U.S. patent number 3,785,862 [Application Number 05/097,796] was granted by the patent office on 1974-01-15 for method for depositing refractory metals.
This patent grant is currently assigned to RCA Corporation. Invention is credited to William Augustus Grill.
United States Patent |
3,785,862 |
Grill |
January 15, 1974 |
METHOD FOR DEPOSITING REFRACTORY METALS
Abstract
A method for depositing a refractory metal on a semiconductor
oxide coating, comprising simultaneously etching the oxide coating
with the metallic hexafluoride and depositing a relatively thin
layer of the refractory metal by reduction of the hexafluoride, and
thereafter depositing a relatively thick layer of the refractory
metal by reduction of the hexafluoride alone.
Inventors: |
Grill; William Augustus
(Parsippany, NJ) |
Assignee: |
RCA Corporation (New York,
NY)
|
Family
ID: |
22265175 |
Appl.
No.: |
05/097,796 |
Filed: |
December 14, 1970 |
Current U.S.
Class: |
438/674; 216/58;
118/725; 427/250; 427/309; 427/404; 438/680; 438/685 |
Current CPC
Class: |
H01L
21/00 (20130101); H01L 23/5227 (20130101); H01L
23/522 (20130101); H01L 2924/0002 (20130101); H01L
2924/0002 (20130101); H01L 2924/00 (20130101) |
Current International
Class: |
H01L
23/522 (20060101); H01L 23/52 (20060101); H01L
21/00 (20060101); B44d 001/18 () |
Field of
Search: |
;117/17.2R,212,217,201,227 ;156/17 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Weiffenbach; Cameron K.
Claims
I claim:
1. An improved process for depositing tungsten or molybdenum on a
silicon dioxide layer, comprising the steps of:
a. heating said silicon dioxide layer in an enclosed chamber to a
temperature of about 500.degree.C. to 800.degree.C.;
b. introducing an inert gas and a reducing gas into said
chamber;
c. treating said silicon dioxide layer with a vaporized substance
selected from the group consisting of tungsten hexafluoride and
molybdenum hexafluoride for a brief period to etch said silicon
dioxide layer and deposit a thin layer of tungsten or molybdenum
thereon,
d. purging all of the unreacted hexafluoride from said chamber,
e. discontinuing the introduction of said inert gas into said
chamber, and thereafter
f. mixing additional reducing gas with more of said vaporized
substance in said chamber to reduce said substance and deposit a
thick layer of the metal constituent thereof on said thin
layer.
2. A process according to claim 1, wherein the ratio of inert gas
to reducing gas is between about 20:1 to 40:1.
3. A process according to claim 2, wherein said reducing gas
consists essentially of hydrogen.
Description
BACKGROUND OF THE INVENTION
The present invention relates to an improved method for depositing
a refractory metal on certain substrates and, more particularly, to
an improved method for depositing tungsten on a substrate which
comprises silicon dioxide.
An important advance in the ability to deposit refractory metals on
silicon dioxide layers is disclosed in U.S. Pat. No. 3,477,872 to
Amick. This method is a two-step process in which the oxide layer
is first etched with the hexafluoride of the refractory metal, in
an inert atmosphere. Thereafter, the refractory metal is deposited
on the etched oxide layer by the hydrogen reduction of the
hexafluoride. This process results in a refractory metal layer
which adheres well to the oxide layer. However, it is often
difficult to control the etching rate in a reproducible manner;
thus, the oxide is often etched back beyond the PN junctions of the
device which extend to the device surface, thereby exposing the
junctions and making the device unusable.
SUMMARY OF THE INVENTION
The present invention comprises an improved process for depositing
tungsten or molybdenum on a silicon dioxide layer. The process
comprises the steps of heating the silicon dioxide layer in an
enclosed chamber to a temperature of about 500.degree.C to
800.degree.C. An inert gas, such as nitrogen, and a reducing gas,
such as hydrogen, are introduced into the chamber in the ratio of
between about 20:1 to 40:1, respectively. The silicon dioxide layer
is then treated with a vaporized substance selected from the group
consisting of tungsten hexafluoride and molybdenum hexafluoride for
a brief period, in order to etch the silicon dioxide layer and
deposit a relatively thin layer of tungsten or molybdenum thereon.
The chamber is then purged of all the unreacted hexafluoride. The
inert gas flow is discontinued, and additional reducing gas and
newly vaporized hexafluoride are mixed in the chamber to reduce the
hexafluoride and deposit a relatively thick layer of the metal
constituent thereof on the thin layer.
Treatment of the silicon oxide surface with the hexafluoride etches
the oxide layer, modifying its properties such that a refractory
metal layer adheres much better than without such treatment;
additionally, the simultaneous reduction of a small amount of the
hexafluoride controls the etching attack during the etching step,
which protects the silicon dioxide over the PN junctions from
further etching.
THE DRAWINGS
FIG. 1 is a cross-section of a semiconductor chip with circuit
components already fabricated therein, and provided with a silicon
oxide layer on which tungsten is to be deposited in accordance with
the method of this invention.
FIG. 2 is a view like that of FIG. 1 showing further steps which
may precede the carrying out of the present method.
FIG. 3 is a schematic diagram, partially in section, of apparatus
that could be used in carrying out the method of the present
invention.
FIG. 4 is a view like that of FIGS. 1 and 2 illustrating a first
step in carrying out the present method.
FIG. 5 is a view like that of FIG. 4 showing a further processing
step in carrying out the method of the present invention.
FIG. 6 is a view like that of FIG. 5 showing a further processing
step that may be used in making a microcircuit.
DETAILED DESCRIPTION -- EXAMPLE
A specific example will now be given of how the method of the
present invention can be utilized in making a microcircuit of the
silicon monolithic type, but it will be understood that this is by
way of example only and that the method is not limited to the
manufacture of any particular product.
As shown in FIG. 1, the microcircuit being fabricated comprises a
single crystal chip of silicon 2 having a transistor 4 and a
diffused resistor 6 fabricated therein. The transistor 4 includes a
base region 8 and an emitter region 10 made by diffusing suitable
impurities into one surface of the chip 2. The transistor 4 also
includes a collector region which is part of the chip 2 outside the
base region 8. The resistor 6 is also made by diffusing suitable
impurities into the chip 2. The entire surface of the chip 2, into
which the circuit components 4 and 6 are fabricated, is covered
with a silicon dioxide layer 12 which protects the PN junctions
exposed at the surface of the silicon chip, and also serves as an
insulating substrate for carrying metal interconnections.
The circuit components are to be interconnected with conductors
made of tungsten. In order that interconnecting conductors can make
contact with the circuit components, as shown in FIG. 2, suitable
openings are made in the silicon dioxide layer 12 using
conventional photoresist masking and etching techniques. By these
techniques, an opening 14 in the layer 12 is made to expose a part
of the base region 8, and an opening 16 is made to expose a part of
the emitter region 10. Similar openings 18 and 20 are provided to
expose portions of the opposite ends of the resistor 6.
In order to carry out the processing steps of the present method,
the chip 2, as shown in FIG. 2, is placed within a quartz furnace
tube 22 which is a part of the apparatus shown in FIG. 3. The
assembly is supported on the top of a susceptor block 24 made of
carbon coated with silicon carbide. The susceptor block rests on a
tilted quartz support 26. The interior of the carbon block contains
a thermocouple 28 connected by wires 29 to an RF generator, not
shown. The furnace tube 22 is provided with an inlet tube 30 and a
flow meter 32 which measures the flow rate of the incoming gas. The
furnace tube is also provided with an outlet tube 34 so that
exhaust gases may be passed off to a fume hood or other disposal
means, not shown. A gas manifold 35 is connected to the flow meter
32 which measures the incoming flow of gas to the furnace tube 22.
Connected to the manifold 35 is a flow meter 36 and an inlet tube
38 provided with suitable valves for admitting measured quantities
of an inert gas to the system; in this example, nitrogen is used.
Also connected to the gas manifold 35 is a second flow meter 40 and
an inlet tube 42, provided with suitable valves, for admitting a
reducing gas into the system; in this example, hydrogen is used.
Included in the hydrogen inlet line is a palladium diffuser 44,
which serves to purify the hydrogen gas. Also connected to the
manifold 35 is a third flow meter 46 and an inlet tube 48 for
admitting tungsten hexafluoride into the system. The gas inlet tube
48 is provided with a branch tube 50 which has a valve for
admitting nitrogen into the line for purging purposes.
Before introducing the microcircuit chip into the furnace tube 22,
the silicon dioxide surface may first be suitably cleaned, e.g., by
rinsing in Methanol, or any other suitable cleaning agent. This
step is not essential and may be omitted if the silicon dioxide
surface is already sufficiently clean.
After the microcircuit is placed within the furnace tube 22, the
tube is closed off and then heated by means of an RF induction coil
52 from the RF generator previously mentioned but not shown, to a
temperature of about 500.degree. C to 800.degree. C (preferably at
about 700.degree.C). Meanwhile, nitrogen is admitted through the
inlet tube 38 and the flow meter 36 so that it passes through the
manifold 35, the flow meter 32 and the inlet tube 30, to enter the
furnace tube 22 at a rate of about 30 cfh (cubic feet per
hour).
Tungsten hexafluoride in gaseous form is then admitted through the
inlet tube 48 and the flow meter 46 to join the nitrogen stream in
the manifold 35 and pass into the furnace tube 22 at a rate of
about 30 cc per minute (about 0.063 cfh). Hydrogen is also admitted
through the inlet tube 42 and the flow meter 40 at a rate of about
1.0 cfh to join the nitrogen and tungsten hexafluoride streams in
the manifold 35, and pass into the furnace tube 22. It is necessary
to maintain the ratio of nitrogen to hydrogen between about 20:1 to
40:1, respectively, because it has been found that a ratio of
significantly below 20:1 results in an undesirable amount of
hydrogen reduction, while a ratio significantly above 40:1 results
in an undesirably high etching rate. A ratio of about 30:1 nitrogen
to hydrogen is optimum.
As the mixture of nitrogen, hydrogen, and tungsten hexafluoride
passes over the microcircuit assembly, the silicon which is exposed
at the bottom of the openings 14, 16, 18, and 20 in the silicon
dioxide layer 12, reacts with the tungsten hexafluoride, and by a
silicon replacement reaction, a thin layer of tungsten 54 is
deposited in the openings and on the silicon (FIG. 4). At the same
time, the tungsten hexafluoride gas etches the surface of the
silicon dioxide layer 12 and roughens it slightly; simultaneously,
the hydrogen reacts with the tungsten hexafluoride, and, by a
hydrogen reduction process a thin layer 56 of tungsten, about
2,000A. thick, is deposited over the silicon dioxide layer 12, as
shown in FIG. 4. The present step of treatment is permitted to
continue for a few seconds.
At the conclusion of the etching and partial deposition step, the
tungsten hexafluoride flow is terminated, and the tungsten
hexafluoride is purged from the apparatus by permitting nitrogen to
continue flowing into the system at a rate of about 4,000 cc per
minute (about 8.4 cfh) for a time sufficient to sweep all the
unreacted hexafluoride out of the furnace tube 22. The nitrogen
flow is then discontinued.
The hydrogen flow is continued through the furnace tube 22 at a
rate of about 2,000 cc per minute (about 4.2 cfh). Next, tungsten
hexafluoride at a rate of about 30 cc per minute (about 0.063 cfh)
is again admitted into the gaseous stream through the inlet tube 48
and the flow meter 46. The heating temperature of the assembly is
the same as mentioned previously. Under these conditions, as shown
in FIG. 5, the hydrogen reduces the tungsten hexafluoride and
deposits tungsten on all of the heated surface. Thus, a relatively
thick layer of tungsten is deposited on the entire surface of the
thin layers of tungsten 54 and 56 over the silicon and the silicon
dioxide. Suitably, the composite thick tungsten layer 56' is about
2.0 microns thick. At the conclusion of the tungsten deposition
process, the tungsten hexafluoride and hydrogen flows are
discontinued, and nitrogen is admitted through the branch line 50
to purge the apparatus of the corrosive tungsten hexafluoride to
prevent attack of the apparatus walls.
In order to remove unwanted tungsten from the layer 56' and leave
only the desired pattern of interconnections, excess tungsten can
be removed with any suitable masking and etching technique,
resulting in a microcircuit like that shown in FIG. 6.
Although the method has been illustrated with an example in which
tungsten is the deposited metal, molybdenum can be similarly
deposited from molybdenum hexafluoride.
* * * * *