Zirconium and/or hafnium oxynitride gate dielectric

Details Zirconium and/or hafnium oxynitride gate dielectric Zirconium and/or hafnium oxynitride gate dielectric

1999-10-20

2001-09-18

Whitehead, Jr., Carl (Department: 2822)

Active solid-state devices (e.g., transistors, solid-state diode

Field effect device

Having insulated electrode

C257S411000, C257S310000, C257S324000

Reexamination Certificate

active

06291866

ABSTRACT:

FIELD OF THE INVENTION
This invention relates generally to semiconductor device structures and methods for forming such, and more specifically to such structures and methods related to gate dielectrics for field effect devices formed on integrated circuits.
BACKGROUND OF THE INVENTION
Semiconductor devices such as field effect transistors are common in the electronics industry. Such devices may be formed with extremely small dimensions, such that thousands or even millions of these devices may be formed on a single-crystal silicon substrate or “chip” and interconnected to perform useful functions in an integrated circuit such as a microprocessor.
Although transistor design and fabrication is a highly complex undertaking, the general structure and operation of a transistor are fairly simple. With reference to
FIG. 1
, a simplified field effect transistor is shown in cross-section. In a field effect transistor a portion of the substrate (or epi-layer)
100
near the surface is designated as the channel
120
during processing. Channel
120
is electrically connected to source
140
and drain
160
, such that when a voltage difference exists between source
140
and drain
160
, current will tend to flow through channel
120
. The semiconducting characteristics of channel
120
are altered such that its resistivity may be controlled by the voltage applied to gate
190
, a conductive layer overlying channel
120
. Thus by changing the voltage on gate
190
, more or less current can be made to flow through channel
120
. Gate
190
and channel
120
are separated by gate dielectric
180
; the gate dielectric is insulating, such that between gate
190
and channel
120
little or no current flows during operation (although “tunneling” current is observed with thin dielectrics). However, the gate dielectric allows the gate voltage to induce an electric field in channel
120
, giving rise to the name “field effect transistor.”
Generally, integrated circuit performance and density may be enhanced by “scaling”, that is by decreasing the size of the individual semiconductor devices on a chip. Unfortunately, field effect semiconductor devices produce an output signal that is proportional to the length of the channel, such that scaling reduces their output. This effect has generally been compensated for by decreasing the thickness of gate dielectric
180
, thus bringing the gate in closer proximity to the channel and enhancing the field effect.
As devices have scaled to smaller and smaller dimensions, the gate dielectric thickness has continued to shrink. Although further scaling of devices is still possible, scaling of the gate dielectric thickness has almost reached its practical limit with the conventional gate dielectric material, silicon dioxide. Further scaling of silicon dioxide gate dielectric thickness will involve a host of problems: extremely thin layers allow for large leakage currents due to direct tunneling through the oxide. Because such layers are formed literally from a few layers of atoms, exacting process control is required to repeatably produce such layers. Uniformity of coverage is also critical because device parameters may change dramatically based on the presence or absence of even a single monolayer of dielectric material. Finally, such thin layers form poor diffusion barriers to impurities.
Realizing the limitations of silicon dioxide, researchers have searched for alternative dielectric materials which can be formed in a thicker layer than silicon dioxide and yet still produce the same field effect performance. This performance is often expressed as “equivalent oxide thickness”: although the alternative material layer may be thick, it has the equivalent effect of a much thinner layer of silicon dioxide (commonly called simply “oxide”). Many, if not most, of the attractive alternatives for achieving low equivalent oxide thicknesses are metal oxides, such as tantalum pentoxide, titanium dioxide, and barium strontium titanate.
Researchers have found formation of such metal oxides as gate dielectrics to be problematic. At typical metal oxide deposition temperatures, the oxygen ambient or oxygen-containing precursor required to form them tends to also oxidize the silicon substrate, producing an oxide layer at the interface between the substrate and the gate dielectric. The presence of this interfacial oxide layer increases the effective oxide thickness, reducing the effectiveness of the alternative gate dielectric approach. The existence of the interfacial oxide layer places an ultimate constraint on the performance of an alternative dielectric field effect device.
SUMMARY OF THE INVENTION
The present invention includes a semiconductor device structure utilizing either a zirconium oxynitride or a hafnium oxynitride gate dielectric layer, and a method for making the same. This method also encompasses gate dielectrics formed from oxynitrides of mixtures of Zr and Hf. With the present invention, a zirconium (or hafnium) oxynitride gate dielectric may be formed with a dielectric constant substantially higher than that of either conventional thermal silicon dioxide or silicon nitride dielectrics. Thus, the metal (Zr or Hf) oxynitride dielectric layer may be made substantially thicker than a conventional gate dielectric with equivalent field effect. Additionally, the presence of nitrogen, in at least a partial thickness of the gate dielectric, helps to prevent the diffusion of boron, such as from a boron-doped polysilicon gate electrode, to the channel region.
Conventional researcher wisdom has been to avoid nitrogen-based compounds for gate dielectrics. Additionally, integrated circuit manufacturing researchers tend to hesitate before investigating the addition of new materials, and especially material types, for mass produced integrated circuits. In spite of this, our investigations suggest that HfO
x
N
y
and ZrO
x
N
y
(with relatively small N levels) are stable next to Si, so there will not be a reaction to form SiO
2
(silicon oxide reactions are at least minimized to the extent that the dielectric properties are not substantially corrupted). Combining this, and the high permittivities achievable, with our research into understanding the silicon/oxynitride interface has allowed us to recognize the usability of zirconium oxynitride and hafnium oxynitride gate dielectrics.
In one embodiment, a graded zirconium (or hafnium) oxynitride layer is formed, such that near the silicon interface the dielectric layer has a large oxynitride component, while the upper portion of the oxynitride layer has a large zirconium component. Such a structure may employ primarily silicon/oxynitride bonding at the silicon interface, with acceptable interface state densities. However, the zirconium and/or hafnium included in the oxynitride layer can significantly increase the dielectric constant of the film. The present invention also provides for amorphous gate dielectrics, which have dense microstructures and avoid many of the problems associated with grain boundaries in polycrystalline dielectrics.
In one aspect of this invention, a method of fabricating a semiconductor device is disclosed that includes providing a single-crystal silicon substrate, which usually includes structures, such as a channel region; forming a metal oxynitride gate dielectric layer on the substrate, and forming a conductive gate overlying the gate dielectric layer. This metal can be Zr, hafnium, or a mixture of the two. Suitable base layers for the metal oxynitride layer include bare silicon, silicon oxynitride, and other passivated Si layers, such as hydrogen terminated Si. These other passivation schemes may require removal of the passivant before formation of the zirconium oxynitride.
In one zirconium-based approach, the zirconium oxynitride dielectric layer is formed by forming zirconium on the substrate, and annealing the formed metal in an atmosphere including oxygen and nitrogen, thus forming a metal oxynitride layer on the substrate. In some embodiments, the atmosphere includes NO, or a remote nitrogen/oxy

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