WO2018200212A1

WO2018200212A1 - Selective deposition of tungsten for simplified process flow of tungsten oxide pillar formation

Info

Publication number: WO2018200212A1
Application number: PCT/US2018/027284
Authority: WO
Inventors: Yihong Chen; Ziqing Duan; Yong Wu; Abhijit Basu Mallick; Srinivas Gandikota
Original assignee: Applied Materials Inc
Current assignee: Applied Materials Inc
Priority date: 2017-04-25
Filing date: 2018-04-12
Publication date: 2018-11-01
Anticipated expiration: 2019-10-25
Also published as: TWI760481B; US10636659B2; TW201908509A; US20180308694A1

Abstract

Methods comprising depositing a film material to form an initial film in a trench in a substrate surface are described. The film is treated to expand the film to grow beyond the substrate surface.

Description

SELECTIVE DEPOSITION OF TUNGSTEN FOR SIMPLIFIED PROCESS FLOW OF

TUNGSTEN OXIDE PILLAR FORMATION

TECHNICAL FIELD

[0001] The present disclosure relates generally to methods of depositing and processing thin films. In particular, the disclosure relates to processes for filling trenches in substrates.

BACKGROUND

[0002] The semiconductor industry is rapidly developing chips with smaller and smaller transistor dimensions to gain more functionality per unit area. As the dimensions of devices continue to shrink, so does the gap/space between the devices, increasing the difficulty to physically isolate the devices from one another. Filling in the high aspect ratio trenches/spaces/gaps between devices which are often irregularly shaped with high-quality dielectric materials is becoming an increasing challenge to implementation with existing methods including gapfill, hardmasks and spacer applications. Selective deposition methods typically include depositing a mask material on a substrate and patterning the mask material to form a patterned mask. Regions of the substrate may then be exposed though the patterned mask after the patterning of the mask. The patterned mask may be removed from the substrate to expose non-implanted regions of the substrate and a material may be selectively deposited on selected regions of the substrate.

[0003] There is a need in the art for new methods for chip designs with smaller critical dimensions. Additionally, there is an ongoing need for high quality metal oxide films for hardmasks and spacer applications, as well as methods for forming patterned films on substrates. SUMMARY

[0004] One or more embodiments of the disclosure are directed to processing methods comprising providing a substrate surface having at least one trench. The at least one trench extends a depth from the substrate surface to a bottom surface and has a width defined by a first sidewall and a second sidewalk A film material is selectively deposited to form a film substantially only in the trench. The film has a film material volume and comprises a material selected from the group consisting of Co, Cr, Fe, Mn, Nb, Os, Ta, U, W and V. The film is treated to expand the film material volume to provide an expanded film which extends beyond the substrate surface.

[0005] Additional embodiments of the disclosure are directed to processing methods comprising providing a substrate surface having at least one trench. The at least one trench extends a depth from the substrate surface to a bottom surface and has a width defined by a first sidewall and a second sidewalk A film material is selectively deposited to form an initial film having a film material volume in the trench and not on the substrate surface. The film material has a Pilling-Bedworth ratio of greater than 2 and comprises a material selected from the group consisting of Co, Cr, Fe, Mn, Nb, Os, Ta, U, W and V. The initial film is treated to form a nitride of a metal selected from the group consisting of Co, Cr, Fe, Mn, Nb, Os, Ta, U, W or V to expand the film material volume to provide an expanded film which extends beyond the substrate surface. [0006] Further embodiments of the disclosure are directed to processing methods comprising providing a substrate surface having at least one trench. The at least one trench extends a depth from the substrate surface to a bottom surface and has a width defined by a first sidewall and a second sidewall. A film material is selectively deposited to form an initial film having a film material volume in the trench and not on the substrate surface. The film material has a Pilling-Bedworth ratio of greater than 2 and comprising a material selected from the group consisting of Co, Cr, Fe, Mn, Nb, Os, Ta, U, and V. The initial film is treated to form an oxide of a metal selected from the group consisting of Co, Cr, Fe, Mn, Nb, Os, Ta, U, or V to expand the film material volume to provide an expanded film which extends beyond the substrate surface. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this disclosure and are therefore not to be considered limiting of its scope, for the disclosure may admit to other equally effective embodiments.

[0008] FIG. 1 shows a cross-sectional view of a substrate feature in accordance with one or more embodiments of the disclosure; and [0009] FIGS. 2A through 2C show a cross-sectional schematic of a gapfill process in accordance with one or more embodiments of the disclosure.

DETAILED DESCRIPTION

[0010] Before describing several exemplary embodiments of the disclosure, it is to be understood that the disclosure is not limited to the details of construction or process steps set forth in the following description. The disclosure is capable of other embodiments and of being practiced or being carried out in various ways.

[0011] A "substrate" as used herein, refers to any substrate or material surface formed on a substrate upon which film processing is performed during a fabrication process. For example, a substrate surface on which processing can be performed include materials such as silicon, silicon oxide, strained silicon, silicon on insulator (SOI), carbon doped silicon oxides, amorphous silicon, doped silicon, germanium, gallium arsenide, glass, sapphire, and any other materials such as metals, metal nitrides, metal alloys, and other conductive materials, depending on the application. Substrates include, without limitation, semiconductor wafers. Substrates may be exposed to a pretreatment process to polish, etch, reduce, oxidize, hydroxylate, anneal, UV cure, e-beam cure and/or bake the substrate surface. In addition to film processing directly on the surface of the substrate itself, in the present disclosure, any of the film processing steps disclosed may also be performed on an underlayer formed on the substrate as disclosed in more detail below, and the term "substrate surface" is intended to include such underlayer as the context indicates. Thus for example, where a film/layer or partial film/layer has been deposited onto a substrate surface, the exposed surface of the newly deposited film/layer becomes the substrate surface.

[0012] One or more embodiments of the disclosure are directed to methods for depositing metal oxide films for any conformal, nonconformal and/or low to high aspect ratio gap/trench/void filling applications. Embodiments of the disclosure advantageously provide methods of depositing a film (e.g., a metal oxide film) in high aspect ratio (AR) structures with small dimensions. Some embodiments of the disclosure advantageously provide methods of filling gaps without formation of a seam in the gap. One or more embodiments of the disclosure advantageously provide methods of forming self-aligned vias.

[0013] Tungsten oxide pillars can be formed in features for self-aligned patterning applications. A conformal tungsten ALD film can be used to fill a trench. After filling the trench, the over-burden (i.e., tungsten deposited on top of the substrate outside of the trenches) is removed by a chemical-mechanical planarization (CMP) process to separate the tungsten lines. The resulting tungsten lines can be annealed with oxidizing atmosphere to form tungsten oxide pillars. One drawback of this method is the use of wet process CMP to remove the over-burden. This decreases the yield and makes defect control more difficult.

[0014] FIG. 1 shows a partial cross-sectional view of a substrate 100 with a feature 1 10. The Figures show substrates having a single feature for illustrative purposes; however, those skilled in the art will understand that there can be more than one feature. The shape of the feature 1 10 can be any suitable shape including, but not limited to, trenches and cylindrical vias. In specific embodiments, the feature 1 10 is a trench. As used in this regard, the term "feature" means any intentional surface irregularity. Suitable examples of features include, but are not limited to trenches which have a top, two sidewalls and a bottom, peaks which have a top and two sidewalls extending upward from a surface and vias which have sidewalls extending down from a surface with an open bottom. Features or trenches can have any suitable aspect ratio (ratio of the depth of the feature to the width of the feature). In some embodiments, the aspect ratio is greater than or equal to about 5:1 , 10:1 , 15:1 , 20:1 , 25:1 , 30:1 , 35:1 or 40:1 .

[0015] The substrate 100 has a top surface 120. The at least one feature 1 10 forms an opening in the top surface 120. The feature 1 10 extends from the top surface 120 to a depth D to a bottom surface 1 12. The feature 1 10 has a first sidewall 1 14 and a second sidewall 1 16 that define a width W of the feature 1 10. The open area formed by the sidewalls and bottom are also referred to as a gap. [0016] With reference to FIGS. 2A through 2C, the substrate 100 is provided for processing. As used in this regard, the term "provided" means that the substrate is placed into a position or environment for further processing. The substrate 100 illustrated in FIG. 2A has a first surface 150 and a second surface 160. The first surface 150 and the second surface 160 are different surface materials on the substrate 100. The feature 1 10 is formed with the bottom 1 12 being the first surface 150 and the sidewalls 1 14, 1 16 and the top surface 120 being the second surface.

[0017] In FIG. 2B, a film 130 is formed selectively on the first surface 150 relative to the second surface 160. The film 130 can be any suitable film formed by any suitable process including, but not limited to, chemical vapor deposition, plasma- enhanced chemical vapor deposition, atomic layer deposition, plasma-enhanced atomic layer deposition and/or physical vapor deposition. In some embodiments, the film 130 is formed by atomic layer deposition or plasma-enhanced atomic layer deposition. [0018] The materials of the first surface 150 and the second surface 160 can be chosen to allow selective deposition of the film 130 on one surface relative to the other. In the example shown, the film 130 is formed on the first surface 150 and not the second surface 160. However, those skilled in the art will understand that the film could be formed selectively on the second surface and not the first surface. [0019] According to the embodiment shown, the processing method includes selectively depositing a film 130 within the trench to a height H less than or equal to the depth D of the feature 1 10. The film can be any suitable material including, but not limited to, Co, Cr, Fe, Mn, Nb, Os, Ta, U, W and V.

[0020] The processing method further comprises treating the film 130 to expand the film material volume to provide an expanded film 140, as shown in FIG. 2C. The expanded film 140 extends beyond the substrate surface 120.

[0021] In one embodiment, the film 130, fills at least 10% of the volume of the trench. In other embodiments, the film 130 fills at least 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100% of the volume of the trench. In some embodiments, the film 130 deposited in the feature 1 10 has a height H that is less than or equal to about 98%, 95%, 90%, 80%, 70%, 60% or 50% of the depth D of the feature 1 10.

[0022] In the embodiment shown, the film extends from the first sidewall 1 14 to the second sidewall. In one or more embodiments, treating the film results in the film volume increasing by at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, 150%, 200%, 250%, 300%, 350% or 400%. When a plurality of features 1 10 (not shown) are filled with the film 130, a plurality of pillars 145 can be formed to provide a pattern without using a mask.

[0023] In one embodiment, treating the film 130 comprises exposing the film to an oxidizing environment. In embodiments in which treating the initial film comprises exposing the initial film to an oxidizing environment the expanded film 140 comprises a material selected from the group consisting of CoO, Fe2O3, Fe3O₄, MnO2,Mn₂O3, Mn₃O₄, MoO₃, Nb₂O₅, Ta₂O₅, OsO₂, UO₂, and V₂O₅.

[0024] In some embodiments, treating the film 130 comprises exposing the initial film to a nitridating environment. In embodiments in which the initial film is exposed to a nitridating environment, the film material is selected from the group consisting of Cr, Mo and Os. In such embodiments, the expanded film comprises a material selected from the group consisting of CrN₂, MoN₂ and OsN₂.

[0025] In some embodiments, treating the film 130 comprises exposing the initial film to an oxidizing agent comprising one or more of O₂, O3, N₂O, H₂O, H₂O₂, CO, CO₂, NH₃, N₂/Ar, N₂/He or N₂/Ar/He and/or a nitridation agent comprising one or more of ammonia, hydrazine, NO₂ or nitrogen plasma.

[0026] In some embodiments, treating the initial film occurs at a temperature less than or equal to about 450 ^QC, or 400 ^QC, or 350 ^QC, or 300 ^QC, or 250 ^QC or 200 ^QC. In some embodiments, the film 130 is a tungsten film that is formed at a temperature in the range of about 150 ^QC to about 200 ^QC.

[0027] In some embodiments, the film 130 is a metal film or a metal-containing film. Suitable metal films include, but are not limited to metals having a Pilling-Bedworth ratio greater than 2, greater than 2.25, or greater than 2.5. Pilling-Bedworth ratio refers to a ratio of a volume of the elementary cell of a metal oxide or metal nitride to the volume of the elementary cell of the corresponding metal from which the oxide or nitride is formed. The Pilling-Bedworth ratio is defined as the V_0XiCie/V_metai or Vnitride metai, where V is volume. For determining the Pilling-Bedworth ratio of a metal oxide, Voxide equals the molecular mass of the of the metal oxide multiplied by the density of the metal, and V_met_ai equals the number of atoms of metal per one molecule of the oxide multiplied by the atomic mass of the metal multiplied by the density of the oxide. For determining the Pilling-Bedworth ratio of a metal nitride, V_nitride equals the molecular mass of the of the metal nitride multiplied by the density of the metal, and Vmetai equals the number of atoms of metal per one molecule of the nitride multiplied by the atomic mass of the metal multiplied by the density of the nitride. Examples of such films include one or more of Co, Mo, W, Ta, Ti, Ru, Rh, Cu, Fe, Mn, V, Nb, Hf, Zr, Y, Al, Sn, Cr, Os, U and/or La. In some embodiments, the metal is selected from the group consisting of Co, Fe, Mn, Nb, Os, Ta, U, and V. In some embodiments, the metal has a Pilling-Bedworth ratio of greater than 2.5 and is selected from the group consisting of Mo, Os, and V. In some specific embodiments, the metal film comprises tungsten. In some specific embodiments, the metal film excludes tungsten. Suitable metal containing films include derivatives of a metal film. Suitable derivatives of the metal film include, but are not limited to, nitride, boride, carbide, oxynitride, oxyboride, oxycarbide, carbonitride, borocarbide, boronitride, borocarbonitride, borooxycarbonitride, oxycarbonitride, borooxycarbide and borooxynitride. Those skilled in the art will understand that the metal film deposited may have a non- stoichiometric amount of atoms with the metal film. For example, a film designated as WN may have different amounts of tungsten and nitrogen. The WN film may be, for example, 90 atomic % tungsten. The use of WN to describe a tungsten nitride film means that the film comprises tungsten and nitrogen atoms and should not be taken as limiting the film to a specific composition. In some embodiments, the film consists essentially of the designated atoms. For example, a film consisting essentially of WN means that the composition of the film is greater than or equal to about 95%, 98% or 99% tungsten and nitrogen atoms. In some embodiments, the film 130 comprises tungsten. In some embodiments, the film 130 consists essentially of tungsten. In one or more embodiments, the film comprises titanium. In some embodiments, the film consists essentially of titanium or titanium nitride. [0028] In some embodiments, the film 130 is formed substantially seamlessly within the feature 1 10. In some embodiments, a seam may be formed within the width W of the feature 1 10. The seam can be any gap, space or void that forms between the walls 1 14, 1 16 of the feature 1 10. [0029] In some embodiments, substantially all of the film 130 is formed within the feature 1 10. As used in this regard, the term "substantially all" means that greater than or equal to about 95%, 98% or 99% of the film is formed within the feature 1 10 on a weight basis. If the film 130 is formed on the top surface 120, the film 130 can be removed from the top surface 120 by any suitable etch process. [0030] The film 130 can then be expanded to cause volumetric expansion to fill the feature and allow the film 130 to extend from the feature. As shown in FIG. 2C, expanding the film causes a volumetric expansion of the original film 130 to fill the feature. The expansion of the film 130 can be in the range of about 10% to about 1000%, or in the range of about 50% to about 800%, or in the range of about 100% to about 700%. In some embodiments, the film 130 expands by an amount greater than or equal to about 150%, 200%, 250%, 300% or 350%. In some embodiments, the film 130 expands an amount in the range of about 300% to about 400%.

[0031] In some embodiments, the film 130 is expanded by exposure to a siliciding agent or siliciding conditions to convert the metal or metal containing film to a metal silicide film. The siliciding agent can be any suitable siliciding agent including, but not limited to, silane, disilane, trisilane, tetrasilane, pentasilane, hexasilane, trimethyl silane, compounds with trimethylsilyl substituents and combinations thereof. In some embodiments, the siliciding conditions comprise a thermal siliciding, plasma enhanced siliciding, remote plasma siliciding, microwave and radio-frequency (e.g., ICP, CCP). [0032] In some embodiments, the film 130 is expanded by exposure to a germanium agent or germaniciding conditions to convert the metal or metal containing film to a metal germanicide film. The germaniciding agent can be any suitable germaniciding agent including, but not limited to, germane, digermane, trigermane, tetragermane, pentagermane, hexagermane, trimethyl germanium, compounds with trimethylgermanyl substituents and combinations thereof. In some embodiments, the germaniciding conditions comprise a thermal germaniciding, plasma enhanced germaniciding, remote plasma germaniciding, microwave and radio-frequency (e.g., ICP, CCP).

[0033] As shown in FIG. 2C, during expansion, the fidelity of the feature shape is maintained on the top of the feature so that the film 130 grows straight up from the feature 1 10. As used in this regard, "straight up" means that the sides of the expanded film 140 are substantially coplanar with the sidewall 1 14, 1 16 of the feature 1 10. A surface is coplanar with the sidewall 1 14 where the angle formed at the junction of the sidewall 1 14 and the surface is ±10^Q.

[0034] In some embodiments, the film 130 is doped with a dopant prior to expansion. The dopant can be incorporated into the film 130 at the same time as the formation of the film 130 or in a separate process sequentially with the film deposition. For example, depositing the film 130 may occur followed by doping the film 130 with the dopant in a separate process in either the same process chamber or a different process chamber. In some embodiments, the deposition of the film 130 occurs with the doping in a single process. For example, the film precursor and dopant can be co- flowed into the processing chamber to form the filml 30.

[0035] Some embodiments include an optional treatment process. The treatment process treats the film 130 to improve some parameter of the film. In some embodiments, the treatment process comprises annealing the film. In some embodiments, treatment can be performed by in-situ anneal in the same process chamber used for deposition and/or reduction. Suitable annealing processes include, but are not limited to, rapid thermal processing (RTP) or rapid thermal anneal (RTA), spike anneal, or UV cure, or e-beam cure and/or laser anneal. The anneal temperature can be in the range of about 500 ^QC to 900 ^QC. The composition of the environment during anneal may include one or more of H₂, Ar, He, N₂, NH₃, SiH₄, etc. The pressure during anneal can be in the range of about 100 imTorr to about 1 atm.

[0036] According to one or more embodiments, the substrate is subjected to processing prior to and/or after forming the layer. This processing can be performed in the same chamber or in one or more separate processing chambers. In some embodiments, the substrate is moved from the first chamber to a separate, second chamber for further processing. The substrate can be moved directly from the first chamber to the separate processing chamber, or it can be moved from the first chamber to one or more transfer chambers, and then moved to the separate processing chamber. Accordingly, the processing apparatus may comprise multiple chambers in communication with a transfer station. An apparatus of this sort may be referred to as a "cluster tool" or "clustered system," and the like.

[0037] Generally, a cluster tool is a modular system comprising multiple chambers which perform various functions including substrate center-finding and orientation, degassing, annealing, deposition and/or etching. According to one or more embodiments, a cluster tool includes at least a first chamber and a central transfer chamber. The central transfer chamber may house a robot that can shuttle substrates between and among processing chambers and load lock chambers. The transfer chamber is typically maintained at a vacuum condition and provides an intermediate stage for shuttling substrates from one chamber to another and/or to a load lock chamber positioned at a front end of the cluster tool. Two well-known cluster tools which may be adapted for the present invention are the Centura® and the Endura®, both available from Applied Materials, Inc., of Santa Clara, Calif. However, the exact arrangement and combination of chambers may be altered for purposes of performing specific steps of a process as described herein. Other processing chambers which may be used include, but are not limited to, cyclical layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etch, pre-clean, chemical clean, thermal treatment such as RTP, plasma nitridation, degas, orientation, hydroxylation and other substrate processes. By carrying out processes in a chamber on a cluster tool, surface contamination of the substrate with atmospheric impurities can be avoided without oxidation prior to depositing a subsequent film.

[0038] According to one or more embodiments, the substrate is continuously under vacuum or "load lock" conditions, and is not exposed to ambient air when being moved from one chamber to the next. The transfer chambers are thus under vacuum and are "pumped down" under vacuum pressure. Inert gases may be present in the processing chambers or the transfer chambers. In some embodiments, an inert gas is used as a purge gas to remove some or all of the reactants. According to one or more embodiments, a purge gas is injected at the exit of the deposition chamber to prevent reactants from moving from the deposition chamber to the transfer chamber and/or additional processing chamber. Thus, the flow of inert gas forms a curtain at the exit of the chamber.

[0039] The substrate can be processed in single substrate deposition chambers, where a single substrate is loaded, processed and unloaded before another substrate is processed. The substrate can also be processed in a continuous manner, similar to a conveyer system, in which multiple substrate are individually loaded into a first part of the chamber, move through the chamber and are unloaded from a second part of the chamber. The shape of the chamber and associated conveyer system can form a straight path or curved path. Additionally, the processing chamber may be a carousel in which multiple substrates are moved about a central axis and are exposed to deposition, etch, annealing, cleaning, etc. processes throughout the carousel path.

[0040] During processing, the substrate can be heated or cooled. Such heating or cooling can be accomplished by any suitable means including, but not limited to, changing the temperature of the substrate support and flowing heated or cooled gases to the substrate surface. In some embodiments, the substrate support includes a heater/cooler which can be controlled to change the substrate temperature conductively. In one or more embodiments, the gases (either reactive gases or inert gases) being employed are heated or cooled to locally change the substrate temperature. In some embodiments, a heater/cooler is positioned within the chamber adjacent the substrate surface to convectively change the substrate temperature.

[0041] The substrate can also be stationary or rotated during processing. A rotating substrate can be rotated continuously or in discreet steps. For example, a substrate may be rotated throughout the entire process, or the substrate can be rotated by a small amount between exposures to different reactive or purge gases. Rotating the substrate during processing (either continuously or in steps) may help produce a more uniform deposition or etch by minimizing the effect of, for example, local variability in gas flow geometries.

[0042] Reference throughout this specification to "one embodiment," "certain embodiments," "one or more embodiments" or "an embodiment" means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the disclosure. Thus, the appearances of the phrases such as "in one or more embodiments," "in certain embodiments," "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily referring to the same embodiment of the disclosure. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

[0043] Although the disclosure herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present disclosure. It will be apparent to those skilled in the art that various modifications and variations can be made to the method and apparatus of the present disclosure without departing from the spirit and scope of the disclosure. Thus, it is intended that the present disclosure include modifications and variations that are within the scope of the appended claims and their equivalents.

Claims

What is claimed is:

1 . A processing method comprising:

providing a substrate surface having at least one trench, the at least one trench extending a depth from the substrate surface to a bottom surface, the at least one trench having a width defined by a first sidewall and a second sidewall;

selectively depositing a film material to form a film substantially only in the trench, the film having a film material volume comprises a material selected from the group consisting of Co, Cr, Fe, Mn, Nb, Os, Ta, U, W and V ; and

treating the film to expand the film material volume to provide an expanded film which extends beyond the substrate surface.

2. The method of claim 1 , wherein the film material is selected from the group consisting of Co, Fe, Mn, Nb, Os, Ta, U, and V.

3. The method of claim 2, wherein treating the initial film comprises exposing the initial film to an oxidizing environment.

4. The method of claim 3, wherein the expanded film comprises a material selected from the group consisting of CoO, Fe₂O₃, Fe₃O₄, MnO₂,Mn₂O₃, Mn₃O₄, MoO₃, Nb₂O₅, Ta₂O₅, OsO₂, UO₂, and V₂O₅.

5. The method of claim 1 , wherein the film material has a Pilling-Bedworth ratio of greater than 2.5 and is selected from the group consisting of Mo, Os, and V.

6. The method of claim 4, wherein treating the initial film comprises exposing the initial film to an oxidizing environment.

7. The method of claim 5, wherein the expanded film comprises a material selected from the group consisting of MoO3, OsO2 and V2O5.

8. The method of claim 1 , wherein treating the film comprises exposing the initial film to a nitridating environment.

9. The method of claim 8, wherein the film material is selected from the group consisting of Cr, Mo and Os.

10. The method of claim 8, wherein the expanded film comprises a material selected from the group consisting of CrN2, MoN2 and OsN2.

1 1 . The method of claim 1 , wherein treating the film comprises exposing the initial film to an oxidizing agent comprising one or more of O2, 03, N2O, H2O, H2O2, CO, CO2, NH3, N2/Ar, N2/He or N2/Ar/He and/or a nitridation agent comprising one or more of ammonia, hydrazine, NO2 or nitrogen plasma.

12. The method of claim 1 , wherein treating the film occurs at a temperature greater than about 300 ^QC.

13. A processing method comprising:

selectively depositing a film material to form an initial film having a film material volume in the trench and not on the substrate surface, the film material having a Pilling-Bedworth ratio of greater than 2 and comprising a material selected from the group consisting of Co, Cr, Fe, Mn, Nb, Os, Ta, U, W and V; and

treating the initial film to form a nitride of a metal selected from the group consisting of Co, Cr, Fe, Mn, Nb, Os, Ta, U, W or V to expand the film material volume to provide an expanded film which extends beyond the substrate surface.

14. The method of claim 13, wherein the film material comprises a metal selected from the group consisting of Cr, Mo and Os.

15. The method of claim 13, wherein the expanded film comprises a material selected from the group consisting of CrN₂, MoN₂ and OsN₂.