U.S. patent application number 09/097489 was filed with the patent office on 2001-05-31 for chemical vapor deposition apparatus with liquid feed.
Invention is credited to SANDHU, GURTEJ S., WESTMORELAND, DONALD L..
Application Number | 20010001949 09/097489 |
Document ID | / |
Family ID | 27490264 |
Filed Date | 2001-05-31 |
United States Patent
Application |
20010001949 |
Kind Code |
A1 |
WESTMORELAND, DONALD L. ; et
al. |
May 31, 2001 |
CHEMICAL VAPOR DEPOSITION APPARATUS WITH LIQUID FEED
Abstract
The invention is a method directed to the use of a nonvolatile
precursor, either a solid precursor or a liquid precursor, suitable
for chemical vapor deposition (CVD), including liquid source CVD
(LSCVD), of a semiconductor film. Using the method of the invention
the nonvolatile precursor is dissolved in a solvent. The choice of
solvent is typically an inorganic compound that has a moderate to
high vapor pressure at room temperature and that can be liquified
by a combination of pressure and cooling. The solution thus formed
is then transported at an elevated pressure and/or a reduced
temperature to the CVD chamber. In CVD the solution evaporates at a
higher temperature and a lower pressure upon entry to the CVD
chamber, and the nonvolatile precursor, in its gaseous state, along
with a gas reactant, produces a product which is deposited as a
thin film on a semiconductor wafer. In LSCVD the liquid enters the
chamber, contacts the wafer, evaporates, produces a product which
is deposited as a thin film on the wafer surface.
Inventors: |
WESTMORELAND, DONALD L.;
(BOISE, ID) ; SANDHU, GURTEJ S.; (BOISE,
ID) |
Correspondence
Address: |
SCHWEGMAN, LUNDBERG, WOESSNER
& KLUTH, P.A.
P.O. BOX 2938
MINNEAPOLIS
MN
55402
|
Family ID: |
27490264 |
Appl. No.: |
09/097489 |
Filed: |
June 15, 1998 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
09097489 |
Jun 15, 1998 |
|
|
|
08909695 |
Aug 12, 1997 |
|
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Current U.S.
Class: |
118/715 ;
427/255.23; 427/255.28 |
Current CPC
Class: |
C23C 16/4485
20130101 |
Class at
Publication: |
118/715 ;
427/255.23; 427/255.28 |
International
Class: |
C23C 016/06; C23C
016/00 |
Claims
What is claimed is:
1. A method for performing a chemical vapor deposition of a film on
a surface of a wafer, comprising the following steps: a)
solubilizing a nonvolatile precursor in an inorganic solvent to
form a liquid solution; b) transporting said liquid solution as a
continuous liquid stream to a control chamber, said transporting
performed at a temperature and a pressure to ensure a state of said
nonvolatile precursor remains liquid; c) evaporating said liquid
solution in said control chamber to change said state of said
nonvolatile precursor to a vapor; d) creating a reaction between
said vapor of said nonvolatile precursor and a reactant vapor; and
e) depositing the film on the surface of the wafer in response to
said reaction.
2. The method as specified in claim 1, further comprising the step
of eliminating contaminates during the depositing of the film by
selecting said inorganic solvent and said nonvolatile precursor to
ensure non-reaction of said inorganic solvent and said nonvolatile
precursor in said solution.
3. The method as specified in claim 1, further comprising the
following steps: a) creating a by-product during said step of
depositing; and b) removing said by-product from said chamber.
4. The method as specified in claim 1, further comprising the
following steps: a) injecting said liquid solution into said
control chamber; and b) controlling the temperature and pressure of
said control chamber such that the temperature is high enough and
the pressure is low enough to rapidly effect said step of
evaporating said liquid solution when said liquid solution enters
said control chamber.
5. The method as specified in claim 4, further comprising the step
of heating said wafer to a temperature greater than said vapor of
said nonvolatile precursor thereby precipitating said step of
depositing.
6. The method as specified in claim 1, wherein said step of
evaporating comprises the steps of: a) heating said wafer to a
temperature capable of evaporating said liquid solution; b)
applying said liquid solution to the surface of the wafer; and c)
increasing a temperature of said liquid solution to said
temperature capable of evaporating said liquid solution in response
to said step of applying and said step of heating thereby effecting
said step of evaporating.
7. The method as specified in claim 6, further comprising the
following steps: a) nebulizing said liquid solution at said control
chamber in order to create a mist of said liquid solution prior to
said step of applying; and b) uniformly covering the surface of the
wafer with said mist during said step of applying.
8. The method as specified in claim 6, further comprising the
following steps: a) heating the wafer to a temperature greater than
a temperature of said liquid solution prior to said step of
applying; and b) controlling a temperature and a pressure of said
control chamber in order to effect said step of evaporating.
9. The method as specified in claim 1, further comprising the step
of creating said reactant vapor during said step of
evaporating.
10. The method as specified in claim 1, further comprising the step
of injecting said reactant vapor into said control chamber.
11. The method as specified in claim 1, wherein said nonvolatile
precursor is a nonvolatile solid at a temperature at or above 1500
degrees Kelvin and at a pressure at or below 10.sup.-10 Torr.
12. The method as specified in claim 11, wherein said nonvolatile
solid is selected from the group consisting of Tiaz, ZrCl4, and
biscyclopentadienyltitanium diclhoride.
13. The method as specified in claim 1, wherein said nonvolatile
precursor is a nonvolatile liquid at a normal temperature and
pressure.
14. The method as specified in claim 13, wherein said nonvolatile
liquid is selected from the group consisting of
indenyltris(dimethylamido)zircon- ium,
cyclopentadienyltris(diethylamido)titanium, and
bis(cyclopentadienyl)bis(dimethylamido)titanium.
15. The method as specified in claim 1, wherein said inorganic
solvent is selected from the group consisting of liquid ammonia
(NH.sub.3), liquid NO.sub.2, liquid SO.sub.2, liquid TiCl.sub.4,
liquid TaCl.sub.5, liquid WF.sub.6, liquid SiCl.sub.4, borazine,
hydrazine, liquid xenonfluorides, liquid phosphine, liquid arsine,
diethylzinc, BCl.sub.3, BF.sub.3, SF.sub.6, H.sub.2S, SiF.sub.4,
CBrF.sub.3, CCl.sub.2F.sub.2, CCl.sub.3F, CClF.sub.3, CCl.sub.4,
SiH.sub.2Cl.sub.2.
16. The method as specified in claim 1, wherein said reactant vapor
is selected from the group consisting of hydrogen, ammonia, and
silane.
17. The method as specified in claim 1, wherein said step of
transporting further comprises transporting said liquid solution in
pulses.
18. A method for depositing a film on a surface, comprising the
following steps: a) combining a nonvolatile precursor and an
inorganic solvent to form a solution; b) adjusting a temperature
and a pressure in order to maintain said solution in a liquid
state; c) transporting said solution as a liquid stream to a
chamber; d) vaporizing the solution at said chamber to form a
precursor vapor; e) creating a reaction with a reactant vapor and
said precursor vapor; and f) depositing the film on the surface in
response to said step of creating.
Description
FIELD OF THE INVENTION
[0001] The invention relates to the manufacture of semiconductor
circuits on semiconductor wafers, and more particularly to chemical
vapor depositions of materials on the wafer.
BACKGROUND OF THE INVENTION
[0002] A large number of nonvolatile metal organic precursors which
are suitable in microelectronics applications for chemical vapor
deposition (CVD) of thin films are solids at temperatures at or
below 1500 Kelvin and at pressures at or above 10.sup.-10 Torr. In
fact, a majority of metal-organic compounds with attributes
desirable for CVD are solids. These compounds have chemical
stability, molecular structures, and reactivity which make them
ideally suited for CVD application. However, vapor transport is
difficult to perform under temperatures and pressures typically
utilized in semiconductor manufacture. Thus, vapor transport of
these precursors is a major hinderance to the implementation of the
precursors in a production environment. If the precursor has a
sufficient vapor pressure, then sublimation of the precursor for
transportation of its vapor is the only option available, however
this is difficult to control in a manufacturing environment. Solid
precursors have been dissolved, transported, and delivered in
organic solution, but these solutions usually leave a large carbon
residue.
OBJECTS OF THE INVENTION
[0003] It is an object of the invention to provide reliable
production worthy methods for fast delivery of nonvolatile
precursors to the chemical vapor deposition (CVD) chamber.
[0004] The invention features dissolving a nonvolatile precursor,
either solid or liquid, in a solution and delivering the precursor
in the solution to a CVD chamber.
[0005] The invention is a very efficient method for transporting a
nonvolatile precursor for CVD in the manufacturing environment and
incorporates a minimum amount of unwanted by-product in the desired
film. The method entails a process which is easily controlled and
therefore predictable with repeatable results.
SUMMARY OF THE INVENTION
[0006] The invention is a method directed to the use of a
nonvolatile precursor, either solid or liquid, in a chemical vapor
deposition (CVD) process. A solid precursor, as referenced herein,
is a precursor which is in a solid state at a temperature at or
below 1500 Kelvin and at a pressure at or above 10.sup.-10 Torr,
and a liquid precursor, as referenced herein, is a precursor which
is in a liquid state at a temperature at or below 1500 Kelvin and
at a pressure at or above 10.sup.-10 Torr. Using the method of the
invention the nonvolatile precursor is dissolved in a solvent to
form a solution. The nonvolatile precursor is then transported in
the solution at a pressure and a temperature necessary to maintain
it as a liquid to the CVD chamber. The solution is transported in a
continuous liquid stream to the CVD chamber. A continuous liquid
stream is an unbroken non-nebulized stream of liquid which may be
passed to the chamber without interruption or may be passed to the
chamber in a pulse or batch. The pulse or batch can be thought of
as a portion of the solution.
[0007] In a first embodiment the solution becomes a gas during
rapid evaporation of the solution at a high temperature and at a
low pressure. The gaseous form of the precursor reacts with a
reactant at the heated surface of the wafer.
[0008] In a second embodiment the method of the invention can be
used in liquid source chemical vapor deposition where the solution
is applied to the wafer before being evaporated.
BRIEF DESCRIPTION OF THE DRAWING
[0009] FIG. 1 is a cross section of a simplified representation of
the equipment used to perform a chemical vapor deposition on a
semiconductor wafer.
DETAILED DESCRIPTION OF THE INVENTION
[0010] The invention is a method directed to the use of a
nonvolatile precursor suitable for chemical vapor deposition (CVD).
The nonvolatile precursor may be a solid or a liquid. The solid
precursor, as referenced herein, is a precursor which is in a solid
state at a temperature at or below 1500 Kelvin and at a pressure at
or above 10.sup.-10 Torr, and the liquid precursor, as referenced
herein, is in a liquid state at a temperature at or below 1500
degrees Kelvin and at a pressure at or above 10.sup.-10 Torr. The
method can be understood by studying FIG. 1 in conjunction with the
following description. Using the method of the invention, the
nonvolatile precursor is dissolved in a solvent to form a solution
1 of the precursor and the solvent. It is important that the
precursor and the solvent do not react with each other in liquid
form. The solvent can be either a reactive component which makes up
a part of the film or it can be simply a nonreactive inert
carrier.
[0011] The solution 1 is formed in a chamber 2. The solution 1 is
then transported in liquid form at elevated pressures and/or
reduced temperatures to a chamber 3 through a transport device 4.
The liquid is transported as a continuous liquid stream to the
chamber 3. A continuous liquid stream is an unbroken non-nebulized
stream of liquid which may be passed to the chamber without
interruption or may be passed to the chamber in a pulse or batch.
The pulse or batch can be thought of as a portion of the solution.
When the solution 1 reaches the chamber 3, at least two options are
available.
[0012] In a first embodiment the solution 1 becomes a gas upon
entry to the chamber 3. The chamber 3 is held at a high enough
temperature and a low enough pressure to effect rapid evaporation
of the solution 1. The precursor remains in the gas phase until it
reacts with a reactant at a heated surface of the wafer 5. The
reactant may be either the solvent in its gaseous state or may be
another gas injected into the chamber 3. In either case a material
is produced during the reaction and deposited as a film on the
wafer 5. Typically, a gaseous by-product is also produced in the
reaction.
[0013] One example of the first embodiment comprises a solid
precursor of bis(cyclopentadienly)titanium diazide (Tiaz) dissolved
in liquid ammonia (LNH.sub.3) to form a solution 1 of Tiaz in
LNH.sub.3 in chamber 2 when the temperature of chamber 2 is
20.degree. C. or less and the pressure is 120 psi or greater. The
Tiaz in LNH.sub.3 is then transported to the chamber 3 through the
transport device 4. The temperature and pressure of the transport
device 4 are regulated in order to keep the solution in it liquid
form. In this example the temperature is 20.degree. or less and the
pressure is 120 psi or greater. The solution 1 immediately
vaporizes upon entry into chamber 3. The rapid evaporation occurs
because the chamber 3 is held at a temperature of 100.degree. C.
and a pressure of 500 millitorr and the water surface is held at
550.degree. C. Hydrogen is injected into the chamber and combines
with the vaporized Tiaz to form titanium nitride which is deposited
on the wafer as a thin film. A by-product cyclopentadiene remains
and is pumped from the chamber with the ammonia vapor.
[0014] The temperatures and pressures may be varied as long as the
temperature and pressure of the chamber and transport device allow
the precursor to remain dissolved in the solution. In addition the
temperature and pressure of the chamber may vary as long as the
solution is vaporized.
[0015] In a second embodiment, the solution 1 is applied to the
wafer 5 before being evaporated. This is typically referred to as
liquid source chemical vapor deposition. The solution is delivered
through a nebulizer which delivers a very fine mist that settles
evenly over the entire wafer. When the solution first contacts the
wafer the temperature of the wafer 5 may be either higher, or
lower, or the same as the temperature of the solution 1. In the
first case the wafer temperature and chamber 3 pressure must be
maintained so that the solvent evaporates upon contact with the
wafer surface and so that the precursor reacts immediately with the
reactant gas, which is either injected into the chamber or formed
during evaporation of the solution, to deposit a film. In the
latter two cases, the solution remains on the wafer until the wafer
temperature is increased to evaporate the solvent. As in the case
of the first embodiment the gaseous state of the precursor reacts
with a gas reactant thereby producing a material deposited as a
film on the wafer surface. The reaction typically produces a
gaseous by-product in addition to the deposited film. The
by-product and the solvent vapor, in the case where the vapor
doesn't react with the precursor to form the film, are then removed
from the chamber 3.
[0016] An example of the process of the second embodiment comprises
a precursor, zirconium tetrachloride, dissolved in a solvent,
silicon tetrachloride, to form a solution in chamber 2 when the
temperature of the chamber 2 is between 60.degree. and 10.degree.
C. and the pressure is 60 psi or greater. The solution is then
transported to the chamber 3 through the transport device 4. The
temperature and pressure of the transport device 4 are regulated in
order to maintain the solution in its liquid form. In this example
the temperature and pressure of the transport device 4 are the same
as the temperature and pressure of chamber 2. Chamber 3 is held at
a pressure of 10 torr in order to help facilitate the vaporization
of the solution on the wafer. The wafer temperature is 600.degree.
C. The zirconium tetrachloride in silicon tetrachloride solution is
injected into the chamber 3 and reacts at the wafer surface to form
a vapor and combines with hydrogen to form zirconium silicide which
is deposited on the wafer to form a thin film. A by-product,
hydrogen chloride, is formed and is pumped from the chamber with
the excess silicon tetrachloride.
[0017] It is important to use the correct solvent when performing
the method of the invention. The solvent must be able to evaporate
quickly and leave no contaminates in the product film. Therefore
common hydrocarbon solvents are unacceptable because they leave
carbon residue incorporated in the wafer film, dependent on the
wafer. Ideal solvents for this application are inorganic liquids
such as: liquid ammonia (NH.sub.3), liquid NO.sub.2, liquid
SO.sub.2, liquid TiCl.sub.4, liquid TaCl.sub.5, liquid WF.sub.6,
liquid SiCl.sub.4, borazine, dimethyl hydrazine, liquid
xenonflourides, liquid phosphine, liquid arsine, diethylzinc,
BCl.sub.3, BF.sub.3, SF.sub.6, H.sub.2S, SiF.sub.4, CBrF.sub.3,
CCl.sub.2F.sub.2, CCl.sub.3F, CClF.sub.3, CCl.sub.4,
SiH.sub.2Cl.sub.2. Many of these solvents are gases at room
temperature but are easily maintained as liquids with elevated
pressure and reduced temperature. For example, ammonia boils at
-33.degree. C. and is an excellent solvent. It is a further
advantage that these gases are easily available at a low cost at
the present time.
[0018] The following gases may be selected as reactant gases for
forming the deposited film: hydrogen, ammonia, or silane.
[0019] The following are some of the solid precursors suitable for
forming films on semiconductor wafers by the method of the
invention: bis(cyclopentadienyl) titanium dichloride, ZrCl4, and
tungsten carbonyl.
[0020] The following are some of the nonvolatile liquid precursors
suitable for forming films on semiconductor wafers by the method of
the invention: indenyltris(dimethylamido)zirconium,
cyclopentadienyltris(diet- hylamido)titanium, and
bis(cyclopentadienyl)bis(dimethylamido)titanium.
[0021] There are various combinations of nonvolatile precursors,
solvents and reactants that may be used in the process of the
invention.
[0022] It has been shown that the invention provides an efficient
method for transporting nonvolatile precursors for CVD in the
manufacturing environment.
[0023] Although the invention has been described in terms of a
depositing materials on semiconductor wafers during chemical vapor
depositions, the circuit and method have utility in other processes
where a chemical vapor deposition is desired. Accordingly the
invention should be read as limited only by the claims.
* * * * *