U.S. patent number 3,750,620 [Application Number 05/120,983] was granted by the patent office on 1973-08-07 for vapor deposition reactor.
This patent grant is currently assigned to U.S. Philips Corporation. Invention is credited to Franciscus Cornelis Eversteijn, Hermanus Leonardus Peek.
United States Patent |
3,750,620 |
Eversteijn , et al. |
August 7, 1973 |
VAPOR DEPOSITION REACTOR
Abstract
The invention relates to a reactor in which during operation a
susceptor is heated and indirectly also a substrate, for example,
of semiconductor material arranged on the susceptor. The heated
substrate reacts with a gas stream so that the substrate may be
etched or oxidized. As an alternative material may be deposited on
the substrate from the gas stream. It is a drawback that, viewed in
the direction of the gas stream, the rate of performance of these
processes decreases. An appreciable improvement is obtained by
using a reactor tube having a section which tapers in the direction
of the gas stream.
Inventors: |
Eversteijn; Franciscus Cornelis
(Emmasingel, Eindhoven, NL), Peek; Hermanus Leonardus
(Emmasingel, Eindhoven, NL) |
Assignee: |
U.S. Philips Corporation (New
York, NY)
|
Family
ID: |
19809548 |
Appl.
No.: |
05/120,983 |
Filed: |
March 4, 1971 |
Foreign Application Priority Data
|
|
|
|
|
Mar 11, 1970 [NL] |
|
|
7003431 |
|
Current U.S.
Class: |
118/725;
118/729 |
Current CPC
Class: |
C30B
25/14 (20130101); C23C 16/45585 (20130101) |
Current International
Class: |
C23C
16/455 (20060101); C30B 25/14 (20060101); C23C
16/44 (20060101); C23c 013/10 () |
Field of
Search: |
;118/48-49.5 ;148/175
;117/106-107.2 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Kaplan; Morris
Claims
What is claimed is:
1. A reactor for carrying out a process involving a gas stream and
at least one substrate, said reactor comprising an elongated tube
and being provided with a device for heating the substrate through
a susceptor having a temperature exceeding the ambient temperature
and with members for passing a gas stream in the direction of
length of the tube characterized in that at least that tube portion
in which the process is performed exhibits a descreasing sectional
area viewed in the direction of the gas stream.
2. A reactor as claimed in claim 1, characterized in that means are
provided for the continuous displacement of substrates through the
reactor during the process.
3. A reactor as claimed in claim 2, characterized in that at right
angles to the longitudinal direction the tube has a substantially
rectangular section, two horizontal sides of which have a
substantially constant length, viewed in the direction of the gas
stream, whereas the lengths of the two vertical sides decrease
substantially proportionally to the length of the tube so that the
prolongations of the top and bottom surfaces of the tube are at an
angle (.phi.).
4. The reactor of claim 3 wherein in the tube the tangent of angle
(.phi.) lies between 0.03 and 0.06, said reactor being intended for
the deposition of silicon by thermal decomposition of silane.
5. The reactor of claim 3 wherein in the tube the tangent of the
angle (.phi.) lies between 0.01 and 0.05, said reactor being
intended for the deposition of silicon by the reduction of
trichlorosilane with hydrogen.
6. The reactor of claim 3 wherein in the tube the tangent of the
angle (.phi.) lies between 0.005 and 0.02, said reactor being
intended for the production of silicon by the reduction of silicon
tetrachloride by hydrogen.
Description
The invention relates to a reactor for carrying out a process
involving a stream of gas and at least one substrate, said reactor
comprising an elongated tube and being provided with a device for
heating the substrate through a susceptor having a temperature
exceeding the ambient temperature and with members for passing a
stream of gas in the direction of length of the tube.
Such a reactor is known, for example, from semiconductor
manufacture, where it may be employed for carrying out processes
such as the deposition of a semiconductor material from a gas
stream on a semiconductor substrate in single- or polycrystal form,
for etching semiconductor substrates by a gaseous etchant or for
converting a semiconductor surface into a nitride or an oxide with
the aid of a gas stream.
When such a reactor is used, the susceptor operates as a heat
source for the substrate and over a heat source outside the tube it
has the advantage that the tube is at a lower temperature and may
even be cooled so that unwanted depositions on the tube wall can be
avoided and the desired processes are performed on or near the
substrate.
Such a reactor is described, for example, in an article of E.F.
Cave and B.R. Czorny in R.C.A. Review Vol.24, pages 523 to 545
(1963).
This reactor comprises an elongated, horizontal tube provided with
a device comprising a high-frequency inductance coil for heating a
susceptor of a material suitable for induction heating, on which
single-crystal substrates of semiconductor material are disposed.
The substrates are heated in a stream of gas. The tube is provided
with connections for passing the flow of gas in the direction of
length of the reactor. By chemical reaction semiconductor material
is deposited on the substrates from the stream of gas in epitaxial
manner.
In known reactors material is deposited in a tube portion having a
constant diameter. Such reactors have the disadvantage that the
material deposited from the stream of gas on the substrates often
forms a layer of non-uniform thickness, which adversely affects the
properties of semi-conductor devices made from the substrates with
the layers deposited thereon. Viewed in the direction of the stream
of gas the thickness of the deposited layer decreases. This applies
both to the separate substrates and to several substrates relative
to each other.
It is known to improve the uniformity of the thickness of the
deposited layer by arranging the substrates on a susceptor inclined
to the axis of the tube (see, for example, the article of S.E.
Mayer and D.E. Shea in "Journal Electro-Chemical Society" Vol. 11,
pages 550 to 556 (1964). The uniformity is correlated to an
increasing rate of gas flow with a decreasing concentration of
material to be deposited in this flow. The inclined susceptor has,
however, the disadvantage that, if it does not perfectly join the
tube wall, gas can escape towards the lower side of the susceptor.
This drawback can be avoided only with difficulty, particularly
when the deposition is performed at a high temperature, which is
often the case and due to the difference between the expansion
coefficients of the material of the susceptor and that of the tube
the junction between the susceptor and the tube wall may be very
bad at said high temeprature. Moreover, at the ambient temperature
an amount of play between the tube wall and the susceptor is
required to allow an unhindered slip of the susceptor into and out
of the tube.
Said unsatisfactory junction disturbs the flow profile above the
susceptor, since gas can escape towards the lower side of the
susceptor, which results in an undesirable thickness variation of
the deposited layer viewed in the direction of the gas stream and
at right angles thereto.
The aforesaid variations in the process on inclined and
non-inclined susceptors occur not only in the deposition of
material but, for example, also in the removal of material from
substrates, for example, in etching with the aid of a gaseous
etchant. During the etching process the substrate also exhibits an
undesirable variation in thickness.
The invention has for its object inter alia to avoid the
disadvantages described above.
The reactor of the kind set forth is characterized in accordance
with the invention in that at least that tube portion in which the
process is performed exhibits a decreasing sectional area viewed in
the direction of the gas stream.
The reactor according to the invention has the advantage that
variations in thickness of the deposited material viewed in the
direction of the gas stream and at right angles thereto are reduced
to a considerable extent.
The reactor embodying the invention preferably comprises means for
continuously displacing substrates through the reactor during the
process.
Such means are understood to include, for example, a pushing member
for continuously shifting substrates on susceptors through a
horizontal tube.
A continuous operation with inclined susceptors would yield
unsatisfactory results, since the discontinuities between
successive susceptors would give rise to undesirable disturbances
of the flow profile.
It might be remarked that layers of uniform thickness are also
obtained in a tube whose portion intended for the performance of
the process has a constant diameter viewed in the direction of
length, provided the process is continuous.
However, in the latter case, if, for example, semiconductor
material having a given concentration of doping impurities has to
be deposited on substrates the choice of the impurity is very
critical, since the impurity concentration in the deposited
material is frequently dependent upon the rate of deposition of the
semiconductor material.
This would mean that in continuous operation of a reactor
comprising a constant-diameter tube the impurity is not
homogeneously distributed in the deposited layer because the rate
of deposition is not constant, which often involves a disadvantage.
On the contrary, in a continuous operation of a reactor comprising
a tube having a sectional area tapering in the direction of the gas
stream the impurity can be homogeneously distributed in the
deposited layer because the rate of deposition can be kept
constant. The constant rate of deposition is obtained inter alia by
means of an increasing linear speed of the gas stream with a
decreasing concentration of material to be deposited in this gas
stream.
Continuously operating reactors provide an appreciably higher yield
of substrates with deposited material than discontinuously
operating reactors because heating-up of continuously operating
reactors need take place only once, whereas in discontinuously
operating reactors every charge requires heating and cooling.
A satisfactory control of the thickness of the deposited material
is particularly obtained in a reactor embodying the invention which
comprises a tube having a substantially rectangular section at
right angles to the direction of length, two horizontal sides of
which have a constant length, viewed in the direction of the gas
stream, whereas the length of the two vertical sides decreases
substantially proportionally to the length of the tube so that the
prolongations of the top and bottom surfaces of the tube are at an
angle .phi..
If silicon is deposited by thermal decomposition of silane tan
.phi. preferably lies between 0.03 and 0.06. In the case of
reduction of trichlorosilane (SiHCl.sub.3) with hydrogen it
preferably lies between 0.01 and 0.05 and with the reduction of
silicon tetrachloride (AiCl.sub.4) it lies preferably between 0.005
and 0.02.
The invention furthermore relates to a method of manufacturing a
semiconductor device in which a process is employed which involves
a gas stream and at least one heated substrate in a reactor
embodying the invention which is characterized in that the
relation:
1.10.sup.-.sup.8 < V.sub.o tan.sup.2 .phi./T.sub.S T.sub.M b
0,5D.sub.O 1,5 < 100.10.sup.-.sup.8
is satisfied, wherein V.sub.o is the gas rate in cms/sec at normal
temperature and pressure at the inlet of the tube portion where the
process takes place, T.sub.s is the temperature of the substrate in
degrees Kelvin, T.sub.m is the temperature of the gas in the tube
portion where the process is performed in degrees K, b is the
distance between the susceptor and the top surface of the reactor
at the inlet of the tube portion where the process is performed in
centimetres and D.sub.o is the diffusion coefficient in sq.cms/sec
of the compound in the gas stream which determines the rate of the
process.
If the aforesaid factors which determine of an appreciable extent
the variations in thickness of the deposited material, are adjusted
to each other in this manner, the process is performed
uniformly.
It should be noted that the value of the diffusion coefficient used
may differ from that found for the same compound in literature.
This is due to the fact that T.sub.s and T.sub.m often differ
considerably so that apart from diffusion under the action of
difference in concentrations also the phenomenon of
thermo-diffusion occurs. For example, the value of D.sub.o for
SiH.sub.4 used for the deposition of silicon by thermal
decomposition is 0.2 sq.cm/sec, whereas the values of D.sub.o for
SiHCl.sub.3 and SiCl.sub.4 used for the deposition of silicon by
hydrogen reduction are 0.10 sq.cm/sec and 0.04 sq.cm/sec
respectively.
Said factors preferably satisfy the relation: 3,10.sup.-.sup.7 <
V.sub.o tan.sup.2 .phi./T.sub.S T.sub.M b.sup.0,5 Do.sup.1,5 <
7.10.sup.-.sup.7
A constant concentration of a doping impurity, if any, is obtained
in a preferred form of the method embodying the invention by
continuously displacing the substrates through the tube during the
deposition.
The invention furthermore relates to a semiconductor device
manufactured by the method embodying the invention.
The method will now be described with reference to the drawing and
a few examples.
FIG. 1 is a schematic longitudinal sectional view of a first
embodiment of the reactor in accordance with the invention.
FIG. 2 is a schematic longitudinal sectional view of a second
embodiment of the reactor in accordance with the invention.
EXAMPLE 1.
FIG. 1 shows a reactor 1 for the deposition of material from a gas
stream. The reactor 1 comprises an elongated tube 2 having a
substantially rectangular section at right angles to the direction
of length and is provided with a device formed by a high-frequency
induction coil 3 for heating a plurality of substrates 4. The
reactor is furthermore provided with members (not shown) intended
to pass a gas stream in the direction of the arrows 5 through the
tube 2. A portion 6 of the tube, where material is deposited, has a
section tapering in the direction 5 of the gas stream so that,
viewed in the direction of the gas stream two horizontal sides of
the rectangular section have substantially constant lengths and the
lengths of the two vertical sides decrease substantially
proportionally to the length of the tube.
The tube 2 may be cooled by water or air.
The substrates 4 are located during the heating process on a
susceptor 7, which may consist of graphite, a surface layer of
which is converted, for example, in the reactor 1 by treatment in a
gas stream containing suitable silicon compound into silicon
carbide.
Viewed in the direction of length of the tube, the susceptor 7 is
enclosed between two auxiliary pieces 8 and 9 of quartz and joins
the upright walls of the tube.
The susceptor may have a length of 60 cms, a width of 10 cms and a
thickness of 1 cm. Such susceptors can accommodate in the
longitudinal direction 11 silicon substrates of a diameter of 5 cms
and in the lateral direction 3 substrates (in total 33 substrates).
A conventional thickness of such substrates is 200 to 250
.mu.m.
In a method of manufacturing a semiconductor device, in which the
reactor described above is employed, silicon is epitaxially
deposited, for example, from a hydrogen stream having 0.1 percent
by volume of SiH.sub.4. V.sub.o = 50 cms/sec, tan .phi. =0.045,
T.sub.s = 1350.degree.K, T.sub.m = 700.degree.K, b= 5 cms and
D.sub.o = 0.20 sq.cm/sec.
Under these conditions the relation: V.sub.o tan.sup.2
.phi./T.sub.s T.sub.M b.sup.0,5 Do1,5 is 5.4 . 10.sup.-.sup.7.
The average rate of deposition of material is 0.4.mu.m/min. with a
variation in thickness in the direction of length of the susceptor
of less than about 2 percent.
A similar rate of deposition and variation in thickness are
obtained in the case of a hydrogen stream containing 0.2 percent by
volume of SiHCl.sub.3 : V.sub.o = 70 cms/sec, tan .phi.=0.025,
T.sub.s = 1500.degree.K, T.sub.m = 900.degree.K, b =3 cms, D.sub.o
= 0.10 sq.cm/sec and
V.sub.o tan.sup.2 .phi./T.sub.S T.sub.M b.sup.0,5 D.sub.o 1,5
is 6. 10.sup.-.sup.7.
EXAMPLE II.
FIG. 2 shows a portion of a second embodiment of the reactor 1 in
accordance with the invention, which differs from the foregoing
Example in that means (not shown) are provided for continuously
displacing substrates 4 through the reactor 1 during the deposition
of material. The closing means for the susceptor can be omitted and
a pluraltiy of susceptors 21 are shifted one after the other
through the tube 2 during the deposition process.
The direction of displacement of the susceptors 21 may be equal to
the direction of the gas stream or opposite thereto. The rate of
passage of the susceptors will usually be low as compared with
V.sub.o. The one form of the method embodying the invention, in
which substrates are continuously passed through the tube during
the deposition, the rate of passage being 2 cms/min, V.sub.o is 40
cms/sec for a hydrogen stream containing 0.3 percent by volume of
SiCl.sub.4, tan .phi.= 0.015, T.sub.s = 1,500.degree. K, T.sub.m
=900.degree. K, b = 3 cms and D.sub.o =0.04 sq.cm/sec, and the
relation:
V.sub.o tan.sup.2 .phi. /T.sub.S T.sub.M b.sup.0,5
D.sub.o.sup.1,5
is 4.5 . 10.sup.-.sup.7.
The average rate of epitaxial deposition of silicon is 0.4
.mu.m/min. If the gas stream contains a dopant, for examples, in
the form of the compound PH.sub.3, the variation in the
concentration of the impurity throughout the thickness of the
deposited silicon layer is less than about 4 percent.
As a matter of course the invention is not restricted to the
Examples described above.
In the manufacture of semiconductor devices both epitaxial and
polycrystalline layers may be deposited. Apart from semiconductor
material compounds of semiconductor materials, for example, silicon
nitride may be deposited. The substrates thus treated can be worked
up in a conventional manner often into many semiconductor devices
in each substrate.
Etching processes on substrates may also be carried out in the
manner described above.
* * * * *