Electrical characteristics of TiN contacts to N silicon

M. Wittmer, B. Studer, and H. Melchior

Citation: Journal of Applied Physics 52, 5722 (1981); doi: 10.1063/1.329512
View online: http://dx.doi.org/10.1063/1.329512
View Table of Contents: http://scitation.aip.org/content/aip/journal/jap/52/9?ver=pdfcov
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Electrical characteristics of TiN contacts to N silicon

M. Wittmer
Brown Boveri Research Center, 5405 Baden-Da'ttwil, Switzerland

B. Studer and H. Melchior

Swiss Federal Institute a/Technology, 8049 Ziirich, Switzerland

(Received 19 February 1981; accepted for publication 15 May 1981)

We have performed a detailed investigation of TiN contacts on n-type silicon. The barrier height
was found to be 0.49 0.01 V and the contact resistivity on 0.001-11 cm substrates below 10- 4
2
11 cm . The TiN layers were produced by reactive sputtering. The resistivity of the layers depends
on the partial pressureofN2 in the N2 + Arsputtering gas mixture. A minimum of 55 J.l11 cm was
obtained, which is below the resistivity of pure Ti films. Finally, we have developed two etching
solutions which allow patterning of TiN layers using conventional photolithography techniques.
PACS numbers: 73.40.Ns, 73.40.Cg, 73.60.Dt, 8l.l5.Cd
INTRODUCTION

EXPERIMENTAL

The use of transition-metal mononitrides as diffusion

barriers in metallization schemes to silicon semiconductor
devices has recently received great attention. 1-4 Excellent
metallurgical stability of contact metallization is achieved
with such diffusion barrier layers during subsequent thermal
treatments up to 600 0c. TiN is the most attractive compound among the various mononitrides, since it has one of
the lowest electrical resistivities of the transition-metal
mononitrides. 5
Contact metallizations incorporating a diffusion barrier are multilayer structures consisting of at least three layers: a silicide layer providing uniform contact to silicon, a
diffusion barrier, and a top layer for bonding and low-resistivity interconnection. In general, different materials are
used for each of the three layers, complicating the fabrication of such contact structures. For mass production of contact metallizations it is advantageous to reduce the number
ofIayers by omitting the silicide layer and using the diffusion
barrier simultaneously as contact to silicon.
In a three-layer metallization, where the bottom metal
layer is reacted with the Si to form a silicide contact, a Si
layer usually 500 A thick is consumed for silicide formation.
Though the silicide formation creates a new metal-semiconductor interface beneath the original Si surface, which is advantageous for obtaining good contact performance, the
consumption of such an amount of Si is intolerable for the
formation of contacts to shallow junction bipolar devices. In
these cases, a two-layer contact metallization consisting of a
TiN contact layer and a low-resistivity top metal layer is a
very attractive concept.
The feasibility of this concept, however, depends on the
electrical characteristics of TiN contacts to Si. First results
of sputtered TiN contacts on solar-cell-type Si 6 are very
promising. We have therefore performed a detailed analysis
of the electrical resistivity of sputtered TiN films, of the barrier height of TiN on n-type Si and of the contact resistivity
of TiN films on n-type Si of various doping levels. The results
are presented together with the description of two types of
etching solutions which can be used for patterning of TiN
films on Si or Si02 with conventional photolithography
techniques.

Commercially available single-crystal Si wafers of (100)

orientation and resistivities in the range of 0.001 to 10011 cm
were used throughout this work. The. wafers were n-type
doped and Syton polished on one side. Prior to loading in a
sputtering system the wafers were dipped in dilute HF to
remove the native oxide layer on Si. TiN films of 2000- and
3ooo-A thickness were reactively sputtered with a triode
sputtering system in a mixed N2-Ar atmosphere. The sputtering gases were of the highest available purity (99.999%).
Before sputter deposition the system was thoroughly flushed
with the N2 and Ar gases and then pumped down to a final
pressure of 2 X 10 - 7 Torr. The temperature of the wafers
during sputtering was below 150C.
The composition of the TiN films was monitored by
analyzing as-sputtered layers on a vitreous carbon substrate
with Rutherford backscattering (RBS) and x-ray diffraction.
The TiN films were homogeneous in composition, and a possible oxygen contamination was below the detection limit of
RBS (0.1 %). The thickness of the sputtered TiN films was
measured with RBS and evaluated assuming bulk values for
the stopping cross sections.
The electrical characteristics of TiN contacts were measured with a Keithley current source and a Hewlett-Packard digital voltmeter. Four-point probe measurements were
used to investigate the resistivity of sputtered TiN layers and
the contact resistivity of TiN on Si was measured with two
different techniques as described below. Separate probes
were used for current feeding and voltage sensing. Barrier
height measurements of TiN on Si were performed on
Schottky diodes surrounded by a field-effect guard ring.
Conventional lithography and processing was used to fabricate the diodes on Si0 2-covered Si wafers. The diode characteristics were measured with a Tektronix curve tracer or a
ramp generator and a plotter driven by a Keithley
electrometer.

5722

J. Appl. Phys. 52(9), September 1981

RESULTS AND DISCUSSION

A. Electrical resistivity of sputtered TiN films

A series of TiN films were reactively sputtered onto

Baltragon miscroscope slides in different mixtures ofN 2 and

0021-8979/81/095722-05$01.10

1981 American Institute of Physics

5722

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300

E<J
c::::l.

-200

>-

l-

S;
~
Vl

Vi
W
cr

100
000

10

10 ]

10'

PARTIAL PRESSURE OF N2

!Torrl

FIG. I. Dependence of the resistivity of reactively sputtered TiN films on

N2 partial pressure of the N 2 + Ar sputtering gas mixture. The resistivity of
a sputtered layer of pure Ti is indicated by the arrow on the left-hand side of
the diagram. The chemical composition of the films, as found with x-ray
analysis, is indicated in the diagram.

Ar. The total sputtering pressure was kept constant at

1 X 10- 3 Torr and the N2-Ar mixed atmosphere was varied
by changing the partial pressure ofN 2 and Ar, respectively.
The input rfpower was 1 kW. The electrical resistivity of the
TiN films, as found with four-point probe measurements, is
shown in Fig. 1 as a function of the partical pressure ofN 2. A
pronounced minimum in resistivity is found in Fig. 1 at a N2
partial pressure of 6 X 10- 5 Torr. The resistivity increases
for higher and lower partial pressures ofN 2 and reaches a
maximum at the lower end of the pressure scale around
2 X 10- 5 Torr. Below this partial pressure the resistivity
drops again and approaches the value for pure Ti, which is
indicated by the arrow marked "Ti" on the left hand side of
the diagram.
A similar behavior of the electrical resistivity of reactively sputtered TiN films on partial pressure ofN 2 has been
reported by Gerstenberg. 7 He found a maximum in resistivity at a N2 partial pressure of 3 X 10- 5 Torr but no minimum. The missing minimum and the much higher values of
the resistivity of his films may be a result of oxygen
contamination.
The minimum film resistivity of 55 /-til cm in Fig. 1 is
lower than the resistivity of 65 /-til cm for the pure Ti film.
This fact agrees with the observation made by Nelson 8 that
many of the transition-metal mononitrides and borides have
a specific electrical resistivity which is lower than the one of
the pure metal. Electrical resistivities of about 50/-til cm
have also been measured by Maenpaa et al. 6 for TiN films
reactively sputtered with a diode system in an atmosphere of
20% N2 and 80% Ar at a total pressure of 8 X 10- 3 Torr.
For the remainder of this work we have used TiN films of a

specific electrical resistivity of 55 /-til cm.

We have investigated the composition of the sputtered
TiN films with a Seeman-Bohlin x-ray camera and CuKa
radiation. The results are included in the diagram of Fig. 1.
Above a N2 partial pressure of 3 X 10- 5 Torr the sputtered
films are composed of the phase TiN. Films sputtered with a
N2 partial pressure around 2X 10- 5 Torr, which exhibit a
maximum in electrical resistivity, are a mixture of the phases
Ti2N and TiN. Below this partial pressure the sputtered
films contain Ti2N and unreacted Ti.
The diffraction lines of the TiN films were smeared out,
which points to a fine-grain microstructure. Transmission
electron microscopy (TEM) showed indeed that the average
grain size of the sputtered films was below 50 A.
The adherence of TiN films sputtered onto Si is excellent. Peeling is absent even after annealing of deposited TiN
films for 30 min in vacuum or H2 at temperatures up to
600 C. However, the adherence of sputtered TiN films on
Si0 2 is poor. Peeling starts following sputter deposition, if
the films are thicker than 2000 A. This problem can be
solved by interposing a thin layer of pure Ti between Si0 2
and TiN. The Ti film is best deposited by sputtering ofTi in a
pure Ar atmosphere. We have annealed TiN films on Si02
with a lOO-A-thick Ti intermediate layer up to 900C without any sign of peeling.
B. Etching solutions for patterning of TiN films

Metallizations have to be patterned following deposition over the entire wafer to define the contact areas and the
interconnections. A widely used method for patterning of
metallizations is the lift-off process. This process is adequate
for cases where a silicide layer is used for contact to silicon.
However, a lift-off process is inappropriate for a two-layer
metallization without silicide contact layer. The reason is
that the Si area, where the metallization has to make contact,
cannot be cleaned such that no residues of photoresist are left
behind. Such contaminations in the contact window can impair contact performance, especially in the case of Schottky
barrier diodes. It is therefore highly desirable to have an
etching solution at hand which allows patterning of the metallization after its deposition over the entire wafer. For this
reason we have developed two different etching solutions for
TiN. They are characterized in Table I and described in the
following.
Solution A consists of 15 parts HCI, 5 parts HN03 , and
1 part HF. It is a modification of aqua regia and is used at
room temperature. The etching rate for TiN is about 600
A/min and for Si02 is abouf40 A/min. Solution A attacks Si
very slowly. However, it develops nitrous gases as it is well
known of aqua regia. During etching gas bubbles can get

TABLE I. Characteristics of etching solutions for patterning of TiN films with conventional photolithography techniques.
Solution

Composition

Temperature

Etching rates
TiN

A
B

5723

HCI:HNO,:HF = 15:5:1
HNO,:CH,COOH:HF = 20:20:1

RT
30'C

J. Appl. Phys., Vol. 52, No.9, September 1981

55~50

500-600

Edge definition
Si0 2

A/min
A/min

40
40

satisfactory
excellent

Wittmer, Studer, and Melchior

5723

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annealed for 30 min in H2

0.50

>

"

as sputtered

"6

>

;::;-4

0.45

1Sl'".

E
.!,!
~
Q:

0.40

200

400

600

TEMPERATURE (OCl

FIG. 2. Optical micrograph of a contact pattern used for the measurements

of the contact resistivity. The pattern was defined with conventional photolithography and etched with solution B.

stuck at photoresist edges, which results in uneven etching

along edges. Good stirring during etching is therefore very
important for solution A. Though the edge definition might
be satisfactory for many cases, it may not be good enough for
very fine line geometries.
Solution B consists of 20 parts HN0 3 , 20 parts
CH 3 COOH (acidic acid), and 1 part HF. Best results were
obtained if the etching solution is used at 30 C. The etching
rates are about 550 A/min for TiN and about 40 A/min for
Si0 2 The etching rate for TiN can be doubled by heating the
solution to 40 C, but this results in considerable underetching of the TiN areas covered with photoresist. Solution B
attacks Si so slowly that it can be neglected. Good stirring of
the solution assures uniform etching. Figure 2 shows an optical micrograph of a TiN pattern etched with solution B. As it
can be seen from Fig. 2, excellent edge definition is obtained
with solution B. In the following we have exclusively used
solution B.
The etching rates of solution A and B for TiN necessitate longer etching times than those usually encountered in
device manufacture. The thickness of the photoresist has
therefore to be selected for longer etching times. We used 4,um-thick photoresist layers of Way coat SC for patterning of
3000-.A-thick TiN layers.

c. Barrier height of TiN on n-Si

We have prepared TiN Schottky-barrier diodes on ntype Si of 1-ncm resistivity. Following preparation of the
diodes we were not able to measure a rectifying effect. The
diode characteristic resembled a pure resistor. It is well
known that sputtering introduces strong radiation damage
in a surface region of the silicon wafer. We have therefore
annealed the diodes for 30 min in pure H2 at various temperatures. Annealing in pure H2 for 30 min at 450 C is a
standard process in metal oxide semiconductor (MOS) technology to reduce radiation damage. A Schottky effect could
be found following annealing at 400 C and at higher temperatures. The barrier height was evaluated from measurements of the forward current-voltage characteristics of the
5724

J. Appl. Phys., Vol. 52, No.9, September 1981

FIG. 3. Barrier height and reverse current IR at a reverse voltage of VR = I

V for TiN Schottky diodes on n-Si as a function of annealing temperature in
a H2 ambient. Annealing time was 30 min.

diodes. The results are shown in Fig. 3. Each data point is an

average of measurements performed on 10 diodes. The barrier height increases with increasing annealing temperature
below 500C and saturates at a value of <PBn = 0.488 0.01
V at annealing temperatures above 500 C. For comparison,
the barrier height is 0.500 0.01 V for Ti on n Si9 and
0.60 0.01 V for TiSi 2 on n Si.1O It is interesting to note the
small difference between the barrier height of TiN-Si and
Ti-Si. An analogous fact is well known for silicide-forming
metals, where the barrier heights of metal-silicon and corresponding silicide-silicon vary only little. There might be a
similar trend for metal-silicon and corresponding nitridesilicon barrier heights. Included in Fig. 3 is the dependence
of the reverse current I R at a reverse voltage of VR = 1 Vof
the Schottky diodes following annealing at various temperatures. The value of I R before annealing is indicated by the
arrow on the left hand side of the diagram. Figure 3 shows
that the reverse current drops with increasing annealing
temperature in correspondence with the increase of the barrier height. The reverse current is high due to the low barrier
height. It can be calculated from the well known current
equation of a reverse biased Schottky diode: II

IR = A

** T 2exp (

2qND (

E = [ ~ VR

_ q<p Bn )ex p [ .3..... (

kT
kT

+ VB; -

.-!l ) 112],
41TEEo

qkT )]112.

(1)

With a Richardson constant of A ** = 120 A/cm 2iK 2 , a

donor impurity density of N D = 5.5 X 10 15 cm- 3 , a dielectric constant of E = 12 and VB! - kT / q = 0.21 V, II one obtains a reverse current of IR = 0.2 A/cm 2 at VR = 1 V and
T = 300 K. The measured reverse currents of most of our
experimental diodes showed an appreciable spread around a
mean value of 0.9 A/cm 2 Only the best diodes approached
reverse currents close to the theoretical value. Whether the
higher reverse currents originate from striations of the wafers or incomplete anneal of the radiation damage remains to
be determined.
Wittmer, Studer, and Melchior

5724

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D. Contact resistivity of TIN on n-SI

We have measured the contact resistivity of TiN on n-Si

ofresistivities in the range of 0.001-100 n cm using the
transmission-line models (TLM) outlined by Berger 1213 and
Reeves. 14 The method described by Berger uses contact pads
with in-line geometry and variable spacing. Such a test pattern is shown in Fig. 2. Patterns with contact areas of twice
the size shown in Fig. 2 were also used for measurements.
Following the fabrication of the TiN contact pattern, long
mesas were formed to isolate the contact pattern by etching
the Si in CP 8 to a depth of about 7 pm (not shown in Fig. 2).
This measure confines the current flow laterally, and a linear
current flow was obtained by making the contact width
equal to the width of the mesa. If the contact width is less
than the width of the mesa, then current crowding occurs at
the contact, which results in an increased resistance in the
semiconductor layer outside the contact. 12 The contact resistance Rc can be calculated from the measured resistance
R between the contacts and the contact resistivity is then
given byl3

Pc = (w 2R ~/Rs)'

(2)

where w is the width of the contact and Rs is the Si sheet

resistance beneath the contact. Equation (2) is valid if the
contact length d fulfills the inequality d ~ 2(PclRii2. Rs
can be calculated from a plot of the measured resistance R
versus contact spacing L according to 13
(3)

R, = w(dR /dL ).

Thereby it is assumed that the sheet resistance beneath the

contact is equal to the sheet resistance of the substrate. In our
case this is true, because no reaction has taken place between
the TiN film and the Si substrate. We have checked the calculated values of Rs with four-point probe measurements

performed on the back side of the Si wafers and found good

agreement. The ohmic nature of the TiN contacts were
checked with a curve tracer. The 1/ V characteristic of the
contacts was linear in a voltage range of at least 0.5 V for
all substrate resistances. The measurements of the contact
resistances were performed in the linear region of the voltage
range. The absence of the Schottky effect at higher substrate
resistances is probably due to the radiation damage induced
by the sputtering process. The filled dots in Fig. 4 show the
measured contact resistivity as a function of the silicon substrate resistivity. Each data point is an average of 50 measurements performed on several wafers.
The method described by Reeves 14 eliminates the necessity for mesa isolation by using a contact pattern of circular
symmetry. We have prepared in-line and circular contact
patterns on the same Si substrate and measured the contact
resistance with the circular patterns prior to etching the mesas. The dimensions of the ciruclar pattern were the same as
those used by Reeves. The results of the measurements are
shown by the open squares in Fig. 4. Good agreement is
obtained between the two models.
The contact resistivity is related to the substrate resistivity by the equation 15

Pc =axp~,

(4)

where a and b are constants. A least squares analysis of Eq.

(4) was applied to the data and the fitted line is plotted in Fig.
4. The straight line is described by the equation

Pc

0.013 Xp~849.

(5)

The value of the contact resistivity of TiN on 0.001-

n cm Si is low enough for applications to silicon semiconductor devices. 16

CONCLUSIONS

In summary we have shown that TiN has the characteristics of a good contact material to silicon. Thus it makes the
concept of a two-layer contact metallization consisting of a
TiN layer for contact to Si and a low-resistivity metal layer
for interconnects feasible. Since standard photolithography
techniques can be used for patterning of the TiN, it is possible to clean the Si in the contact windows thoroughly before
deposition of the metallization. Becaue the barrier height of
TiN on Si is about half the gap energy, TiN contacts can be
used equally well on p-type Si. Finally, the chemical and
metallurgical stability of TiN renders its use in contact metallizations to semiconductor devices very attractive.

TiN contacts on n - Si
10-!
N

E
0

S
>-

I-- 10"

:>

t=

If)

Vi
w

0::

I-- 10. 3

<{

9c ~ 0.013 x 95,0.81.9

I--

Z
0

ACKNOWLEDGMENTS

U
K)"4

105=-'---'-~:::-'--~-,:,--""~""""""""""'--'----'--'--'...L--'---'-.........J
0.001
0.01
0.1
1.0
10
100

We thank M. Maenpaa for sending us a preprint of his

work and M. -A. Nicolet for fruitful discussions. The preparation of the samples by H. Keser and R. Weder is gratefully acknowledged. We are indebted to R. Pixley of the University of Zurich for the use of the Van de Graff accelerator.

SLBSTRATE RESISTIVITY (Clem)

FIG. 4. Contact resistivity of TiN on n-Si as a function of substrate resistivity as measured by the method of Berger (see Refs. 12 and 13) (e) and by the
method of Reeves (see Ref. 14) (0). The straight line is a fit of the equation
p, = ap~ to the data.
5725

J. Appl. Phys., Vol. 52, No.9, September 1981

'M. Wittmer, Appl. Phys. Lett. 36, 45611980).

2M. Wittmer, Appl. Phys. Lett. 37, 540 11980).
'N. W. Cheung, H. Von Seefeld, and M. -A. Nicolet, in Proceedings a/the
Wittmer, Studer, and Melchior

5725

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Symposium on Thin Film Interfaces and Interactions, October 14-19, Los

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published I.
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"C. W. Nelson, in Proceedings of the International Symposium on Hybrid
Microelectronics, September 29-October I, 1969, Dallas (Int. Soc. of Hy-

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brid Microelectronics, Montgomery, 19691.

9A. M. Crowley, Solid-State Electron. 12,403 (19701.
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"F. Nibler, J. AppJ. Phys. 34,1572 (19631.
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19781

Wittmer, Studer, and Melchior

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