CHAPTER 3

LITERATURE REVIEW OF MATERIALS

3.1 Tin Oxide (SnO2)

Tin Oxide (SnO2), being a highly transparent material is the most commonly

chosen Transparent Conducting Oxide (TCO) when compared to other TCOs like Zinc

Oxide (ZnO), Indium Tin Oxide (ITO), Cadmium Stannate (Cd2SnO4), etc. This is due to

the excellent optical and electrical properties of this material like high transmittance, high

conductivity, low reflectance and low sheet resistance (depends on doping). CdTe/CdS

solar cells with a record efficiency of 15.8 %[4] have been fabricated with SnO2 as the

TCO layer. SnO2 can also be used when high temperature processing of CdS and CdTe is

to be followed, because of its stable nature even at high temperatures[16]. SnO2 films can

be deposited by various methods like spray pyrolysis, APCVD, MOCVD, Sputtering, etc.

SnO2 is a wide bandgap semiconductor (3.49 eV) with a tetragonal rutile structure[17] as

shown in figure 21. Each tin atom is at the center of six oxygen atoms and each oxygen

atom in turn is surrounded by three tin atoms. The oxygen vacancies present are

responsible for the n-type conductivity of the SnO2 film. The conductivity of the SnO2

films can be further enhanced by appropriate doping. Fluorine has proven to be an

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efficient dopant for SnO2 because of the higher conductivity, optical transmission and

infrared reflection that the fluorine doped SnO2 (SnO2:F) films possess[18].

Figure 21 Tin Oxide (SnO2) Structure[17]

3.1.1 Deposition Techniques for SnO2 Films

Some of the deposition techniques that are being followed for SnO2 film

deposition have been discussed in this section.

3.1.1.1 Atmospheric Pressure Chemical Vapor Deposition

Atmospheric Pressure Chemical Vapor Deposition (APCVD) technique

is very widely used for SnO2 deposition since it offers good control over

the equipment and film properties, can employ lower growth temperatures,

and can be used to deposit large area films continually. A conveyor

furnace maintained at atmospheric pressure was used for the deposition of

the SnO2:F films. A constant temperature zone of 300-1200oC was

maintained in the middle of the furnace where the deposition normally

takes place. SnCl4 was used as the source for tin and oxygen and fluorine

(C2H4F2) were introduced into the chamber as reaction gas and dopant.

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 High purity N2 was used as the carrier gas[19]. Figure 22 shows the XRD

pattern of the SnO2 films deposited by APCVD at various substrate

temperatures, Ts. Curves a to d correspond to the XRD pattern of SnO2:F

films deposited at increasing Ts and curve e corresponds to the XRD

pattern of undoped SnO2 film deposited at the same temperature as c.

Figure 22 XRD Pattern of SnO2 Films by APCVD[5]. Curves a to d = Doped

samples, Curve e = undoped sample. Curve a: Ts = 400oC, Curve b: Ts = 450oC,

Curve c: Ts = 500oC, Curve d: Ts = 550oC, Curve e: Ts = 500oC[19].

The XRD patterns show that SnO2:F films deposited at Ts>400oC were

polycrystalline. Also, the preferred crystalline growth orientations of these films

varied with Ts. When Ts<450oC, films with (110) orientation were obtained, but

when Ts>450oC, films with (200) orientation were obtained. It was also found that

fluorine doping affected the preferred orientation of the films, i.e., when the Ts

was 500oC, the preferred orientation was along the (200) plane whereas the

preferred orientation for the undoped films at the same Ts was along the (211)

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plane. The average total transmittance and diffuse transmittance spectra for these

films were over 90% and 14%[19] as shown in figure 23.

Figure 23 Transmission of SnO2 Films by APCVD[5]. Films a, b, c = Total

Transmittance, Films d, e, f = Diffused Transmittance. Curves a and d: SnO2:F

films; Ts = 550oC, Curves b and e: SnO2:F films; Ts = 450oC, Curves c and f:

SnO2 films; Ts = 400oC[19].

The SnO2:F films deposited by APCVD also had very low resistivities of around

5 x 10-4 cm.

3.1.1.2 Spray Pyrolysis Technique

Spray pyrolysis technique is a simple and scaleable process and has been

adopted to deposit high quality SnO2:F films. An organometallic tin compound

namely Dimethyl Tin Chloride ((CH3)2SnCl2) was used as the tin source and HF +

NH4F compounds were used as the fluorine doping agents for the SnO2 films[20].

The compound to be deposited was heated to about 500-530oC and the vapor

generated was transported using air or oxygen as the carrier gas and was then
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sprayed on to the substrates[20]. Figure 24 shows the XRD spectra of SnO2:F

films deposited at 450-500oC having preferential (110) orientation.

Figure 24 XRD of SnO2:F Films by Spray Pyrolysis Technique[20]

Figure 25 Transmission of SnO2:F Films by Spray Pyrolysis Technique[20]

SnO2:F films deposited by this technique had transmittance of around 85% as

shown in figure 25 in the visible region and resistivities of 4.1 x 10-4 cm.

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3.2 Zinc Oxide (ZnO)

Zinc Oxide (ZnO) film with a large bandgap of about 3.3 eV is one of the most

potential materials for being used as a TCO because of its good electrical and optical

properties, abundance in nature, absence of toxicity[21,22] and the ability to deposit these

films at relatively low temperatures[23]. The oxygen vacancies and/or zinc interstitials

correspond to the n-type conductivity of the ZnO films. The resistivity of these films can

be further lowered by doping them with group III elements like B, Al, Ga or In. Among

all these elements, Al is considered to be a good dopant for opto-electronic applications

like solar cells due to the high transmittance that Al-doped ZnO films exhibit. ZnO has a

hexagonal wurtzite structure as shown in figure 26 with the divalent cation (Zinc) in

tetrahedral coordination with oxygen, and each oxygen in tetrahedral coordination with

four divalent cations (zinc)[24].

Figure 26 ZnO Crystal Structure[24]

ZnO films can be deposited by various methods like sputtering, MOCVD[25],

spray pyrolysis[26], pulsed laser deposition[27] and sol-gel method[28]. Among all these

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techniques, sputtering is the most widely used deposition technique due to better

adhesion of the deposit, higher density of films and the ability to work at low deposition

temperatures. The sputtering targets used in the experiment were high purity ZnO

(99.99%) and Al(OH)3 (99.99%) powders[22]. Six targets (pure ZnO, 2, 4, 6, 8 and 10

wt.% of Al(OH)3 doped ZnO) were prepared to study the properties of films deposited by

each target. The base pressure in the chamber was ~ 3 x 10-6 Torr and the working

pressure was 32 mTorr with high purity (99.99%) Ar as the sputtering ambient. The

substrate to target distance (Dts) was varied from 35-80 mm, the substrate temperature

(Ts) was varied from room temperature to 250oC and a RF power of 150 watts was used.

Figure 27 shows the high resolution XRD pattern obtained for Al-doped ZnO films of

varying thicknesses (75-2330 nm) with (002) preferred orientation in all the films.

Figure 27 XRD of Al-doped ZnO Films of Varying Thicknesses[22]

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Figure 28 shows the resistivity being affected due to (a) Dts, (b) Al(OH)3 content in the

target and (c) substrate temperature, Ts.

Figure 28 Resistivity of Al-doped ZnO Films[22] as a Function of (a) Dts (b) Al(OH)3

Content in Target (c) Ts

We can see from figure 28(a) that the resistivity remains nearly constant when Dts<50

mm. A similar effect is seen in figure 28(b) with respect to the Al(OH)3 content in the

target below and above 6wt.% of Al(OH)3. The reason for the very low resistivities of Al-

doped ZnO films prepared with less than 6%wt.% Al(OH)3 doped ZnO might be due to

the Al doping concentration, oxygen vacancies, Al and Zn concentrations at the

interstitial sites, grain boundaries and ionized impurity scattering[29]. Figure 28(c) shows

the effect of Al(OH)3 content in the target below and above 6wt.% of Al(OH)3 at Ts =

250oC. Figure 29 shows the transmittance of Al-doped ZnO films under different

conditions. From figures 29(a) and 29(b), it is evident that the transmittance decreases as

the deposition time increases and Dts decreases. The decrease in transmittance due to
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increase in thickness was due to the thickness effect, which lead to a decrease in light

scattering losses[22].

Figure 29 Transmittance of Al-doped ZnO Films[22] with (a) Thickness (b) Dts (c)

Al(OH)3 content in target (d) Plot showing the optical bandgap for different Zn

concentrations

The effect of bandgap (Eg) with increase in Al(OH)3 content in the target is shown in

figure 29(d) which shows that as the Al(OH)3 content increases, the absorption edge

shifts to the shorter wavelength region. In other words, Eg widens with increase in Al

content.
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3.3 Zinc Stannate (Zn2SnO4)

Zinc Stannate, Zn2SnO4 (ZTO) is a highly transparent and highly conducting TCO

which may be used as a suitable replacement for Cd2SnO4 (CTO) which has a relatively

lesser conductivity[30]. ZTO is also used a high resistive buffer layer in CdTe/CdS solar

cells resulting in higher currents. ZTO has an inverse cubic spinel structure as shown in

figure 30.

Figure 30 Zn2SnO4 Crystal Structure[17]

A spinel structure can be divided into two types namely normal and inverse spinel

structure. In normal spinel structure, the A cations occupy the tetrahedral sites and the B

cations occupy the octahedral sites. The usual notation for this type of occupancy is

(A)[B2]O4, where ( ) represents the tetrahedral sites and [ ] represents the octahedral sites.

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Sometimes the A cations switch places with one half of the B cations, resulting in a

structure known as the inverse spinel structure which is given by the notation (B)[AB]O4.

In some spinel structures, partial inversion takes place and this can be denoted by a

parameter x, known as the degree of inversion[30]. This can be better understood by the

formula (A1-xBx) [AxB2-x] O4. Here, if x equals zero, it is a normal spinel structure, and if

x equals one, it is an inverse spinel structure.

The ZTO films were deposited by RF magnetron sputtering using a ZTO target.

The chamber was pumped down to a base pressure of 3 x 10-6 to 2 x 10-7 Torr and was

backfilled with ultra high purity (99.993%) oxygen or argon to about 20mTorr. The films

were deposited at 550-650oC at 250 watts RF power[30]. Post deposition anneals in Ar at

600oC were done to increase the crystallanity (amorphous to crystalline) and conductivity

of the ZTO films. The XRD patterns of the as deposited or amorphous ZTO and annealed

ZTO films is as shown in figure 31[31].

Figure 31 XRD of RF Sputtered ZTO Films[31]

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3.4 Cadmium Zinc Telluride (Cd1-xZnxTe)

Cadmium Zinc Telluride, Cd1-xZnxTe (CZT), an alloy of Cadmium Telluride

(CdTe) and Zinc Telluride (ZnTe) is a ternary compound with a tunable bandgap from

1.4 2.26 eV[32,33], which makes it a suitable candidate in the field of optoelectronic

devices. CZT can also be used in gamma ray detectors and electro-optical

modulators[34]. One of the most important applications of CZT film is its use as the top

cell absorber material in a tandem solar cell structure due to its high bandgap[35]. Using

a tandem solar cell structure, we can achieve cell efficiencies of greater than 20%. In a

tandem solar cell structure, a high bandgap material is used as the absorber for the top

cell and a low bandgap material is used as the absorber for the bottom cell. CIS and its

alloys have been reported to be very good candidates for the bottom cell with efficiencies

of 16-18%[36]. CZT and Cadmium Selenide (CdSe) are suitable choices for the top cell

because of their high bandgap.

Top cells with CZT as the absorber layer have yielded efficiencies of ~7%[37].

CZT can be deposited by evaporation, sputtering, closed spaced sublimation, etc. CZT

crystallizes in a zinc blende structure as shown in figure 32, similar to both CdTe and

ZnTe. The transition from CdTe (x = 0) to ZnTe (x = 1) in Cd1-xZnxTe occurs in a single

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 Figure 32 Cd1-xZnxTe Crystal Structure

phase i.e., the structure of CdTe does not change until all the cadmium ions get replaced

by zinc. The concentration of zinc (x) in Cd1-xZnxTe is governed by Vegards law, which

states that the lattice parameter has a linear relationship with the zinc concentration. In

CZT films, the lattice parameter decreases (Table 1) with the increase in the zinc

concentration as shown in figure 33.

Table 1 Lattice Constants for Different Zn Concentrations

Cd1-xZnxTe Lattice Constant(Ao)

CdTe(x=0) 6.481

Cd0.95Zn0.05Te 6.465

Cd0.70Zn0.30Te 6.364

Cd0.50Zn0.50Te 6.287

ZnTe(x=1) 6.102

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 6.5
6.45
6.4

Lattice Constant
6.35
6.3
6.25
6.2
6.15
6.1
6.05
0 0.2 0.4 0.6 0.8 1 1.2
Zn Concentration

Figure 33 Zn Concentration vs. Lattice Constant

By curve fitting the points in figure 33, we get the equation for finding the concentration

of zinc (x) as follows,

a = 6.481 0.3837(x)

Where,

a = Lattice constant (found from XRD data)

In the evaporation process discussed here, two different sources (CdTe and ZnTe) were

co-evaporated[32] to form CZT films. 5N pure CdTe and ZnTe compounds, used as the

evaporation sources were put into two separate crucibles. The two sources were

positioned in such a way so that the substrates placed above were uniformly exposed to

both the sources during deposition. The substrates were kept at 573 K and the chamber

was pumped down to a base pressure of 5 x 10-6 Torr. The deposition rate of CdTe was

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kept at 20 /sec whereas the deposition rate of ZnTe was varied to obtain Cd1-xZnxTe

films of different Zn(x) compositions. The XRD of the films are as shown in figure 34.

Figure 34 XRD of Cd1-xZnxTe Films[32]

The XRD pattern revealed that the films were polycrystalline in nature with preferred

(111) orientation which represents a cubic structure. There were no diffraction peaks

associated with CdTe and ZnTe, which indicated that the CZT films were of single phase.

The optical transmission of CZT films for varying x values is shown in figure 35.

Figure 35 Transmission of Cd1-xZnxTe Films[32]

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High transmission in the longer wavelength region was observed and the absorption edge

was found to shift towards the shorter wavelengths as the Zn content in the films

increased.

Figure 36 Bandgap of Cd1-xZnxTe Films[32]

The bandgap (Eg) of the CZT films with varying Zn concentration was estimated by

calculating (h)2 and plotting it against h as shown in figure 36.

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