Structural Studies On I N D I U M Oxide, Tin Oxideandindium T I N Oxide Thin Films
Structural Studies On I N D I U M Oxide, Tin Oxideandindium T I N Oxide Thin Films
Structural Studies On I N D I U M Oxide, Tin Oxideandindium T I N Oxide Thin Films
STRUCTURAL STUDIES ON INDIUM OXIDE, T I N OXIDE AND INDIUM T I N OXIDE THIN FILMS
5.1
Introduction
The applications of indiun oxide, tin oxide and indium tin oxide have
size are important parameters for high sensitivity and rapid response. In this chapter the structural properties of indium oxide, tin oxide and indium tin oxide films are dealt with. It is known that indium oxide crystallizes in two different structures as body centered cubic and hexagonal. The body centered cubic structure is a bixbyite Mn203type, also called C-type rare earth oxide structure. The i.e., 80 atoms, resulting in a rather unit cell consists of 16 mol~?cules, complex structure. This phase is obtained at a low or normal pressure. The hexagonal type is a high-pressure type phase obtained at 68 Kbar and at a temperature 8 0 0 - l f i 0 0 ~ ~The . structure is of the corundum, or
CCAl203
There are two crystallographically non-equivalent indium atoms but only one type of oxygen atom. The indium is six-fold coordinated and oxygen is four-fold coordinated. The oxygen atoms around In (1) are equidistant (In-0 = 0.218 nm) and lie nearly at the comers of a cube with two body diagonally opposite corners unoccupied. In (2) is also surrounded by six oxygen atoms nearly at the corners of the cube, but with two face-diagonally opposite corners unoccupied. In this polyhedron the six In-0 distances have, three different values: 0.213nm, 0.219 nm and 0.223 nm.
Tin oxide (Sn02) single crystal has tetragonal rutile structure with space group
~ ' ~ (P42/mnm). ~ t , It
formula units per unit cell. The unit cell contains six atoms, two tin and four oxygen. The coordination is 6:3. The oxygen atoms are placed approximately at the corners of a regular octahedron, and tin atoms are The lattice located approximately at the colFnersof an equilateral triang~e.~ parameters are a0 = 0.473 nm and co= 0.3186 nm. The structure of I T 0 is essentially tin doped indium oxide, which is known to crystallize in body centered cubic and hexagonal structures. When small amount of tin is added to indium oxide all the tin atoms enter substitutionally in the cation sub lattice. The tin doping has been observed to induce a change in the lattice constant. Some authors
6-8
obtained 'a' higher than 'a6 of undoped indium oxide, which may suggest
. substitutionally or at the incorporation of larger ~ n ions " at either In3+ s~te
interstitial positions. Agnihotri et a/..' observed a reduction of the lattice constant with increase in tin concentration in IT0 films. Such a lattice contraction indicates the replacement of ln3+ ion by sn4' ions that are smaller. Mossbauer results
"'
observed a
change in preferred orientation between (222) and (400) planes when deposition rate is increased.
5 . 2
Indium Oxide
Indium oxide thin films have been prepared using the vacuum
coating unit and a tantalum boat as described in Chapter 4 (Section 4.4). The samples are prepared in an oxygen partial pressure of 3x10'~ mbar at substrate temperatures 125, .75, 200 and 225OC. The thickness of the films are 500nm each. XRD spectrum of these samples are recorded using X-ray diffractometer (Philips - PW 3710) as described in chapter 2 (section 2.23). The radiation used is CuKa and the operating potential is 25KV and current 10mA. The scanning rate is 1/minute. Fig 5.1 to 5.4 gives the XRD pattern of the indium oxide thin films deposited at 125O~, 175OC, 2 0 0 ' ~ and 2 2 5 ' ~ and annealed for 30 minutes at 250'~. At 175'C, the peak obtained at 20 = 30.5' is examined and identified as the reflection from (222) plane of indium oxide using ASTM (American Society fcr Testing Materials) data card. The other peaks are identified and are given in Table 5.1.
Fig. 5.1 XRD pattern of indiurnoxide thin film deposited at substrate temperature 125'~.
LR -t
Fig. 5.2 XRD pattern of indium oxide thin film deposited at substrate temperature 175'~.
28 ,
Fig. 5.3
Fig. 5.4 XRD pattern of indiurn oxide thin film deposited at a substrate temperature 225OC.
Table 5.1 The calculated values of d and the ASTM standard values and annealed of d for indium oxide film deposited at 1 7 5 ' ~ at 2 5 0 ' ~ for 30 minutes
C:alculated (nm)
12.92 100 23.7 6.0 29.5 4.12 2.92 2.53 1.98 1.79
ASTM (nm)
4.13 2.921 2.529 1.984 1.788
ulo
14 100 30 0 35
hkl
21.5 30.5
35.46
45.7 50.98
The grain size of the films are determined from the Full Width at Half Maximum (FWHM) intensity of the X-ray peaks using Scherrer's formu~a.'~
1 6 ~ =
angle 28 at half maximum intensity and b is the effect of the instrument as determined from the broadening of the monocrystalline silicon diffraction line. The values of the grain :size are given in Table 5.2.
Table 5.2
The grain size of Indium oxide thin films deposited at various substrate temperatures Grain size (nm)
+ r
The grain size is found to increase with increase in substrate temperature. Goswami and 3oswami
l3 and
Burns
l4
vacuum evaporated indium oxide films may dissociate to species like InO, In or 02. As observed, a preferential orientation (222) for indium oxide has been obtained by Sundaram ttnd Bhagavat l5 and Weng et a1.I6 It is also reported that the preferred olentation depends on film thickness17 and deposition conditions. 18
5.3
Tin Oxide Thin films of tin oxidct have been prepared using the thermal
evaporation technique. The procedure for the preparation is described in Chapter 4 (Section 4.5). Thickness of the sample is 500 nm each. XRD spectra of the samples have heen recorded using the Philips (PW -3710) X-ray diffractometer.
Figures 5.5 to 5.8 show the X- ray diffraction pattern of tin oxide ~ an ~ oxygen partial pressure of 1x10.~ mbar and films deposited at 1 0 0 in annealed in air at temperatures 200c, 225'~, 250% and 275OC respectively for 30 minutes. When annealed, prominent peak is observed at 28 = 44.82' for annealing temperature of 200% and 225Oc, which corresponds to reflection from (211) plane. For samples annealed at which
corresponds to reflection from (200) plane. The values of the grain size are evaluated using Scherrer's formula and are given in Table 5.3.
Table 5.3 The grain size of tin oxide thin films deposited at 1 0 0 in ~~ an oxygen partial pressure of lo4 mbar and annealed at various temperatures Annealing temperature (OC) Grain size (nm)
In tin oxide thin films crystallization to stoichiometric Sn02 from amorphous phase takes place through Sn203 or Sn304 state. Films of lower substrate temperature easily crystallize to Sn02 phase. 19 Yamazaki from Rutherford back scattering studies reports the
20
decrease in the value of x in SnO, as substrate temperature is increased. So at lower substrate temperature the sample has an initial higher value
Fig. 5.5 XRD pattern of tin oxide thin film annealed at 200'~ for 30 minutes.
F;
.: g n
20
30
40
50
60
20 -f
Fig.5.6 XRD pattern of tin oxide thin film annealed at 225'~ for 30 minutes.
Fig.5.7 XRD pattern of tin oxide thin film annealed at 2 5 0 ' ~for 30 minutes.
Fig. 5.8
of x, which takes the crystalline structure of Sn02 more easily, on at a high substrate temperature. annealing, than does a film dept~sited The composition of the reactively evaporated films are between stoichiometric SnOx and SnO:, where x ranges from 1.25 to 1.57 and corresponds to intermediate oxide Sn304with x = 1.33.2' The structure of amorphous SnO films can be assumed to consist of slightly distorted, corner connected oxygen octahedral having central sn4' ions and strained octahedra. These strained octahedra possess sn2' ions and oxygen vacancies. The presence of diqerent oxidation states is mainly influenced by the production procedure and post-deposition annealing conditions.
5.4
evaporating different alloys of indium and tin (Indium: Tin = 80: 20, 85: 15, 90: 10 and 95: 5 by weight percentage) from a tantalum boat in a vacuum coating unit. The method of making alloy is described in chapter 3 section 3.5.The deposition conditions are also described in section 3.5 .The films are prepared at a substrate temperature of 2 0 0 ' ~ in an oxygen atmosphere with various tin concentrations. The thickness of the films are 500 nm each. X ray spectra are recorded using the X ray diffractometer (Philips- PW3710). The radiation used is Cu Ka and the operating potential is 25 kV at 10 mA.
Fig. 5.9 to 5.13 show the XRD spectra of the films deposited at substrate temperature 200% alid annealed at 3 0 0 ' ~for 30 minutes and having tin concentrations of O'/O, 574, lo%, 15% and 20% respectively. The most prominent peak i!; found to be at 28 = 30.54', which
corresponds to reflection from 1222)plane. The other peaks are identified and are given in figure 5.10. The grain sizes of the samples are determined. The grain size is found to decrease with increase in concentration of tin. The values are given in Table 5.4. The present results are in good agreement with the observations of Mizuhashi. 22
Table 5.4 Grain size of IT0 thin films with various tin concentrations Tin concentration (%)
The d values of the indium tin oxide thin film deposited with 5% tin concentration are calculated and are given in Table 5.5.
Fig. 5.9 XRD pattern of indium oxide thin film deposited at 200'~
Fig.5.10 XRD pattern of IT0 thin film with 5% tin concentration deposited at 200C
Fig.5.11
XRD pattern of 1 1 . 0thin film with 10% tin concentration deposited at 200C
--._ I
,..
. .U a . . . . , . .. .. B
20 +
Fig. 5.12 XRD pattern of I T 0 rhin film with 15% tin concentration deposited at 200%
5.13
XRD pattern of I T 0 thin film with 20% tin concentration deposited at 200C
Table 5.5 The calculated d values for Ts = 2 0 0 ' ~along with the standard d values from ASTM data for I T 0 thin film with 5% tin concentration
Calculated
ASTM
1.789
It is found that the c;ilculated values agree well with the ASTM
data. The film exhibits the reflection from the (222) planes as the most predominant peak in the X- ray diffraction pattern. None of the spectra indicated any characteristic peaks of Sn, SnO or Sn02, which indicates that the tin atoms are doped substitutionally into the indium oxide lattice. For all the three materials, the peaks obtained in the diffraction spectra are sharp indicating (he highly crystalline nature of the films. Studies on the grain size on indium oxide thin films show that the grain size increases with increase in substrate temperature. Grain size of tin oxide thin films increases with increase in annealing temperature. Grain size of I T 0 thin films is found to decrease with increase in tin concentration.
References
1.
2.
3.
G. Sberveglieri, P. Bcinussi, S. Groppelli and P. Nelli, Thin Solid Films, 186 (1990) 349
4.
Landolt, Bornstein, Numerical Data and Functional Relationships in Science and Technology, New Series (Springer, Verlag 11117 bl.
64, 1975).
5.
12. F. Iwatsu, T. Kobayashi and N. Uyea, J. Phys. Chem., 83 (1980) 3223. 13. A. Goswami and A. P. Goswami, Pramana, 8 (1977) 335. 14. R. P. Burns, J. Chem. Phys., 44 (1966) 3307. 15. K. 8. Sundaram and G. K. Bhagavat, Phy. Stat. Sol., 63 (1981)
K15.
16. S. Weng,
4 (1992) 1428. 17. S. Mirzapour, S. M. Rozati, M. G. Takwale, B. R. Marathe, V. G. Bhide, Mater. Res. Bull., 27 (1992) 1133. 18. S. Naseem, I. A. Rauf, K. Hussain, N. A. Malik, Thin Solid Films, 126 (1988) 161. 19. M. H. M. Reddy, S. R. Jawalekar and A. N. Chandorkar, Thin Solid Films, 169 (1989) 117. 20. T. Yamazaki, U. Mi2:utani and Y. Iwama, Jpn. J. Appl. Phys., 21 (1982) 440. 21. H. G. Newman, P. Zeggel and K. Melzer, J. Non-Cryst Solids, 108 (1989) 128. 22. M. Mizuhashi, Thin Solid Films, 76 (1981) 97.