
150 0.06

Badawy [45] observed that the specific conductivity of antimony oxide film is

independent of thickness of the films. He had obtained the conductivity value as 2.5

x l~l"!d/cm. Samples prepared at higher temperatures show n type conductivity. It

Fig. 3.22 Plot of conductivit Vs 1000/T f o r antimony
Y
oxide thin film deposi ed a t room t e m p e r a t u r e .
Fig. 3.23 Plot of log G- Vs 1000/T for antimony oxide
thin f i l m f o r different thickness.
Fig. 3.24 Plot of conductivity Vs time for antimony
oxide thin film at the onset of steam.
Fig. 3.25 Plot of conductivity Vs time for antimony
oxide thin film after the removal of steam.
is attributed to the high concentration in mobility of charge carriers. Nikam et a1 [46]

I-eporl that films of antimony oxide are semiconducting in nature irrespective of their

thiclo~ess.In their study,the activation energy changes from 0.92 to 1.59 eV when

the filrn thickness decreases frorn 1780 nm to 348 nm.

Cor~clusion

.['lie electrical conductivity study reveales that bismuth thin film exhibitsmetallic

as well as semiconducting property. The activation energy of bismuth film increases

fl-om 4.9 meV to 7.0 meV as the thickness increases from 120 to 600 nm. and it

changes from 14.19 meV to 5.41 meV when the substrate temperature increases

from 75 to 250 "C. The antimony thin film shows a metallic nature. Comparison of

conductivity of bismuth oxide and antimony oxide films in air and vacuum is made.

The conductivity in air is greater than that in vacuum. The activation energy of

Bi,O,, film decreases from 0.31 eV to 0.25 eV when the substrate temperature

changes from 30 to 250 "C and the activation energy of Sb203 film changes from

0.10 lo .06 eV when the thickness of the filrn decreases from 280 to 150 nm. The

response of the electrical conductivity for bismuth oxide and antimony oxide film in

stearn is also noted as a function of time. The use of Bi203 and Sb203as humidity

ser1sot.s is suggested.
Referetlces

1. H.T.Chu, P.N.Henriksen, Jing Jing, Hong Wang, and Xiofeng Xu, Phys. Rev.

B, 45 (1992)11233.

2. J.lH.Mangez, J.P.Issi and J.Heremans, Phys. Rev. 8, 14, (1976)4381.

3. S.V.Bengus, Yu.A.Bogod and P.E.Finkel, Fiz. Nirk. Temp., 16 (1990)1395.

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