WO1999019532A1

WO1999019532A1 - Method of chemical vapor deposition of metal films

Info

Publication number: WO1999019532A1
Application number: PCT/US1998/021113
Authority: WO
Inventors: Chantal Arena; Ronald T. Bertram; Emmanuel Guidotti; Joseph T. Hillman
Original assignee: Tokyo Electron Arizona; Tokyo Electron Limited
Priority date: 1997-10-09
Filing date: 1998-10-07
Publication date: 1999-04-22
Also published as: TW432486B; US6121140A; JP4079591B2; DE69801231D1; KR100624351B1; KR20010030989A; EP1021589B1; EP1021589A1; AU9789498A; DE69801231T2; JP2001520314A

Abstract

A method of producing a thick metal film on a substrate surface with a substantially smooth surface morphology and low resistivity. A substrate is exposed to a plasma. A first thin metal film is deposited on the substrate by chemical vapor deposition. The substrate with the film deposited thereon is exposed to a plasma, and a second thin metal film is deposited on top of the first film. The substrate may undergo subsequent cycles of plasma exposure and film deposition until a desired film thickness is obtained. The resulting film has a smooth surface morphology and low resistivity.

Description

METHOD OF CHEMICAL VAPOR DEPOS ITION OF METAL FILMS

Field of the Invention

This invention relates generally to chemical vapor

deposition (CVD) of a metal film on a semiconductor substrate, and

more specifically to a method of producing a substrate surface

having a metal film coating that is relatively smooth and has low

resistivity.

Backorouπd of the invention

In the formation of integrated circuits (IC) , thin fiims

containing metal and metalloid elements are often deposited upon

the surface of a semiconductor substrate to provide conductive and

ohmic contacts in the circuits and between the various devices of an IC. For example, a thin film of a desired metal might be applied

to the exposed surface of a contact or via hole on a semiconductor

substrate. The film, passing through the insuiative layers on the

substrate, provides plugs of conductive material for the purpose of

making interconnections across the insulating layers.

One well known process for depositing a thin metal

film is chemicai vapor deposition (CVD) . In CVD, a thin film is

deposited using chemicai reactions between various deposition or

reactant gases at the surface of the substrate. Reactant gases are

pumped into proximity to a substrate inside a reaction chamber,

and the gases subsequently react at the substrate surface resulting

in one or more reaction by-products which form a film on the

exposed substrate surface.

A thin metal film deposited by chemical vapor

deposition on a substrate has a smooth, mirror-iike surface

morphology. As more film is deposited, however, the surface

morphology of the film becomes rough and hazy in direct

proportion to the film thickness. A rough surface is undesirable

because it results in electromigration, whereby metal atoms are

transported along grain boundaries driven by the force exerted by

flowing electrons under high current densities. As a result, voids form at one end and extrusions form at the other end of the metal

lines. This leads to an increased probability of circuit failure in the

area of the voids.

Where a copper film is deposited, in addition to a

smooth surface morphology, it is desirable for commercial

production of semiconductor substrates that the films have a

resistivity that is close to a bulk resistivity of 1 .68 μohms-cm,

which is the resistivity of pure copper metal. Copper films with a

resistivity higher than about 2 μohms-cm have less viability as a

manufacturing technology since other metals with similar high

resistivities can replace copper. Factors that may influence film

resistivity include film thickness, density, purity, and grain size.

Accordingly, there is provided a method of producing

substrates coated with thick metal films that have a smooth

surface morphology and low resistance.

Summary of the Invention

To this end, and in accordance with the principles of

the present invention, one objective of the present invention is to

provide a metal film on a substrate surface that has a substantially

smooth surface morphology.

Another objective of the present invention is to provide a metal film on a substrate surface that has a low

resistivity.

A further object of the present invention is to provide

a copper film on a substrate surface that has a substantially

smooth surface morphology and low resistivity.

A still further object of the present invention is to

provide a substrate having a copper film coating greater than about

750 A thick with a substantially smooth surface morphology and a

resistivity of less than about 2 μohm-cm.

Specifically, this invention is directed to a method of

depositing, on a substrate surface, a metal film having a smooth

surface morphology and low resistivity. More specifically, this

invention is directed to a method of depositing, on a substrate

surface, a copper film that has thickness of greater than about 750

Λ with a smooth surface morphology and a resistivity comparable

to copper films less than about 750 Λ thick.

According to principles of the present invention, a

method is provided in which a substrate is exposed to a plasma. A

thin metal film is deposited on the substrate surface by chemical

vapor deposition. The coated substrate is exposed to a piasma. A

second thin metal film layer is subsequently deposited over the previously deposited film layer on the substrate surface. The

substrate is again exposed to a plasma. Successive cycles of

depositing additional film layers and exposing to a plasma are

performed to yield films of a desired thickness. In a preferred

embodiment, the plasma is a hydrogen/argon plasma and the film is

a copper film. Copper films deposited using the method of this

invention exhibit a resistivity close to the bulk resistivity of pure

copper metal and have a substantially smooth surface morphology.

By virtue of the foregoing, there is thus provided a

method for providing a substantially smooth surface morphology

and low resistivity of thick metal films deposited on a substrate by

chemicai vapor deposition. These and other objects and

advantages of the present invention shall be made apparent from

the accompanying drawings and description thereof.

Brief Description of the Drawings

FIG. 1 is a schematic of a susceptor and a substrate.

FIG. 2 is a schematic cross-sectional view of a

reaction chamber for copper CVD.

Detailed Description of the Drawings

With reference to FIG. 1 , a susceptor 20 for a

semiconductor substrate 22 during copper CVD is shown. A 99/19532

-6- typical susceptor 20 has a native oxide layer 24 on its top 26a and

side 26b surfaces. A substrate 22 is supported upon the susceptor

20 for processing. The substrate 22 has as its top surface 28 a

native oxide layer 30 of about 1 0 Λ to about 20 Λ thick. This top

layer 30 is, in turn, on top of a TiN layer 32 of about 500 A thick

which, in turn, is coated on a layer of silicon 34.

With reference to FIG. 2, a reactor 45 for copper

deposition on a surface 28 of a semiconductor substrate 22 by

chemical vapor deposition is illustrated. The reactor 45 includes a

reaction chamber 46 which encloses a processing space 48. In the

reaction chamber 46, which is shown as containing a substrate 22

on a susceptor 20, reactant gases for CVD are delivered to a

processing space 48. A gas delivery system such as the system

described in U.S. Patent No. 5,628,829 METHOD AND

APPARATUS FOR LOW TEMPERATURE DEPOSITION OF CVD AND

PECVD FILMS, which is assigned to the Assignee of the present

invention and is hereby specifically incorporated in its entirety by

reference, provides the proper flow and distribution of the gases for

the CVD process. Generally, gas delivery systems contain gas-

dispersing elements, such as a flat showerhead 50, in the reaction

chamber 46. The showerhead 50 spreads the entering reactant gases around the processing space 48 of the reaction chamber 46

to ensure a uniform distribution and flow of the gases proximate

the susceptor 20 and substrate 22. Uniform gas distribution and

flow is desirable for a uniform and efficient deposition process, a

dense plasma, and a uniformly deposited film.

For copper film deposition two molecules of the

copper precursor, copper' hexafluoroacetylacetonate

trimethylvinyisilane (Cu'(hfac) (tmvs)), react to generate copper

metal in the following disproportionation reaction:

2 Cu' (hfac) (tmvs) -Cu° + Cu" (hfac)₂ + 2 (tmvs)

The tmvs ligand stabilizes the precursor during its vaporization

stage, and the hfac ligand activates the precursor toward a higher

metallization rate at the substrate surface. Typical conditions in

the reaction chamber 46 are: substrate temperature of about

1 70°C, reaction pressure of about 0.5 torr to about 2.0 torr,

precursor flow of about 0.2 ml/min to about 1 .0 ml/min of liquid

(equivalent to about 1 6-80 seem of vapor), and diluent flow of

about 100 seem.

According to one embodiment of the present

invention, the reactor 45 is equipped with a plasma producing

apparatus 51 for exposing the susceptor 20 to a hydrogen/argon plasma prior or subsequent to the placing of the substrate 22

thereon for processing. The apparatus 51 to expose the susceptor

20 to the hydrogen/argon plasma may be the type described in co-

pending U.S. Patent Application Serial No. 08/797,397 PROCESS

FOR CHEMICAL VAPOR DEPOSITION FOR TUNGSTEN ONTO A

TITANIUM NITRIDE SUBSTRATE SURFACE, which is assigned to

the Assignee of the present invention and is expressly incorporated

herein by reference. The apparatus 51 preferably includes a radio

frequency (RF) generator 52, capable of generating 450 KHz,

which is attached to the showerhead 50.

In the method of the present invention, a substrate 22

supported on a susceptor 20 is exposed to a hydrogen/argon

plasma in the reaction chamber 46. The conditions in the reaction

chamber 46 are: chamber pressure of about 1 torr; power of about

750 W; frequency of about 450 KHz; hydrogen flow of about 200

seem; argon flow of about 50 seem, time of about 1 0 sec; and

substrate temperature of about 1 70°C.

Copper¹ (hfac) (tmvs) is deposited in a thin layer by

chemical vapor deposition on the substrate 22 to form a thin

copper film. In a preferred embodiment, the copper film is approximately 500 A thick. The conditions in the reaction chamber

46 are as follows: substrate temperature of about 1 70°C; chamber

pressure of about 0.5-2.0 torr; precursor flow rate of about 0.2-1 .0

ml/min; and diluent flow rate of about 1 00 seem.

The substrate 22 is subsequently exposed to a

hydrogen/argon plasma under the same conditions as previously

described for plasma exposure. A second thin layer of copper is

subsequently deposited on top of the first layer under the

conditions in the reaction chamber 46 as previously described for

copper deposition. Preferably, the second copper film layer is

about 300 Λ thick. Subsequent additional cycles of plasma

exposure followed by copper deposition may be used to produce a

copper film of a desired thickness.

While the present invention has been illustrated by

description of embodiments, and while the illustrative embodiments

have been described in considerable detail, it is not the intention of

the inventor to restrict or in any way limit the scope of the

appended claims to such detail. Additional advantages and

modifications will readily appear to those skilled in the art. For

example, the susceptor 20 may be pretreated with a metal film to

eliminate an edge effect on the substrate 22, as described in the concurrently filed application entitled "METHOD OF ELIMINATING

EDGE EFFECT IN CHEMICAL VAPOR DEPOSITION OF A METAL,"

which is expressly herein incorporated by reference in its entirety.

The invention in its broader aspects is therefore not limited to the

specific details, representative apparatus and methods, and

illustrative examples shown and described. Accordingly,

departures may be made from such details without departing from

the spirit or scope of applicant's general inventive concept.

Having described the invention, what is claimed is:

Claims

C l a ims :

1 . A method for depositing a metal film on a

semiconductor substrate surface by chemicai vapor deposition,

comprising the steps of:

(a) exposing a substrate to a plasma;

(b) depositing a first metal film on at least one surface

of the substrate;

(c) exposing the substrate having a film deposited

thereon to a plasma; and

(d) depositing a second metal film on top of the first

metal film on the surface of the substrate.

2. The method of claim 1 , further comprising repeating

steps (c) and (d) to achieve a desired film thickness.

3. The method of claim 1 , wherein the exposing steps (a)

and (c) comprise exposing a substrate to a hydrogen/argon plasma

and the depositing steps (b) and (d) comprise depositing a copper

film.

4. The method of claim 3, further comprising repeating

steps (c) and (d) to achieve a desired film thickness.

5. The method of claim 3, the depositing steps occurring

in a reaction chamber under a pressure in the range of about 0.1 -

10 torr, and preferably in the range of about 0.5 torr to 2.0 torr.

6. The method of claim 3, the depositing steps occurring

in a reaction chamber at a precursor flow in the range of about

0.01 ml/min to about 5 ml/min, and preferably in the range of

about 0.2 ml/min to about 1 .0 ml/min.

7. The method of claim 3, the depositing steps occurring

in a reaction chamber under a hydrogen flow in the range of about

10-1 500 seem, and preferably about 1 00 seem.

8. The method of claim 3, the depositing steps occurring

in a reaction chamber at a susceptor temperature in the range of

about 120-280┬░C, and preferably about 1 70┬░C.

9. The method of claim 3, the exposing steps occurring

in a reaction chamber under a pressure in the range of about 0.1 -

25 torr, and preferably about 1 torr.

10. The method of claim 3, the exposing steps occurring

in a reaction chamber at a power in the range of about 50-1 500 W,

and preferably about 750 W.

1 1 . The method of claim 3, the exposing steps occurring

in a reaction chamber at a frequency in the range of about 250-500

KHz, and preferably about 450 KHz.

1 2. The method of claim 3, the exposing steps occurring

in a reaction chamber under a hydrogen fiow in the range of about

50-5000 seem, and preferably about 200 seem.

1 3. The method of claim 3, the exposing steps occurring

in a reaction chamber under an argon flow in the range of about

1 0-1 500 seem, and preferably about 50 seem.

14. The method of claim 3, the exposing steps occurring

in a reaction chamber at a susceptor temperature in the range of

about 1 20-280┬░C, and preferably about 1 70┬░C.

15. The method of claim 3, the exposing steps occurring

in a reaction chamber for a time in the range of about 2-240

seconds, and preferably about 1 0 seconds.

1 6. A method for producing a CVD-copper film on a

semiconductor substrate, comprising the steps of:

(a) exposing a substrate supported on a susceptor to a

hydrogen/argon plasma;

(b) depositing a first copper film of about 500 ╬¢ thick

on at least one surface of the substrate;

(c) exposing the substrate containing the copper film

to a hydrogen/argon plasma; and

(d) depositing a second copper fiim of about 300 ╬¢

thick on top of the first copper film on the surface of the substrate.

17. The method of claim 1 6, further comprising:

repeating steps (c) through (d) to achieve a desired

film thickness.

1 8. The product of the method of claim 1

1 9. The product of the method of ciaim 2.

20. The product of the method of ciaim 3.

21 . The product of the method of claim 4.

22. The product of the method of claim 1 6.

23. The product of the method of claim 17.