# Patent

## Title
Selective dry etching of tantalum and tantalum nitride

## Abstract

The invention describes a method for the selective dry etching of tantalum and tantalum nitride films. Tantalum nitride layers (30) are often used in semiconductor manufacturing. The semiconductor substrate is exposed to a reducing plasma chemistry which passivates any exposed copper (40). The tantalum nitride films are selectively removed using an oxidizing plasma chemistry.

## Background
FIELD OF THE INVENTION
The present invention relates to a dry etching process for the selective removal of tantalum and tantalum nitride layers. The dry etch process used etches tantalum and tantalum nitride without significantly attacking copper layers and silicon oxide based dielectric layers.
BACKGROUND OF THE INVENTION
The use of copper for forming the metal interconnect lines in integrated circuits is finding increasing usage due to the superior properties of copper compared to the widely used aluminum lines. One of the primary challenges in integrated circuit fabrication is reducing the RC time delay. An important component of the RC time delay is the resistance and the capacitance present in the metal lines that connect the various devices that comprise the integrated circuit. The resistivity of copper is 1.72×10−6 Ohm-cm versus that of aluminum which is 2.82×10−6 Ohm-cm. This reduced resistivity will reduce the RC delay associated with copper lines. In addition copper has superior resistance to electromigration and higher reliability when compared to commonly used aluminum alloys.
In general integrated circuit metal lines are formed in dielectric layers. These dielectric layers typically comprise silicon oxide or contain silicon oxide. In a typical damascene process for forming an integrated circuit copper line a trench is first formed in a dielectric layer which is formed over a silicon substrate containing electronic devices such as transistors, diodes, etc. This is illustrated in FIG. 1 where the dielectric layer 10 is formed over a silicon substrate. Using standard silicon processing technology a trench 20 is formed in the dielectric layer 10. Because copper reacts with silicon oxide, it is necessary to confine it using a barrier layer. A commonly used barrier layer is tantalum nitride (TaxNy) which is formed on the dielectric layer before the formation of the copper layer. A TaxNybarrier layer 30, 35 is shown in FIG. 1. The TaxNyis formed in a blanket deposition resulting in region 35 which lines the trench and region 30 which forms on the surface on the dielectric layer 10 outside the trench. Following the formation of the TaxNybarrier layer a thick layer of copper is formed. Using standard processing techniques such as chemical mechanical processing (CMP) the excess copper is removed leaving that portion of copper 40 which forms in the trench. To complete the process the portions of the barrier layer which are not cover by copper (i.e. regions 30 in FIG. 1) must be removed. Using existing methods the selective removal of the TaxNy layer is a very difficult process. CMP processes are often used to remove the exposed TaxNy layer 30 but this often results in dishing of the exposed copper surface an erosion of the underlying dielectric layer 10. Wet chemical etching of the exposed TaxNy layer is difficult because most of the chemical solutions which etch TaxNy will attack the underlying dielectric material and etch or damage the exposed copper surfaces. A method is therefore needed to selectively etch TaxNy layers without damaging the underlying dielectric layer and/or the exposed copper surface.
SUMMARY OF INVENTION
Tantalum and tantalum nitride layers are often formed during integrated circuit formation. The instant invention recites a method to selectively etch tantalum nitride. The instant invention comprises exposing a semiconductor substrate comprising at least one tantalum layer and/or tantalum nitride layer to reducing plasma chemistry where this reducing chemistry passivates any exposed copper or dielectric layers exposed to the reducing chemistry. All or a portion of the tantalum and/or tantalum nitride layers can then be selectively removed by exposing the semiconductor substrate to an oxidizing plasma chemistry.



BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a cross section diagram illustrating a tantalum nitride barrier layer beneath a copper region.
FIG. 2 is a cross section diagram showing the removal of a tantalum nitride layer.



DETAILED DESCRIPTION OF THE INVENTION
A two step dry etch process is used to selectively etch TaxNy and/or Tantalum (Ta). The subscripts x and y in the chemical symbol for tantalum nitride (i.e. TaxNy) represent integer numbers that depend on the form of the tantalum nitride alloy. The etch process of the instant invention will selectively etch all forms of tantalum nitride alloys and well as tantalum metal. The process conditions are described in the following table:


















Reducing
Oxidizing



Indices
Units
Step 1
Step 2





















Wafer
Celsius
>60
<100



Temperature



Pressure
milliTorr
500-900
500-900



N2
Sccm
 250-1000
0



NH3
Sccm
1000-4000
0



O2
Sccm
0
1000-5000



H2
Sccm
0
0



C2F4
Sccm
0
 20-100



Power
Watts
 700-1200
 800-1800










As shown in above table, the first step of the process comprises a plasma process with nitrogen (N2) and ammonium (NH3) as the active gases. In addition to N2 and NH3 other gases, including carrier gases such as argon, can be present in the chamber without departing from the instant invention. In an embodiment of the instant invention the flow rates of N2 and NH3 are preferably 480 Sccm and 2200 Sccm respectively, the power 900 Watts, and the wafer temperature approximately 250° C. This step modifies the surfaces of the TaxNy and/or Ta layers by exposing the surfaces to a reducing plasma chemistry. In addition to modifying the surface of the TaxNy and/or Ta, the first step of the process passivates the copper surfaces exposed to the first step (e.g. 40 in FIG. 1) thereby reducing the oxidation rate of the copper surface. Therefore the first step of the etch process simultaneously modifies the surface of the TaxNy and/or Ta layers and passivates the exposed copper surfaces reducing the oxidation rate of the copper surface.
The second step of the process comprises a plasma process with oxygen (O2) and tetrafluoroethylene (C2F4) as the active gases. In addition to O2 and C2F4 other gases can be present in the chamber without departing from the instant invention. In an embodiment of the instant invention the flow rates of O2 and C2F4 are preferably 2900 Sccm and 60 Sccm respectively, the power 1200 Watts, and the wafer temperature approximately 60° C. This step uses an oxidizing plasma chemistry to remove the modified TaxNy and/or Ta layer without significantly attacking the dielectric layer. In addition the passivated copper surface from step one will be highly resistant to the oxidizing chemistry of the second step and therefore will not be significantly attacked during step two of the process. The two step etch process of the instant invention therefore results in a selective process for etching (or removing) TaxNy and/or Ta layers without attacking any underlying dielectric layers or exposed copper surfaces. The removal of the TaxNy layer 30 is illustrated in FIG. 2.
The above described two step etch process can be performed in the same plasma chamber or may be performed in separate chambers. In addition to etching the TaxNy and/or Ta barrier layers in copper metallization process, the process of the instant invention can be used to etch TaxNy and/or Ta layers and films in any application.
While this invention has been described with reference to illustrative embodiments, this description is not intended to be construed in a limiting sense. Various modifications and combinations of the illustrative embodiments, as well as other embodiments of the invention will be apparent to persons skilled in the art upon reference to the description. It is therefore intended that the appended claims encompass any such modifications or embodiments.

## Claims

1. A method to selectively etch tantalum nitride, comprising:
providing a semiconductor substrate comprising at least one tantalum nitride layer; 
exposing said semiconductor substrate to reducing plasma chemistry wherein said reducing chemistry passivates an exposed copper region; and 
exposing said tantalum nitride layer to an oxidizing plasma chemistry selectively removing all or a portion of said tantalum nitride layer.

2. The method of claim 1 wherein said reducing plasma chemistry comprises nitrogen and ammonium.

3. The method of claim 1 wherein said oxidizing plasma chemistry comprises oxygen and tetrafluoroethylene.

4. The method of claim 2 wherein gas flow rates of nitrogen and ammonium are 250 Sccm to 1000 Sccm and 1000 Sccm to 4000 Sccm respectively.

5. The method claim 3 wherein said gas flow rates of oxygen and tetrafluoroethylene are 1000 Sccm to 5000 Sccm and 20 Sccm to 100 Sccm respectively.

6. The method of claim 4 wherein plasma power of said reducing plasma chemistry is 700 Watts to 1200 Watts.

7. The method of claim 5 wherein said plasma power of said oxidizing plasma chemistry is 800 Watts to 1800 Watts.

8. The method of claim 6 wherein temperature of said tantalum nitride is greater than sixty degrees centigrade during said exposing of said tantalum nitride layer to said reducing plasma chemistry.

9. The method of claim 7 wherein temperature of said tantalum nitride is less than one hundred degrees centigrade during said exposing of said tantalum nitride layer to said oxidizing plasma chemistry.