Process for improving copper line cap formation

Abstract

An integrated circuit includes a semiconductor substrate, a low-k dielectric layer over the semiconductor substrate, a first opening in the low-k dielectric layer, and a first diffusion barrier layer in the first opening covering the low-k dielectric layer in the first opening, wherein the first diffusion barrier layer has a bottom portion connected to sidewall portions, and wherein the sidewall portions have top surfaces close to a top surface of the low-k dielectric layer. The integrated circuit further includes a conductive line filling the first opening wherein the conductive line has a top surface lower than the top surfaces of the sidewall portions of the diffusion barrier layer, and a metal cap on the conductive line and only within a region directly over the conductive line.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the present invention, and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:

FIG. 1 illustrates a conventional interconnect structure, wherein metal caps extend onto top edges of the respective diffusion barrier layers;

FIGS. 2 through 7C are cross-sectional views of intermediate stages in the manufacturing of a preferred embodiment; and

FIG. 8 illustrates a dual damascene structure embodiment of the present invention.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The making and using of the presently preferred embodiments are discussed in detail below. It should be appreciated, however, that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed are merely illustrative of specific ways to make and use the invention, and do not limit the scope of the invention.

FIGS. 2 through 7C are cross-sectional views of intermediate stages in the making of a preferred embodiment of the present invention. FIG. 2 illustrates the formation of trenches 22 and 24 in a dielectric layer 20. In the preferred embodiment, dielectric layer 20 is an inter-metal dielectric (IMD) layer with a dielectric constant (k value) lower than about 3.5. Low-k dielectric layer 20 preferably contains nitrogen, carbon, hydrogen, oxygen, fluorine, and combinations thereof. The exemplary materials include un-doped silicate glass (USG), fluorinated silica glass (FSG), and the like. Furthermore, the k value of low-k dielectric layer 20 may be lower than about 2.5 (hence referred to as an extremely low-k dielectric layer).

A dielectric layer 21, which acts as a chemical mechanical polish (CMP) stop layer, is formed on dielectric layer 20. Preferably, CMP stop layer 21 comprises a material selected from silicon nitride, silicon oxynitride, oxides, carbon-doped oxides, tetra-ethyl-ortho-silicate (TEOS), and combinations thereof. The preferred formation method is plasma enhanced chemical vapor deposition (PECVD). However, other commonly used methods such as high-density plasma CVD (HDPCVD), atomic layer CVD (ALCVD), and the like can also be used. In an exemplary embodiment wherein CMP stop layer 21 comprises silicon nitride or silicon carbide, the formation is preferably performed in a chamber in which gaseous precursors such as silane (SiH₄) and ammonia (NH₃) are introduced for a chemical reaction.

FIG. 3 illustrates a blanket formation of a diffusion barrier layer 28, which covers the sidewalls and bottoms of trenches 22 and 24. Diffusion barrier layer 28 is preferably formed of a material comprising titanium, titanium nitride, tantalum, tantalum nitride, ruthenium, ruthenium nitride, titanium compound, tantalum compound, and combinations thereof. The preferred formation methods include physical vapor deposition (PVD), atomic layer deposition (ALD), and other commonly used methods.

Referring to FIG. 4, a seed layer (not shown), which preferably includes copper or copper alloys, is formed on diffusion barrier layer 28. A conductive material 30 is then filled into trenches 22 and 24, preferably using plating. Conductive material 30 preferably comprises copper or copper alloys, although other materials such as aluminum, tungsten, silver, and combinations thereof, can also be used.

Referring to FIG. 5, a CMP is performed to remove excess materials, and the top surface of the conductive material 30 is reduced until level with a top surface of low-k dielectric layer 20 (or a top surface of CMP stop layer 21 if it exists). In the case where CMP stop layer 21 exists, the CMP stops at CMP stop layer 21. As a result, diffusion barrier layers 40 and 42 and conductive lines 32 and 34 are formed. Throughout the description, conductive lines 32 and 34 are alternatively referred to as copper lines 32 and 34 although they may include other conductive materials.

Referring to FIG. 6, copper lines 32 and 34 are preferably recessed to form recesses 44 and 46, which preferably have a depth of between about 100A and about 300A, and more preferably between about 100A and about 200A. Typically, after the CMP process, the top surface of copper lines 32 and 34 tend to have a natural copper oxide layer 38 (refer to FIG. 5) due to the exposure of the copper lines in an oxygen-containing environment. Copper oxide layer 38 is then removed using an acid and thus recesses 44 and 46 are formed. The thickness of the naturally formed surface copper oxide layer 38, however, may be greater than or less than the desired depth of the recesses. When the thickness of the copper oxide layer 38 is less than desired, this thickness is increased preferably by oxidizing metal lines 32 and 34 in an oxygen-containing environment, for example, in a plasma chamber, using oxygen plasma or downstream plasma. Copper oxide layer 38 is then removed in a wet cleaning process, for example, using H₂SO₄, citric acid and a wetting agent. This embodiment (forming copper oxide layer 38, and then removing oxide layer 38) is advantageous over the method of directly etching metal lines 32 and 34 to form recesses. The reason is the thickness of oxide layer is more controllable, as after an oxide layer having certain thickness is formed, the process for further oxidizing underlying metal lines 32 and 34 will be slowed down due to the fact that oxygen atoms/ions now need to penetrate the oxide layer before they can reach metal lines 32 and 34.

Conversely, if the thickness of copper oxide layer 38 is greater than desired, only an upper portion of the copper oxide layer 38 is removed, and the lower portion of copper oxide layer 38 is reduced to copper. The reduction process may also be performed as a cleaning process to remove naturally formed copper oxide. As is known in the art, the sheet resistance of copper lines 32 and 34 is proportional to their heights. Therefore, it is undesirable to recess copper lines 32 and 34 too much as to cause a reduction in the sheet resistance. A reduction reaction is thus performed to reduce the remaining oxide to copper. The reduction reaction is preferably performed in a reduction solution using either an electroless method or an electrolytic method.

For the electroless reduction, the reduction solution preferably includes a cyclic borane compound. Examples of such cyclic borane compounds include morpholine borane, piperidine borane, pyridine borane, piperazine borane, 2,6-lutidine borane, N,N-diethylaniline borane, 4-methylmorpholine borane, 1,4-oxathiane borane, and combinations thereof. In other embodiments, reduction solutions include, but are not limited to, dimethylaminoborane (DMAB), diethylaminoborane, morpholine borane, and combinations thereof. In yet other embodiments, reduction solutions may include ammonium, alkali, alkaline earth metal borohydrides, hypophosphites, sulfites, bisulfites, hydrosulfites, metabisulfites, dithionates, tetrathionates, thiosulfates, thioureas, hydrazines, hydroxylamines, aldehydes (including formaldehyde and glyoxal), glyoxylic acid, reducing sugars, and combinations thereof.

Alternatively, the reduction action may be performed using an electrolytic method by applying an electric current, wherein the reduction of copper oxide to metallic copper is performed in an alkaline-based solution containing, for example, LiOH or KOH.

FIG. 7A illustrates metal caps 48 and 50 formed on conductive lines 32 and 34, respectively. The metal caps 48 and 50 preferably comprise materials such as cobalt, nickel, tungsten, molybdenum, silicon, zinc, chrome, boron, phosphorus, nitrogen, and combinations thereof. Metal caps 48 and 50 may also be composite layers comprising more than one layer, wherein each of the layers includes one or more of the above-discussed materials. The preferred thickness of metal caps 48 and 50 is preferably between about 25A and about 250A, and more preferably between about 100A and about 200A.

In the preferred embodiment, metal caps 48 and 50 are formed by electroless plating and are selectively formed only on exposed surfaces of copper lines 32 and 34, respectively. One advantageous feature of selective formation of metal caps 48 and 50 is that top surfaces of metal caps 48 and 50 may be deposited higher, level with, or lower, than the respective diffusion barrier layers 40 and 42, depending on the design preferences. Electroless plating is preferably performed, for example, by using a plating liquid containing cobalt ions, a complexing agent, a pH buffer, a pH adjusting agent, and an alkylamine borane as a reducing agent. Depending on the preferred composition of metal caps 48 and 50, the plating liquid may further contain refractory (high-melting point) metals such as tungsten ions or molybdenum ions. The cobalt ions contained in the plating liquid may be supplied from a cobalt salt, for example, cobalt sulfate, cobalt chloride or cobalt acetate. Other desired components preferred in metal caps 48 and 50 are also included in the plating liquid in the form of ions. The structure formed in the previously discussed steps is submerged in the plating liquid, wherein the temperature of the plating liquid is preferably in a range of between about 30° C. and about 90° C.

In the preferred embodiment, metal caps 48 and 50 are selectively formed only on the respective copper lines 32 and 34, but not on top edges of diffusion barrier layers 40 and 42 and dielectric layer 20. This may be achieved by using a non-palladium catalyst, thus enabling a direct electroless plating. In other embodiments, metal caps 48 and 50 can be formed by depositing a metal cap layer using common techniques such as PVD, sputtering, and ALD, and then etching the metal cap layer to form metal caps 48 and 50.

During the formation of metal caps 48 and 50, due to process variations, a small amount of metal cap materials may be undesirably formed on top edges of diffusion barrier layers 40 and 42, and thus a post-cap cleaning is performed to remove undesired portions. For example, an etching process may be performed to remove portions of metal caps 48 and 50 on barrier layers 40 and 42, so that only the portions in the recesses are left. Alternatively, a CMP process may be performed.

In the preferred embodiment, in order to achieve the optimum results, the top surfaces of metal cap layers 48 and 50 are leveled with the top edges of the diffusion barrier layers 40 and 42 and the CMP stop layer 21 (or the top surface of low-k dielectric layer 20 if no CMP stop layer 21 is formed). However, the top surfaces of metal caps 48 and 50 may be higher or lower than the top surfaces of the diffusion barrier layers 40 and 42, as is illustrated in FIGS. 7B and 7C. The difference D′ is preferably less than about 50A.

As is known in the art, leakage currents and parasitic capacitance are more significant when the copper lines are close to each other. The preferred embodiments are therefore preferably used for dense patterns. For example, if the spacing S2 (refer to FIG. 7A) is less than about 0.9 μm, and more preferably less than about 0.4 μm, and even more preferably less than about 0.2 μm, the preferred embodiment is applied. Alternatively, the decision of whether to apply the preferred embodiment is determined by the relative spacing. If a ratio of spacing S2 to a width W of the copper line (including diffusion barrier layer 40) is less than about 10, the preferred embodiment is preferably applied. If the ratio is less than about one, the preferred embodiment is more preferably used. On the other hand, if the ratio is greater than about 10, whether to apply the process of the present invention is a design decision, and other factors such as cost may be taken into account.

In the embodiments provided in the preceding paragraphs, a single damascene process is discussed to explain the concepts of the preferred embodiment. One skilled in the art will realize that the teaching is readily available for dual damascene processes. FIG. 8 illustrates an interconnect structure comprising dual damascene structures. Similarly, in this embodiment, metal caps 60 and 62 are preferably formed only on respective copper lines 64 and 67, but not the diffusion barrier layers 66 and 68. One skilled in the art will realize the corresponding formation steps.

By using the preferred embodiments of the present invention, both the parasitic capacitances and leakage currents of the interconnect structures can be reduced.

Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, and composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed, that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present invention. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.

Claims

1. A method of forming an integrated circuit, the method comprising: providing a semiconductor substrate;forming a low-k dielectric layer over the semiconductor substrate;forming an opening extending from a top surface of the low-k dielectric layer into the low-k dielectric layer;forming a diffusion barrier layer in the opening covering the low-k dielectric layer in the opening, wherein the diffusion barrier layer has a top edge substantially level with a top surface of the low-k dielectric layer;filling a copper line into the opening;recessing a top surface of the copper line; andforming a metal cap on the copper line using a selective deposition method, wherein the metal cap is only formed substantially within a region directly over the copper line.

2. The method of claim 1, wherein the metal cap has a top surface higher or lower than the top edge of the diffusion barrier layer.

3. The method of claim 2, wherein the step of recessing the top surface of the copper line comprises: oxidizing the top surface of the copper line to form a copper oxide layer; andremoving the copper oxide layer from the top surface of the copper line.

4. The method of claim 3, wherein the step of oxidizing the top surface of the copper line comprises oxygen plasma oxidation.

5. The method of claim 1 further comprising reducing a copper oxide layer on the top surface of the copper line to copper.

6. The method of claim 1, wherein the step of forming the metal cap is performed using electroless plating.

7. The method of claim 6, wherein the electroless plating is free from palladium catalysts.

8. The method of claim 1, wherein the diffusion barrier has a spacing from an additional diffusion barrier layer of a neighboring copper line, and wherein a ratio of the spacing to a combined width of the copper line and the diffusion barrier layer is less than about one.

9. A method of forming an integrated circuit, the method comprising: providing a semiconductor substrate;forming a low-k dielectric layer over the semiconductor substrate;forming a opening extending from a top surface of the low-k dielectric layer into the low-k dielectric layer;forming a diffusion barrier layer in the opening and covering the low-k dielectric layer in the opening;filling copper into the opening;planarizing the copper to form a copper line;oxidizing a top layer of the copper line to form a copper oxide layer;removing the copper oxide layer; andforming a metal cap on the copper line.

10. The method of claim 9 further comprising forming a chemical mechanical polish (CMP) stop layer on the low-k dielectric layer before the step of forming the opening, wherein after the step of planarizing the copper, a top edge of the diffusion barrier layer is level with a top surface of the CMP stop layer.

11. The method of claim 9, wherein the metal cap is formed using electroless plating with palladium-free catalysts, and wherein the metal cap is only within a region directly over the copper line.

12. The method of claim 9 wherein after the step of planarizing the copper, horizontal portions of the diffusion barrier layer are removed.

13. The method of claim 9, wherein the step of oxidizing the top layer of the copper line comprises oxygen plasma oxidation.

14. The method of claim 9 further comprising, before the step of forming the metal layer, reducing a copper oxide layer on a top surface of the copper line to copper.

15. The method of claim 14, wherein the step of reducing is performed in a reduction solution comprising a cyclic borane compound selected from the group consisting essentially of morpholine borane, piperidine borane, pyridine borane, piperazine borane, 2,6-lutidine borane, N,N-diethylaniline borane, 4-methylmorpholine borane, and 1,4-oxathiane borane, and combinations thereof, and wherein the reduction solution further comprises a reducer selected from the group consisting essentially of dimethylaminoborane (DMAB), diethylaminoborane, morpholine borane, and combinations thereof.

16. The method of claim 14, wherein the step of reducing is performed in a reduction solution comprising a reducer selected from the group consisting essentially of ammonium, alkali, alkaline earth metal borohydrides, hypophosphites, sulfites, bisulfites, hydrosulfites, metabisulfites, dithionates, tetrathionates, thiosulfates, thioureas, hydrazines, hydroxylamines, aldehydes (including formaldehyde and glyoxal), glyoxylic acid, reducing sugars, and combinations thereof.

17. The method of claim 14, wherein the step of reducing is performed by applying a current in an alkaline-based solution.

18. The method of claim 9, wherein the metal cap has a top surface higher or lower than the top edge of the diffusion barrier layer.