# Patent

## Title
Method for reducing the effective thickness of gate oxides by nitrogen implantation and anneal

## Abstract

A method for reducing the effective thickness of a gate oxide using nitrogen implantation and anneal subsequent to dopant implantation and activation is provided. More particularly, the present invention provides a method for fabricating semiconductor devices, for example, transistors, which include a hardened gate oxide and which may be characterized by a relatively large nitrogen concentration at the polysilicon/gate oxide interface and a relatively small nitrogen concentration within the gate oxide and at the gate oxide/substrate interface. Additionally, the present invention provides a method for fabricating a semiconductor device having a metal gate strap (e.g., a metal silicide layer) disposed over the polysilicon layer thereof, which device includes a hardened gate oxide and which may be characterized by a relatively large nitrogen concentration at the silicide/polysilicon interface to substantially prevent cross-diffusion.

## Background
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to semiconductor devices and methods for their fabrication. More particularly, the present invention relates to hardening of gate oxides in semiconductor devices by nitrogen implantation and anneal subsequent to dopant implantation and activation to increase the dielectric constant thereof and, accordingly, decrease the effective thickness of the gate oxide.
2. State of the Art
Higher performance, enhanced reliability and greater packaging density are constant goals of the semiconductor industry. However, as components of integrated circuits become increasingly smaller to meet these goals, it has become more and more difficult to produce semiconductor devices capable of reliable, long-term operation, particularly in view of the operational stresses each component of a state of the art semiconductor device must endure. For instance, as surface P-channel transistors decrease in size, the size and thickness of the gate oxides included in such transistors must also decrease. However, as gate oxide thickness continues to be compressed, the gate oxides become increasingly permeable to dopants included in the overlying polysilicon gate electrodes. Further, they become less resistant to hot electron degradation and more susceptible to breakdown voltages below normal operating voltages.
To address these problems, various processes for hardening gate oxides and, accordingly, reducing the effective thickness thereof, have become highly beneficial to the fabrication of state of the art semiconductor devices. For instance, a method well known in the art for forming hardened gate oxides involves implanting nitrogen into a semiconductor substrate (e.g., a silicon substrate) followed by thermal oxide growth on the top surface of the substrate. During the thermal oxide growth, oxynitride is formed at the gate oxide/substrate interface. As oxynitride has a higher dielectric constant than pure oxide, the resultant oxide effective thickness is smaller than it would be without the nitrogen implantation.
Another conventional method for forming hardened gate oxides involves implanting nitrogen into the gate oxide after formation thereof. The method includes providing a semiconductor substrate, forming a gate oxide layer over the semiconductor substrate and subjecting the gate oxide layer to a nitrogen implantation treatment. The nitrogen penetrates the top surface of the gate oxide layer but does not initially bind therewith. As such, the nitrogen implantation is followed by an oxidative anneal, which results in the formation of oxynitride in the gate oxide layer and at the gate oxide/substrate interface. Again, due to the increased dielectric constant of the oxynitride relative to pure oxide, the resultant gate oxide layer has a smaller effective thickness than it would have without the nitrogen implantation.
In addition to having an increased dielectric constant, relative to nonhardened devices, gate oxides hardened by known methods are generally less permeable to dopants included in polysilicon electrodes, more resistant to hot electron degradation and less susceptible to breakdown voltages below normal operating voltages. However, known processes for hardening gate oxides also have drawbacks. For example, in order to prevent diffusion of dopants from the polysilicon electrode and-into and through the gate oxide, known hardening processes often provide a high concentration of nitrogen at the interface of the gate oxide and the underlying semiconductor substrate. However, as is known to those of ordinary skill in the art, excessive nitrogen at the gate oxide/substrate interface significantly degrades transistor performance.
Accordingly, in terms of device performance and reliability, it has been found to be advantageous to fabricate a gate oxide layer having a relatively small nitrogen concentration at the gate oxide/substrate interface with the bulk of the nitrogen concentration being located at the polysilicon/gate oxide interface. The relatively large nitrogen concentration at the polysilicon/gate oxide interface effectively prevents diffusion of dopants from the polysilicon electrode and into and through the gate oxide layer while the relatively small nitrogen concentration at the gate oxide/substrate interface confers resistance to hot electron degradation without substantially affecting device performance. Further, in addition to the nitrogen concentration at the gate oxide/substrate interface, it has been found to be advantageous for a relatively small concentration of nitrogen to be located within the gate oxide to aid in increasing the dielectric constant of the gate oxide and, accordingly, in reducing the effective thickness thereof. While some known processing techniques (e.g., rapid plasma nitridation (RPN) and decoupled plasma nitridation (DPN)) provide transistors including a gate oxide having a relatively large nitrogen concentration at the polysilicon/gate oxide interface and a relatively small nitrogen concentration within the gate oxide and at the gate oxide/substrate interface, such techniques are often prohibitively expensive.
At least one method has been developed in an attempt to provide a transistor including a gate oxide having some of the above-stated characteristics. U.S. Pat. No. 6,017,808 to Wang et al. (hereinafter “the ′808 patent”) describes a method for hardening a gate oxide designed to provide a transistor wherein a large peak of nitrogen exists within the polysilicon and gate oxide layers at the polysilicon/gate oxide interface, while a relatively smaller nitrogen peak occurs within the gate oxide layer and the underlying semiconductor substrate at the gate oxide/substrate interface. To achieve this structure, the method of the ′808 patent requires implanting nitrogen through a first polysilicon layer and into the gate oxide layer followed by an anneal step. After the implantation and annealing steps, a first, relatively large, nitrogen peak occurs entirely within the first polysilicon layer, a second, relatively smaller, nitrogen peak occurs at the polysilicon/gate oxide interface, and a third, relatively smaller still, nitrogen peak occurs at the gate oxide/substrate interface. However, due to its magnitude, the first nitrogen peak located entirely within the first polysilicon layer is somewhat counterproductive because it retards activation of subsequently implanted dopants, such as boron, within the first polysilicon layer. Therefore, the method of the ′808 patent requires removal of the portion of the first polysilicon layer, which includes the first nitrogen peak, without removing the portion of the first polysilicon layer, which includes the second nitrogen peak (i.e., the peak occurring at the polysilicon/gate oxide interface), to form a second polysilicon layer. Once the portion of the first polysilicon layer including the first nitrogen peak is removed to form the second polysilicon layer, a third, nitrogen-free polysilicon layer may be optionally formed over the second, nitrogen-implanted, polysilicon layer.
As will be readily appreciated, achieving the structure disclosed in the ′808 patent using the methods described therein is at best difficult, particularly in light of the continually decreasing thickness of polysilicon electrodes included in state of the art semiconductor devices. One of the most troublesome aspects of the method described in the ′808 patent is the need to remove only the portion of the nitrogen-implanted polysilicon layer including the first nitrogen peak. The reference teaches that this task may be accomplished using known wet etch, dry etch, or chemical mechanical processing techniques. However, the polysilicon layers used for polysilicon electrodes in state of the art transistors are exceedingly thin. The polysilicon electrodes of some state of the art devices may be as thin as seven or fewer molecular monolayers, and known etching and polishing processes are difficult to control with sufficient precision to remove only predetermined portions of material layers of such minute thicknesses. Moreover, in this context, the polysilicon layer will include varying concentrations of nitrogen at any given depth, and as the nitrogen concentration varies, the etch rate will also vary, making precise control of the etching process even more difficult. Thus, removing only the portion of the first polysilicon layer, including the first nitrogen peak, is extremely difficult, and known removal processes will most likely result in removal of too much or too little polysilicon material, resulting in transistors exhibiting impaired performance or reduced reliability.
A further problem, that of cross-diffusion, is encountered when a metal gate strap (e.g., a metal silicide layer) is disposed over the polysilicon layer. Cross-diffusion occurs, for example, in surface P-channel transistors having both P-type and N-type dopants that may diffuse across the silicide/polysilicon interface and contaminate underlying layers. A relatively large concentration of nitrogen at the silicide/polysilicon interface may substantially prevent dopant diffusion across the interface. However, known processing techniques do not provide semiconductor devices having a relatively large concentration of nitrogen at the silicide/polysilicon interface. In particular, a transistor fabricated utilizing the methods described in the ′808 patent would not alleviate cross-diffusion as the portion of the first polysilicon layer including the first nitrogen peak is removed therefrom. If, in later processing, a silicide layer were to be formed over the second polysilicon layer, there would be insufficient nitrogen at the silicide/polysilicon interface to effectively substantially prevent cross-diffusion across the interface. As an alternative embodiment, the ′808 patent describes a method wherein a third, nitrogen-free, polysilicon layer may be formed over the second polysilicon layer. If, in later processing, a metal gate strap were to be formed over the third polysilicon layer, there would be a substantial absence of nitrogen at the silicide/polysilicon interface and cross-diffusion would probably occur.
It would, therefore, be desirable to provide a method for fabricating semiconductor devices, for instance, transistors, which include a hardened gate oxide and which may be characterized by a relatively large nitrogen concentration at the polysilicon/gate oxide interface and a relatively small nitrogen concentration within the gate oxide and at the gate oxide/substrate interface, which may be easily incorporated into current fabrication processes and is not prohibitively expensive. Further, it would be desirable to provide a method for fabricating semiconductor devices (e.g., transistors), which include a metal gate strap disposed over the polysilicon layer thereof and which include a hardened gate oxide, the devices characterized by a relatively large nitrogen concentration at the silicide/polysilicon interface to substantially prevent cross-diffusion.
BRIEF SUMMARY OF THE INVENTION
The present invention, in one embodiment, includes a method for fabricating a semiconductor device, for example, a transistor, which includes a hardened gate oxide and which may be characterized by a relatively large nitrogen concentration at the polysilicon/gate oxide interface and a relatively small nitrogen concentration within the gate oxide and at the gate oxide/substrate interface. The method includes providing a semiconductor substrate having a gate oxide layer formed thereover, depositing a polysilicon layer atop the gate oxide layer, implanting dopants into the polysilicon layer, activating the implanted dopants and subjecting the resultant structure to a nitrogen implantation treatment sufficient such that nitrogen penetrates the polysilicon layer, the gate oxide layer and at least a portion of the semiconductor substrate. The dosage of nitrogen and the energy at which it is implanted may be adjusted such that the bulk of the implanted nitrogen is concentrated in the polysilicon layer while a relatively small concentration of nitrogen penetrates below the polysilicon/gate oxide interface. In later processing, an anneal may be performed that alters the nitrogen concentration profile such that a relatively large nitrogen concentration is exhibited in the polysilicon and oxide layers at the polysilicon/gate oxide interface and a relatively small nitrogen concentration is exhibited within the gate oxide and at the gate oxide/substrate interface.
In a semiconductor device having a gate oxide hardened utilizing the method of the present invention, the nitrogen at the polysilicon/gate oxide interface acts as a diffusion barrier to prevent diffusion of dopants from the polysilicon layer into and through the gate oxide layer. Additionally, nitrogen concentrated at the gate oxide/substrate interface also aids in preventing dopant diffusion; however, this concentration is not so great as to substantially impair device performance. Further, the nitrogen within the gate oxide layer reacts with the pure oxide to form oxynitride, which has an increased dielectric constant. Accordingly, the effective thickness of the gate oxide layer is reduced.
In another embodiment, the present invention includes a method for fabricating a semiconductor device, e.g., a transistor, which includes a metal silicide layer disposed over the polysilicon layer thereof and a hardened gate oxide, the device characterized by a relatively large nitrogen concentration at the silicide/polysilicon interface, a relatively smaller nitrogen concentration at the polysilicon/gate oxide interface and a relatively smaller still nitrogen concentration within the gate oxide and at the gate oxide/substrate interface. The method includes providing a semiconductor substrate having a gate oxide layer formed thereover, depositing a polysilicon layer atop the gate oxide layer, implanting dopants into the polysilicon layer, activating the implanted dopants, depositing a metal silicide layer over the polysilicon layer and subjecting the resultant structure to a nitrogen implantation treatment sufficient such that nitrogen penetrates the metal silicide layer, the polysilicon layer, the gate oxide layer and at least a portion of the semiconductor substrate. The dosage of nitrogen and the energy at which it is implanted may be adjusted such that the bulk of the implanted nitrogen is concentrated at the silicide/polysilicon interface while a relatively small concentration of nitrogen penetrates below the polysilicon/gate oxide interface. In later processing, an anneal may be performed that alters the nitrogen concentration profile such that a relatively large nitrogen concentration remains at the silicide/polysilicon interface, a relatively smaller concentration of nitrogen is exhibited at the polysilicon/gate oxide interface and a relatively smaller still concentration of nitrogen is exhibited within the gate oxide layer and at the gate oxide/substrate interface.
In a semiconductor device having a metal gate strap and a gate oxide hardened utilizing the method of the present invention, the nitrogen concentrated at the silicide/polysilicon interface acts to substantially prevent cross-diffusion of dopants across the interface and the concentration of nitrogen at the polysilicon/gate oxide interface acts as a diffusion barrier to prevent diffusion of dopants from the polysilicon layer into and through the gate oxide layer. Nitrogen concentrated at the gate oxide/substrate interface also aids in preventing dopant diffusion; however, this concentration is not so great as to substantially impair device performance. Further, the nitrogen within the gate oxide layer reacts with the pure oxide to form oxynitride and, accordingly, increases the dielectric constant of the gate oxide layer and reduces the effective thickness thereof.
Other features and advantages of the present invention will become apparent to those of ordinary skill in the art to which the present invention pertains through consideration of the ensuing description, the accompanying drawings and the appended claims.



BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
While the specification concludes with claims particularly pointing out and distinctly claiming that which is regarded as the present invention, the advantages of this invention may be more readily ascertained from the following description of the invention when read in conjunction with the accompanying drawings in which:
FIG. 1 is a side cross-sectional view schematically illustrating an intermediate structure in the fabrication of a semiconductor device having a hardened gate oxide formed in accordance with the method of the present invention;
FIG. 2A illustrates areas of nitrogen concentration in the intermediate structure of FIG. 1 after nitrogen implantation;
FIG. 2B illustrates areas of nitrogen concentration in the intermediate structure of FIG. 1 subsequent to anneal;
FIG. 3 is a side cross-sectional view schematically illustrating a second intermediate structure in the fabrication of a semiconductor device having a metal gate strap and a hardened gate oxide formed in accordance with the method of the present invention;
FIG. 4A illustrates areas of nitrogen concentration in the second intermediate structure of FIG. 3 after nitrogen implantation; and
FIG. 4B illustrates areas of nitrogen concentration in the second intermediate structure of FIG. 3 subsequent to anneal.



DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a method for reducing the effective thickness of a gate oxide using nitrogen implantation and anneal subsequent to dopant implantation and activation. More particularly, the invention is directed to a method for fabricating semiconductor devices, for example, transistors, which include a hardened gate oxide and which may be characterized by a relatively large nitrogen concentration at the polysilicon/gate oxide interface and a relatively small nitrogen concentration within the gate oxide and at the gate oxide/substrate interface. Additionally, the invention is directed to a method for fabricating a semiconductor device, e.g., a transistor, having a metal gate strap (e.g., a metal silicide layer) disposed over the polysilicon layer thereof, which device includes a hardened gate oxide and which may be characterized by a relatively large nitrogen concentration at the silicide/polysilicon interface to substantially prevent cross-diffusion. The particular embodiments described herein are intended in all respects to be illustrative rather than restrictive. Other and further embodiments will become apparent to those of ordinary skill in the art to which the present invention pertains without departing from its scope.
With initial reference to FIG. 1, a cross-sectional view of an intermediate structure 10 in the formation of a semiconductor device, e.g., a transistor, fabricated according to the method of the present invention is illustrated. It should be understood and appreciated that the methods and structures described herein do not form a complete process for manufacturing transistors or other semiconductor devices. The remainder of the process is known to those of ordinary skill in the art and, therefore, only the process steps and structures necessary to understand the present invention are described herein. Additionally, it should be understood that while the depicted method illustrates formation of a gate stack for use in a transistor, the method may also be applied to any structure wherein a reduced oxide electrical thickness is desired including, without limitation, capacitors. It should be further understood that the figures presented in conjunction with this description are not meant to be actual cross-sectional views of any particular portion of an actual transistor or other semiconductor device, but are merely idealized representations that are employed to more clearly and fully depict the method of the invention than would otherwise be possible. Elements common between the figures maintain the same numeric designation.
The method of the present invention includes providing a semiconductor substrate 12 having a gate oxide layer 14 formed thereover. The semiconductor substrate 12 may be formed of any suitable material known to those of ordinary skill in the art, and the gate oxide layer 14 may be formed over the semiconductor substrate 12 using any known process and any suitable material known in the art. For example, the semiconductor substrate 12 may be fabricated using silicon and the gate oxide layer 14 may include silicon dioxide (SiO2) that has been thermally grown or vapor deposited using well-known methods. The gate oxide layer 14 may be formed in various thicknesses to suit various fabrication processes. By way of example and not limitation, the gate oxide layer 14 may have a thickness of about 50 angstroms or less. For use in state of the art 0.18 micron technology, a gate oxide layer 14 having a thickness in the range of about 30 angstroms to about 40 angstroms is currently preferred.
A polysilicon layer 16 is formed over the gate oxide layer 14 using conventional deposition processes. The polysilicon layer 16 may also be formed in various thicknesses to suit various fabrication processes. However, it is currently preferred that the polysilicon layer 16 have a thickness of about 400 angstroms to about 1000 angstroms, more preferably about 600 angstroms. Dopants, such as boron, are subsequently implanted into the polysilicon layer 16 followed by an anneal, as is known to those of ordinary skill in the art.
After dopant implantation and anneal, nitrogen is implanted into the intermediate structure 10 at a dosage and energy sufficient to penetrate the polysilicon layer 16, the gate oxide layer 14 and at least a portion of the semiconductor substrate 12. The dosage and energy should be sufficient such that the bulk of the nitrogen concentration is located entirely within the polysilicon layer 16 while a relatively small concentration of nitrogen penetrates below the polysilicon/gate oxide interface 18. By way of example, and not limitation, greater than about 90% by weight of the total amount of nitrogen implanted may be located entirely within the polysilicon layer 16 while less than about 10% by weight of the total amount of nitrogen implanted may penetrate below the polysilicon/gate oxide interface 18.
Typically, the nitrogen implantation takes place at room temperature at a dosage ranging from between about 1×1015 atoms/cm2 to about 1×1016 atoms/cm2, and at an energy ranging from between about 10 keV to about 40 keV. A desired nitrogen concentration profile of the intermediate structure 10 after nitrogen implantation is illustrated in FIG. 2A, wherein areas of nitrogen concentration are indicated by line 21 and nitrogen concentration is increased in the direction of the arrow. The concentrations and the size of peak 23 depend on the thickness of the polysilicon layer 16, the gate oxide layer 14 and the semiconductor substrate 12, as well as the implantation dosage and energy. Accordingly, FIG. 2A should be used for a qualitative, rather than a quantitative, understanding. Typically, not more than about 1×1014 atoms/cm2 to about 1×1015 atoms/cm2 penetrates below the polysilicon/gate oxide interface 18.
In later processing, an anneal may be performed at between about 850° C. and 1050° C. in an ambient nitrogen environment for between about 10 seconds and 30 minutes to alter the nitrogen concentration profile of the intermediate structure 10. A desired nitrogen concentration profile of the intermediate structure 10 after anneal is illustrated in FIG. 2B, wherein areas of nitrogen concentration are indicated by line 21′ and nitrogen is increased in the direction of the arrow. As is evident from FIG. 2B, the nitrogen concentration profile of the intermediate structure 10 subsequent to anneal includes a relatively large nitrogen concentration in the polysilicon 16 and gate oxide layers 14 at the polysilicon/gate oxide interface 18 and a relatively small nitrogen concentration within the gate oxide layer 14 and at the gate oxide/substrate interface 20. As with FIG. 2A, FIG. 2B should be used for a qualitative, rather than a quantitative, understanding.
In the intermediate structure 10 shown in FIG. 2B, the nitrogen at the polysilicon/gate oxide interface 18 acts as a diffusion barrier to prevent diffusion of dopants from the polysilicon layer 16 into and through the gate oxide layer 14. Nitrogen concentrated at the gate oxide/substrate interface 20 also aids in preventing dopant diffusion. However, the concentration of nitrogen at the gate oxide/substrate interface 20 is not so great as to substantially impair device performance. Further, the nitrogen within the gate oxide layer 14 reacts with the pure oxide to form oxynitride, which has an increased dielectric constant. Accordingly, the effective thickness of the gate oxide layer 14 is reduced. Utilizing the method of the present invention, an increase of about 5.0% to about 10.0% in the dielectric constant of the gate oxide layer 14 may be achieved. Equivalently, a reduction of about 5.0% to about 10.0% in the effective thickness of the gate oxide layer 14 may be achieved. Thus, an exemplary gate oxide layer 14 having a thickness of about 30 angstroms may instead have a thickness of about 28.5 angstroms if hardened using the method of the present invention.
As known to those of ordinary skill in the art, a metal gate strap 22 (e.g., a metal silicide layer) is often disposed over the polysilicon layer 16 to lower the resistance of the resultant semiconductor device (see, FIG. 3). However, semiconductor devices, for instance, surface P-channel transistors, having both P-type and N-type dopants may encounter cross-diffusion when a metal silicide layer 22 is used. As more fully described below, using the method of the present invention, cross-diffusion may be substantially prevented.
Referring now to FIG. 3, a cross-sectional view of a second intermediate structure 24 in the formation of a semiconductor device having a metal silicide layer 22 formed over the polysilicon layer 16 thereof is illustrated. The metal silicide layer 22 may be formed of any suitable material known to those of ordinary skill in the art including, but not limited to, tungsten silicide, and may be formed over the polysilicon layer 16 using known processes. The metal silicide layer 22 may be formed over the polysilicon layer 16 subsequent to dopant implantation and anneal and may be formed in various thicknesses to suit various fabrication processes. However, it is currently preferred that the metal silicide layer 22 have a thickness of about 200 angstroms to about 1000 angstroms, more preferably about 600 angstroms.
In this embodiment, nitrogen is implanted into the second intermediate structure 24 at a dosage and energy sufficient such that the peak of the nitrogen concentration occurs within the metal silicide layer 22 and in the polysilicon layer 16 at a silicide/polysilicon interface 26 while a relatively small amount of implanted nitrogen penetrates below the polysilicon/gate oxide interface 18. Typically, the nitrogen implantation takes place at room temperature at a dosage ranging from between about 1×1015 atoms/cm2 and about 1×1016 atoms/cm2 and at an energy ranging from between about 10 keV and about 40 keV. A desired nitrogen concentration profile of the second intermediate structure 24 after nitrogen implantation is illustrated in FIG. 4A, wherein areas of nitrogen concentration are indicated by line 28 and nitrogen concentration is increased in the direction of the arrow. As with the previous embodiment that does not include a metal silicide layer 22, the relative nitrogen concentration and the size of peak 30 depend on the thickness of the layers 14, 16 and the semiconductor substrate 12, as well as the implantation dosage and energy. Accordingly, FIG. 4A should be used for a qualitative, rather than a quantitative, understanding. Again, as with the previously described embodiment, typically not more than about 1×1014 atoms/cm2 to about 1×1015 atoms/cm2 penetrates below the polysilicon/gate oxide interface 18.
In later processing, an anneal may be performed at between about 850° C. and 1050° C. in an ambient nitrogen environment for between about 10 seconds and 30 minutes to alter the nitrogen concentration profile of the second intermediate structure 24. A desired nitrogen concentration profile of the second intermediate structure 24 after anneal is illustrated in FIG. 4B, wherein areas of nitrogen concentration are indicated by line 28′ and nitrogen is increased in the direction of the arrow. As is evident from FIG. 4B, the nitrogen concentration profile of the second intermediate structure 24 subsequent to anneal includes a relatively large nitrogen concentration at the silicide/polysilicon interface 26, a relatively smaller concentration of nitrogen at the polysilicon/gate oxide interface 18 and a relatively smaller still concentration of nitrogen within the gate oxide layer 14 and at the gate oxide/substrate interface 20. As with FIG. 4A, FIG. 4B should be used for a qualitative rather than a quantitative understanding.
In the second intermediate structure 24 shown in FIG. 4B, the nitrogen concentrated at the silicide/polysilicon interface 26 acts to substantially prevent cross-diffusion of dopants across the interface and the concentration of nitrogen at the polysilicon/gate oxide interface 18 acts as a diffusion barrier to prevent diffusion of dopants from the polysilicon layer 16 into and through the gate oxide layer 14. Nitrogen concentrated at the gate oxide/substrate interface 20 aids in preventing dopant diffusion as well. However, as with the previous embodiment, the concentration of nitrogen at the gate oxide/substrate interface 20 is not so great as to substantially impair device performance. Further, the nitrogen within the gate oxide layer 14 reacts with the pure oxide to form oxynitride and, accordingly, increases the dielectric constant of the gate oxide layer 14 and reduces the effective thickness thereof.
The following describes an exemplary method of forming a transistor having a gate oxide hardened according to the method of the present invention, which transistor is characterized by a relatively large nitrogen concentration at the silicide/polysilicon interface, a relatively smaller nitrogen concentration at the polysilicon/gate oxide interface and a relatively smaller still nitrogen concentration within the gate oxide and at the gate oxide/substrate interface. This example is not in any way limiting of the scope of the invention.
EXAMPLE
A gate oxide layer having a thickness of about 30 angstroms was thermally grown over a silicon substrate using methods known to those of ordinary skill in the art. A layer of polysilicon having a thickness of about 600 angstroms was subsequently deposited over the gate oxide layer followed by deposition of a layer of tungsten silicide having a thickness of about 600 angstroms atop the polysilicon layer. The dielectric constant of the gate oxide was determined and recorded.
Nitrogen was subsequently implanted into the gate stack, at room temperature, at a dosage of about 4×1015 atoms/cm2 and at an energy of about 30 keV. The resultant nitrogen-implanted gate stack had a nitrogen concentration profile approximating that illustrated in FIG. 4A with the bulk of the nitrogen concentration occurring within the metal silicide layer and in the polysilicon layer at the silicide/polysilicon interface while about 10% of the total amount of nitrogen implanted (i.e., about 4×1014 atoms/cm2) penetrated below the polysilicon/gate oxide interface. At least a portion of the implanted nitrogen penetrated into the silicon substrate.
In later processing, an anneal was performed at about 1000° C. in an ambient nitrogen environment for 20 seconds. The resultant gate stack exhibited a nitrogen concentration profile approximating that illustrated in FIG. 4B with a relatively large concentration of nitrogen occurring at the silicide/polysilicon interface, a relatively smaller nitrogen concentration occurring at the polysilicon/gate oxide interface and a relatively smaller still nitrogen concentration occurring within the gate oxide and at the gate oxide/substrate interface.
The dielectric constant of the gate oxide layer was subsequently determined and compared to that recorded prior to nitrogen implantation. It was found that the dielectric constant of the gate oxide layer increased by about 7.0%, resulting in a reduction in the effective thickness of the gate oxide layer of about 7.0%.
The present invention has been described in relation to particular embodiments that are intended in all respects to be illustrative rather than restrictive. It is to be understood that the invention defined by the appended claims is not to be limited by particular details set forth in the above description and that alternative embodiments will become apparent to those of ordinary skill in the art to which the present invention pertains without departing from the spirit and scope thereof.

## Claims

1. A method for hardening a gate oxide in a partially fabricated semiconductor device comprising:
providing a semiconductor substrate having a gate oxide layer disposed over at least a portion thereof;
forming a polysilicon layer over the gate oxide layer, the polysilicon layer having an interface with the gate oxide layer;
implanting dopants into the polysilicon layer;
activating the dopants; and
implanting nitrogen atoms in the polysilicon layer such that the nitrogen atoms penetrate the polysilicon layer, the gate oxide layer, and at least a portion of the semiconductor substrate, wherein the nitrogen atoms are implanted after activating the dopants such that greater than about 90% by weight of a total amount of nitrogen in the polysilicon layer, the gate oxide layer, and the semiconductor substrate is present in the polysilicon layer and above the polysilicon-gate oxide interface.

2. The method of claim 1, wherein implanting nitrogen atoms in the polysilicon layer comprises implanting the nitrogen atoms at a dosage and an energy sufficient such that no more than about 10% by weight of the nitrogen atoms penetrate below the interface of the polysilicon layer and the gate oxide layer.

3. The method of claim 2, wherein:
providing a semiconductor substrate having a gate oxide layer disposed over at least a portion thereof comprises providing a semiconductor substrate having a gate oxide layer with a thickness of between about 30 angstroms and about 40 angstroms disposed over a portion thereof;
forming a polysilicon layer over the gate oxide layer comprises forming a polysilicon layer having a thickness of between about 400 angstroms and about 1000 angstroms over the gate oxide layer; and
implanting nitrogen atoms at a dosage and an energy sufficient such that no more than about 10% by weight of the nitrogen atoms penetrate below the interface of the polysilicon layer and the gate oxide layer comprises implanting nitrogen atoms at a dosage of between about 1×1015 atoms/cm2 and about 1×1016 atoms/cm2 and at an energy of between about 10 keV and about 40 keV.

4. The method of claim 3, wherein implanting nitrogen atoms at a dosage and an energy sufficient such that no more than about 10% by weight of the nitrogen atoms penetrate below the interface of the polysilicon layer and the gate oxide layer comprises implanting nitrogen atoms such that no more than about 1×1014 atoms/cm2 to about 1×1015 atoms/cm2 penetrate below the interface of the polysilicon layer and the gate oxide layer.

5. The method of claim 1, further comprising annealing the nitrogen atoms so that a large concentration of the nitrogen atoms is present at an interface of the polysilicon layer and the gate oxide layer and a small concentration of the nitrogen atoms is present in the gate oxide layer and at an interface of the gate oxide layer and the semiconductor substrate.

6. The method of claim 5, wherein annealing the nitrogen atoms comprises activating the nitrogen atoms.

7. The method of claim 5, wherein annealing the nitrogen atoms comprises annealing the nitrogen atoms at a temperature of between about 850° C. and 1050° C. for between about 10 seconds and 30 minutes.

8. The method of claim 1, wherein providing a semiconductor substrate having a gate oxide layer disposed over at least a portion thereof comprises one of thermally growing an oxide layer over at least a portion of the semiconductor substrate and depositing an oxide layer over at least a portion of the semiconductor substrate.

9. The method of claim 5, wherein annealing the nitrogen atoms occurs after implanting the dopants into the polysilicon layer and activating the dopants.

10. A method for hardening a gate oxide in a partially fabricated electronic device comprising:
providing a semiconductor substrate having a gate oxide layer disposed over at least a portion thereof;
forming a polysilicon layer over the gate oxide layer, the polysilicon layer having an interface with the gate oxide layer;
implanting dopants into the polysilicon layer;
activating the dopants;
forming a metal silicide layer over the polysilicon layer, the metal silicide layer having an interface with the polysilicon layer; and
implanting nitrogen atoms in the metal silicide layer such that the nitrogen atoms penetrate the metal silicide layer, the polysilicon layer, the gate oxide layer, and at least a portion of the semiconductor substrate, wherein the nitrogen atoms are implanted after activating the dopants such that greater than about 90% by weight of a total amount of nitrogen in the polysilicon layer, the gate oxide layer, and the semiconductor substrate is present in the polysilicon layer and above the polysilicon-gate oxide interface.

11. The method of claim 10, wherein activating the dopants comprises activating the dopants prior to forming the metal silicide layer over the polysilicon layer.

12. The method of claim 10, wherein implanting nitrogen atoms in the metal silicide layer comprises implanting nitrogen atoms at a dosage and an energy sufficient such that about 90% by weight of the nitrogen atoms are concentrated in the metal silicide layer and in the polysilicon layer at the interface of the metal silicide layer and the polysilicon layer and no more than about 10% by weight of the nitrogen atoms penetrate below the interface of the polysilicon layer and the gate oxide layer.

13. The method of claim 12, wherein:
providing a semiconductor substrate having a gate oxide layer disposed over at least a portion thereof comprises providing a semiconductor substrate having a gate oxide layer with a thickness of between about 30 angstroms and about 40 angstroms disposed over a portion thereof;
forming a polysilicon layer over the gate oxide layer comprises forming a polysilicon layer having a thickness of between about 400 angstroms and about 1000 angstroms over the gate oxide layer;
forming a metal silicide layer over the polysilicon layer comprises forming a metal silicide layer having a thickness of between about 200 angstroms and about 1000 angstroms over the polysilicon layer; and
implanting nitrogen atoms at a dosage and an energy sufficient such that about 90% by weight of the nitrogen atoms are concentrated in the metal silicide layer and in the polysilicon layer at the interface of the metal silicide layer and the polysilicon layer and no more than about 10% by weight of the nitrogen atoms penetrate below the interface of the polysilicon layer and the gate oxide layer comprises implanting nitrogen atoms at a dosage of between about 1×1015 atoms/cm2 and about 1×1016 atoms/cm2 and at an energy of between about 10 keV and 40 keV.

14. The method of claim 13, wherein implanting nitrogen atoms at a dosage and an energy sufficient such that about 90% by weight of the nitrogen atoms are concentrated in the metal silicide layer and in the polysilicon layer at the interface of the metal silicide layer and the polysilicon layer and no more than about 10% by weight of the nitrogen atoms penetrate below the interface of the polysilicon layer and the gate oxide layer comprises implanting nitrogen atoms such that no more than about 1×1014 atoms/cm2 to about 1×1015 atoms/cm2 penetrate below the interface of the polysilicon layer and the gate oxide layer.

15. The method of claim 10, further comprising annealing the nitrogen atoms so that a large concentration of the nitrogen atoms is present at an interface of the polysilicon layer and the gate oxide layer and a small concentration of the nitrogen atoms is present in the gate oxide layer and at an interface of the gate oxide layer and the semiconductor substrate.

16. The method of claim 15, wherein annealing the nitrogen atoms comprises activating the nitrogen atoms.

17. The method of claim 15, wherein annealing the nitrogen atoms comprises annealing the nitrogen atoms at a temperature of between about 850° C. and 1050° C. for between about 10 seconds and 30 minutes.

18. The method of claim 10, wherein forming a polysilicon layer over the gate oxide layer comprises one of thermally growing the gate oxide layer over the semiconductor substrate and depositing a gate oxide layer over at least a portion of the semiconductor substrate.

19. The method of claim 15, wherein annealing the nitrogen atoms occurs after implanting the dopants into the polysilicon layer and activating the dopants.