Semiconductor device manufacturing: process – Chemical etching – Liquid phase etching
Reexamination Certificate
2000-08-16
2003-09-23
Chen, Kin-Chan (Department: 1765)
Semiconductor device manufacturing: process
Chemical etching
Liquid phase etching
C438S754000, C134S003000
Reexamination Certificate
active
06624086
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a wet chemical etch process for etching fluorinated silicon oxide, TEOS, TiN, TaN, SiN, and copper films in semiconductor processing without damaging the silicon substrate surface. The wet chemical etching process leaves the silicon surface hydrophilic. The process uses a mixture of H
2
O
2
and HF in de-ionized water.
BACKGROUND OF THE INVENTION
In the fabrication of an integrated circuit on a silicon substrate a number of metal alloy layers are formed. Titanium nitride (TiN) films are used as barrier layers for aluminum metal lines. These barriers layers are necessary to prevent the unwanted chemical interaction of the aluminum metal lines with other layers in the circuit. Currently, hot concentrated sulfuric acid and hydrogen peroxide or a hot SC
2
(HCl+H
2
O
2
+DIW) solution is used to wet etch TiN films. Both of these solutions will attach the Silicon substrate leading to a roughening of the surface or the creation of voids. With the advent of the use of copper metal lines, tantalum nitride (TaN) films are finding increasing use as barrier layers for copper films. These TaN films often act as diffusion barriers preventing the diffusion of copper from the metal lines into other parts of the circuit where it would inhibit proper circuit operation. There is not a suitable wet etch process for removing TaN films from a silicon substrate. In addition, it is often necessary to etch these copper film in the presence of a patterned photoresist. Copper can be etched using a hot concentrated sulfuric acid or a hot SC
2
(HCl+H
2
O
2
+DIW) solution. These solutions will attack the photoresist films in current use and therefore cannot be used in the presence of photoresist films. Silicon nitride (SiN) films are used extensively in the fabrication of integrated circuits both as part of the transistor structure and as a barrier layer or liner layers. Current techniques to remove SiN involve the use of phosphoric acid at temperatures as high as 160° C. As in the case of hot sulfuric acid, hot phosphoric acid will attack the silicon substrate. Fluorinated silicon dioxide (FSG) and TEOS are typically etched using HF solutions which can in some instances attack the silicon substrate. In each instance of the above discussed materials/metal-alloys it will be necessary to remove these layers from the silicon substrate without producing damage to the surface. This need might arise during the reworking of a silicon wafer through a particular processing sequence involving one of the above mentioned films. Reworking of a silicon wafer through a processing sequence is often necessary due to mis-processing of the wafer during the sequence. A need therefore exists for a wet chemical process that effectively and completely removes TaN, TiN, SiN, Cu, FSG, and TEOS from the surface of a silicon substrate without damaging said surface.
SUMMARY OF INVENTION
The instant invention is a process to wet-etch TaN, TiN, SiN, Cu, FSG, and/or TEOS films. Solutions of hydrofluoric acid (HF) and hydrogen peroxide (H
2
O
2
) are used for the wet etch. De-ionized water is used to dilute all the solutions used and will be represented by the symbol DIW. In all solutions of the instant invention, the presence of H
2
O
2
in the solution will leave the silicon substrate surface hydrophillic. This will reduce the number of particles left on the surface after the chemical process. In addition, the solutions described will not attack photoresist. This allows the above mentioned films to be etched in the presence of patterned photoresist.
The HF:H
2
O
2
:DIW solution provides a wet chemical process to remove TaN without damaging the silicon substrate. In addition it will not attack photoresist and therefore can be used in a process involving patterned photoresist. In addition, the solution will etch SiN, TiN, FSG, TEOS and Cu either singly or simultaneous along with TaN without damaging the silicon substrate.
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patent: 5798540 (1998-08-01), Boos et al.
patent: 5896875 (1999-04-01), Yoneda
patent: 6149828 (2000-11-01), Vaartstra
patent: 6162671 (2000-12-01), Lee et al.
patent: 6232228 (2001-05-01), Kwag et al.
patent: 6326317 (2001-12-01), Wang et al.
patent: 61-269804 (1986-11-01), None
patent: 02186614 (1990-07-01), None
patent: 09153598 (1997-10-01), None
Brady III W. James
Chen Kin-Chan
McLarty Peter K.
Telecky , Jr. Frederick J.
Texas Instruments Incorporated
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