Slurry for use in polishing semiconductor device conductive...

Details Slurry for use in polishing semiconductor device conductive... Slurry for use in polishing semiconductor device conductive...

2000-08-31

2003-04-22

Powell, William A. (Department: 1765)

Semiconductor device manufacturing: process

Chemical etching

Combined with the removal of material by nonchemical means

C156S345420, C216S038000, C216S089000, C252S079200, C252S079400, C438S745000, C438S754000

Reexamination Certificate

active

06551935

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates generally to slurries that are useful in chemical-mechanical polishing or chemical mechanical planarization processes and, more specifically, to slurries that are used to polish or planarize electrically conductive structures of semiconductor devices that include copper and an adjacent tungsten-containing barrier. The present invention also relates to methods for substantially concurrently polishing or planarizing structures formed from copper and tungsten.
BACKGROUND OF THE INVENTION
CMP
Chemical-mechanical polishing and chemical-mechanical planarization, both of which are referred to in the art as “CMP”, are abrasive techniques that typically include the use of a combination of chemical and mechanical agents to planarize, or otherwise remove material from or planarize a surface of a semiconductor material substrate during the fabrication of devices thereon. A chemical component, typically a slurry that includes one or more oxidizers, abrasives, complexing agents, and inhibitors, oxidizes the surface of one or more material layers that are being polished or planarized (i.e., at least partially removed). A polishing pad formed from a material such as polyurethane or acrylic is used with the slurry and, in combination with abrasives present in the slurry, effects mechanical removal of the layer or layers from the surface of the semiconductor device structure. It should be noted that abrasive-only polishing and planarization, e.g., without the use of active chemical agents to effect material removal, are becoming more prevalent due to environmental concerns. Thus, the term “CMP” as used herein encompasses such abrasive-only (i.e., strictly mechanical) methods and apparatus.
Copper Conductive Structures
The use of copper as a conductive material in semiconductor devices is also ever increasing. When copper is used in semiconductor devices, however, a barrier layer is typically required between the copper and adjacent structures or layers. The barrier layer prevents diffusion of the copper into the adjacent layers or structures, as well as the formation of copper silicides, both of which may cause electrical shorts in semiconductor devices that include copper. Tantalum is an example of a material that is useful as a copper barrier. When tantalum is used, the semiconductor device, including any features thereof into which copper is to be disposed (e.g., trenches), is lined with a layer of tantalum. The tantalum layer is then typically covered with a thin copper layer, often formed by physical vapor deposition (“PVD”) processes. The thin copper layer then acts as a so-called “seed layer” for the formation of a copper structure, such as a conductive line, such as by electroplating processes.
Once the tantalum and copper layers have been formed, it is necessary to isolate separate tantalum-copper conductive structures from one another. CMP processes are typically used to remove the tantalum and copper between the structures from over the active surface of the semiconductor device being fabricated. Slurries that are used in copper CMP processes typically have a pH of about 7.0. Many of these slurries include hydrogen peroxide (H
2
O
2
) as an oxidizing agent. Since hydrogen peroxide readily generates hydroxy free radicals (OH), hydrogen peroxide is a very strong oxidizing agent. Tantalum, however, is substantially chemically inert. Thus, the oxidizers of CMP slurries that remove copper do not effectively oxidize tantalum and, thus, do not adequately effect the removal of tantalum. Likewise, slurries that are useful for removing tantalum by CMP processes are likewise not effective for removing copper. As a result, when conventional CMP processes are used to isolate the tantalum-copper conductive structures of a semiconductor device, two separate slurries must be used.
It has been proposed that tungsten be used in place of tantalum in semiconductor devices as a barrier material for copper conductive structures. Nonetheless, when known copper CMP slurries are used to substantially simultaneously CMP tungsten and copper, the tungsten barrier layer may dissolve, or be removed, at a faster rate than the copper. This is at least partially because, as the following chemical equations illustrate, tungsten (W) is more readily oxidized than copper (Cu):
W+2H
2
O→4H++4
e
−
+WO
2
E
o
=0.12;
Cu→Cu
2+
+2
e
−
E
o
=−0.34.
Thus, in conventional slurries, although both copper and tungsten are simultaneously exposed to the same oxidants, the tungsten will typically be oxidized first. As a result, gaps may form in locations where the barrier material should be located between copper conductive structures and adjacent portions of the semiconductor device structure upon which the conductive structures are being fabricated.
This phenomenon is illustrated in the electron micrograph of
FIG. 1
, which illustrates a semiconductor device structure
10
that includes the portions of a copper layer
20
and an underlying tungsten barrier layer
18
disposed within a recess
14
formed in an active surface
16
of a substrate
12
of semiconductor device structure
10
following CMP thereof using an alumina fixed-abrasive polishing pad and a copper CMP slurry having a pH of about 7. Once an interface
19
between barrier layer
18
and copper layer
20
was exposed during the CMP process, tungsten of barrier layer
18
was oxidized and dissolved at a faster rate than the adjacent copper of copper layer
20
, leaving a gap
21
between copper layer
20
and adjacent regions of substrate
12
, as well as undesirably permitting copper of copper layer
20
to contact and, possibly, diffuse into, unprotected adjacent regions of substrate
12
.
Therefore, it would is desirable to provide a slurry that is useful in CMP processes and that effectively polishes or planarizes both copper and tungsten without causing oxidation or dissolution of the tungsten.
SUMMARY OF THE INVENTION
The present invention includes a method for substantially simultaneously chemical-mechanical polishing a copper conductive structure and an adjacent barrier layer with a polishing pad, as well as slurries that are useful for substantially simultaneously polishing a copper conductive structure and a barrier layer adjacent thereto.
The method of the present invention includes employing a polish pad along with a liquid polishing formulation, which is generally referred to herein as a slurry. The slurry is formulated to oxidize copper and a material of the barrier layer, such as tungsten, at substantially the same rates and without preference between the two materials. Thus, in a slurry incorporating teachings of the present invention, the oxidation energies of copper and the barrier material are substantially the same. Preferably, in the slurry, the oxidation energy of a barrier material, such as a tungsten-containing material (e.g., tungsten (W) and tungsten nitride WN
x
) is about 0.25 volt greater to about 0.2 volt less than an oxidation energy of copper. As copper and the barrier material are oxidized by the slurry at about the same rates, use of a slurry so formulated to substantially simultaneously polish a copper conductive structure and an adjacent barrier layer, prevents dissolution of the barrier layer.
Slurries that are useful in the method of the present invention include at least one oxidizer, at least on inhibitor, and one or more abrasives, and optionally but preferably one or more complexing agents. The relative amounts of the oxidizer, inhibitor, abrasive, and optional complexing agent, are balanced so as to facilitate substantially concurrent polishing of a copper structure and another structure adjacent thereto, such as a barrier layer formed from a tungsten-containing material. Thus, the slurry is formulated such that the relative amounts of the oxidizer, inhibitor, abrasive, and optional complexing agent, to oxidize copper and a barrier material, such as a tungsten-containing material, at substantially the

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