Laser chemical vapor deposition: A technique for selective area deposition

S.D. Allen

Citation: J. Appl. Phys. 52, 6501 (1981); doi: 10.1063/1.328600

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Laser chemical vapor deposition: A technique for selective area deposition
S.D. Allen
Center for Laser Studies, University ofSouthern California, University Park, Los Angeles, California 90007

(Received 5 May 1981; accepted for publication 17 July 1981)

Laser chemical vapor deposition (LCVD) uses a focused laser beam to locally heat the substrate
and drive the CVD deposition reacton. Several different deposition reactions and substrates have
been examined as a function of intensity and irradiation time using a CO 2laser source: Ni on SiO ,
Ti0 2on Si02, TiC on Si02, and TiC on stainless steel. LCVD film thicknesses range from < 1001
to > 20 fJ-m. Deposition rates of mm/min have been observed for LCVD Ni and 20 fJ-m/min for
LCVD Ti0 2. The diameter of the deposited films is dependent on irradiation conditions and can
be as s~all as one tenth of the laser beam diameter. The LCVD films exhibit excellent physical
properties such as adherence, conductivity, hardness, and smoothness.
PACS numbers: 42.60.Kg, 81.15.Gh

INTRODUCTION transparent window and the transparent reactants onto an

Chemical vapor deposition (CVD) is a technique for de-
positing coatings or growing layers on a substrate that is
widely used in the semiconductor, optics, and refractory ma-
terials industries. In conventional CVD gaseous compounds
which do not react at room temperature are passed over a
substrate heated to a temperature at which either the reac-
tants decompose or combine with other constituents to form
a layer on the substrate. In this work the properties of several
different types of films deposited by selective area CVD us-
ing a laser heat source are reported.
The use of a laser as the heat source for chemical vapor
deposition offers several distinct advantages: (a) spatial reso-
lution and control; (b) limited distortion of the substrate; (c)
the possibility of cleaner films due to the small area heated;
(d) availability of rapid, i.e., non-equilibrium, heating and
cooling rates; and (e) the ability to interface easily with laser
annealing and diffusion of semiconductor devices and laser
processing of metals and alloys. It should be possible to gen-
erate deposits of almost any material that can be deposited
by conventional CVD and probably some which cannot.
Possible applications include: Ie mask and circuit repair;
writing interconnects for IC circuits; one-step ohmic con-
tacts; localized protective coatings; localized coatings for
waveguide optics; and localized wear and corrosion resistant
coatings.
The deposition of material by thermal decomposition
using a laser heat source was first reported for graphite from
a hydrocarbon vapor in 1972 1 at the Third International
Conference on Chemical Vapor Deposition. At the same
conference the following year, D. M. Mattox 2 reported the
LCVD ofW by H2 reduction ofWF6 using a multimode CW
CO 2 laser translated across a Si02 substrate. More recently,
the LCVD of polycrystalline Si from SiH4 by Christensen
and Lakin, 3 and CoO from cobalt acety acetonate and air by
Steen4 has been reported. In both cases, a CO 2 laser source
and glass or quartz substrates were used.
absorbing substrate, creating a localized hot spot at which
the reaction takes place. The absorptivities of the reactants
and the substrate determine the laser wavelength which is
used.
Three different cases have been examined as a function
of intensity and irradiation time using a CO 2 laser source:
deposition of a reflecting film on a absorbing substrate, Ni-
/Si0 2; an absorber on an absorbing substrate, Ti0 2 and TiC-
/Si0 2 ; and an absorber on a reflecting substrate, TiC/stain-
less steel.
Initial experiments on LCVD on Si02 substrates were
carried out using the experimental apparatus illustrated in
Fig. 2. The laser was a cw CO 2 rated nominally at 20 W, but
usually run at about 10 W. Attenuation was provided by a
ZnSe Brewster angle polarizer using two Brewster angle
plates at opposing angles to minimize beam walkoff. Al-
though the beam profile without the attenuator is approxi-
mately TEMoo, multiple reflections in the thin ZnSe plates
introduce some distortion in the attenuated beam profile.
The removable power meter and/or fluorescent viewing
plates were used to check power stability and beam quality.
Irradiation time was controlled by a mechanical shutter with
LASER CHEMICAL VAPOR DEPOSITION
TRANSPARENT
REACTANTS

I. EXPERIMENTAL PROCEDURE TRANSPARENT ABSORBING

WINDOW SUBSTRATE
Laser chemical vapor deposition (LCVD) is best de-
scribed by referring to Fig. 1. The laser is focused through a FIG. 1. Requirements for LCVD.

6501 J. Appl. Phys. 52( 11), November 1981 0021-8979/81/116501-05$01.10 © 1981 American Institute of Physics 6501

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 LASER eve APPARATUS DIAMETER. mm

0.8

,..-----,
CO 2 LASER

20W
zs
ATTENUATOR
I I
IL _____ .JI

POWER
o o
SHUTTER AR COATED CELL
0.6

•
METER ZnSe LENS 5.0W •
0.4
3.0W x
2.0W •
0.2 1.0 W •
FIG. 2. Low-power LCVO apparatus. 0.5W.

speeds of 2.9 ms-l.O sec. After the shutter, the beam was
focused onto the absorbing substrate with a lO-in. focal
length AR-coated ZnSe lens through a NaCI window. The
reactions studied to date include:
140'C
Ni(CO)4 - Ni + CO
900'C
TiCl 4 + H2 + CO2 - Ti0 2 + HCl + CO
1200'C
TiCl4 + CH4 - TiC + HCl on quartz and stainless steel.
The temperatures given for the reactions are the minimum
deposition temperatures for the equilibrium CVD process. 5
A. LCVD Ni
The deposition ofNi from Ni(CO)4 is a well-known pro-
cess and forms the basis for a purification technique for Ni,
the Mond process. 6 The equilibrium kinetics of the CVD
reaction have been studied by Carlton and Oxley, 7 who con-
cluded that both heterogeneous and homogeneous reaction
mechanisms contribute to the deposition. The absorption
spectra of Ni(CO)4 in the 9-11 /.lm range is dominated by a
combination band at 920 cm - I (Ref. 8) but at the pressure
used (40 Torr) the absorption of a I-cm pathlength at 10.6
/.lm (943 cm - I) is less than 1%.
Two parameters of importance in evaluating LCVD are
the resolution attainable, i.e., the minimum spot size, and the
thickness of the deposit as a function of the irradiation condi-
tions. For the LCVD of Ni on Si0 2 the spot diameter is
400 800 1200
FIG. 4. Spot diameter (full width) ofNi films deposited on quartz (T oc It 1/2).
Laser beam diameter, D'N = 0.6 mm.
proportional to the square root of the irradiation time t, as
on quartz,
shown in Fig. 3. If the spot diameter is plotted against the
calculated surface temperature as in Fig. 4, the data for a
on quartz, wide range of deposition conditions (lOX in power; 200X in
irradiation time) lie on the same curve. For the range of spot
sizes and irradiation times used, the surface temperature is
proportional to lot 1/2 (Refs. 9,10) where 10 is the incident
intensity and t is the irradiation time. From Fig. 4 it is appar-
ent that there is an effective threshold for the deposition to
occur. The diameter of the Ni spot increases rapidly above
threshold but the rate of increase levels offfor longer irradia-
tion times and higher laser powers. This is particularly ap-
parent for the Po = 0.5 W points. Forincident powers higher
than 0.5 W the deposited spot continued to grow for longer
irradiation times, but at a slower rate. The spot diameters, in
any case, are less than the diameter of the depositing laser
beam, D i/o = 0.6 mm, over most of the range of deposition
conditions. This resolution enhancement can be understood
by referring to Fig. 5. The surface temperature distribution is
a Gaussian and the reaction occurs over that part of the
Gaussian that is above the threshold temperature, effectively
selecting the center of the Gaussian beam. Figure 6(a) is a
profilimeter trace I I of such a deposited spot illustrating the
truncated Gaussian shape.
There is a change in the character of the deposition pro-

103
FWHH, MICRONS

FIG. 3. Spot diameter (full-width at half

height, FWHH) of Ni films deposited on
quartz as a function of irradiation time.
5.0W • Laser beam diameter, 01/..-' = 600 p.m.
3.0W X
2.0W •
• I.OW •
• 0.5 W •

10- 1
IRRADIATION TIME (SEC)

6502 J. Appl. Phys., Vol. 52. No. 11. November 1981 Susan D. Allen 6502

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 TEMPERATURE
o DISTANCE FROM CENTER
file at the point in Fig. 4 where the curve becomes linear. A
profilimeter trace I I of such a spot is given in Fig. 6(b). Except
for the 0.5 W points, all of the films produced in the linear
region of Fig. 4 show this doubled-humped profile. The pro-
filimeter traces, confirmed by SEM photographs, also show
a roughened surface on the inside slopes of the "volcano"
shape. Other parts of the deposited spot were essentially fea-
tureless ( < 100 A) while these areas had surface features on
the order of 2000 A in diameter. There are several possible
explanations for these phenomena which are currently un-
der investigation: (i) convection is beginning to playa role in
the deposition rate, favoring the edge of the spot; (ii) the
center of the spot becomes too hot and the sticking coeffi-
cient for the reactants decreases, favoring deposition in the
5.0W
3msec
laser beam diameter
(8) 0.6 mm
f------i
(b)
100 microns
FIG. 6. Thickness profiles of LCVD Ni films.
6503 J. Appl. Phys., Vol. 52, No. 11, November 1981
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FIG. 5. Temperature distribution on a
surface irradiated by a Gaussian laser
beam.
OF BEAM
cooler regions outside the center of the spot; (iii) at sufficient-
ly high temperatures, carbon can be deposited by dispropor-
tionation of CO on the Ni surface and this might account for
the observed nodules.
The thickness of the deposited Ni films as a function of
irradiation time t for various laser powers is gi' en in Fig. 7.
The functional dependence of the film thickness on irradi-
tion parameters is more complex than in the case of the de-
posited spot diameter. The initial deposition rate is linear in t
and varies from looo,um/min for incident power Po = 5 W,
to 60 ,urn/min for Po = 0.5 W. The deposition rate at all
incident laser powers decreases at a point corresponding to
the onset of linear dependence in Fig. 4. At this same point,
for incident powers greater than 1 W, the film profiles begin
to show the doubled-humped "volcano" shape mentioned
previously. The thickness plot for these data therefore splits
into two curves when the profile shape changes; the upper
curve corresponding to the maximum thickness and the low-
er to the thickness at the center of the deposited spot.
From a knowledge of the optical constants of quartz
and Ni, one would predict that film thicknesses would be
"self-limited" to approximately 200 A using an optical heat
source. The absorptivity ofSi0 2 is approximately 0.9 at 10.6
,urn (Ref. 12) and the absorptivity ofNi is approximately
0.05.13 One would therefore expect that once several hun-
dred angstroms of metal were deposited on the substrate, the
absorptivity of the surface would decrease by a factor of 18,
the laser power absorbed, and the surface temperature
would decrease correspondingly, and metal deposition
would cease. This is obviously not the case as films ofNi on
Si02 up to 1 ,urn in thickness have been deposited. Some
evidence of thickness self-limiting is seen in the Ni deposi-
tion at low-incident laser powers, i.e., Po = 0.5 W, for long
irradiation times. It is also observed in cases of multiple irra-
diation of a single site. The film thickness produced for n
irradiations is less than n X the thickness for a single irradia-
tion. A proper explanation of these results will require a
knowledge of the deposition dynamics.
The hardness of LCVD Ni films was demonstrated by
their resistance to scratching by a hardened steel pin. The
Susan D. Allen 6503
 o
THICKNESS, A

FIG. 7. Thickness of LCVD Ni films

as a function of irradiation time. For
the 5.0- W data. the upper curve is
the maximum thickness and the low-
5.0
3.0
W
W X
• er curve is the thickness at the center
of the spot. Similar branching is ob-
served in the 3.0-and 2.0-W data but

••
2.0 W is not shown for reasons of clarity.
1.0 W
0.5 W •

IRRADIATION TIME, SEC

I

exceptions were those coatings deposited considerably above linear or slightly greater than linear function of the irradia-
threshold, which were softer. The LCVD Ni films passed the tion time, similar to the near-threshold behavior of NilSi02
Scotch tape adherence test with the same exception as in the (Fig. 7). No evidence of self-limiting is observed or would be
hardness tests. Coatings produced by irradiation at high in- expected on the basis of the bulk optical constants. Ti0 2 has
tensities for long times partially peeled when scrubbed with a greater absorptivity than Si02 at 10.6 pm and multiple (n)
an alcohol-soaked cotton swab. The thickness of the LCVD irradiations of the same site produced thicker films than
Ni films ranged from 100 A to 1 pm. The electrical conduc- would be predicted from n X (a single irradiation). Measured
tivity was measured as less than 4 X 10- 5 n cm for a 550-A deposition rates range from 2-20 pm/min.
thick, large area film. Grain size, as measured by SEM, was The resolution enhancement observed in the spot diam-
less than 100 A for most films. Nodules 2000 A in diameter eter of the NilSi0 2 system is also seen in the Ti0 2/Si0 2 but
appeared on the inside slopes of the double-humped films no "volcano" thickness profiles were observed. The spatial
deposited considerably above threshold. profile could be tailored depending on irradiation conditions
as shown in Fig. 8 from flat-topped to sharply peaked. These
B.LCVDTI02 thickness profiles were measured using the interference col-
The reaction for the Ti0 2 deposition in the initial ex- ors observed in reflection microscopy and were checked by
periments belongs to a class known as "water-gas" reactions.
In these reactions, H2 and CO 2 combine at high tempera-
tures to generate H 20 which reacts locally with an easily THICKNESS. MICRONS
Po; 10 W
hydrolyzable compound, in this case, TiCI 4 , to yield the 0.2
product oxide. Deposition of oxide films by conventional D,/e z = 3.0MM
CVD is difficult,5 producing in many cases thin, pinhole- A -0.5 sec
rich films with poor adherence. B - (0.25sec) x 10
TiCl4 was vacuum-distilled into a side-arm tube of the C - (0.12 sec) x 20
deposition cell and 205 Torr each of CO 2 and H2 added. The 0.1
partial pressure of TiCl4 was 12.4 Torr, the room-tempera-
ture vapor pressure. TiCl4 is transparent at the CO 2 -deposit-
ing laser wavelength.
The range of irradiation conditions over which Ti0 2 I
I
I
I ./
I
," ' ,
\\
\
\

_....I I '" ....

,~ \
\
I ; .... -- 150 MICRONS
can be deposited on quartz is narrower than that achieved ~_\

with NilSi02 , because the higher reaction temperature is

close to the Si0 2 melting point. From the limited data avail- FIG. 8. Thickness profiles of LCVD Ti0 2 films. (A) single irradiation of 0.5
able to date, the film thickness for LCVD Ti0 2/Si0 2 is a sec; (B) 10 irradiations of 0.25 sec each; (C) 20 irradiations of 0.12 sec each.

6504 J. Appl. Phys.• Vol. 52. No. 11. November 1981 Susan D. Allen 6504

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 stylus profilimetry.11 For a single irradiation under condi-
tions considerably above threshold the sharply peaked pro-
file of Fig. 8(a) was observed. Multiple irradiation just barely
above threshold produced the flat, uniform profile shown in
Fig. 8(c). For deposition conditions lying between the two
extremes, the broadly-peaked profile of Fig. 8(b) resulted.
Various film thickness profiles are thus possible with a Gaus-
sian laser intensity profile. This result is probably due to a
combination of both diffusion and heat flow kinetics.
The Ti0 2 films were clear and adherent. None was re-
moved with vigorous scrubbing with an alcohol-soaked cot-
ton swab. Preliminary results on the composition of the de-
posited films using scanning Auger microscopy (SAM)
indicate that the composition, TiOx ' changes somewhat over
the diameter of the larger deposited spots.
C. LCVDTiC
In conventional CVD of TiC (Ref. 5) the metal halide is
combined with a hydrocarbon and H 2 • For the LCVD ex-
periments 220 Torr of CH4 was added to a cell with a side-
arm of vacuum distilled liquid TiCI 4. The presence of H2
buffer gas is obviously not necessary for deposition of LCVD
TiC as deposits up to I-f-Lm thick were formed on both steel
and quartz substrates. The combination of a much lower
absorptivity and a higher thermal conductivity means that
the incident intensity necessary to achieve the deposition
temperature for TiC is at least 102 greater on steel than on
quartz. A Photon Sources 1.4-KW cW' CO 2 laser was used for
the steel deposition experiments. Coating thickness on steel
substrates was measured by slant cutting the substrate and
using SEM/EDAX to probe the Ti concentration across the
depth of the coating. Stylus profilimetry was used to mea-
sure coating thickness on quartz and polished steel
substrates.
The thickness of LCVD TiC on Si02 substrates shows a
linear dependence on the irradiation time t similar to that
observed for Ti0 2 and near threshold for Ni on quartz sub-
strates. No evidence of self-limiting was observed for the
range of laser powers and irradiation times used. Multiple
irradiations could be used to build up coating thickness on
both quartz and steel with the rate of increase larger on the
steel substrates. In several cases, multiple irradiations of a
single site resulted in a melted area, indicating a greatly in-
creased coupling efficiency of the laser into the substrate
once a TiC layer had been deposited.
6505 J. Appl. Phys., Vol. 52, No.11, November 1981
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II. CONCLUSIONS
In conclusion, it has been demonstrated that LCVD can
be used to deposit films of several different types of materials
with area resolution equal to or better than the laser beam
diameter. Reflective films deposited on absorbin~ substrates
are not limited in thickness to several hundred A by the
changes in optical absorption as the films are deposited. In
fact, Ni films several microns thick have been produced on
quartz substrates. The cross-section shape of the deposited
spot depends on reactants and irradiation conditions, vary-
ing from truncated Gaussian to flat-topped to a "volcano"
shape. Physical properties of the deposited films are good to
excellent. Other possible combinations oflaser and substrate
for LCVD include: visible lasers for semiconductor sub-
strates, i.e., Si and GaAs, near UV lasers for glass substrates,
and Nd:YAG lasers for metallic substrates.
ACKNOWLEDGMENTS
The author wishes to acknowledge the assistance fur-
nished by Prof. A. Burg in the handling of Ni(CO)4' This
work was supported in part by a grant from AFOSR under
the technical cognizance of H. Schlossberg.
IH. Lydtin, Proceedings of the Third International Conference on Chemi-
cal Vapor Deposition, edited by F. A. GJaski (Am. Nucl. Soc., Hinsdale,
Illinois 1972), p. 121.
2R. S. Berg and D. M. Mattox, Proceedings of the Fourth International
Conference on Chemical Vapor Deposition, edited by F. A. Glaski (Am.
Nucl. Soc., Hindsdale, Illinois, 1913), p. 196.
3C. P. Christensen and K. M. Lakin, Appl. Phys. Lett. 32, 254 (1918).
'w. M. Steen, Adv. in Surface Coating Tech., International Conference on
Advances in Surface Coating Techniques, London, February, 1918.
5C. F. Powell, I. E. Campbell, and B. W. Gonser, Vapor Plating (Wiley,
New York, 1955).
6L. Mond, Proc. R. Inst. G. B. 13,668 (1892).
'H. E. Carlton, and 1. H. Oxley, AIChE112, 86 (1966).
8B. L. Crawford and P. C. Cross, 1. Chem. Phys. 6, S3S (1938).
9M. Sparks,I. Appl. Phys. 47,837 (1976); M. Sparks, and E. Loh,I. Opt.
Soc. Am. 69, 841 (1919).
10M. Lax,I. Appl. Phys. 48,3919 (1911); Appl. Phys. Lett., 33, 186 (1918).
"Talystep Profilimeter measurements performed courtesy of 1. Bennett,
NWC, China Lake, California. Tencor profilimeter measurements cour-
tesy of Griot Assoc., Los Angeles, California.
I2D. E. Gray, American Institute ofPhysics Handbook (McGraw-Hili, New
York, 1972).
13L. E. Howarth and W. G. Spitzer,I. Am. Ceram. Soc. 44, 26 (1961).
Susan D. Allen 6505