# Patent

## Title
Semiconductor processing methods of forming and utilizing antireflective material layers, and methods of forming transistor gate stacks

## Abstract

In one aspect, the invention includes a semiconductor processing method comprising exposing silicon, nitrogen and oxygen in gaseous form to a high density plasma during deposition of a silicon, nitrogen and oxygen containing solid layer over a substrate.
In another aspect, the invention includes a gate stack forming method, comprising: a) forming a polysilicon layer over a substrate; b) forming a metal silicide layer over the polysilicon layer; c) depositing an antireflective material layer over the metal silicide utilizing a high density plasma; d) forming a layer of photoresist over the antireflective material layer; e) photolithographically patterning the layer of photoresist to form a patterned masking layer from the layer of photoresist; and f) transferring a pattern from the patterned masking layer to the antireflective material layer, metal silicide layer and is polysilicon layer to pattern the antireflective material layer, metal silicide layer and polysilicon layer into a gate stack.

## Background
RELATED PATENT DATA
This patent resulted from a continuation application of U.S. patent application Ser. No. 09/891,570, which was filed Jun. 25, 2001, and which is now U.S. Pat. No. 6,727,173; which resulted from a continuation of U.S. patent application Ser. No. 09/146,841, filed Sep. 3, 1998 and which is now U.S. Pat. No. 6,268,282.


TECHNICAL FIELD
The invention pertains to methods of forming and utilizing antireflective material layers, and to methods of forming transistor gate stacks.
BACKGROUND OF THE INVENTION
Semiconductor processing frequently involves providing a photoresist layer over a substrate. Portions of the photoresist layer are subsequently exposed to light through a masked light source. The mask contains clear and opaque regions defining a pattern to be created in the photoresist layer. Regions of the photoresist layer which are exposed to light are made either soluble or insoluble in a solvent. If the exposed regions are soluble, a positive image of the mask is produced in the photoresist. The photoresist is therefore termed a positive photoresist. On the other hand, if the non-irradiated regions are dissolved by the solvent, a negative image results. Hence, the photoresist is referred to as a negative photoresist.
A difficulty that can occur when exposing photoresist to radiation is that waves of radiation can propagate through the photoresist to a layer beneath the photoresist and then be reflected back up through the photoresist to interact with other waves propagating through the photoresist. The reflected waves can constructively and/or destructively interfere with other waves propagating through the photoresist to create periodic variations of light intensity within the photoresist. Such variations of light intensity can cause the photoresist to receive non-uniform doses of energy throughout its thickness. The non-uniform doses can decrease the accuracy and precision with which a masked pattern is transferred to the photoresist. Accordingly, it is desired to develop methods which suppress radiation waves from being reflected by layers beneath a photoresist layer.
A method which has been used with some success to suppress reflected waves is to form an antireflective material beneath a photoresist layer. Antireflective materials are typically materials which absorb radiation and thereby therefore quench reflection of the radiation. Antireflective materials absorb various wavelengths of radiation with varying effectiveness. The number of materials available for use as antireflective materials is limited. Accordingly, it is desired to develop alternative methods of varying the wavelengths absorbed, and effectiveness with which the wavelengths are absorbed, for antireflective materials.
A particular type of antireflective coating material is a deposited antireflective coating (DARC). An exemplary DARC is SixOyNz, wherein x is from about 40 to about 60, y is from about 29 to about 45, and z is from about 10 to about 16. The DARC can comprise, for example, Si50O37N13. A DARC can be formed by, for example, chemical vapor deposition on a substrate at about 400° C. and under a pressure of from about 4 Torr to about 6.5 Torr, utilizing SiH4 and N2O as precursors. The DARC material can be deposited either with or without a plasma being present in a reaction chamber during the deposition. A typical goal in utilizing a DARC film is to reduce reflected radiation reaching an overlying layer of photoresist to less than 10% of incident radiation at the DARC film.
A prior art process utilizing a DARC material is described with reference to a semiconductive wafer fragment 10 in FIG. 1. Wafer fragment 10 comprises a substrate 12. Substrate 12 can comprise, for example, monocrystalline silicon lightly doped with a background p-type dopant. To aid in interpretation of the claims that follow, the term “semiconductive substrate” is defined to mean any construction comprising semiconductive material, including, but not limited to, bulk semiconductive materials such as a semiconductive wafer (either alone or in assemblies comprising other materials thereon), and semiconductive material layers (either alone or in assemblies comprising other materials). The term “substrate” refers to any supporting structure, including, but not limited to, the semiconductive substrates described above.
A gate dielectric layer 14, polysilicon layer 16, and silicide layer 18 are formed over substrate 12. Gate dielectric layer 14 can comprise, for example, silicon dioxide; polysilicon layer 16 can comprise, for example, conductively doped polysilicon; and silicide layer 18 can comprise, for example, tungsten silicide or titanium silicide. Layers 14, 16 and 18 are to be ultimately patterned into a transistor gate structure.
An antireflective coating layer 20 is provided over silicide layer 18, and a photoresist layer 22 is provided over antireflective coating layer 20. Antireflective coating layer 20 can comprise, for example, an inorganic layer such as SixOyNz. In practice the layer can be substantially inorganic, with the term “substantially inorganic” indicating that the layer can contain a small amount of carbon (less than 1%).
Silicide layer 18 is preferably subjected to an anneal to improve a crystalline structure and a conductivity of the silicide layer prior to utilization of the layer in a transistor gate. The anneal of silicide layer 18 can comprise, for example, a temperature of 850° C. and a pressure of 1 atmosphere for a time of 30 minutes.
DARC material 20 is typically provided over silicide layer 18 prior to the anneal to protect layer 18 from gaseous oxygen during the anneal. If gaseous oxygen interacts with layer 18 during the anneal, the oxygen can oxidize a portion of layer 18 and adversely effect conductivity of layer 18. Unfortunately, the anneal conditions can detrimentally influence optical properties of DARC material 20. Specifically, DARC material 20 has optical properties that can be described by a refractive index coefficient (n) and an extinction coefficient (energy absorption coefficient) (k). The anneal conditions which improve conductivity of silicide layer 18 can alter one or both of “n” and “k” of layer 20. A stoichiometry of the materials of layer 20 is typically carefully chosen to adjust “n” and “k” of the material to appropriate parameters which will substantially quench reflected radiation before the radiation reaches photoresist layer 22. The effect of the anneal conditions on “n” and “k” can push such parameters out of an optimum adjusted range. Accordingly, it is desired to develop methods of forming DARC materials wherein “n” and “k” of the materials will be resistant to anneal condition induced changes.
SUMMARY OF THE INVENTION
In one aspect, the invention encompasses a semiconductor processing method wherein silicon, nitrogen and oxygen in gaseous form are exposed to a high density plasma during deposition of a silicon, nitrogen and oxygen containing solid layer over a substrate.
In another aspect, the invention encompasses a semiconductor processing method of photolithographic processing. A metal silicide layer is formed over a substrate. An antireflective material layer is deposited over the metal silicide utilizing a high density plasma. A layer of photoresist is formed over the antireflective material layer. The layer of photoresist is photolithographically patterned.
In yet another aspect, the invention encompasses a transistor gate stack forming method. A polysilicon layer is formed over a substrate. A metal silicide layer is formed over the polysilicon layer. An is antireflective material layer is deposited over the metal silicide utilizing a high density plasma. A layer of photoresist is formed over the antireflective material layer. The layer of photoresist is photolithographically patterned to form a patterned masking layer from the layer of photoresist. A pattern is transferred from the patterned masking layer to the antireflective material layer, metal silicide layer and polysilicon layer to pattern the antireflective material layer, metal silicide layer and polysilicon layer into a transistor gate stack.



BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the invention are described below with reference to the following accompanying drawings.
FIG. 1 is a fragmentary, diagramatic, cross-sectional view of a prior art semiconductive wafer fragment.
FIG. 2 is a fragmentary, diagrammatic, cross-sectional view of a semiconductive wafer fragment at a preliminary processing step of a method of the present invention.
FIG. 3 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 2.
FIG. 4 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 3.
FIG. 5 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 4.
FIG. 6 is a diagrammatic, cross-sectional, schematic view of a reaction chamber which can be utilized in methods of the present invention.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
This disclosure of the invention is submitted in furtherance of the constitutional purposes of the U.S. Patent Laws “to promote the progress of science and useful arts” (Article 1, Section 8).
FIG. 2 illustrates a semiconductive wafer fragment 50 at a preliminary processing step of an embodiment of the present invention. Wafer fragment 50 comprises a substrate 52, a gate dielectric layer 54, a polysilicon layer 56, and a silicide layer 58. Substrate 52, gate dielectric layer 54, polysilicon layer 56, and silicide layer 58 can comprise materials identical to those utilized in the prior art construction of FIG. 1 for substrate 12, gate dielectric layer 14, polysilicon layer 16 and silicide layer 18, respectively.
A DARC material layer 60 is formed over silicide layer 58. In contrast to prior art methods, DARC material 60 is formed using high density plasma deposition. Such deposition can occur within a reaction chamber. To aid in interpretation of the claims that follow, a “high density plasma” is defined as a plasma having a density of greater than or equal to 1010 ions/cm3. The portion of wafer fragment 50 upon which layer 60 is deposited is preferably maintained at a temperature of from about 300° C. to about 800° C. during the deposition, with about 600° C. one preferred example. The temperature of wafer fragment 50 can be controlled by flowing helium against a backside of the wafer during the deposition to cool the wafer. At higher temperatures a denser layer 60 can be formed. Such denser layer 60 can be more stable to anneal conditions than a less dense layer 60. A preferred pressure range within a reaction chamber during deposition of layer 60 is from about 1 mTorr to 100 mTorr. Feed gases utilized in the high density plasma deposition can comprise SiH4, N2, O2, and argon.
An exemplary reaction chamber that can be utilized in a method of the present invention is shown schematically in FIG. 6 as part of a reactor 100. Reactor 100 comprises coils 102 connected to a power source 104. Coils 102 surround a reaction chamber 106 and are configured to generate a plasma within chamber 106. A wafer holder if (chuck) 108 is provided within chamber 106, and holds a semiconductive wafer 110. Wafer holder 108 is electrically coupled to a power source 112. It is noted that power sources 104 and 112 can be separate power sources, or can comprise separate feeds originating from a single power source. The power from source 104 can be, for example, about 2000 watts and can comprise a frequency of about 13.6 megahertz. The power to wafer 110 from source 112 is preferably biased to less than or equal to about 200 watts and more preferably biased to about 100 watts. In practice, the bias power is typically measured at a chuck 108 holding wafer 110, rather than at wafer 110 itself.
An exemplary flow of the feed gases into reaction chamber 106 is SiH4 (100 standard cubic centimeters per minute (sccm)), N2 (150 sccm), O2 (150 sccm), and argon (200 sccm).
During deposition of layer 60 (FIG. 2) onto a semiconductive wafer in a high pressure plasma process of the present invention, there will likely be both deposition and etch processes occurring simultaneously, resulting in a deposition-to-etch ratio. The deposition rate will exceed the etch rate, so a net effect is deposition of material onto the wafer. The rate of deposition can be calculated by providing no bias at the substrate during deposition, and the etch rate can be calculated by determining an etch rate when no deposition precursors are fed into reactor 106. Modification of the deposition-to-etch ratio by, for example, adjusting a bias power to substrate 110, can be utilized to affect the “n” and “k” values of a deposited layer 60 (FIG. 2).
Referring again to FIG. 2, silicide layer 58 is annealed after deposition of DARC material 60. The high pressure plasma deposition of the present invention can reduce variability of the optical properties (such as the “n” and “k” values) of material 60 during the anneal of silicide layer 58. For instance the variability of “n” and “k” induced by an anneal utilizing the conditions discussed in the “Background” section of this disclosure can be limited to changes of less than 10%.
Referring to FIG. 3, a photoresist layer 62 is formed over DARC material 60. Photoresist layer 62 is then patterned by exposure to a masked light source and a solvent to remove portions of layer 62 and form the resulting structure shown on FIG. 4.
A pattern is then transferred from layer 62 to underlying layers 54, 56, 58 and 60 to form a gate stack 70 shown in FIG. 5. It is noted that the application also encompasses embodiments wherein a gate stack encompasses layers 60, 58 and 56, and wherein layer 54 is not patterned. A method of transferring a pattern from photoresist layer 62 to underlying layers 54, 56, 58 and 60 is a plasma etch. After the formation of gate stack 70, photoresist layer 62 can be removed. Also, source and drain regions can be implanted adjacent gate stack 70 and sidewall spacers can be formed along sidewalls of gate stack 70 to form a transistor gate structure from the gate stack.
In compliance with the statute, the invention has been described in language more or less specific as to structural and methodical features. It is to be understood, however, that the invention is not limited to the specific features shown and described, since the means herein disclosed comprise preferred forms of putting the invention into effect. The invention is, therefore, claimed in any of its forms or modifications within the proper scope of the appended claims appropriately interpreted in accordance with the doctrine of equivalents.

## Claims

1. A semiconductor processing method comprising:
forming a metal silicide over a substrate;
depositing a layer containing silicon, oxygen and nitrogen over the metal silicide, the depositing comprising exposure of a gaseous mixture comprising silicon, nitrogen and oxygen to a high density plasma and forming the layer from the gaseous mixture, the layer being characterized by an “n” value and a “k” value; and
exposing the layer and metal silicide to anneal conditions comprising a temperature of at least about 850° C. which anneal the metal silicide, and wherein the “n” and “k” values of the layer change by less than 10% during the exposure to the anneal conditions.

2. The method of claim 1 wherein the layer touches the metal silicide.

3. A semiconductor processing method comprising:
depositing a material comprising Si, N and O over a substrate utilizing a feed gas, the depositing occurring at a first temperature;
exposing the feed gas to a high density plasma during the depositing;
forming photoresist over the material;
photolithographically patterning the photoresist while the photoresist is over the material; and
exposing the material to a second temperature higher than the first temperature after the exposure of the material to the high density plasma; the “n” and “k” values of the material changing by less than 10% during the exposing to the second temperature.

4. The method of claim 3 wherein the second temperature is greater than 800° C.

5. The method of claim 3 wherein the material is SixOyNz, where x is from about 40 to 60, y is from about 29 to about 45, and z is from about 10 to about 16.

6. The method of claim 3 wherein at least a portion of the substrate is maintained at a temperature of from about 300° C. to about 800° C. during the depositing.

7. The method of claim 3 wherein the depositing occurs in a reactor, and wherein a temperature within the reactor during the depositing is from about 300° C. to about 800° C.

8. The method of claim 7 wherein a pressure within the reactor during the depositing is from about 1 mTorr to about 100 mTorr.

9. The method of claim 8 wherein the substrate is biased to a power of about 100 watts during the depositing, and wherein the plasma is induced at a power of about 2000 watts.

10. The method of claim 3 wherein the exposure of the material to the second temperature occurs before photolithographically patterning the photoresist.

11. The method of claim 3 wherein the exposure of the material to the second temperature occurs before forming the photoresist.