Thin Solid Films, 140 (1986) 277 290

277

PREPARATION AND CHARACTERIZATION

C H E M I C A L VAPOR D E P O S I T I O N OF T I T A N I U M N I T R I D E AT LOW
TEMPERATURES
S. R. KURTZ* AND R. G. GORDON

Department of Chemistry, Harvard University, Cambridge, MA 02138 (U.S.A.)

(Received June 14, 1985; revised November 12, 1985; accepted December 2, 1985)

A new method is proposed for making titanium nitride (TIN) films at substrate
temperatures between about 400 and 700 C. The films are formed from TiC14 and
N H 3 by chemical vapor deposition. The method is versatile with growth rates of up
to 0.1 lam s- 1 possible. The optical properties of the films are measured and fitted
theoretically using the Drude theory to obtain the plasma frequency of the films. A
modification of the Drude theory according to Maxwell Garnett explains a
decreased reflectance in the IR region for the thinner films. Use of the films as heat
mirrors and other applications are discussed.

1. INTRODUCTION

Titanium nitride (TIN) has been studied extensively because of its many
potential uses. It is already widely used as a wear-resistant coating I on tools, as a
gold substitute for decorative coatings and for thin film resistors. Recently, it has
been investigated as a diffusion barrier in various semiconductor metallization
schemes 2 5, a contact layer for silicon, a gate electrode in metal/oxide/
semiconductor integrated circuits 6, and as a solar energy absorber and transparent
heat mirror v' 8 because of its optical properties in the visible and IR regions.
Bulk TiN is a bronze-colored refractory metallic compound. It melts at 2930 C
and has a bulk resistivity of about 22 ~tf~cm. It is a very hard material and is very
stable except that it oxidizes readily at elevated temperatures. The oxidation rate is
limited by the oxygen diffusion rate through the product TiO2 film 9.
For semiconductor applications TiN has most often been made by reactive
sputtering of titanium in N 2 3--5,7. It has also been made by reactive evaporation 2,
low temperature chemical vapor deposition (CVD) at about 400 C from titanium
dialkylamides 1, and variations on these methods. Coatings on metals for
decorative and tribological applications have most often been made by CVD from
TIC14, Nz and HE, a s follows
2TIC14 + N2 + 4 H 2 > 750"C 2TiN + 8HCI

(1)

* Present address: Solar Energy Research Institute, 1617 Cole Blvd., Golden, CO 80401, U.S.A,
0040-6090/86/$3.50

Elsevier Sequoia/Printed in The Netherlands

278

S . R . KURTZ, R. G. GORDON

The reaction is thermodynamically favorable above about 750 C but does not give
a significant growth rate below 900 or 1000 C. Temperatures as high as 2200 C are
used1,11. Alternatively, Hojo and Kato 12 used CVD of TiC14 and NH3 (in N 2 and
H2) to make TiN powder at low and high temperatures.
In this paper a new method is presented for making high quality TiN films by
atmospheric CVD from TiCI 4 and N H 3 between 400 and 700 c~C.Careful control of
the reactant mixing conditions permits film deposition rather than the powder
production found previously ~2
This new method is useful for several reasons. It can be used on glass since it
does not require the high temperatures of the TiCl4, N 2 and H 2 CVD system. Also,
since it works at atmospheric pressure, it is well suited for mass production.
Although films can be deposited at low temperature using organometallic CVD, the
new CVD method is superior because it has a considerably greater temperature
range, it produces films with better adhesion properties and it uses less expensive,
less air sensitive and more volatile reagents.
Thick TiN films produced by this method are typically 80~0-90~o reflective at
IR wavelengths and about 20~o reflective to visible light. The optical properties vary
with the temperature of deposition, the reactant concentrations and the thickness of
the film. A decreased reflectance in the IR region for the thinner films is explained by
the partial discontinuity of these films.
2. EXPERIMENTAL METHODS

A reaction for the TiN deposition is as follows:

6TIC14 + 8NH 3

,6TiN + N 2 + 24HC1

(2)

This reaction is thermodynamically favorable above about 300 ~C but does not give
appreciable film growth below 400 or 450C. A discussion of other reactions
between TiC14 and N H 3 is given below.
An atmospheric pressure C V D flow system (Fig. 1) is used for the depositions.
TiCI 4 is easily transported at a concentration of about 1~o (the vapor pressure of
TIC14 is 1.2 kPa at 20 C) by the carrier gas from a bubbler at room temperature
through lines heated to about 60 C. Higher TiCI4 concentrations are obtained by
heating the bubbler. The electronic grade a m m o n i a is diluted with carrier gas before
mixing with the TiCI 4. All gases were obtained from the Matheson Gas Company.
Any inert gas, such as helium, argon, N 2 or H2 can be used as a carrier gas. For
depositions at temperatures above 500 C the deposition rate is diffusion limited and
can be altered by changing the carrier gas. The electrical properties of TiN are
degraded by oxygen contamination of the films. Thus, the quality of the TiN
coatings is sensitive to leaks in the system and to any H 2 0 or 0 2 impurities in the
gases during deposition. For example, H2 containing a m a x i m u m of 100ppm
impurities produced TiO z instead of TiN when 0.01 vol.~ TiC14 was used. Very high
purity (less than 10 p p m impurities) carrier gas is essential if oxygen-free TiN is
desired. The helium carrier gas was purified by passing it through a T i - Z r - N i
gettering furnace (Matheson model 8301). For depositions using high concentrations of TiCI4, these purity requirements are much less stringent.

CVD OF T i N AT LOW TEMPERATURES

279

M
4~
I
H I

e~\\\\\\\\\\\\\\\\\~
L--~

~--3

(----K

Fig. 1. CVD systemusing a rectangular quartz tube for the reactor: A, quartz tube; B, substrate holder;
C, hotplate; D, second hotplate; E, nickel heat distributor; F, temperature probe; G, insulation; H, fourport valve; I, TiCI4bubbler; J, carrier gas inlet; K, dilute NH 3 or purge gas inlet; L, purge gas inlet; M,
exhaust (to aqueous trap, not shown). The TiCI4 is supplied from a stainless steel bubbler. The second
hotplate is maintained between 250 and 350 C.
Rotameters are used to monitor the flow rates and a four-port rotary valve is
used to select whether reactants or pure carrier gas reaches the reaction chamber.
The heat is supplied to the reactor by a hotplate. The nickel plate between the
hotplate and the reactor serves to distribute heat more uniformly. The temperature
is monitored with a thermocouple in the nickel plate. Insulation is placed on top of
the reactor to limit the temperature difference between the substrate and the top
surface of the reactor to 10-50 C. Such a temperature difference is necessary to
produce high quality films in order that powder will be transported to the cooler
surface by the thermophoretic force. It is also critical to have laminar flow
conditions since turbulence causes some of the powder to strike the surface of the
growing film as well.
Two different reactors are used. The first is a rectangular quartz tube of inner
dimensions 10 mm x 50 mm (see Fig.l) with one end open and the other end blown
to a quartz tube of outer diameter 9 mm. The 9 mm tube is readily connected to the
flow system by a compression O-ring-type fitting. Two gas mixtures flow through
concentric ~ and in tubes, the outer tube being connected to the 9 m m
quartz tube and the inner ending just inside the rectangular quartz tube. The two gas
streams mix at the junction of the 9 mm and the rectangular quartz tubes. An 18 cm
length of rectangular quartz tube before the hot zone allows the reactants to mix
laterally, even at high flow rates. A sizable fraction of the reagents falls out as powder
in this 18 cm length if the mixing region is not heated to between 250 and 350 C (see
discussion below). The gases are exhausted directly into a hooded area or through an
aqueous trap. The quartz tube extends about 15 cm after the hot zone to prevent
back diffusion of oxygen from the room during the deposition. When lower flow
rates are used it is necessary to plug the outlet loosely, although the back diffusion is
never great.
Because of the method of mixing, the design of the quartz reactor limits the
width of the reactor to about 5 cm. The Watkins-Johnson Company has designed a
nozzle 13, x4 which mixes gases uniformly along a line. This type of nozzle can be used

280

s . R . KURTZ, R. G. GORDON

to m a k e a r e a c t o r over 30 cm wide. In o u r case we used a nozzle 13 cm wide to s u p p l y

gas for the second r e a c t o r (Fig. 2). Dilute TiCI4, dilute N H 3 and a d d i t i o n a l carrier
gas flow into the nozzle t h r o u g h three ~ in tubes a n d flow out of the other side in
a s t r e a m 13 cm wide with the carrier gas in between the two reactants. The nozzle is
b o l t e d to a thin-walled H a s t e l l o y r e c t a n g u l a r tube. Because the W a t k i n s J o h n s o n
design mixes the gases quickly, the 18 cm required for lateral mixing in the q u a r t z
r e a c t o r can be replaced by 2 cm of a r e c t a n g u l a r duct which also serves as a thermal
b a r r i e r between the nozzle a n d the hot zone. (The nozzle s h o u l d not be heated a b o v e
250"C.) The r e c t a n g u l a r duct is a H a s t e l l o y tube welded to the b o d y of the reactor
which is a r e c t a n g u l a r nickel tube. The b o t t o m a n d t o p pieces of the nickel tube are
nickel plates 0.64 cm thick a n d the sides are nickel or H a s t e l l o y 0.16 cm thick. The
sides are thin walled to reduce heat flow, while the t o p a n d b o t t o m surfaces are thick
to ensure m o r e uniform s u b s t r a t e heating a n d to a v o i d w a r p i n g of the r e a c t o r as it is
heated. The flat m e t a l - t o - m e t a l seals in the nozzle are i m p r o v e d by using Vacseal (a
p r o d u c t of Space E n v i r o n m e n t Lab) as a sealant. A l t h o u g h Vacseal is very effective,
in practice it is not successful in keeping oxygen out of the T i N films g r o w n at low
g r o w t h rates since this process will tolerate an oxygen c o n t a m i n a t i o n of only a few
parts per million. Therefore, a pressure r e g u l a t o r valve located at the exit of the
r e a c t o r restricts flow so as to pressurize the entire r e a c t o r slightly. The valve is
a d j u s t e d m a n u a l l y to m a i n t a i n a pressure of a b o u t 20 k P a , gauge. The slight
positive pressure forces carrier gas out of any leaks, thus slowing diffusion of
c o n t a m i n a n t s into the reactor.

H2
......

C--~

~--J
A

Fig. 2. Simplified schematic diagram of the deposition system using the Watkins Johnson injector: A,
Watkins Johnson injector; B, nickel rectangular tube: C, substrate holder: D, hotplate; E, pressure
gauge; F, pressure control valve: G, four-port valve; H, dilute TiCI4 inlet; 1, purge gas inlet; J, carrier gas
inlet; K, dilute NH 3 inlet.
S u b s t r a t e s are placed either directly in the reactors o r on a thin nickel plate.
C o r n i n g 7059 glass (0.5 m m thick) or silicon wafers were used for most of the films."
The 7059 glass was p r e p a r e d first by r e m o v a l of a p r o t e c t i v e s p r a y ( n u m b e r 34) with
distilled water. Then the 7059 glass was etched for a few seconds with a solution of
1 ~ H F in c o n c e n t r a t e d H N O 3 , rinsed with distilled w a t e r and b l o w n d r y with N 2.

CVD OF T i N AT LOW TEMPERATURES

281

The S i O 2 layer on the silicon substrates was removed with a 1 0 % N H 4 F - 1 0 % H F

solution whenever good electrical contact with the wafer was desired. Inadequate
preparation of the substrates caused poor nucleation of the TiN, leading to a
"patchy" appearance, or caused poor adhesion of thick films.
3. RESULTS
3.1. Growth rates and appearance

Films were grown between 400 and 700 C. Typical conditions and growth
rates are given in Table I. Growth rates as high as 0.1 lam s - 1 were obtained. The low
growth rates require very low 0 2 system contamination in order to obtain high
quality films. High flow rates and a high surface-to-volume ratio are needed for the
deposition of uniform films at high temperature because the film growth rate is
diffusion limited. With a different reactor design depositions at temperatures as high
as 800 C may be obtainable. At temperatures much above 800 C the TiC14-N2-H2
system is probably easier to use.
TABLE I
TYPICAL CONDITIONSAND GROWTHRATESFOR TiN FILMS
TiCla
concentration
(vol.%)

NH 3
concentration
(vol.%)

Carrier
gas

Temperature
(C)

Linear flow
rate
(cm s - 1)

Growth
rate
(nm s - 1)

0.01
0.02
0.1
10

0.1
0.2
1
15

He
Ar
He
He

550
500
600
650

90
60
100
140

1.3
0.4
7.5
100

Thin (less than 0.1 ~tm) TiN films deposited above 450 C are gray and transmit
some greenish gray light. Thicker films are entirely absorbing and have a silvery
appearance. Films deposited at about 400 C or at the entrance to the hot zone are
more transparent and quite yellow, while films deposited at temperatures above
600 C are rose tinted in reflection. The characteristic golden color observed for TiN
films made by other deposition techniques was not observed under any conditions.
Films less than 0.5 ~tm thick adhere very well to both silicon and 7059 glass.
The thickness of the TiN was found by measuring the sputtering time while
analyzing by Auger electron spectroscopy (AES). The sputtering rate was calibrated
by sputtering a step through a mechanical mask and then measuring the step height
with a mechanical stylus profilometer (Dektak). The sputtering rate was found to be
about two thirds (0.7 + 0.1) that of tantalum oxide. The tantalum oxide sputtering
rate was found by sputtering through a 0.1 ~tm Ta205 film formed by anodizing a
piece of tantalum at 66.6 V in a 5.7% H N O 3 solution until the current ceased to flow.
(This is the method recommended by Physical Electronics. Other electrolytes give
similar results; see ref. 15.)
TiN films were also made by CVD of titanium dialkylamides. These films were
brown or gray and had poor adhesion. Films were grown from dimethylamide,

282

S . R . KURTZ, R. G. GORDON

diethylamide and dipropylamide. All of these produced films in the temperature

range 300-400 C in contradiction with the report of Sugiyama et al. 1 that the
lowest possible deposition temperature increased to about 500 C as the length of
the alkyl group increased to propyl. The titanium dialkylamides were transported
from bubblers at 50C, 80~'C and 170C for dimethyl, diethyl and dipropyl
respectively with a 4~oHz-N2 carrier. Dibutylamide decomposed at about 100 C,
which did not provide adequate transport for growing films at atmospheric pressure.
3.2. Substrate effects
Films less than 0.1 I.tm thick deposited onto soda-lime glass at temperatures
below about 600 C had a very different appearance compared with those grown on
7059 glass. They were much more transparent with a higher refractive index,
implying the formation of titanium oxide. Auger analysis confirmed this. The
substrate effect is quite dramatic since a piece of 7059 glass placed in the middle of a
piece of soda-lime glass nucleated a TiN film while the soda-lime glass produced
only an oxide film. Clearly the glass itself was the source of the oxygen. Prolonged
growth (past 0.1 lam or so) would produce a TiN film, but an even thicker film was
required to achieve the same appearance as those on 7059.
This effect seems to be correlated to the sodium content of the glass. Soda-lime
glass which has been boiled in hydrochloric acid solution (to leach the sodium ions
from the surface) supported TiN growth sooner than untreated soda-lime glass.
When a voltage was applied to the glass (film side biased positive) at high
temperature, causing current to flow so that sodium ions were moved away from the
surface, the soda-lime glass near the electrodes supported TiN growth sooner than
regions far from the electrodes. For a substrate temperature of 550 C, enhanced TiN
growth was seen when a voltage between 200 and 400 V was applied independent of
how long the voltage was applied. As the voltage was increased a transient current
could be observed (maximum current of 10-20 mA; total transient time of about 1 s).
Soda-lime glass 0.16cm thick shorted before 500V was reached when the
temperature was 550 C.
The growth of TiN on 7059 glass (a low sodium glass) was poisoned by soaking
the glass in a sodium chloride solution and then drying prior to deposition. On large
sodium chloride or potassium bromide crystals, the nucleation of TiN growth was
also very much delayed, but in these cases, of course, no titanium oxide film was
observed. Growth of approximately 1 ~m of TiN on an adjacent piece of 7059 glass
occurred before nucleation on the salt crystals was successful. However, smaller salt
crystals nucleated TiN film growth almost immediately, visually turning table salt
into pepper.
The alkali inhibition was found to disappear when the depositions were done at
higher temperature. As the soda-lime glass began, to soften near 650C the
nucleation of TiN occurred much more rapidly. The appearance of these films was
slightly different from that of the films grown on 7059 glass, but no oxide growth was
observed, in contrast with the lower temperature depositions.
3.3. Composition
The composition of the films was measured by AES using a thin film analyzer

CVD OF T i N

AT LOW TEMPERATURES

283

(model 540A) from Perkin-Elmer. The oxygen-to-titanium atomic sensitivity ratio

was found from a spectrum of TiO2 to be 1.2. The sensitivity ratio of chlorine to
oxygen is given in the Handbook of Auger Electron Spectroscopy 16 as 2.0 so a
chlorine-to-titanium sensitivity ratio of 2.4 was used. Typical compositions of the
films are given in Table II. Quantitative analysis for nitrogen requires a set of
standards since the nitrogen peak overlaps one of the titanium peaks.
TABLE II
COMPOSITION BY AUGER ELECTRON SPECTROSCOPY AND RESISTIVITY OF TiN FILMS MADEUNDER A VARIETY
OF DEPOSITION CONDITIONS
Ratio of
Cl to Ti

Ratio of
0 to Ti

Resistivity
(p.f2 cm)

Deposition
temperature
(C)

TiCl 4
concentration
(vol.~)

NH3
concentration
(vol.%)

1.26
0.6
0.03
0.06
0.16
0.25
0.27
0.53
0.15

0.10
0.12
0,04
0.04
0.03
0.03
0.02
0.07
0,03

5000
3400
600
350
380
810
390
660
300

400
485
600
550
550
550
630
630
650

0.01
0.01
0.01
0.01
0.01
0.01
10
2
6

0.06
0.06
0.06
0.14
0.04
0.01
15
4
10

Most of the films showed an oxygen level of about 1~o. Since the TiN surface
oxidizes upon exposure to air the films were sputtered during the analyses, but the
observed oxygen may still be from contamination during analysis. Investigators
making TiN films by reactive sputtering report oxygen contamination levels varying
from 0.1~o 17 to about 10~ 2. TiN samples which were cooled in air showed an
oxygen penetration of about 15 nm, while samples cooled under inert carrier gas
showed only about 3 nm of surface oxide.
The chlorine concentration varied considerably with the temperature of
deposition, the location in the reactor and the deposition time. The chlorine
concentration was higher for the films deposited near the entrance of the reactor,
corresponding to incomplete decomposition of the TiC14. The entrance of the
reactor is typically 30C cooler than the center, so that decomposition is less
complete than in the hotter region of the reactor. The chlorine concentration at the
front of the film was as much as seven times larger than that deeper in the film.
Films deposited at about 400 C contained 50~o _ 20~o C1, while films prepared
at 500 and 620 C showed smaller amounts, approximately 5~o + 2 ~ and 0.5~o
+ 0.2~o respectively. These data apply only to slow growth rates. There is more
chlorine in films grown at higher reactant concentrations.

3.4. Optical properties

The spectral reflectance and transmittance were measured on a Varian 2390
spectrometer between 3.0 and 0.35 ~tm. A Nicolet Fourier transform IR spectrometer was used to measure the reflectance in the mid-IR region. The IR reference

284

S.R. KURTZ, R.G. GORDON

mirror was calibrated using a V - W double-reflection attachment purchased from

Harrick Scientific Corporation. The visible results were corrected using the
manufacturer's curve for the reference mirror.
The reflectance spectra for three thick films grown between 500 and 600 '~C are
given in Fig. 3. The theoretical fit given for the data is discussed below. The
reflectance and transmittance of films of varying thicknesses are shown in Fig. 4. The
dip in the reflectance of the thinnest films near 0.25 eV is an effect of the substrate.
Despite the decrease in reflectance in the IR region, a sample which transmits
20/0 _+ 5% of the light in the visible region still reflects more than 50% of the IR light.
The utility of such films as heat mirrors is discussed below.
3.5. Hardness
The hardness was tested using the diamond indentation method at Spire
Corporation. TiN films 3 lam thick grown on stainless steel measured 8.5 on Moh's
hardness scale, on which diamond is 10. Although the films initially adhered to the

0.8 [

~ -J~----~

0.6 /
0

0.~

0.2
0.0 I ; ~

;_ ~ ~ L~.
~
,
]
2
5
10 20
Wavelength (microns)

Fig. 3. TiN reflectance spectra(of thick films)at various deposition temperatures, showing experimental
results and a theoretical fit using the Drude theory with the parameters given in Table III. Film 1:
deposition temperature, 520"C; A , experimental results; .-., theoretical fit. Film 2: deposition
temperature, 580{C; O, experimental results;
~, theoretical fit. Film 3: deposition temperature,
620 ' C : + , experimental r e s u l t s ; - - , theoretical fit.
[

Q)
CD

'

80 -~ ~

G3

60

)<"

q)
I

c~

40

~.o 20

+++++ +

r!

x:~.,<*~9~ + ~ ~

i
Ill

0.5 1.0 1.5 2.0 2.5 3.0

~
[~[]]~C

[2W [1C~

r] [i
QIJ~

~ o

t:
o

J
o

[I

0 . 5 1.0 1 5 2,.0 2 . 5 3 . 0
eV
eV
(b)
Fig. 4. (a) Reflectance and (b) transmittance spectra of TiN films of various thicknesses on 7059 glass:
- - , substrate only; x , 0.04 lain; + , 0.075 p.m; [], 0.11 p.m: - -., 0.15 lain; , 0.22 lain; A, 0.45 lain.

(a)

f]

CVD OF T i N AT LOW TEMPERATURES

285

stainless steel, after a few days the films peeled off. The surface preparation affected
how long the films stuck. About a dozen preparation methods combining acid
etches, degreasing, oxidizing and roughening of the stainless steel were tried. Films
on poorly cleaned stainless steel peeled immediately. None of the techniques
resulted in adhesion for longer than 1 week. Thinner films (less than 0.1 lam) adhered
better.
AES of the peeled films showed that some stainless steel peeled with the TiN.
This, along with the fact that the delayed peeling does not occur from glass or silicon,
implies that the problem lies with the stainless steel (rather than with stress in the
TiN film). We speculate that chloride, which is known to be corrosive to stainless
steel, may diffuse into grain boundaries near the surface of the stainless steel,
corroding and weakening it over a few days.
3.6. Resistivity
The "bulk" resistivity is given by the product of the sheet resistance and the
thickness of the film. The sheet resistance was measured using a four-point probe,
and the thickness by sputtering while monitoring with Auger analysis. Resistivities
measured ranged from 200 to 6000 ~tf~cm. Films made at lower temperatures
(containing chlorine) had the higher resistivities. Also, the resistivity is quite sensitive
to oxygen contamination. Films with little oxygen or chlorine contamination had
resistivities of 500 Ixf~cm or less. The bulk resistivity of TiN is 22 pD cm, but this is
seldom seen for thin films. Wittmer et al. 17 have shown that the bulk resistivity of
TiN depends on the ratio of nitrogen to titanium. Titanium and TiN have the lowest
resistivities (55 lad cm) while TiNx with 0 < x < 1 or x > 1 tends to have higher
resistivities (200-250 ~tf~cm).

4. DISCUSSION
4.1. Gas mixing
The TiC14-NH 3 system differs from most CVD systems in that the reagents
react at room temperature. The exact species formed depend upon the temperature
at which TiC14 and N H 3 are mixed. The general equation for mixing below about
200 C is as follows:

TiCla(g ) + nNH3(g ) < 200cc TiC14.nNH3(s )

(3)

The powder formed is light yellow at room temperature and becomes orange as the
mixing temperature is raised. Hojo and Kato 12, studying this reaction over a wide
temperature range (150-700C), reported an orange-yellow powder at about
200 C with n = 2. Fowles and Pollard is found n = 8 when mixing occurred at
between - 3 6 and - 6 3 C. Upon heating, this adduct evolved N H 3 and at 180 C
TiC14.2NH 3 was observed, in agreement with the results of Hojo and Kato. A
slightly different result has been reported by Brager 19 who performed X-ray studies
of TiC14-4NH 3 formed at - 3 0 C. Brager reported no change in composition upon
heating to 200C. No investigation of the titanium-to-nitrogen ratio of these
powders was carried out in the present study, but visual observations agreed very
closely with those of Hojo and Kato.

286

S. R. K U R T Z , R. G. G O R D O N

Despite the fact that a solid is formed at room temperature neither powder nor
much film is formed when TiCI4 and N H 3 are mixed between about 250 and 350 C.
At about 400~'C a yellow film containing titanium, nitrogen and substantial
amounts of chlorine (as detected by AES) is formed. (Hydrogen is also likely to be
present but cannot be detected by AES.) The structure of these TiNxCly films was
not determined, but both Brager 19 and Fowles and Pollard 18 observed TiNC1 when
TiC14.nNH 3 was heated at 350 C. It is possible that the yellow film observed at
about 400 C contains some TiNC1, but is probably not pure TiNC1 since TiNC1 is
reported to be black. Above 500 C TiN (more than 95'~'~)is deposited.
4.2.

T h e o r y o f l R reflectivity

For flee-electron metals the Drude theory predicts a high reflectivity in the IR
region, decreasing sharply in the visible or UV region. The location of the reflection
edge varies with the plasma frequency defined as
2 ) 1'2
=

(4)

where N is the flee-carrier concentration, e is the electronic charge and m* is the

effective electron mass. Karlsson et al. 2 have summarized the literature for the
plasma frequency of TiN films, giving values ranging from 6.7 to 8.9 eV. Roux et al. 7
show that for nitrogen-deficient films the reflectance edge shifts to higher energy and
becomes less distinct, approaching the reflectance curve of titanium metal. For films
made by our CVD method the location of the edge is somewhat dependent upon the
deposition temperature. Figure 3 and Table III show computer fits and corresponding parameters for films made at three different deposition temperatures. At
deposition temperatures around 600 C the plasma wavelength decreases towards
those of sputtered films. In this case the reflectance edge extends slightly into the
visible region giving the films a rose color in reflection. For films deposited at lower
temperatures the refectance edge does not extend into the visible region, so that the
films look metallic in reflection.
This systematic variation in the reflection edge correlates with the systematic
variation in the chlorine contamination. Roux et al. 7 qualitatively model the Fermi
level shifts in TiNx and TiNxCy as follows. In pure TiN there is effectively a transfer
of one d electron from a titanium to a nitrogen atom, and the Fermi level is in the
T A B L E III
PARAMETERS CALCULATED FROM FIT OF DATA SHOWN IN FIG. 1, USING THE DRUDE THEORY

Film

Deposition
temperature

Plasma
wavelength

Damping
wavelength

('C)

lam (eV)

(p.m)

520
580
620

0.221 (5.62)
0.216 (5.74)
0.199 (6.25)

0.98
1.33
0.99

Number of
effective
carriers per
Ti atom
0.45
0.47
0.56

Product o/ mobilit.v
and ~fffective mass
(cm2 V - 1 s 1)

5.74
7.80
5.74

CVD OF T i N

AT LOW TEMPERATURES

287

titanium d band (in this case the conduction band) which has one remaining electron
per titanium atom. If a nitrogen or carbon a t o m is added, respectively one or two
additional electrons are transferred out of the titanium d band, lowering the Fermi
level into a region with a lower density of states. Since chlorine is similar in
electronegativity to nitrogen and carbon, adding chlorine is likely to have the same
effect as adding nitrogen or carbon. It should receive an electron from the titanium d
band and thereby lower the Fermi level. This explanation is consistent with our
observation that the plasma frequency shifts to lower energies (lower carrier
concentrations) for films with more chlorine contamination (lower deposition
temperatures).
For applications to architectural windows, an "ideal" heat mirror should reflect
IR light and transmit visible light. Depending upon whether increased efficiency is
desired for cooling or heating seasons, the near-IR portion of the solar spectrum is
reflected or transmitted respectively. In the summer, windows should reflect all
wavelengths greater than about 700 nm 21 and transmit a fraction of the shorter
wavelengths (visible light). As can be seen in Fig. 3, TiN is an excellent candidate for
a summer heat mirror, since its reflectance changes most abruptly between 650 and
750 nm.
In the summer, to reduce heating and glare, transmission of about 10%-20% of
visible light may be considered optimal. The optimal thickness of a TiN film to be
used as a heat mirror can be found from Fig. 4. A film which transmits 10%-20% of
the visible light will reflect about 60%-80% of the IR light.
It should be noted that, although the Drude theory predicts an increasing
reflectance as the wavelength is increased, the thinner films do not display this high
reflectivity in the long wavelength IR region. For thinner films, the Drude theory
predicts a lower reflectance but never one which decreases in the IR region as is
observed in Fig. 4. A change in n and k was observed for thin TiN films by Valkonen
et al. a They calculated the reflectance and transmittance of thin films assuming the
bulk optical constants for comparison. They found that the integrated emittance
measured in the IR region was higher for the thin films than would have been
expected from the bulk optical properties. They also observed a higher n and a lower
k for films less than 40-50 nm thick measured at 0.6 and 1.0 lxm. They suggest that
the change in the optical properties is caused by island formation for very thin films
but do not attempt to model the films.
Sennett and Scott 22, studying thin metal films, have observed a decreased
reflectance in the IR region. They modeled the films using a theory derived by
Maxwell Garnett 23 to describe metal particles in glass. This theory calculates the
optical constants of metal spheres dispersed in a medium. Using the fraction q of
volume occupied by the metal spheres, the bulk metal's optical constants are
modified. From these new constants the reflectance and transmission of thin
discontinuous films can then be calculated using equations which include multiple
reflections and interference effects.
The Maxwell Garnett theory does not fit our data, since it predicts too high a
transparency at long wavelengths. This discrepancy may be because our films were
partly continuous and partly discontinuous. Therefore, we introduce a second
parameter, f , the fraction of the film which retains the bulk properties. The set of

288

S. R. K U R T Z , R. G. G O R D O N

relevant equations is as follows:

3qb
(1 - q a ) 2 +4q2h 2

n'k' =

(5)

3( 1 - qal
(1 - q a ) 2 +4qZb 2

k ' 2 - n '2 = 2

(6)

(k2-n2 + 1)(kZ-n2-

2)+4n2k 2
(k 2 _ n 2 _ 2) 2 + 4n2k 2

a =

b = (k 2 _ n2 _

3nk
2) 2 +

n" = n f +n'(l

(71

4nZk 2

(8)

.[)

(9)

k" = k f + k'(1 - f t

{10)

where n and k are the real and imaginary refractive indices calculated from the
D r u d e theory, f and q, as defined above, are confined to values betweeen zero and
unity, and n" and k" are the real and imaginary refractive indices used to calculate
the reflectance spectrum.
This theoretical fit for three of the films is shown in Fig. 5. The same plasma and
d a m p i n g frequencies were used for all the fits; only the volume fraction q, the
fraction f of the film with bulk-like properties and the thickness t were varied. The
model shows that, as the film thickness decreases, the density of the film, i.e. q, and
the fraction f of bulk-like film both decrease as expected. The thicknesses used for
the fit are within a factor of 2 of the measured values and are in the appropriate ratios
c o m p a r e d with the deposition times. The optical constants of the 7059 glass
substrate were assumed to be F/glass ~- 1.53 and kglass = 0. These values are accurate in
the visible region but do not include the IR absorption. Thus, we do not expect to
model the films perfectly in the mid-lR region.
1.0

o8!
}

-~

~1

0.2
0.0

,s.

,s

o
L~I,

1
2
Wavelength

i i,~iJ

t
1

:1

5
10
20
(microns)

Fig. 5. T h e o r e t i c a l a n d e x p e r i m e n t a l reflectances for films of v a r i o u s thicknesses. T h e p a r a m e t e r s for the

theoretical fits using e q u a t i o n s (5-10) were as follows:
, t = 0.25 g m , q - I: . . . , t = 0.054 tam,
q = 0.95, f = 0.5: . . . . , t = 0.034 tam, q - 0.9, f = 0.3. O t h e r p a r a m e t e r s were held constant, as follows:
p l a s m a energy, 5.45 eV (0.228 tam): d a m p i n g w a v e l e n g t h , 1.63 tam.

CVD OF T i N AT LOW TEMPERATURES

289

The theoretical fits are remarkably good considering the simplicity of the
model. The observed nucleation problems on alkali-containing substrates are
consistent with this explanation. We believe that with improved nucleation these
films will not show decreased reflectance in the IR region. Investigation of improved
nucleation techniques is under way.
5. CONCLUSION

A new method for depositing TiN thin films by atmospheric CVD from TIC14
and NH3 has been presented. High quality films were obtained at deposition
temperatures of around 600 C for growth rates as high as 0.1 ~tm s- ~. The films
showed unusual nucleation effects on alkali-containing substrates. The transmission
and reflectance spectra of the very thin films imply that the nucleation on even
sodium-flee glass is not perfect under these deposition conditions. The performance
of the films as heat mirrors will be improved when the nucleation problem is solved.
Even so, the films are suitable as heat mirrors for summer architectural applications
and as very hard protective coatings. The use of TiN as a diffusion barrier for a
transparent tin oxide electrode on silicon is discussed elsewhere 24'25"
ACKNOWLEDGMENTS

We should like to thank the Watkins-Johnson Company for use of its nozzle
and the Spire Corporation for the hardness tests. We should also like to thank J.
Chapple-Sokol, D. Wink and J. Hayes for useful conversations. We gratefully
acknowledge financial support from the Solar Energy Research Institute, the
National Science Foundation and the Materials Research Laboratory at Harvard
University.
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S . R . KURTZ, R. G. GORDON

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16