The present invention relates to a process for etching materials in semiconductor products.

In fabricating semiconductor products, materials such as titanium are sometimes combined with other materials such as silicon to form a resultant material of low resistivity. In the case of titanium and silicon, the titanium may be combined with silicon to form titanium silicide (TiSi ) which may have a resistance which is lower than the resistance of silicon by a factor of twenty. This low resistivity material is known to be useful in a variety of applications, such as the formation of relatively long word lines in semiconductor memories.

A known problem with the use of suicides (which, as used herein, means silicide compounds) in semiconductor products is the difficulty with which silicide is etched. Where the silicide overlies a layer of polysilicon, it has been difficult to etch through the silicide and through the polysilicon without undercutting the polysilicon material or etching the dielectric layer. Such difficulty presumably arises because of the tendency of the etchant to remove polysilicon faster than it removes the silicide.

An associated problem is that of obtaining an anisotropic etch, i.e. an etch ideally in one direction only, such as required to obtain apertures having substantially vertical si ewalls. Existing l terature in the semiconductor field purports to obtain anisotropic etching in polysilicon using plasma etching techniques and certain gases, for example, see U.S. Patent Nos. 4,208,241 and 4,211,601. However, these existing techniques do not provide anisotropic etching of suicides, at least not of the character which is required for high volume production.

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Another difficulty with existing etching techniques is their tendency to etch deeper than desired so as to remove portions of an underlying layer which is intended to be left intact. When the underlying layer is a gate oxide, removal of the gate oxide leads to difficulties with which those skilled in the art are familiar.

It is an object of the present invention to provide an improved process for etching materials which include suicides.

According to the present invention there is provided a process for etching selected materials in a semiconductor product having a lower layer, an intermediate layer, and an upper sil cide layer, the process comprising the steps of:

exposing the semiconductor product to a first gas comprising substantially C2C1F5 at reduced pressure for a time sufficient for said first gas to etch through the silicide layer; and exposing the semiconductor product to a second gas comprising Cl2 at reduced pressure for a time sufficient for said second gas to etch through the intermediate layer.

The invention also extends to a technique enabling titanium silicide or other substances to be etched anisotropically by using at least two steps wherein the silicide is etched using Freon 115 (C2CIF5) or a suitable substitute in a reactive ion etch (RIE) followed by etching the underlying layer, typically polysilicon, with a mixture of chlorine and fluorine obtained from, for example, perf1uoroethane {C2F6) and chlorine gas

(Cl2). This mixture has a higher selectivity for polysilicon than for silicon oxide (S1o2>t so that the entire process can be used to etch a silicide layer and intermediate polysilicon layer without substantially etching an underlying silicon oxide layer.

An embodiment of the present invention will hereinafter be described, by way of example, with reference to the accompanying drawings, in which:

Figure 1 is a sectional view of a portion of a wafer which may be etched according to the invention;

Figure 2 is a schematic representation of the plates in a parallel plate reactor, illustrating a polya ide film which preferably covers surfaces of the plates and a wafer supported by the lower plate; and

Figure 3 illustrates a portion of an etched wafer having redeposited silicon and bristles of the type which are eliminated by the present invention.

The present etching technique is particularly applicable to the fabrication of semiconductor memories which employ silicide word lines. However, the invention is generally applicable to any semiconductor product in which patterns are etched through a silicide structure which overlies polysilicon.

An exemplary structure which may be etched by a process of the invention is shown in Figure 1. The illustrated, structure is a portion of a semiconductor wafer having a substrate 10 covered, at least in part, by a dielectric layer 12 which is usually silicon dioxide.

Covering the dielectric 12 is a layer of doped polysilicon 14, and covering the polysilicon is a layer of titanium silicide (TiSi2) 16. To form a target area which is to be etched, a pattern-defining layer of photoresist, for example, is established conventionally at 18 and 20 to leave an aperture A.

The layers of silicide 16 and polysilicon 14 which are beneath the aperture A will be etched as described below. It is to be understood, however, that many more such apertures will normally be formed to define a large number of target areas which are etched simultaneously.

The purpose of the present process is to remove the polysilicon 14 and the silicide 16 where they underlie the aperture A so as to leave substantially vertical sidewalls as indicated by the dashed lines 22 and 24. In addition, the photoresist is not to be undercut or substantially damaged, nor is the dielectric layer 12 to be etched to any substantial degree.

To meet these objectives, a two step etching process is performed in a reaction vessel such as a conventional parallel plate plasma etching chamber. The first etching step is a reactive ion etch, as opposed to a plasma etch. Plasma etching and reactive ion etching (RIE) can occur when reactive gases are introduced into a partially evacuated chamber containing two electrodes to which an AC potential is applied. The potential is dropped across a sheath region near the walls and electrodes and ions and electrons in those regions are accelerated. When these ions strike a target surface (a wafer placed on an electrode), they can pysically knock atoms off the surface (sputtering) or they can act as a catalyst for chemical reactions. If the chemical reaction at the surface results in the formation of a volatile molecule, some of the surface is removed (etched) by this process. Since the bombardment occurs on the surface of the target and not on any walls that might be patterned into the surface by photolithography techniques, most of the etching can be made to occur on the surface with very little effect on the walls. This is called anisotropic etching. In RIE the pressure and electrode power arrangements are set up to increase the ion bombardment relative to the normal plasma etch configuration.

Thus, a reactive ion etch is employed in which, for example, the lower plate of the chamber is powered and a low pressure (usually less than about 100 millitorr) is maintained, as contrasted with a plasma etch which is achieved traditionally by powering the upper plate and using a pressure generally greater than 100 millitorr. .

During this first step of the present process, the silicide is removed, and preferably part of the polysilicon is also removed. Oxygen can be added to this first etch at about 5 SCCM thereby to increase the etch rate by about 16$. However, oxygen also attacks the photoresist so must be added with care, and in the preferred example descri ed herein, it is not used.

In the second step, a different gas is used to remove the remainder of the polysilicon without substantially removing any of the underlying dielectric layer.

Two specific techniques using this two step etching process will now be described; the first technique involves covering the chamber plates with a substance, whilst the second technique does not.

In the first technique, both etching steps are carried-out after the surfaces of the chamber plates have been covered with an organic film-forming material comprised of carbon hydrogen and oxygen, but which is free of metal ions and halogen atoms, such as polyamide, which emits molecules of the character which are included in the pattern defining layer 18, 20. Where the pattern defining layer 18, 20 is conventional photoresist, the covering of the chamber plates is selected to release atoms such as hydrogen, oxygen or carbon, and to avoid releasing molecules of metal and certain active species such as chlorine and fluorine.

The polyamide film permits the second etch step etching to occur using higher pressures without eroding the photoresist and using higher precentage of (Cl2) without reducing the an sotropy of the etch. This results in a higher selectivity of the etch over oxide. At the same time, the formation of br stles on the dielectric layer and polysilicon redeposition are avoided. Also the uniformity of the resultant etch is improved when the chamber is coated with polyamide.

The effects attributed to this coating have been determined experimentally by the inventors. Since the film is an insulator, the effects due to covering the chamber electrodes and walls with this material will be complex. For example, secondary electrons emitted from the electrodes and walls during ion coll sions will be greatly increased. This, in turn, will increase the electron temperature in the chamber. The electron temperature has a major effect on the cracking pattern of the gases used so the composition of the plasma will be changed by the film.

The two techniques are shown by the examples in the following table for 4000A of polysilicon covered by 2200A of TiSι ^' 2.

Example 1 Example 2

(with polyamide) (no polyamide)

Freon 115 pressure 12 mT 12 mT

Freon 115 flow rate 10 SCCM 10 SCCM power (1st etch) 650 watts 650 watts etch rate (1st etch) 300 A/min 330 A/min plate temperature

(1st etch) 23°C 230C

Cl2 amount 25% (volume) 16% (volume)

Cl flow rate 4.5 SCCM 0.8 SCCM

C2F6 flow rate 13.5 SCCM 4.2 SCCM

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pressure (2nd etch mixture) 100 mT 50 T power (2nd etch) 150 watts 150 watts etch rate (2nd etch) 175 A/min 200 A/min plate size 55.9cm Dia. 55.9cm Dia. plate spacing 4.1cm 4.1cm frequency 13.56 MH _Z 13.56 MH _Z plate temperature

The specific etching chamber used i s a Pl asma-Therm P -2440 Dual reactive Ion and Plasma Etch System, avail able from Plasma-Therm, Inc. , Route 73, Kresson, NJ 08053. Other chambers can be used.

As shown in Figure 2, the top surface of the chamber' s l ower pl ate 26 is covered with a polyami de film 28 whose thickness may be about five mil s. One such film which provides sati sfactory resul ts i s known as Kapton made by Dupont. apton incl udes a sil icone adhesive backing for adheri ng the film to the plate. The wafer 30 to be processed sits on the film 28.

The lower surface of the chamber upper plate 32 is covered with a similar polyamide film 34. In practice, however, the entire inner surface of the etching chamber may be covered by -a similar film although satisfactory results can be provided merely by covering the plates.

After having applied the polyamide film, the wafer is placed in the etching chamber. Gaseous Freon 115 ^ClFs) is introduced into the chamber, whose power and pressure are selected to provide a reactive ion etch. In the preferred technique, a power of about 650 watts is employed, the Freon 115 is maintained at a flow rate of 12 SCCM (standard cubic centimeters per minute) at

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10 mill torr, and the temperature of the lower plate is maintained at 23°c. These conditions are maintained at least until the silicide 16 has been etched through. A typical etch rate for a silicide layer is about 300 Angstroms per minute.

In the second step of the process, the semiconductor wafer remains in the etching chamber, which need not have been opened. The previously used gas is replaced by a second gas having Cl2 as one component and preferably perf1uoroethane (C2F6) as another component. The amount of Cl2 included in this second step is selected to provide a highly anisotropic etch for polysilicon without substantially etching the dielectric layer 12. Taking this constraint into account, the second gas mixture is preferably about 25 percent Cl2 by volume, the remainder comprising perfluoroethane {C2F6 With the lower pl te at a temperature of 23 ⁰ Q, the C2F6 is held at a flow rate of about 13.5 SCCM, the Cl2 is held at a flow rate of about 4.5 SCCM, the pressure is maintained at 100 millitorr, and a power of 150 watts is applied. Under these conditions, the remainder of the polysilicon is removed without substantially etching the underlying layer of oxide. A typical etch rate for a heavily o doped polysilicon layer is 175 A/min. The underlying layer of o oxide will be etched at about 11 A/min.

In the second technique, the polyamide film is not used. The first step of etching through the silicide is achieved exactly as in the first techn que described above by exposing the wafer to gaseous Freon 115 ^ClFs) at a pressure of about 12 millitorr and a flow of about 10 SCCM and a power of 650 watts is applied. In the second step, the wafer is exposed to the same chlorine and perf1uoroethane gases except that the flow of chlorine is reduced substantially to about 0.8 SCCM and the flow of perfluoroethane is about 4.2 SCCM. The pressure is reduced to 50 millitorr,

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and a power of 150 watts is applied. The reason for operating at such a low pressure is to avoid the formation of bristles and the redeposition of polysilicon which can occur at higher pressures when the polyamide film is not used. To explain more fully, 5 Figure 3 illustrates bristles 36 (greatly enlarged) which form on the polysilicon during etching at higher pressures without the polyamide film.

The amounts of gases set forth in Example 1 and Example 2 can be 10 varied. In the second etching step, it has been determined that the process does work where the volume percentage of chlorine is in a range of from about 8 percent to about 35 percent. Also, it has been determined that the pressure of the Freon 115 gas can be in a range of 10 millitorr to 300 millitorr, but that best 15 results obtain when the pressure is from 10 to 40 millitorr. Further, good results are expected at pressures down to 1 millitorr. The second gas may be at a pressure in a range of about 50 to about 350 millitorr, although results at a pressure higher than 150 millitorr show a degradation of anisotropy of the 20 etch.

An advantage of the present invention over processes of the prior art relates to the problem of the redeposition of etched polysilicon on the walls of the Aperture A as shown at 38. Such 25 redeposition can fall off when the photoresist is removed and can form an unwanted mask for subsequent etching steps. Both of these problems are avoided by each of the two techniques described above.

* 30 When the second techn que is employed, the photoresist may be eroded slightly, but not critically, by the ion bombardment. On

^ the other hand, no erosion of the photoresist occurs when the polyamide film is used at the higher pressures, nor are bristles or polysilicon redeposition encountered. Also, the uniformity

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of the etch over the area of the wafer is improved when the polyamide film is used. Accordingly, at present the first technique is preferred.

With both of the techniques described, a very high degree of anisotropy results. Undercutting of the photoresist and etching of the oxide are substantially eliminated.

In practicing the invention, the etch times are determined by measuring etch rates and applying those rates to the thickness of o the film to be etched. For example, for an etch of 2200 A of o

TiS 2 on 4000 A of heavily doped poly. Use the first etch for 15 o minutes, which leaves about 1700 A of the poly. Use the second etch for 12 minutes. This would be about 2 minutes of overetch to ensure clearing the poly off of the oxide. The edges of the wafer might clear early allowing the second etch to work on the o oxide for as much as 7 minutes. At the rate of 11 A/Min on o oxide, this would use up 77 A of gate oxide. This is perfectly acceptable.

The invention has been described above in terms of two techniques for applying the process to structure to be etched. Of course, alternate techniques can be used. For example, a different etching chamber can be used, such as a "hex" etching chamber. This differs from a conventional parallel plate system in that the cathode is in the form of a hexagon surrounded by a larger anode to give a high ratio of anode to cathode area. The pressure, flow, and power levels required to optimize the etch will change with the plate size, plate spacing and frequency of the reactor which is used to perform the etching steps.

Additionally, the preferred percentages of gases may be altered to obtain various combinations of anisotropy and selectivity.

Indeed, the gases need not be the same as described above to practice the process of the invention. We consider that if one arranges the plasma to contain the same ratio of reactants and recombinants under similar electrical conditions, the etch will be basically the same regardless of the parent gases used. Thus, other combinations of gases containing fluorine and chlorine could be used as long as the percentages after cracking are similar. The C F5 could be replaced by perhaps, C3F8, or any other carbon-fluorine compound, with some experimentation. The inventors have tried to use CFC13 (Freon 13) in place of C2F plus Cl2, but the chlorine percentage was too high and the result was an isotropic etch, as is well known for Freon 13 on poly. The selection depends on percentages after cracking, and the cracking pattern depends on the electron temperature, which in turn depends on the gases. In addition, the process may generally be used with other suicides such as tantalum and tungsten suicides on doped polysilicon.

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