US 6,254,792 B1Grant
Isotropic dry cleaning process for noble metal integrated circuit structures
Issue Date:2001-07-03
•44 Claims
•3 Drawing Sheets
Abstract
A method for removing from a microelectronic device structure a noble metal residue including at least one metal selected from the group consisting of platinum, palladium, iridium and rhodium, by contacting the microelectronic device structure with a cleaning gas including a reactive halide composition, e.g., XeF2, SF6, SiF4, Si2F6or SiF3and SiF2radicals. The method may be carried out in a batch-cleaning mode, in which fresh charges of cleaning gas are successively introduced to a chamber containing the residue-bearing microelectronic device structure. Each charge is purged from the chamber after reaction with the residue, and the charging/purging is continued until the residue has been at least partially removed to a desired extent. Alternatively, the cleaning gas may be continuously flowed through the chamber containing the microelectronic device structure, until the noble metal residue has been sufficiently removed.
Metadata
Assignee
- Advanced Technology Materials, Inc.
Inventors
- Peter C. Van Buskirk
- Frank DiMeo, Jr.
- Peter C. Kirlin
- Thomas H. Baum
Application Information
Application Number:US 09/093,291
Filing Date:1998-06-08
Priority Date:1997-11-10
Art Unit:7
Classifications
IPC:
C23F 112
Field of Search:
216 6216 13216 38216 63216 65216 66216 67216 73134 1134 11134 12134 13134 1921134 251134 254134902438906438963252 791
Patent Drawings (3 sheets)
Description
Cross-Reference to Related Applications
[0002] This application is a continuation-in-part of U.S. patent application Ser. No. 08/966,797, filed Nov. 10, 1997 and issued Jan. 25, 2000 as U.S. Pat. No. 6,018,065.
Background of the Invention
[0004] 1. Field of the Invention
[0005] The present invention relates to an isotropic dry cleaning process for noble metal integrated circuit structures.
[0006] 2. Description of the Related Art
[0007] Thin films of noble metals (Pt, Pd, Ir, Rh) have become technologically important in integrated circuits (ICs) as electrodes for ferroelectric and high ε thin films in FeRAMs, DRAMs, RF and microwave MMICs, pyroelectric IR focal plane detector arrays, etc.
[0008] The absence of viable dry etching techniques for submicron patterning of these electrodes is a chronic problem that has threatened to retard or even prevent widespread use of these materials. The present dry-etching approaches utilize plasmas for reactive ion etching (RIE), are chlorine-based, and result in significant residue being left on the microelectronic device structure after the etch process has been completed.
[0009] Depending on the type of structure that is being formed by the patterning, this post-etch residue may result in short circuiting, undesired topography or other deficiencies in the operation of the circuit element in subsequent use of the product microelectronic device. Prevention of the formation of such residues may be achieved in some instances by manipulating the reactive ion etching (RIE) process parameters, but such process manipulation results in undesirable sidewall slopes in the microelectronic device structure that effectively prevent useful submicron capacitors from being fabricated.
[0010] Alternatively, the residue resulting from RIE can be removed by wet rinsing techniques, after the etch process has been completed. Wet rinsing techniques are however generally unsatisfactory, because a significant fraction of the residue may be transported in suspension in the rinse media, allowing a small fraction of the residue solids to redeposit on the wafer, and thereby reducing device yield.
[0011] Further, in some microelectronic device structure geometries, the residue may not be removed using wet rinsing methods.
[0012] Another drawback of wet rinsing methods is the need for a separate process tool to implement the wet rinsing clean-up, which adds to the capital equipment and operating costs of the process system.
[0013] It would therefore be a significant advance in the art of integrated circuit device fabrication, in which noble metal films are formed on the device substrate as electrodes or other structural components of the device, to provide an effective cleaning process for removing unwanted residues on the integrated circuit structure after etching or other process fabrication steps.
Summary of the Invention
[0014] The present invention relates to a method for removing noble metal residue from a microelectronic device structure during the fabrication thereof, by contacting the microelectronic device structure with a gas-phase reactive halide composition, e.g., XeF2, SF6, Si2F6, SiF4, or SiF2and/or SiF3radicals, for sufficient time and under sufficient conditions to at least partially remove the noble metal residue.
[0015] Such “dry clean” method of the invention effects an isotropic dry etching of the noble metal residue for removal thereof. The isotropic dry etching is carried out under low-pressure exposure of the noble metal residue to the reactive halide gas.
[0016] The reactive halide may comprise any suitable halide substituent, e.g., fluorine, bromine, chlorine, or iodine, with fluorine generally being most preferred. The reactive halide agent may itself comprise the reaction product of an initial reaction, such as the reaction of XeF2with silicon to form SiF2and/or SiF3radicals as the reactive halide agent. In this manner SF6, SiF4or Si2F6may be used with an activation source (ion beam, electron beam, ultra violet or laser) to produce the reactive radical species.
[0017] The invention contemplates two main cleaning techniques for using the reactive halide gas as an isotropic noble metal etch agent to remove residual noble metal deposits from the microelectronic device structure.
[0018] The first technique is a batch contacting method wherein a chamber containing the microelectronic device structure is evacuated and backfilled with the reactive halide gas or a mixture of the reactive halide gas and other gas(es), either inert or reactive. After the reactive halide is allowed to react for a predetermined amount of time, the chamber is evacuated and backfilled again with fresh cleaning gas. The evacuation pressure can be less than or equal to 50 mTorr. The backfill pressure can be from about 50 mTorr to about 2 Torr, the exposure time can be from about 10 seconds to about 10 min, and the number of exposure cycles is not limited, but will depend on the amount of material to be removed.
[0019] The second technique using the reactive halide gas as an isotropic etch agent is a continuous gas flow method. In this technique, a steady state flow of the reactive halide gas, e.g., XeF2, SF6, Si2F6or SiF4, is introduced to the chamber containing the microelectronic device structure to be cleaned. Either pure reactive halide gas or a mixture of the reactive halide and other gas(es), either inert or reactive, may be used. The partial pressure of the reactive halide gas can be from about 50 mTorr to about 2 Torr and total flow rate of the reactive halide gas can be from about 1 standard cubic centimeter per minute (sccm) to about 10 standard liters per minute (slm).
[0020] In either case of batch or continuous operation, the microelectronic device structure to be cleaned may be held at temperatures in the range of from about −50° C. to about 200° C.
[0021] In the foregoing methodology, the reactive halide gas may for example comprise a XeF2vapor. Such vapor may be obtained from the sublimation of XeF2solid crystals. XeF2will sublime at room temperature, but may be heated to increase the rate of sublimation.
[0022] Additionally, the XeF2may first be reacted with elemental silicon, and the resultant reaction product used as the etching gas. It is known that XeF2etches silicon to produce SiF4Si2F6and SiF2and SiF3radicals.
[0023] The reactive halide composition may also be produced in an upstream plasma, e.g., SiF2and SiF3radicals may be formed by passing SiF4gas through a remote plasma.
[0024] The method of the invention is usefully employed for removal of noble metal residues comprising Ir, Rh, Pd and/or Pt, and may be utilized for cleaning hybrid electrodes comprising alloys or combinations of such metals, as well as alloys or combinations of one or more of such metals with other (non-noble) metals.
[0025] Other aspects, features and embodiments of the invention will be more fully apparent from the ensuing disclosure and appended claims.
Brief Description of the Drawings
[0026] FIG. 1 is a process flow of a fabrication sequence embodying the method of the present invention, in one aspect thereof.
[0027] FIG. 2 is a schematic representation of a process flow of an alternative method embodiment of the invention.
[0028] FIG. 3 is a schematic representation of a process flow for yet another method embodiment of the present invention.
Detailed Description of the Invention and Preferred Embodiments Thereof
[0029] The disclosure of U.S. patent application Ser. No. 08/966,796 filed Nov. 10, 1997 in the names of Thomas H. Baum and Frank DiMeo, Jr. for “METHOD FOR ETCH FABRICATION OF IRIDIUM-BASED ELECTRODE STRUCTURES,” is incorporated herein by reference in its entirety.
[0030] In accordance with the method of the present invention, noble metal residue is removed from a microelectronic device structure including same, by contacting the microelectronic device structure with a gas-phase reactive halide composition, e.g., XeF2, SF6, SiF4, Si2F6, or SiF3and/or SiF2radicals for sufficient time and under sufficient conditions to at least partially remove the noble metal residue.
[0031] The method of the invention may be advantageously used to remove residue from a microelectronic device structure, subsequent to reactive ion etching of noble metal electrode films thereon, for patterning of the electrode in the fabrication of the microelectronic device, and/or following chemical mechanical polishing (CMP) of the electrode or a precursor structure therefor.
[0032] As used herein, the term “microelectronic device structure” refers to a microelectronic device or a processing step towards the formation of a structure for the microelectronic device that must be subjected to subsequent processing or treatment steps in order to fabricate the final product device.
[0033] The method of the present invention obviates the deficiencies of the prior art wet rinsing techniques that have been used to remove residues when noble metal structures are formed on the surface of a microelectronic substrate, device or precursor article.
[0034] The isotropic dry etch method of the present invention may be practiced with reactive halogenated compounds such as XeF2and/or other halide compositions as agents for removing extraneous noble metal residues that are present on the microelectronic device structure subsequent to forming noble metal electrodes or other integrated circuit components thereon, and reactive ion etching (RIE) and/or chemical mechanical polishing (CMP) thereof. Alternatively, the removal agent for the noble metal residue may comprise a halogenated radical species such as SiF2or SiF3radicals, formed by prior reaction as hereinafter more fully disclosed.
[0035] As used herein, the term “noble metal” means a metal of the platinum group, viz., platinum, palladium, iridium or rhodium, as well as alloys and combinations including one or more of such metals, e.g., with other non-noble metal(s).
[0036] The invention contemplates two main cleaning techniques for using the reactive halide gas as an isotropic noble metal etch agent to remove residual noble metal deposits from the microelectronic device structure.
[0037] The first technique is a batch contacting method wherein a chamber containing the microelectronic device structure is evacuated and backfilled with the reactive halide gas or a mixture of the reactive halide gas and other gas(es), either inert or reactive. After the reactive halide is allowed to react for a predetermined amount of time, the chamber is evacuated and backfilled again with fresh cleaning gas. The evacuation pressure can be less than or equal to 50 mTorr. The backfill pressure can be from about 50 mTorr to about 2 Torr, the exposure time can be from about 10 seconds to about 10 min, and the number of exposure cycles is not limited, but will depend on the amount of material to be removed.
[0038] The second technique using the reactive halide gas as an isotropic etch agent is a continuous gas flow method. In this technique, a steady state flow of the reactive halide gas, e.g., XeF2, SF6, Si2F6or SiF4, is introduced to the chamber containing the microelectronic device structure to be cleaned. Either pure reactive halide gas or a mixture of the reactive halide and other gas(es), either inert or reactive, may be used. The partial pressure of the reactive halide gas can be from about 50 mTorr to about 2 Torr and total flow rate of the reactive halide gas can be from about 1 standard cubic centimeter per minute (sccm) to about 10 standard liters per minute (slm).
[0039] In either case of batch or continuous operation, the microelectronic device structure to be cleaned may be held at temperatures in the range of from about −50° C. to about 200° C.
[0040] The dry clean process of the present invention may be carried out at any suitable process condition, including ambient temperature, low temperature and elevated temperature regimes, as well as varying pressure regimes. For example, the cleaning process may be carried out at room temperature conditions involving the sublimation of XeF2to generate an active cleaning agent. XeF2may also be first reacted with another compound, such as a silicon-containing, to generate an active cleaning agent comprising SiF2or SiF3radicals.
[0041] The time and contacting conditions for the reactive halide etch process may be readily determined by those of ordinary skill in the art. The nature and extent of the etching of the deposited noble metal-based material may be empirically determined while varying the time and/or contacting conditions (such as temperature, pressure, concentration and partial pressure) of the etching agent to identify the process conditions producing a desired etching result.
[0042] In the dry clean of the noble metal residue to etchingly remove same from the microelectronic device structure, the etch rates of the cleaning agent can optionally be enhanced through the use of Lewis-based adducts or electron back-bonding species, e.g., carbon monoxide, trifluorophosphine, trialkylphosphines, etc. These cleaning enhancement agents accelerate the rate of etching by enhancing the volatility of the etch by-products and noble metal (halide)x species or noble metal (halide radical)xspecies.
[0043] For example, in the case of iridium and/or iridium oxide as the noble metal on the substrate, the step of contacting the iridium-based material with a cleaning gas including the xenon halide etching reagent may be carried out with a cleaning enhancement agent such as carbon monoxide to assist in the volatilization and removal of Ir(X)1-6(where X=halide) species from the iridium-based material on the substrate. Where X=chlorine, bromine, fluorine or iodine in the presence of CO serves to enhance the reactant volatility through the formation of (CO)yIr(X)1-6. These enhancement agents can be used advantageously for etching Ir in halogen-based plasmas, ion beams and in hybrid etching schemes. Corresponding use of CO or other platinum metal hexafluorides may be utilized to remove other platinum metal residues on semiconductor device structures.
[0044] In another example, in the case of iridium and/or iridium oxide as the noble metal on the substrate, the step of contacting the iridium-based material with a cleaning gas including the xenon halide etching reagent may be carried out with a co-etchant such as SF6, Si2F6, SiF4or radical species such as SiF3and SiF2to assist in the volatilization and removal of Ir(X)1-6(where X=silicon halide complex ) species from the iridium-based material on the substrate.
[0045] The etching process using the xenon halide etching agent may also be enhanced by use of inert gases. In general, ion beam-assisted, plasma-assisted or photo-assisted techniques may be employed to enhance the etching removal of the noble metal residue, as for example by decreasing the time required for removal, or increasing the extent of removal in a given time, etc.
[0046] In application to the fabrication of specific types of microelectronic device structures, the invention has illustrative utility in the fabrication of capacitor structures. There are three principal types of capacitor geometries and associated processing paths, hereafter referred to as Type 1, Type 2 and Type 3, in which the method of the present invention offers a significant economic or enabling advantage over the methods of the prior art.
[0047] Capacitor arrays in high-density memories (>64 Mb) are typically made by patterning the bottom electrode prior to deposition and patterning of the dielectric and top electrode layers. This is referred to as a Type 1 structure.
[0048] For Type 1 structures, the prior art has used a combination of mechanical liquid agitation and partial dissolution of the residue to “clean up” the noble metal residues.
[0049] The process of the present invention provides an effective alternative to such prior art wet methods for removing noble metal residues from RIE-patterned bottom electrodes.
[0050] The process of the invention is also usefully applied to patterning approaches that define the entire capacitor in one step, including RIE of the entire metal-dielectric stack (Type 2) and chemical mechanical planarization, or chemical mechanical polishing, as such operation is sometimes termed (Type 3).
[0051] In chemical mechanical planarization, capacitors are formed in recesses and excess protruding dielectric and metal is removed by polishing, as more fully described in copending U.S. application Ser. No. 08/975,366 filed Nov. 20, 1997 in the names of Peter C. Van Buskirk and Peter S. Kirlin for “CHEMICAL MECHANICAL POLISHING OF FeFRAM CAPACITORS,” the disclosure of which hereby is incorporated herein by reference in its entirety.
[0052] Type 1 Capacitor Structures
[0053] As mentioned, this structure is used for very high-density memories, such as those with memory density >64 Mb. Parts of the capacitor are formed on the sidewalls, with potential large increases in capacitor area.
[0054] Referring to FIG. 1A of the drawings, a Type 1 capacitor array is formed over an array of transistors (not shown), which are contacted preferably by conductive plugs 1. The conductive plugs are planarized on the surface of the isolation dielectric 2, or subsequent to capacitor formation by etching vias in which conductive plugs are formed, as shown in FIG. 1A.
[0055] Next, as shown in FIG. 1B, the barrier layer 3 and bottom electrode 4 are deposited, using conventional methods such as CVD or sputtering. The bottom electrode is then patterned using RIE or a similar metal etch, as illustrated in FIG. 1C, prior to capacitor dielectric (high ε, ferroelectric, etc.) deposition.
[0056] When the electrode is patterned using the predominantly physical mechanism of the impinging ions, involatile material that is sputtered from between the electrodes is redeposited on the sidewalls of the photoresist (or hard mask), and when the mask is removed, the redeposited layers remain. These redeposited features 5, sometimes characterized as “ears,” are surprisingly robust.
[0057] The dry etch cleaning method of the present invention is usefully applied in the fabrication of such Type 1 structure and may be advantageously implemented in-situ in the RIE reactor. As shown in FIG. 1D, the isotropic nature of the dry clean etch effectively removes the ears that were formed by the highly anisotropic RIE process.
[0058] The result is smooth bottom electrodes 6 that will increase device yield because of the absence of sharp features which would if otherwise present serve to enhance E-fields in the capacitor dielectric. Subsequent processing of the capacitor may then proceed (not shown), comprising dielectric deposition, dielectric patterning, top electrode deposition and patterning, and metallization post oxidizing bake step to complete the formation of the integrated circuit.
[0059] In this Type 1 application, the process of the present invention provides a significant economic advantage over prior art wet methods. As mentioned, prior art wet methods, although effective, result in significant decrease in device yield as well as decreased throughput.
[0060] Type 2 Capacitor Structures
[0061] This type of structure is illustrated in FIG. 2 and is usefully employed in lower density memory arrays (<64 Mb), where the area of the capacitor allows sufficiently high capacitance or remenant polarization.
[0062] In the process flow of FIG. 2, the capacitor array is formed on a planar surface of an isolation dielectric 22, over an array of transistors (not shown). The transistors in this structure are contacted by conductive plugs 21 that have been planarized using CMP or other planarization techniques that are well known in the art. The plug and dielectric structure is illustrated in FIG. 2A.
[0063] In this fabrication method, the entire capacitor system of layers, including conductive barrier 23, bottom electrode 24, dielectric (high ε, ferroelectric, etc.) material 25 and top electrode 26 are deposited sequentially, to produce the structure shown in FIG. 2B.
[0064] The capacitors are next defined using conventional microlithography and anisotropic dry etching processes, using either 2 mask levels or 1 mask level. The use of 1 mask level is the preferred embodiment to produce the structure of FIG. 2C, and is currently the most widespread technique for fabricating FeRAM capacitors.
[0065] The comparative advantages of a 2 mask process are well known, and include reducing the tendency for increased leakage currents that occur when a 1 mask approach is used. A 2 mask approach patterns the top electrode (TE) and bottom electrode (BE) to different areas (the TE is smaller), thereby reducing the chance for short circuits at the electrode edge. The 2-mask approach nonetheless is less economical than the 1 mask approach.
[0066] The method of the present invention permits the 1 mask approach to be utilized advantageously without the high level of leakage susceptibility that has been characteristic of prior art products made by such mask approach.
[0067] Due to the predominantly physical nature of the reactive ion etching process, residue collects on the sides of the capacitor structure 27, making short circuiting more likely. Additionally, sharp features (“ears”) may also be present on the top edges of the top electrode 28, for the same reason as discussed hereinabove in connection with the fabrication of the Type 1 structure.
[0068] The process of the present invention is employed to remove the sidewall residue and the “ears”. This process step in FIG. 2D removes metallic conductive residue from the edges of the capacitor, analogous to the use of the dry cleaning method of the invention in the fabrication of the Type 1 structure as described hereinabove.
[0069] In addition to the isotropic dry clean process, a post oxidizing bake may be performed, similar to that described above for the fabrication of the Type 1 structure. The result is a capacitor structure 29 that is formed with high yield in terms of short circuiting. In addition, the capacitor structure 29 does not have protrusions from the top edges of the top electrode. Such protrusions when present complicate the subsequent isolation of the capacitor array that is required before metallization can be carried out to complete the memory circuits of the structure.
[0070] The method of the present invention is of an enabling character in application to the fabrication of the Type 2 structure, since prior art wet methods do not effectively clean nominally planar surfaces with embedded metallic contamination.
[0071] Type 3 Capacitor Structures
[0072] This fabrication technique is shown in the process flow schematically illustrated in FIG. 3. Such fabrication technique may be utilized to completely avoid the need for RIE processes to pattern noble metals and complex oxide thin films, e.g., those comprising PbZrTiO3, SrBiTiO3and BaSrTiO3.
[0073] The FIG. 3 fabrication technique can be used to fabricate either high or low-density capacitor arrays, since enhanced capacitor area can be obtained from the sidewall contribution, if the aspect ratio of the recesses (depth/width) is large enough.
[0074] Such technique can also be used to fabricate low-density memory arrays, due to the inherent economic advantages of this methodology in minimizing the patterning complexity and the number of steps.
[0075] The capacitor array in the FIG. 3 fabrication method is formed on a planar surface of an isolation dielectric 32, over an array of transistors (not shown), which are contacted by the conductive plugs 31 illustrated in FIG. 3A. In this fabrication technique, capacitor recesses 33 are formed in a conventional dielectric material 34 (SiO2or Si3N4, for example).
[0076] The capacitor recesses are aligned over the conductive plugs 31, as shown in FIG. 3B. The capacitor recesses 33 will correspond to self-aligned capacitors over such conductive plugs once the patterning of the capacitors is completed.
[0077] The entire capacitor system of layers is then deposited sequentially to form the structure shown in FIG. 3C. The respective layers include conductive barrier 35, bottom electrode 36, dielectric (high ε, ferroelectric, etc.) material 37, and top electrode 38.
[0078] The individual capacitors are next defined by chemical mechanical polishing (CMP) of the entire layer system to yield the structure shown in FIG. 3D. Once the structure is formed by CMP there may be significant metal contamination 39 along the edges of the capacitor on the top surface (which has been planarized) that will result in short circuiting of the capacitor if not removed from the structure. Such metallic contamination is typically due to incomplete removal and smearing of noble metal electrode material during the chemical mechanical polishing operation.
[0079] The process of the present invention next is utilized to remove the conductive metallic residue, to produce the structure as shown in FIG. 3E, and thereby allow the capacitors to function as intended.
[0080] In addition to the isotropic dry clean process, a post oxidizing bake may be employed to heal surface and/or subsurface damage to the dielectric (high ε, ferroelectric, etc.) material. Such damage may be either chemical or physical in nature. The post oxidizing bake thereby imparts optimum insulating or ferroelectric properties (depending on the material of construction) to the dielectric material.
[0081] The result is a capacitor structure 40 shown in FIG. 3E that is formed with high yield (in terms of non-short circuiting device elements), in a highly economical manner. In this application (the fabrication of Type 3 structures), the process of the present invention is enabling in character, since wet cleaning methods of the prior art do not work well to clean planar surfaces with embedded metallic contamination.
[0082] Accordingly, while the invention has been described herein with reference to specific features, aspects and embodiments, it will be recognized that the invention may be widely varied, and that numerous other variations, modifications and other embodiments will readily suggest themselves to those of ordinary skill in the art. Accordingly, the ensuing claims are to be broadly construed, as encompassing all such other variations, modifications and other embodiments, within their spirit and scope.
Claims
What is claimed is:
1. A method for removing from a microelectronic device structure a noble metal residue including at least one metal selected from the group consisting of platinum, palladium, iridium and rhodium, the method comprising contacting the microelectronic device structure with a gas-phase reactive halide composition comprising XeF2in an amount effective to remove sufficient residue from the microelectronic device structure to reduce noble metal residue-caused deficiencies in the operation of the microelectronic device.
2. The method according to claim 1, wherein the contacting is carried out at a temperature from about −50° C. to 200° C.
3. The method according to claim 1, wherein the microelectronic device structure is disposed in a chamber, said method further comprising: evacuating the chamber, filling the chamber with a cleaning gas comprising the reactive halide composition, and retaining the reactive halide composition in the chamber to react with the residue for a time sufficient to effect removal of the noble metal residue from the microelectronic device structure.
4. A method according to claim 3, wherein the pressure of the cleaning gas is from about 50 mTorr to about 2 Torr, and the cleaning gas is maintained in the chamber for a period of time which is from about 10 seconds to about 10 min.
5. The method according to claim 1, wherein the microelectronic device structure is disposed in a chamber, and a cleaning gas comprising the reactive halide composition is continuously flowed through the chamber to effect the removal of the noble metal residue from the microelectronic device structure.
6. The method according to claim 5, wherein the reactive halide composition is at a vapor pressure from about 50 mTorr to about 2 Torr, and the cleaning gas through the chamber has a flow rate from about 1 standard cubic centimeter per minute to 10 standard liters per minute.
7. The method according to claim 1, wherein XeF2in the reactive halide composition is generated by an inherent vapor pressure of XeF2.
8. The method according to claim 1, wherein XeF2in the reactive halide composition is generated by sublimation of solid crystalline XeF2.
9. The method according to claim 1, wherein the noble metal residue comprises platinum.
10. The method according to claim 1, wherein the noble metal residue comprises palladium.
11. The method according to claim 1, wherein the noble metal residue comprises iridium.
12. The method according to claim 1, wherein the noble metal residue comprises rhodium.
13. A method for removing from a microelectronic device structure a noble metal residue comprising iridium, the method comprising contacting the microelectronic device structure with a gas-phase reactive halide composition comprising XeF2to remove the residue.
14. The method according to claim 13, further comprising, contacting the microelectronic device structure with an as agent to assist in volatilizing and removing the noble metal residue on the microelectionic device structure.
15. The method according to claim 14, wherein the agent is selected from the group consisting of Lewis bases and electron back-bonding species.
16. The method according to claim 14, wherein the agent is selected from the group consisting of carbon monoxide, trifluorophosphine, and trialkylphosphines.
17. The method according to claim 1, wherein the contacting of the microelectronic device structure with the gas phase reactive halide composition is carried out with an agent to assist in volatilizing and removing the noble metal residue on the microelectronic device structure and the contacting comprises an enhancement step selected from the group consisting of:
(a) providing an inert gas in the agent;
(b) carrying out the contacting in an ion-beam-assisted manner;
(c) carrying out the contacting in a plasma-assisted manner;
(d) carrying out the contacting in a photo-assisted manner; and
(e) carrying out the contacting in a laser assisted manner.
18. The method according to claim 1, wherein the noble metal residue comprises iridium, and carbon monoxide is present in the gaseous mixture during the contacting.
19. The method according to claim 1, wherein a hexafluoride compound of the noble metal is present in the gaseous mixture during the contacting.
20. The method according to claim 1, wherein a silicon fluoride compound is present in the gaseous mixture during the contacting.
21. The method according to claim 1, wherein the noble metal residue comprises iridium, and IrF6is present in the gaseous mixture during the contacting.
22. The method according to claim 1, wherein a Lewis base ligand is present in the gaseous mixture during said contacting, to enhance the removal of the noble metal residue.
23. The method according to claim 1, wherein the microelectronic device structure comprises a capacitor.
24. The method according to claim 23, wherein the capacitor is selected from the group consisting of a Type 1-capacitor structure, a Type 2-capacitor structure and a Type 3-capacitor structure.
25. The method according to claim 1, wherein the contacting of the microelectronic device structure with the reactive halide composition is conducted after reactive ion etching of a noble metal electrode film on the microelectronic device structure.
26. The method according to claim 1, wherein the contacting of the microelectronic device structure with the reactive halide composition is conducted after chemical mechanical polishing of a noble metal electrode film on the microelectronic device structure.
27. The method according to claim 1, wherein the microelectronic device structure comprises a patterned bottom electrode of a capacitor structure, and the contacting is carried out after patterning of the bottom electrode.
28. The method according to claim 1, wherein the microelectronic device structure comprises a Type 2 capacitor structure, and the contacting comprises removing sidewall residue and ears of the capacitor structure.
29. The method according to claim 1, wherein the microelectronic device structure comprises a Type 3 capacitor structure, and the contacting is carried out to remove residue from a chemical mechanical polishing of the Type 3-capacitor structure.
30. A method for removing from a microelectronic device structure a noble metal residue comprising iridium the method comprising contacting the microelectronic device structure with a cleaning gas comprising gas-phase XeF2to at least partially remove the noble metal residue.
31. The method according to claim 30, wherein the contacting is carried out at a temperature from about −50° C. to about 200° C.
32. The method according to claim 30 wherein elemental silicon is exposed within the reaction chamber during said contacting.
33. The method according to claim 30, wherein the microelectronic device structure is disposed in a chamber, said method further comprising evacuating the chamber, filliig the chamber with the cleaning gas, and retaining the cleaning gas in the chamber to react with the residue, to effect the removal of the noble metal residue from the microelectronic device structure.
34. The method according to claim 33, wherein the pressure of the chamber upon evacuation is less than or equal to 50 mTorr, the cleaning gas is at a pressure from about 50 mTorr to about 2 Torr, and the reaction time for each fill of cleaning gas is from about 10 seconds to about 10 min.
35. The method according to claim 33, wherein elemental silicon is present in the chamber.
36. The method according to claim 30, wherein the microelectronic device structure is disposed in a chamber, and the cleaning gas is continually flowed through the chamber, in combination with an energetic dissociation source.
37. The method according to claim 36, wherein the energetic dissociation source is selected from the group consisting of a plasma source, an ion source, an ultra violet source and a laser source.
38. A method for removing from a microelectronic device structure a noble metal residue including at least one metal selected from the group consisting of platinum, palladium, iridium and rhodium, the method comprising contacting the microelectronic device structure with a gas-phase reactive halide composition comprising XeF2, to remove the residue, wherein the microelectronic device structure is disposed in a chamber, said method further comprising:
(a) evacuating the chamber;
(b) filling the chamber with a cleaninig gas comprising the reactive halide composition; and
(c) retaining the reactive halide composition in the chamber to react with the residue; and
(d) sequentially repeating said steps of filling and evacuating to effect removal of the noble metal residue from the microelectronic device structure.
39. A method for removing from a microelectronic device structure a noble metal residue comprising at least one metal selected from the group consisting of platinum, palladium, iridium and rhodium, the method comprising contacting the microelectronic device structure with a gas-phase reactive halide composition comprising XeF2, wherein the halide component is present in an amount and for a time sufficient to remove sufficient residue to reduce noble metal residue-caused deficiencies in the operation of the microelectronic device structure.
40. A method for etching a noble metal composition comprising iridium comprising contacting the noble metal with an etchant comprising XeF2.
41. A method for etching iridium comprising contacting the iridium with an etchant comprising XeF2.
42. A method for removing from a microelectronic device structure a noble metal residue including at least one metal selected from the group consisting of platinum, palladium, iridium and rhodium, the method comprising contacting the microelectronic device structure with a gas-phase reactive halide composition comprising XeF2, in an amount effective to at least partially remove the residue.
43. A method for removing from a microelectronic device structure a noble metal residue including at least one metal selected from the group consisting of platinum, palladium, iridium and rhodium, the method comprising contacting the microelectronic device structure with a gas-phase reactive halide composition consisting essentially of XeF2, in an amount effective to at least partially remove the residue, and optionally including:
(a) an agent selected from the group consisting of Lewis bases and electron back-bonding species; and/or
(b) selected from the group consisting of carbon monoxide, trifluorophospiline, and trialkylphosphines.
44. A method for removing from a microelectronic device structure a noble metal residue including at least one metal selected from the group consisting of platinum, palladium, iridium and rhodium, the method comprising contacting the microelectronic device structure with a gas-phase reactive halide composition comprising XeF2, wherein the halide component is present in an amount effective to remove sufficient residue from the microelectronic device structure to eliminate noble residue-caused deficiencies in the operation of the microelectronic device.
Patent Citations (4)
Non-Patent Literature (16)
- Koteki, D.E., “A Review of High Dielectric Materials for DRAM Capacitors”, Integ. Ferro., 1997, vol. 16, pp. 1-19.Applicant
- Jeon, et al., “Thermal Stability of Ir/Polycrystalline-Si Structure for Bottom Electrode of Integrated Ferroelectric Capacitors”, Appl. Physics Lett., 1997, vol. 71(4), pp. 467-469.Applicant
- Williams, et al., “Etch Rates for Micromachining Processing”, Journ. For Microelectromechanical Systems, Dec. 1996, vol. 5 (4), pp. 256-269.Applicant
- Vugts, et al., “Si/XeF2 Etching-Temperature Dependence”, 1996, J. Vac. Sci. Tech. A, vol. 14(5), pp. 2766-2774.Applicant
- P.C. Fazan, et al., “Stacked Capacitor Modules for 64 Mb DRAMs and Beyond”, Semiconductor Inter., 1992, vol. 108, pp. 108-112.Applicant
- L. H. Parker, et al., Ferroelectric Materials for 64Mb and 256Mb DRAMs, IEEE Circuits and Devices Mag., Jan. 1990, pp. 17-26.Applicant
- R. E. Sievers, et al., “Volatile Barium B-Diketonates for Use as MOCVD Precursors”, Coord. Chem. Rev., 1993, pp. 285-291.Applicant
- C. Farrell, et al., “A Reactive Ion Etch Study for Producing Patterned Platinum Structures”, Presented at ISIF 96, Mar. 18,19,20, 1996 Tempe AZ. (to be published in Integrated Ferroelectrics).Applicant
- K. R. Milkove and C. X, Wang, “Insight into the dry cleaning of Fence Patterned Platinum Sturctures”, J. Vac. Sci. Tech. A, 1997, vol. 15(3), pp. 596-603.Applicant
- Chang, F.I., et al., “Gas Phase Silicon Micromachining with Xenon Difluoride”, Proc of SPIE, 1995, vol. 2641, pp. 117-128.Applicant
- Bensaola, A. et al., “Low Temperature Ion Beam Enhanced Etching of Tungsten Films with Xenon Difluoride”, Appl. Phys. Lett., Dec. 1986, vol. 49(24), pp. 1663-1664.Applicant
- G. Stauf, “BaSrTiO3 Etching for Advanced Microelectronic Devices”, U.S. Army Missile Command, Report No., DAAH01-96-C-R035, Jan. 10, 1996-Jan. 30, 1998.Applicant
- Ebsworth, E.A.V., et al., “Formation of Iridium Fluoroacyl Complexes by Reaction of Iridium Carbonyls with Xenon Difluoride and Reactions of these to Generate Unusual Acyl Complexes”, J. Chem. Soc., Dalton Trans., 1993, ISS. 7, pp. 1031-1037.Applicant
- Blake, A.J., et al., “Novel Reaction of an Iridium Carbonyl Complex with Xenon Difluoride: The First Metal Fluoracyl Complex”, J. Chem. Soc., Chem. Commun., 1988, ISS.8, pp. 529-530.Applicant
- Sladkey, F.O., et al., “Xenon Difluoride as a Fluoride Ion Donor” J. Chem. Soc. A, 1969, vol. 14, pp. 2179-2788.Applicant
- Floy I. Chang et al., Gas-Phase Silicon Micrmachining with Xenon Difluoride, Proc. of SPIE vol. 2641, pp. 117-128, Dec. 1995.Examiner