# Patent

## Title
Effective solution and process to wet-etch metal-alloy films in semiconductor processing

## Abstract

A solution and method is described for etching TaN, TiN, Cu, FSG, TEOS, and SiN on a silicon substrate in silicon device processing. The solution is formed by combining HF at 49% concentration with H2O2 at 29%–30% concentration in deionized water.

## Background
This application is a divisional of application Ser. No. 09/640,250, filed on Aug. 16, 2000, now U.S. Pat. No. 6,624,086.


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 H2O2 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 SC2 (HCl+H2O2+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 SC2 (HCl+H2O2+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 (H2O2) 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 H2O2 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:H2O2: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.


DETAILED DESCRIPTION OF THE INVENTION
It is often necessary to remove TiN, TaN, SiN, Cu, FSG and/or TEOS from a silicon substrate without damaging the surface of said substrate. The instant invention describes a wet chemical etch method for the removal of such films from a silicon substrate. For all the chemical solution examples described herein, it should be assumed that the hydroflouric acid (HF) used has a 49% concentration (24.5moles/L) and the hydrogen peroxide (H2O2) used has a 29%–30% concentration (8.8 moles/L). In an embodiment of the instant invention, HF with a concentration of 49% and H2O2 with a concentration of 29%–30% is mixed together and diluted in deionized water to specific volume rations for etching TaN, TiN, SiN, Cu, TEOS, and FSG. TEOS is used to represent silicon oxide formed by the pyrolysis of the alkoxy compound tetraethoxysilane.
An embodiment of the wet chemical etch solution is a volume ratio of 2:1:21 of HF:H2O2:DIW. For most applications in the processing of semiconductor integrated circuits, this volume ratio will result in reasonable etch rates for TaN. In addition to etching TaN without damaging the silicon substrate, the 2:1:21 solution will simultaneously etch all the above compounds with a selectivity of FSG>TEOS>CU>SiN>TiN>TaN. Changing the volume ratios of HF and H2O2 will affect the etch rate of each material but the overall trend in etch rate selectivity will remain unchanged. It should be noted that the 2:1:21 (HF:H2O2:DIW) solution is effective at room temperature and should be used at such. It can however be used at temperatures greater than room temperature. This solution and all solutions described in the instant invention can be used by immersing the silicon substrate in the solution as part of a batch type process or by spraying the solution unto the surface of each wafer.
Another embodiment of the wet chemical etch solution is a volume ratio of 3:2:10 of HF:H2O2:DIW and a third embodiment is a volume ratio of 3:1:10 of HF:H2O2:DIW. In general, the more concentrated the solution the faster the reaction rate.
For the etching of TaN, the lowest volume ratio (ie., volume:volume:volume)of HF:H2O2:DIW that can be practically used is 1:1:20. However, SiN, TiN, FSG, TEOS and Cu can be removed with a minimum volume ratio of 1:1:30 of HF:H2O2:DIW. More concentrated solutions of the HF:H2O2 solution can be used with a change in the etch rates for the above mentioned materials/metal-alloys. In all embodiments, use of a higher temperature such as 40° C. to 50° C. will increase the reaction rate of the solutions to TiN, TaN, SiN, Cu, Al while all FSG type oxides remain relatively unchanged.
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 for etching one or more of the following: TiN, Cu, FSG, TEOS, and SiN from a semiconductor body in semiconductor device processing, comprising the steps of:
forming a solution by combining HF with a concentration of about 49% with H2O2 with a concentration of from about 29% to about 30% in deionized water (DIW), said solution having of a volume ratio of HF:H2O2:DIW selected from the group consisting of from about 2:1:21, 3:2:10, 3:1:10 and 1:1:30; and
applying said solution to said semiconductor body with said solution being at at least about room temperature.

2. The method of claim 1 wherein said method further comprises applying said solution in the presence of photoresist.

3. A method for etching one or more of the following: TaN, TiN, Cu, FSG, TEOS, and SiN from a semiconductor body in semiconductor device processing, comprising the steps of:
forming a solution by combining HF with a concentration of about 49% with H2O2 with a concentration of about 30% in deionized water, said forming a solution further consisting of a volume ratio of about 2 parts HF, about 1 part H2O2 and about 21 parts deionized water; and
applying said solution to said semiconductor body with said solution being at about room temperature.

4. The method of claim 3 wherein said method further comprises applying said solution in the presence of photoresist.

5. A method for etching TaN from a semiconductor body in semiconductor device processing, comprising the steps of:
forming a solution by combining HF with a concentration of about 49% with H2O2 with a concentration of about 29 to about 30% in deionized water wherein said forming a solution further consists of using a volume ratio greater than 1 part HF, 1 part H2O2 and 20 parts deionized water; and
applying said solution to said semiconductor body with said solution being at a temperature of 40° C. to 50° C.

6. The method of claim 5 wherein said method further comprises applying said solution in the presence of photoresist.

7. A method for etching one or more of the following: TaN, TiN, Cu, FSG, TEOS, and SiN from a semiconductor body in semiconductor device processing, comprising the steps of:
forming a solution by combining HF with a concentration of about 49% with H2O2 with a concentration of about 30% in deionized water wherein said forming a solution further consists of using a volume ration of about 2 part HF, about 1 part H2O2 and about 21 parts deionized water; and
applying said solution to said semiconductor body with said solution being at a temperature of from about 40° C. to about 50° C.

8. The method of claim 7 wherein said method further comprises applying said solution in the presence of photoresist.