FIB Process for Selective and Clean Etching of Copper

Abstract

Etch assisting agents for focused ion beam (FIB) etching of copper for circuit editing of integrated circuits both prevent loss of adjacent dielectric due to sputtering by the ion beam, and render sputtered re-deposited copper on adjacent surfaces non-conductive to avoid electrical short circuits. The agents comprise hydrazine and hydrazine derivatives having an N—N(N being Nitrogen) bonding in their molecules and boiling points between about 70° and 220° C., and NitrosAmine derivatives saturated with two hydrocarbon groups selected from Methyl, Ethyl, Propyl and Butyl. Preferred agents are Hydrazine monohydrate (HMH), HydroxyEthylHydrazine (HEH), NDMA, NMEA, NDEA, NMPA, NEPA, NDPA, NMBA or NEBA, alone or in combination with Nitrogen Tetroxide. The agents are effective for etching copper in high aspect ratio (deep) holes.

Description

CROSS REFERENCE TO RELATED APPLICATIONS[0001]This application is a continuation-in-part (CIP) of U.S. application Ser. No. 12 / 547,368, filed Aug. 25, 2009.BACKGROUND OF THE INVENTION[0002]This invention relates generally to focused ion beam etching of copper and copper materials, and more particularly to the chemically-assisted etching of copper over dielectric materials.[0003]Copper (Cu) is the primary material used in integrated circuits (ICs) to create electrically conductive interconnects, and the etching of copper in ICs using focused ion beam (FIB) techniques is important in the field of circuit editing (CE) for failure verification and debugging of the ICs. Circuit editing of ICs with a focused-ion-beam (FIB) system requires that copper planes and traces be milled (cut) uniformly and cleanly so as to electrically isolate circuit elements across the separation created.[0004]Achieving clean uniform FIB etching of copper for CE is difficult. In spite of significant past efforts ...

AI Technical Summary

Benefits of technology

[0016]The invention affords FIB copper etching processes and agents that address the foregoing and other known problems of FIB copper etching processes and agents for CE of ICs. In particular, the invention affords FIB copper etch assisting agents that address the two principal problems with known etch assisting agents, i.e., protection of the adjacent dielectric when etching copper, and rendering sputtered and re-deposited conductive copper non-conductive to prevent electrical short circuiting. The etch assisting agents of the invention protect the adjacent dielectric during copper etching by having low volatility which affords high stickiness and long resident time when absorbed on the dielectric surface, and by being formed of compounds that form oxides or nitrides and contribute to the replenishment of dielectric lost by ion beam sputtering. The etch assisting agents additionally afford efficient oxidation of re-deposited copper to convert the sputtered and re-deposited conductive copper to non-conductive compounds.

Problems solved by technology

Achieving clean uniform FIB etching of copper for CE is difficult.

In spite of significant past efforts to improve the quality of FIB copper etching processes, problems persist and improvements are needed in two main areas.

Both of these problems arise from the properties of copper.

This can inevitably lead to the unwanted re-deposition of conductive copper which causes problems as discussed below.

Grains with different orientations exhibit significantly different FIB etching rates and, therefore, FIB etching of copper is very non-uniform and uneven.

It results in a very rough surface on the etched copper, and may perforate the copper layer down to the underlying dielectric.

This may lead to significant damage of the underlying dielectric, and may result in electrical short circuiting of IC interconnections from re-deposited electrically conductive copper.

As copper removal by volatilization is impossible, the selectivity that is achievable for copper etching is low relative to other materials, e.g., aluminum, where volatile etching byproducts are created and the efforts to improving copper removal have focused principally on protecting the dielectric rather than enhancing the removal of copper.

This creates significant problems since the milled copper material that is intended to be removed re-deposits in this area, making electrical isolation of a signal difficult or impossible.

However, not all oxidizing agents will work with copper.

Halogens, with the exception of fluorine, spontaneously react with and corrode copper without any activation by an ion beam, and they seriously degrade the conductivity of the copper.

Even if halogen agents such as chlorine, bromine and iodine are carefully controlled, they can remain in the FIB vacuum chamber for a long time and continue to corrode any exposed copper.

Otherwise, subsequent operations can be seriously affected.

As shown, the underlying dielectric is heavily damaged in areas where the copper removal was the greatest, while in other areas significant amounts of copper remain to be removed.

Since copper removal is due to ion beam sputtering (not volatilization), copper removal occurs relatively non-uniformly and unevenly on different grains.

However, these compounds have been found to be useless for protecting the new low-k dielectrics being increasingly used in ICs.

The main problem is that many low-k dielectrics contain carbon as one of the main components of the dielectric structure, which is why low-k dielectrics are sometimes called “organic” dielectrics.

While Nitro-ethanol has been effective in limiting dielectric etching, it has not been very effective addressing the problem of re-deposition of sputtered conductive copper material on surfaces adjacent to the IC work area.

This re-deposited material may render the IC partially or totally inoperative by electrically short circuiting interconnects or grounding copper power planes.

From the figure, it can be concluded that while the Nitro-ethanol copper etch assisting compound functioned well to protect the underlying dielectric, it is not effective in addressing conductive copper re-deposition.

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