Process for improving the etch stability of ultra-thin photoresist

Information

  • Patent Grant
  • 6815359
  • Patent Number
    6,815,359
  • Date Filed
    Wednesday, March 28, 2001
    23 years ago
  • Date Issued
    Tuesday, November 9, 2004
    19 years ago
Abstract
An integrated circuit fabrication process is disclosed herein. The process includes exposing a photoresist layer to a plasma, and transforming the top surface and the side surfaces of the photoresist layer to form a hardened surface. The process further includes etching the substrate in accordance with the transformed feature, wherein an etch stability of the feature is increased by the hardened surface. The photoresist layer is provided at a thickness less than 0.25 μm, for use in deep ultraviolet lithography, or for use in extreme ultraviolet lithography.
Description




FIELD OF THE INVENTION




The present invention relates generally to integrated circuit (IC) fabrication. More particularly, the present invention relates to a process for improving the etch stability of ultra-thin photoresist utilized in IC fabrication.




BACKGROUND OF THE INVENTION




The semiconductor or IC industry aims to manufacture integrated circuits (ICs) with higher and higher densities of devices on a smaller chip area to achieve greater functionality and to reduce manufacturing costs. This desire for large scale integration has led to a continued shrinking of circuit dimensions and device features. The ability to reduce the size of structures, such as, gate lengths in field-effect transistors and the width of conductive lines, is driven by lithographic performance.




With conventional lithography systems, radiation is provided through or reflected off a mask or reticle to form an image on a semiconductor wafer. Generally, the image is focused on the wafer to expose and pattern a layer of material, such as, photoresist material. In turn, the photoresist material is utilized to define doping regions, deposition regions, etching regions, or other structures associated with integrated circuits (ICs) to one or more layers of the semiconductor wafer. The photoresist material can also define conductive lines or conductive pads associated with metal layers of an integrated circuit. Further, the photoresist material can define isolation regions, transistor gates, or other transistor structures and elements.




Presently, lithography systems are typically configured to expose the photoresist material at a radiation having a wavelength of 248 nanometers (nm). However, because the resolution of features is, in part, proportional to the inverse of the exposure wavelength, it is desirable to pattern photoresist material using radiation at shorter exposure wavelengths (e.g., 193 nm, 157 nm, 126 nm, or 13.4 nm). Unfortunately, materials, equipment, and/or fabrication techniques suitable for 248 nm lithography do not provide similar results at the shorter exposure wavelengths. Moreover, few, if any, materials or processes tailored for use with shorter exposure wavelengths exist.




One of the problems associated with the use of organic-based photoresist materials conventionally used in 365 nm or 248 nm lithography is the high optical absorption per unit thickness at the shorter wavelength lithographic radiation. Conventional photoresist materials become increasingly opaque at the shorter wavelengths and the necessary photochemical change will not occur throughout the entire thickness of the photoresist material.




To overcome this drawback, a thinner layer of photoresist material is used for the shorter lithographic wavelengths. A standard or conventional thickness of photoresist material for 248 nm lithography is more than 0.5 μm. The 248 nm photoresist materials are typically based on phenolic polymers. For 193 nm lithography, 193 nm photoresist materials based on acrylite and/or alicyclic polymers may be provided at a thickness of 0.4 to 0.3 μm. For even shorter lithographic wavelengths or to further enhance 193 nm lithography, ultra-thin resists (UTRs) are used, which are conventional photoresist materials provided at a thickness of less than 0.25 μm.




A certain amount of photoresist material (e.g., vertical thickness) is typically consumed during IC fabrication processes, e.g., resist trimming and/or etch processes. Unfortunately, when a thinner layer of photoresist material is used, such as, photoresists in 193 nm application or ultra-thin photoresists, there may not be enough photoresist material remaining after consumption to maintain pattern integrity, survive subsequent processes, and/or with which to successfully transfer the pattern to underlying layers. In other words, thinner layers of photoresist material suffer from the disadvantage of low or insufficient etch stability.




Thus, there is a need for a process for effectively extending the use of conventional photoresist materials for shorter lithographic applications in the vacuum ultraviolet (VUV), deep ultraviolet (DUV), or extreme ultraviolet (EUV) wavelength range. There is a further need for a process for increasing the etch stability of photoresists used in 193 nm application or ultra-thin photoresists.




BRIEF SUMMARY OF THE INVENTION




One exemplary embodiment relates to a method of increasing an etch stability of a photoresist layer. The method includes providing the photoresist layer at a thickness less than 0.25 μm, for use in vacuum ultraviolet lithography, deep ultraviolet lithography, or extreme ultraviolet lithography. The method further includes exposing the photoresist layer to a plasma, and transforming the exposed surfaces to form a hardened shell. The photoresist layer includes exposed surfaces, and the hardened shell increases the etch stability of the photoresist layer.




Another exemplary embodiment relates to an integrated circuit fabrication process. The process includes patterning a feature on a photoresist layer disposed over a substrate. The feature is patterned in accordance with a pattern provided on a mask or reticle and a radiation at a deep ultraviolet or extreme ultraviolet lithographic wavelength. The process further includes developing the photoresist layer, and exposing the photoresist layer to a plasma. The process still further includes transforming the top surface and the side surfaces to form a hardened surface, and etching the substrate in accordance with the transformed feature. The patterned photoresist layer includes at least one feature having a top surface and side surfaces. The exposing step occurs after the developing step and before the etching step. An etch stability of the feature is a function of the hardened surface.




Still another exemplary embodiment relates to a feature patterned on a photoresist layer disposed over a semiconductor substrate. The feature includes exposed surfaces, and an untreated region enclosed by the exposed surfaces. The exposed surfaces are structurally denser than the untreated region due to at least one of a fluorination, an ion implantation, and an electron beam curing. The feature is lithographically patterned using at least one of a deep ultraviolet lithographic wavelength, a vacuum ultraviolet lithographic wavelength, and an extreme ultraviolet lithographic wavelength or has a vertical thickness less than approximately 0.25 μm.











BRIEF DESCRIPTION OF THE DRAWINGS




The exemplary embodiments will become more fully understood from the following detailed description, taken in conjunction with the accompanying drawings, wherein like reference numerals denote like elements, in which:





FIG. 1

is a general schematic block diagram of a lithographic system for patterning a wafer in accordance with an exemplary embodiment;





FIG. 2

is a flow diagram showing a process for increasing the etch stability of the photoresist layer in accordance with an exemplary embodiment;





FIG. 3

is a cross-sectional view of the wafer, showing a development step;





FIG. 4

is a cross-sectional view of the wafer illustrated in

FIG. 3

, showing a fluorination step; and





FIG. 5

is a cross-sectional view of the wafer illustrated in

FIG. 4

, showing an etch step.











DETAILED DESCRIPTION OF THE EXEMPLARY EMBODIMENTS




Referring to

FIG. 1

, there is shown a wafer


24


in a lithographic system


10


. Lithographic system


10


includes a chamber


12


, a light source


14


, a condenser lens assembly


16


, a mask or a reticle


18


, an objective lens assembly


20


, and a stage


22


. Lithographic system


10


is configured to transfer a pattern or image provided on mask or reticle


18


to wafer


24


. Lithographic system


10


may be a lithographic camera or stepper unit. For example, lithographic system


10


may be a PAS 5500/900 series machine manufactured by ASML, a microscan DUV system manufactured by Silicon Valley Group, or an XLS family microlithography system manufactured by Integrated Solutions, Inc. of Korea.




Wafer


24


includes a substrate


26


, a layer


28


, and a photoresist layer


30


. Photoresist layer


24


is disposed over layer


28


, and layer


28


is disposed over substrate


26


. Wafer


24


can be an entire integrated circuit (IC) wafer or a part of an IC wafer. Wafer


24


can be a part of an IC, such as, a memory, a processing unit, an input/output device, etc. Substrate


26


can be a semiconductor substrate, such as, silicon, gallium arsenide, germanium, or other substrate material. Substrate


26


can include one or more layers of material and/or features, such as lines, interconnects, vias, doped regions, etc., and can further include devices, such as, transistors, microactuators, microsensors, capacitors, resistors, diodes, etc.




Layer


28


can be an insulative layer, a conductive layer, a barrier layer, or other layer of material to be etched, doped, or layered. In one embodiment, layer


28


can comprise one or more layers of materials, such as, a polysilicon stack comprised of a plurality of alternating layers of titanium silicide, tungsten silicide, cobalt silicide, etc. materials. In another embodiment, layer


28


is a hard mask layer, such as, a silicon nitride layer or a metal layer. The hard mask layer can serve as a patterned layer for processing substrate


26


or for processing a layer upon substrate


26


. In yet another embodiment, layer


28


is an anti-reflective coating (ARC). Substrate


26


and layer


28


are not described in a limiting fashion, and can each comprise a conductive, semiconductive, or insulative material.




Photoresist layer


30


can comprise a variety of photoresist chemicals suitable for lithographic applications. Photoresist layer


30


is selected to have photochemical reactions in response to electromagnetic radiation emitted from light source


14


. Materials comprising photoresist layer


30


can include, among others, a matrix material or resin, a sensitizer or inhibitor, and a solvent. Photoresist layer


30


is preferably a chemically amplified, positive or negative tone, organic-based photoresist. Photoresist layer


30


may be, but is not limited to, an acrylate-based polymer, an alicyclic-based polymer, or a phenolic-based polymer. For example, photoresist layer


30


may comprise PAR700 photoresist manufactured by Sumitomo Chemical Company.




Photoresist layer


30


is deposited, for example, by spincoating over layer


28


. The thickness of photoresist layer


30


is configured for use in vacuum ultraviolet lithography, deep ultraviolet lithography, and/or extreme ultraviolet lithography (e.g., 193 nm, 157 nm, 126 nm, or 13.4 nm lithography wavelength). Photoresist layer


30


is preferably provided at a thickness of approximately 0.25 μm or less, hereinafter also referred to as a ultra-thin photoresist.




Chamber


12


of lithographic system


10


can be a vacuum or low pressure chamber for use in vacuum ultraviolet (VUV) lithography. Chamber


12


can contain any of numerous types of atmospheres, such as, nitrogen, etc. Alternatively, lithographic system


10


can be utilized in various other types of lithography including lithography that uses electromagnetic radiation at any number of wavelengths.




Light source


14


provides light or electromagnetic radiation through condenser lens assembly


16


, mask or reticle


18


, and objective lens assembly to photoresist layer


30


. Light source


14


is an excimer laser, in one embodiment, having a wavelength of 193 nm, 157 nm, or 126 nm, or a soft x-ray source at a wavelength of 13.4 nm. Alternatively, light source


14


may be a variety of other light sources capable of emitting radiation having a wavelength in the ultraviolet (UV), vacuum ultraviolet (VUV), deep ultraviolet (DUV), extreme ultraviolet (EUV), or x-ray range.




Assemblies


16


and


20


include lenses, mirrors, collimators, beam splitters, and/or other optical components to suitably focus and direct a pattern of radiation (i.e., radiation from light source


14


as modified by a pattern or image provided on mask or reticle


18


) onto photoresist layer


30


. Stage


22


supports wafer


24


and can move wafer


24


relative to assembly


20


.




Mask or reticle


18


is a binary mask in one embodiment. Mask or reticle


18


includes a translucent substrate


32


(e.g., glass or quartz) and an opaque or patterned layer


34


(e.g., chromium or chromium oxide) thereon. Opaque layer


34


provides a pattern or image associated with a desired circuit pattern, features, or devices to be projected onto photoresist layer


30


. Alternatively, mask or reticle


18


may be an attenuating phase shift mask, an alternating phase shift mask, or other type of mask or reticle.




An exemplary embodiment of the invention will be described with reference to a flow diagram shown in FIG.


2


. The flow diagram includes a pattern photoresist step


40


, a develop patterned photoresist step


42


, a fluorination step


44


, and an etch step


46


.




Utilizing lithography system


10


, the pattern or image provided on mask or reticle


18


is patterned on photoresist layer


30


in the pattern photoresist step


40


. Next in step


42


, wafer


24


, including patterned photoresist layer


30


, undergoes development to define features, such as, a feature


50


, on photoresist layer


30


(FIG.


3


). Feature


50


can define, but is not limited to, a conducting line, a transistor gate, a contact hole, a via, or a trench. The size and shape of feature


50


is not shown in a limiting fashion.




After the patterned photoresist layer


30


has been developed but before such a pattern is transferred onto any of the underlying layers, such as, layer


28


, fluorination step


44


(or alternatively, an electron beam curing step or an ion implantation step) is performed on wafer


24


. It should be understood that wafer


24


may be removed from chamber


12


and placed within a different chamber and/or a different environment which provides fluorination tools, such as, the Lam Research Corp. 4500 Model plasma etch system. Flood electron beam curing can be done in a tool, such as, the ElectronCure 1200-PR Model manufactured by Electron Vision Corporation. Alternatively, chamber


12


may be configured to include additional chambers and/or tools suitable to perform step


44


.




Referring to

FIG. 4

, there is shown a cross-sectional view of a portion of wafer


24


undergoing fluorination step


42


. Wafer


24


is exposed to a fluorine-based plasma (not shown) to modify the exposed surfaces of photoresist layer


30


. Alternatively, wafer


24


may be exposed to a flood electron beam or ions. The exposed surfaces of photoresist layer


30


, for example, a shell


52


comprising the top surface and side walls of feature


50


, are chemically and structurally changed upon interaction with the fluorine-based plasma, electron beam, or implanted ions. The exposed surfaces are densified, becoming harder or structurally more rigid, and therefore more resistant to high-energy ions and/or reactive radicals present in the plasma processes that will be used to subsequently etch the layers of wafer


24


not covered by layer


30


.




In one embodiment, the surface fluorination occurs utilizing CF


4


plasma at about 1000 sccm flow rate, 50 mTorr chamber pressure, 400 W radio frequency (RF) power, and 50° C. lower electrode temperature. Alternatively, the fluorine-based plasma may be other fluorocarbon chemistries, such as, C


2


F


6


, CHF


3


, or C


4


F


8


, and including combination of gases possibly including additives, such as, inert gases, at operating parameters of 10-2000 sccm flow rate, 5-1000 mTorr chamber pressure, 50-2000 W RF power, and 20-80° C. lower electrode temperature.




Shell


52


has a thickness in the range of 20-500 Å relative to the initial thickness or height of feature


50


. The extent of fluorination of the photoresist increases and shell


52


is thicker when fluorination process time is increased, or at higher plasma flow rates, moderate powers, higher chamber pressures, and/or lower electrode temperatures.




Fluorination step


44


causes a slight loss or reduction in the thickness of layer


30


, typically in the range of a few Angstroms. However, the remaining thickness of layer


30


, including the surface fluorinated feature


50


, will have a much enhanced etch stability or etch resistance in comparison to its unfluorinated counterpart. In one embodiment, the etch stability is increased by approximately 20-50%. Etch stability is also referred to as hardness.




Upon completion of fluorination step


44


, pattern transfer to underlying layers, such as, layer


28


, can occur using etch step


46


. In one embodiment, etch step


46


comprises a dry etch using a plasma etchant, such as, Cl


2


/HBr-based plasmas for etching silicon-based conductors, Cl


2


/BCl


3


-based plasmas for etching metals, C


4


F


8


/O


2


-based plasmas for etching inorganic dielectrics, or N


2


/H


2


-based plasmas for etching organic dielectrics. As shown in

FIG. 5

, the increased etch stability of layer


30


permits features thereon, such as, feature


50


, to maintain pattern integrity (i.e., survive etch step


46


) to be effectively defined on layer


28


. Accordingly, the benefit of the full resolving power of 193 nm exposures and/or the enhanced depth of focus provided by ultra-thin photoresist can be realized without introducing subsequent fabrication failure or errors due to insufficient photoresist thickness of ultra-thin photoresists.




It is contemplated that before or after fluorination step


44


, wafer


24


may undergo other fabrication processes, such as, a resist trimming process, before etch step


46


. It is also contemplated that shell


52


may be formed by an ion implantation step or by an electron beam exposure step in place of fluorination step


44


. In the case of the ion implantation step, ions such as argon or fluorine may be utilized. Such ions would cause a certain depth of the exposed surfaces of layer


30


to densify, thereby making such areas less porous and making it harder for the etchant in etch step


46


to erode layer


30


. In the case of the electron beam exposure step, a flood exposure electron beam of sufficient energy and dose will cause decarboxylation, cross-linking, and densification of the material comprising layer


30


, again increasing the etch stability of layer


30


in subsequent processes.




It is understood that although the detailed drawings, specific examples, and particular values describe the exemplary embodiments of the present invention, they are for purposes of illustration only. The exemplary embodiments of the present invention are not limited to the precise details and descriptions described herein. For example, although particular materials or chemistries are described, other materials or chemistries can be utilized. Various modifications may be made in the details disclosed without departing from the spirit of the invention as defined in the following claims.



Claims
  • 1. A method of increasing an etch stability of a photoresist layer, the method comprising the steps of:providing the photoresist layer at a thickness less than 0.25 μm, for use in vacuum ultraviolet lithography, deep ultraviolet lithography, or extreme ultraviolet lithography; exposing the photoresist layer to a plasma, the photoresist layer including exposed surfaces; and transforming the exposed surfaces to form a shell before using the photoresist layer to etch an underlying layer, wherein the shell increases the etch stability of the photoresist layer.
  • 2. The method of claim 1, wherein the plasma has a plasma characteristic of approximately 50 mTorr chamber pressure.
  • 3. The method of claim 2, wherein the plasma has plasma characteristics of approximately 100 sccm flow rate, 400 W radio frequency (RF) power, and 50° C. lower electrode temperature.
  • 4. The method of claim 1, wherein the etch stability is increased by 20-50% as compared to the etch stability of the photoresist layer before exposure to the plasma.
  • 5. The method of claim 1, wherein the transforming step includes transforming the exposed surfaces by a depth of up to approximately 50 nm.
  • 6. The method of claim 1, wherein the transforming step includes at least one of decarboxylation, cross-linking, and densification of the exposed surfaces to form the shell, the shell being hardened.
  • 7. An integrated circuit fabrication process, the process comprising:patterning a feature on a photoresist layer disposed over a substrate, the feature patterned in accordance with a pattern provided on a mask or reticle and a radiation at a deep ultraviolet or extreme ultraviolet lithographic wavelength; developing the photoresist layer, the patterned photoresist layer including at least one feature having a top surface and side surfaces; exposing the photoresist layer to a fluorine-based plasma densifier; transforming the top surface and the side surfaces with the densifier to form a hardened surface; and etching the substrate in accordance with the transformed feature, wherein the exposing step occurs after the developing step and before the etching step, and an etch stability of the feature is a function of the hardened surface.
  • 8. The process of claim 7, further comprising providing the photoresist layer at a thickness of less than approximately 0.25 μm.
  • 9. The process of claim 7, wherein the transforming step includes decarboxylation.
  • 10. The process of claim 9, wherein the exposing step includes providing the fluorine-based plasma at operating parameters of 10-2000 sccm flow rate, 5-1000 mTorr chamber pressure, 50-2000 WRF power, and 20-80° C. lower electrode temperature.
  • 11. The process of claim 7, wherein the densifier is a flood electron beam.
  • 12. The process of claim 7, wherein the densifier is an ion implantation.
  • 13. The process of claim 7, wherein the hardened surface has a depth of 2-50 nm.
  • 14. The process of claim 7, wherein the transforming step includes at least one of decarboxylation cross-linking, and densification of the top surface and the side surfaces to form the hardened surface.
  • 15. An integrated circuit fabrication process, the process comprising:patterned a feature on a photoresist layer disposed over a substrate, the feature patterned in accordance with a pattern provide on a mask or reticle and a radiation at a deep ultraviolet or extreme ultraviolet lithographic wavelength; developing the photoresist layer, the patterned photoresist layer including at least one feature having a top surface and side surfaces; exposing the photoresist layer to a fluorine-based or argons densifier; transforming the top surface and the side surfaces with the densifier to form a hardened surface; and etching the substrate in accordance with the transformed feature, wherein the exposing step occurs after the developing step and before the etching step, and an etch stability of the feature is a function of the hardened surface, wherein the transforming step includes fluorinating the top surface and the side surfaces.
  • 16. A method of using a feature on a photoresist layer disposed above a layer or substrate, the feature including exposed surfaces, the feature being lithographically patterned using at least one of a deep ultraviolet lithographic wavelength, a vacuum ultraviolet lithographic wavelength, and an extreme ultraviolet lithographic wavelength or has a vertical thickness less than approximately 0.25 μm, and the method comprising:transforming the exposed surfaces to be structurally denser than the untreated region due to at least one of a fluorination, a fluorine ion implantation and argon ion implantation; and etching or doping the layer or substrate according to the feature, wherein the exposed surfaces are structurally denser due to the fluorination, the fluorination including the feature being exposed to a fluorine-based plasma.
  • 17. The method of claim 16, wherein a depth of the exposed surfaces is in the range of 2-50 nm.
  • 18. The method of claim 16, wherein the exposed surfaces comprise a top surface and side surfaces of the feature.
  • 19. The method of claim 16, wherein the transforming step includes cross-linking.
  • 20. The method of claim 16, wherein the fluorine-based plasma has operating parameters of 10-2000 sccm flow rate, 5-1000 mTorr chamber pressure, 50-2000 W RF power, and 20-80° C. lower electrode temperature.
  • 21. The feature of claim 16, wherein the material comprising the photoresist layer is an organic-based photoresist material based on at least one of phenolic polymers, acrylate polymers, and alicyclic polymers.
  • 22. The method of claim 16, wherein the photoresist layer comprises an acrylate or alicyclic polymer and the feature is lithographically patterned using a 193 nm wavelength of radiation.
  • 23. The method of claim 16, wherein the feature is at least one of a conducting line, a gate for a transistor device, a contact hole, a via structure, or a trench.
CROSS REFERENCE TO RELATED APPLICATIONS

The present application is related to U.S. application Ser. No. 09/819,692 by Okoroanyanwu et al., filed Mar. 28, 2001, entitled “PROCESS FOR PREVENTING DEFORMATION OF PATTERNED PHOTORESIST FEATURES BY ELECTRON BEAM STABILIZATION;” U.S. application Ser. No. 09/820,143 by Okoroanyanwu et al., filed Mar. 28, 2001, entitled “IMPROVING SEM INSPECTION AND ANALYSIS OF PATTERNED PHOTORESIST FEATURES;” U.S. application Ser. No. 09/819,344 by Okoroanyanwu et al., filed Mar. 28, 2001, entitled “PROCESS FOR REDUCING THE CRITICAL DIMENSIONS OF INTEGRATED CIRCUIT DEVICE FEATURES;” U.S. application Ser. No. 09/819,342, by Shields et al., filed Mar. 28, 2001, entitled “PROCESS FOR FORMING SUB-LITHOGRAPHIC PHOTORESIST FEATURES BY MODIFICATION OF THE PHOTORESIST SURFACE;” and U.S. application Ser. No. 09/819,343 by Gabriel et al., entitled “SELECTIVE PHOTORESIST HARDENING TO FACILITATE LATERAL TRIMMING,” and all assigned to the Assignee of the present application.

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