INFLUENCE OF THE DEPOSITION PARAMETERS ON THE

ELECTRICAL AND MECHANICAL PROPERTIES OF PHYSICALLY

VAPOR-DEPOSITED IRIDIUM AND RHODIUM THIN FILMS

Ilan Golecki* and Margaret Eagan

Honeywell International, Inc. (formerly AlliedSignal, Inc.), Research and Technology, 101
Columbia Road, Morristown, NJ 07962.
*Phone (973) 455-4938; Fax (973) 455-4339 or -3008; e-maih Ilan. Golecki@alliedsignal.com

ABSTRACT

Iridium and rhodium thin films have been formed by e-gun physical vapor deposition on
thin-chromium-coated, thermally-oxidized, silicon substrates. Cr, hr and Rh deposition rates
and substrate temperature during deposition were measured and controlled. The effects of the
latter deposition parameters on the sheet resistance and stress of the Ir and Rh films are
presented and it is demonstrated that both stress and sheet resistance can be desirably
minimized by proper choice of the process conditions. The resistivity of these Rh and Ir thin
films has been measured at room temperature. Rh can be formed in a wider process window
than Ir. Rh films with Rsh = 0.1 Q/square have been obtained at a thickness of 0.6 ltm.

INTRODUCTION AND MOTIVATION

Iridium and rhodium are attractive candidates for use in electronic metallizations. These
refractory elements crystallize in the face-centered cubic lattice, are chemically inert, possess
relatively high intrinsic electrical conductivities, high values of Young's moduli and tensile
strengths and acceptable thermal expansion coefficients. Selected room-temperature physical
constants and melting points for Ir, Rh and Au are given in Table I; gold is a well established
electronic metallization material. Actual values of these properties, especially in thin films,
depend on the microstructure and purity levels, which are functions of the processing method
and conditions. Thus, we have undertaken a systematic study of the relevant physical properties
of lr and Rh thin films and their dependencies on the process conditions.

Table I. Bulk physical properties f gold, rhodium and iridium.

Metal Resistivity Thermal Melting Density Young's Tensile strength
(pohm.cm) expansion temperature (g/cm3 ) modulus (MPa)
coefficient (CC) (GPa)
(ppm/ 0C)
Au 2.2 14.1 1063 19.3 78 130-220
Rh 4.7 10.3 1966 12.4 379 690-2070
Ir 5.1 7.9 2454 22.5 528 550-1100

EXPERIMENTAL CONDITIONS

In this study', Ir and Rh thin films have been deposited in high vacuum on thin-chromium-
coated (0.01-0.03 im Cr), thermally-oxidized (-0.5 Pmn SiO2 ), four-inch diameter, (100)
oriented, single-crystalline silicon substrates by means of electron-gun physical vapor
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 deposition. The thermal oxide was present on both front and back of each substrate. The
baseline chamber pressure was in the low 10-7 Torr range. The substrates were mounted face
down on a planetary having both axial and azimuthal rotations; i.e. each substrate rotated around
its own axis as well as around the chamber axis (the latter at several rpm). The rotating
substrates were heated during deposition with quartz halogen lamps. The substrate temperature
was measured and controlled by means of a stationary thermocouple placed in close proximity to
the substrates and verified to be within +/- 15TC of the indicated value using sets of thermal
liquid dots placed on the back of one substrate per deposition run. The thin-film deposition rates
and thicknesses were measured and controlled during deposition using a quartz crystal monitor
calibrated for each metal. Film thicknesses were measured post-deposition by means of stylus
profilometry on steps created intentionally on the wafers. The electrical sheet resistance of the
metal films was measured and mapped across each wafer using a high-sensitivity, commercial
four-point probe. The data given here were multi-point averages. The general relationship
between sheet resistance, Rsh and resistivity, p is given by equation (1):

Rsh (Q/square) = p (Q.cm)/t (cm) (1)

where t is the film thickness. In the present case, the Cr and Rh (or Cr and Ir) films are
electrically connected in parallel. Since the thickness of the Cr film is 10-60 times less than that
of either Ir or Rh film and the Cr resistivity was measured to be much higher than the resistivity
of Ir or Rh, this type of measurement provides an accurate representation of the resistivity of the
much thicker, top Ir or Rh film. Sheet conductance is thd inverse of sheet resistance and is
measured in Siemens.square (1 Siemens = 1 /0).
The biaxial stresses of the metal films were measured using a commercial, non-contact,
optical curvature-measuring instrument. The substrate curvatures, R were acquired along two
directions, parallel and perpendicular to the major flat. Measurements were performed at room
temperature prior to metal deposition on the oxidized Si substrates and then again after
deposition. Using Stoney's equation, equation (2), the stress, cr is calculated from the known
elastic constants of the (100) Si substrate and the measured substrate and film thicknesses:

a = (1/6)(E/I - v)(ts2/tt)(Rf-l' - R,-') (2)

In equation (2), E = 130 GPa and v = 0.27 are the Young's modulus and Poisson's ratio of the Si
substrate, and the subscripts 's' and 'f denote substrate and film, respectively. The data given
here are averages of the two measurements (at 0 and 90' from the major flat) for each substrate.

RESULTS

Both Ir and Rh films were obtained which exhibited desirable resistivities, thermal stabilities
and good bondability to gold wires. These thin films were structurally polycrystalline as
measured by X-ray diffraction. 4500 A thick Ir films having sheet resistances of 0.17-0.18
Q/square and tensile stresses of 316-372 MPa were deposited at 350TC and 1.2 A/s. No
interdiffusion between the Ir and the underlying Cr was detected by Rutherford backscattering
spectrometry after a 1 h, 400 0C annealing in air. The variation of the electrical sheet
conductance with Ir and Rh film thickness, is depicted in Figure 1. The resistivities were
obtained from the slopes of the straight lines. Within the thickness range where the

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 measurements fall on the straight line, the data indicate that in terms of scattering mechanisms of
the charge carriers, the nature of these films is not changing as a function of thickness; i.e. the
microstructure and purity level are not dependent on film thickness to first order and the films
are not microcracking or delaminating. For Rh, the data between 3000 and 9000 A thickness fall
on the straight line, while for Ir, the data between 1500 and 4500 A thickness fall on the straight
line. The point at 5200 A for Ir deviates somewhat from the straight line. Ir films having
thicknesses of 6000 and 9000 A tended to microcrack due to the high as-deposited tensile stress;
these films were deposited at 3500 and 300 0C, at deposition rates of 4 and 1.5 A/s, respectively,
and had sheet resistances of 0.26 and 0.24 C/square and stresses of 2460 and 1220 MPa. The
measured sheet resistances of Ir films in the 6000-9000 A range were higher than predicted, due
to the microcracks (probe separation of the four-point probe was 1 mm).
The ratio between the measured Ir and Rh thin-film resistivities is equal to the ratio for the
bulk materials given in Table I, within experimental error. The absolute values of these
measured Ir and Rh thin-film resistivities are higher than the reported bulk values by 26-30%.

'h16
S14
S12 p(Rh) =5.9 pQacm -a

8
6

2 4 -/ p(Ir) =6.6 gO.cmn

0 2000 4000 6000 8000 10000

Rhodium or Iridium thickness (A)

Figure 1. Inverse sheet resistance vs. Rh and Ir film thickness, for films deposited at 1 A.s
and 3500C on 100 A Cr-coated, oxidized Si substrates.

Figure 2 depicts the dependence of Rh film stress and sheet resistance on deposition rate. At
constant thickness (6000 A), both sheet resistance and stress showed only weak dependencies on
deposition rate from 1 through 9 A/s, at substrate temperatures of 270 and 350TC. This has
important practical implications. The Rh films deposited at 270'C, however, had much lower
tensile stress and slightly higher sheet resistance, compared to the films deposited at 350TC.
Figure 3 shows the dependence of Rh thin-film stress and sheet resistance on the substrate
temperature during deposition, for 6000 A thick Rh films deposited at 1 A/s. The sheet
resistance decreased monotonically from nominally room temperature (practically 130-150'C) to
350TC. Above -220'C the sheet resistance varied only slightly with temperature. The behavior
of stress vs. temperature was more complex. The tensile stress in these Rh films exhibited a
maximum at -170 0C and a minimum at -270 0 C. The existence of the latter feature is explained
semi-quantitatively in the next section. When the temperature axis is transformed into the
dimensionless reduced temperature 0 = Ts(K)/Tm(K), where the subscripts 's' and 'in' denote
substrate and melting, the temperature at minimum film stress corresponds to 0 = 0.24.

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 0.5
1000
0.4w
800 3500C
0.3
M, 600
0
270 C
400 0.2
2700 C
200 350 0 C 0.1
, i I I , I
0 0.0~
0 2 4 6 8 10
Rhodium deposition rate (A/ s)

Figure 2. Dependence on Rh deposition rate of stress (squares) and sheet resistance

(circles) of 6000 A thick Rh thin films deposited at 270 and 3500 C on 100 A Cr-coated,
oxidized Si substrates.

1400
Rhodium
0.5 Z
.1200 0.4 '

S1000
" 800 *0 D 0.3
3 * C.)
S600 a [] 0.2 W
w 400 I,3,
0.1
- 200
(1A d
0 3.4
50 100 150 200 250 300 350 400 z
Deposition temperature (0 C)
Figure 3. Variation with substrate temperature of stress (squares) and sheet resistance
(circles) of 6000 A thick Rh films deposited at 1 A/s on 100 A Cr-coated, oxidized Si
substrates.

DISCUSSION

The overall stress in polycrystalline thin films is due to two separate contributions: (a)
internal or intrinsic stress and (b) thermal-expansion-mismatch induced stress. The dependence
of these two contributions on deposition temperature is shown schematically in Figure 4 2. The
intrinsic stress is due to the fact that at relatively low temperatures, the atoms or larger moieties

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 arriving at the substrate surface have too low surface diffusivities and therefore are "quenched"
at less than optimal positions on the surface. As larger microstructures such as islands or grains
are formed, they are mutually misaligned and push against one another, resulting in generally
tensile stress in the film. As the deposition temperature increases, the surface diffusivities
increase and the internal contribution to stress goes down.

STotal

Deposition Temperature

Figure 4. Qualitative variation of intrinsic and thermal stresses in an evaporated thin

film on a substrate with substrate temperature during deposition [After Figure 156 in
Ref. 2]. For the thermal mismatch component, the film is assumed to have a higher
thermal expansion coefficient than the substrate.

The thermal-mismatch stress, on the other hand, increases with increasing deposition
temperature for the present case, in which the film has a higher thermal expansion coefficient
than the substrate. The calculated thermal-mismatch stresses vs. deposition temperature for Rh
and Ir deposited on Si are shown in Figure 5. In these calculations, the thermal expansion data
for Rh, Ir and Si were taken from the literature3 4 and the bulk elastic constants (Table I) were
assumed for Ir and Rh. The presence of the thin Cr layer and the thicker thermal SiO 2 layers
were ignored in these calculations. The calculated values agree semi-quantitatively with the
measured stresses at the higher temperature ranges. This approach can be used to estimate the
dependence of intrinsic stress vs. deposition temperature from the measured total stress and the
calculated thermal stress.

.~1000

~500

.~n0

0 100 200 300

Teq M
(wle

Figure 5. Calculated thermal stresses vs. deposition temperature in rhodium (squares)

and iridium (triangles) thin films deposited on (100) silicon substrates.

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 It is thus surmised that the observed overall behavior of the stress shown in Figure 3 is due to
changes in the microstructure of the deposited Rh films with substrate temperature. Preliminary
texture measurements performed by X-ray diffraction indicate that the highest stress films,
which were deposited at lower temperatures, have less preferred orientation than the films with
the lowest stresses. However, changes in the grain morphology 5-6 which may not necessarily
impact the crystalline texture in a measurable manner may also account for the differences in the
stress. Limited characterization by means of scanning electron microscopy indicates that the Ir
and Rh films examined had a columnar structure. A transition from a porous to a columnar
microstructure occurring at 0 = 0.3 was predicted in several models for deposited thin films 56 ,
although those models were based on much thicker films of different materials than studied in
the present work.
The monotonic decrease of the sheet resistance with increasing deposition temperature seen
for Rh films in Figure 3 can be understood qualitatively in terms of reduced scattering of the
charge carriers at grain boundaries or other microstructural irregularities. Increasing the
deposition temperature would result in higher atom mobility on the substrate surface and less
defective microstructure. Additional analytical characterization is needed to elucidate these
behaviors in greater quantitative detail.

SUMMARY

Iridium and rhodium thin films were deposited on oxidized silicon substrates by electron-gun
physical evaporation. Very good adhesion was obtained using a thin chromium adhesion layer.
Low sheet resistances were measured for both iridium and rhodium films for film thicknesses
below 1 tm. Good bondability to gold wires was demonstrated. Rh film deposition exhibited a
wider process window than Ir deposition under the same conditions. Rh films remained intact
and their resistivity was independent of thickness to at least a thickness of 9000 A. Both Ir and
Rh were thermally stable in air to at least 4000 C. Deposition conditions for minimizing the
measured stress and sheet resistance in such electrically conducting films were described.

REFERENCES

1. Ilan Golecki and Margaret Eagan, Abstract # A6.33, Symp. on Polycrystalline Thin Films -
Processing-Structure-PropertyRelationships, 1998 Fall Meeting of the Mater. Res. Soc.,
Dec. 1998, Boston, MA.
2. Ludmila Eckertova, Physics of Thin Films (Plenum Press: New York/ SNTL: Prague,
1986), Ch. 6.
3. Y.S. Touloukian, R.K. Kirby, R.E. Taylor and P.D. Desai, Thermal Expansion, Metallic
Elements and Alloys, Thermophysical Properties of Matter 12 (IFIIPlenum: New York,
1975).
4. Y.S. Touloukian, R.K. Kirby, R.E. Taylor and T.Y.R. Lee, Thermal Expansion, Nonmetallic
Solids, ThermophysicalPropertiesof Matter 13 (IFI/Plenum: New York, 1977).
5. B.A. Movchan and A.V. Demchishin, Fiz. Metal. Metalloved. 28 (4) 653 (1969).
6. John A. Thornton, Ann. Rev. Mater. Sci., 7, 239 (1977).

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