Middle-process dielectric layer engineering for prevention of through-hole voids

Abstract

Embodiments of the present disclosure provide techniques for fabricating a semiconductor device having less via voids (e.g., a gap between a dielectric layer and a metal filler of the semiconductor device). One such technique involves forming a dielectric layer over a surface of a substrate; forming one or more openings in the dielectric layer; filling the one or more openings with a metal, wherein the metal is disposed on a surface of each of the one or more openings; and injecting an oxygen-containing substance into the dielectric layer to provide a dose of the oxygen-containing substance to a surface of each of the one or more openings and the metal disposed thereon.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 409,657 filed on September 23, 2022 and U.S. Provisional Application No. 63 / 409,658 filed on September 23, 2022, the entire contents of which are hereby incorporated by reference. Technical Field

[0003] Embodiments of the present disclosure generally relate to a method for manufacturing a semiconductor device. Background Art

[0004] Reliably producing features below 100nm or smaller is one of the key technical challenges for the next generation of very large scale integration (VLSI) and ultra-large-scale integration (ULSI) semiconductor devices. However, the ever-shrinking dimensions of VLSI and ULSI technologies have placed additional demands on processing capabilities as the limits of circuit technology are pushed. Reliably forming gate structures on substrates is important to the success of VLSI and ULSI and to the ongoing efforts to improve the circuit density and quality of individual substrates and dies.

[0005] As the circuit density of the next generation of devices increases, the width of the interconnects (such as through holes, trenches, contacts, gate structures and other features) and the dielectric materials therebetween are reduced to a size of 45nm and 32nm or lower, while the thickness of the dielectric layer remains substantially constant, resulting in an increase in the depth-to-width ratio of the features. In order to enable the manufacture of next generation devices and structures, the three-dimensional (3D) stacking of semiconductor chips is often used to improve the performance of transistors. By arranging transistors in a three-dimensional manner rather than in a conventional two-dimensional manner, multiple transistors can be placed very close to each other in an integrated circuit (IC). The 3D stacking of semiconductor chips shortens the wire length and keeps the wiring delay low. In the manufacture of the 3D stacking of semiconductor chips, a stepped structure is often used to allow multiple interconnect structures to be set on the stack, thereby forming a high-density vertical transistor device.

[0006] Due to the materials used in conventionally configured devices, conventional interconnect formation processes and interconnect designs lead to the formation of high resistance structures. In conventional methods, via filling is accomplished with metal barriers, liners, and bulk fill metals. Metal barriers and liners are used to achieve reliability and gap filling robustness. However, materials used for barrier and liner layers (such as titanium nitride (TiN) or tantalum nitride (TaN)) typically have high resistivity, which may result in high interconnect resistance when deposited at the bottom of the via. As a result of RC delay and power loss due to IR drop, interconnect resistance will affect the speed of the formed device. As design rules continue to shrink, the priority of reducing interconnect resistance becomes increasingly important. In particular, interconnect resistance has a great impact on the total resistance of short interconnects, smaller via sizes (e.g., less than 40nm), and multilayer wiring with via stacking, i.e., the resistance through the interconnect may be higher than the resistance through the line. Therefore, reducing interconnect resistance has become increasingly important for achieving chip performance.

[0007] Therefore, there is a continuing need for improved methods of forming interconnects to reduce integrated circuit manufacturing costs, memory cell size, and power consumption and to address the above-mentioned issues. Summary of the invention

[0008] One or more embodiments of the present disclosure are directed to a method for manufacturing a semiconductor device. The method includes forming a dielectric layer above a surface of a substrate; forming one or more openings in the dielectric layer; filling the one or more openings with a metal, wherein the metal is disposed on a surface of each of the one or more openings; and injecting an oxygen-containing substance into the dielectric layer to provide a dose of the oxygen-containing substance to the surface of each of the one or more openings and the metal disposed thereon.

[0009] One or more embodiments of the present disclosure relate to a method for manufacturing a semiconductor device. The method includes injecting an oxygen-containing substance into a patterned dielectric layer disposed on a substrate. The patterned dielectric layer includes a dielectric layer, the dielectric layer includes a plurality of openings, each opening includes a metal layer disposed on a surface of the opening, and the oxygen-containing substance is injected into the dielectric layer to provide a dose of the oxygen-containing substance to the surface of each of the plurality of openings and the metal layer disposed thereon. After injecting the oxygen-containing substance, the patterned dielectric layer is heated to oxidize the surface of each of the plurality of openings exposed to the dose of the oxygen-containing substance and the metal layer.

[0010] One or more embodiments of the present disclosure relate to a semiconductor device, comprising a substrate; a patterned dielectric layer disposed above the substrate, the patterned dielectric layer comprising a plurality of openings; a metal layer disposed on surfaces of the plurality of openings; and a metal oxide layer located at an interface between the metal layer and the surfaces of the plurality of openings.

[0011] One or more embodiments of the present disclosure are directed to a method for manufacturing a semiconductor device. The method includes forming a dielectric layer, wherein at least a portion of the dielectric layer comprises a non-stoichiometric compound; forming one or more openings in the dielectric layer; filling the one or more openings with a metal, wherein the metal is disposed on a surface of each of the one or more openings; and exposing the dielectric layer and the metal disposed in the openings to an oxidizing atmosphere, wherein exposing the dielectric layer and the metal in the openings results in oxidation of the non-stoichiometric compound.

[0012] One or more embodiments of the present disclosure relate to a method for manufacturing a semiconductor device. The method includes exposing a patterned dielectric layer disposed on a substrate to an oxidizing atmosphere. The patterned dielectric layer includes a first dielectric layer, the first dielectric layer includes a plurality of openings, each opening includes a metal layer disposed on a surface of the opening, and the first dielectric layer includes a non-stoichiometric compound. Exposing the patterned dielectric layer to the oxidizing atmosphere results in oxidation of the non-stoichiometric compound at the surface of the opening. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] In order to be able to understand the above-mentioned features of the present disclosure in detail, the present disclosure briefly summarized above may be described more particularly with reference to the embodiments, some of which are illustrated in the accompanying drawings. However, it should be noted that the accompanying drawings illustrate only exemplary embodiments and therefore should not be considered as limiting the scope thereof, and other equally effective embodiments may be allowed.

[0014] Figure 1 Illustrated is a side cross-sectional view of an interconnect formed on a substrate in which one or more embodiments of the present disclosure may be implemented.

[0015] Figure 2 A method for manufacturing a semiconductor device according to one or more embodiments of the present disclosure is illustrated.

[0016] Figure 3 The use of one or more embodiments according to the present disclosure is illustrated. Figure 2 A cross-sectional view of a portion of a semiconductor device formed by a method.

[0017] Figure 4

[0046] A multi-chamber processing system is illustrated that may be used to implement one or more embodiments of the present disclosure.

[0018] To facilitate understanding, identical reference numerals have been used, where possible, to designate elements that are shared among the figures. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation. DETAILED DESCRIPTION

[0019] Before describing several exemplary embodiments of the present disclosure, it should be understood that the present disclosure is not limited to the details of construction or processing steps set forth in the following description. The present disclosure is capable of other embodiments and can be practiced or carried out in various ways.

[0020] As used in this specification and the appended claims, the term "substrate" refers to a surface or portion of a surface of a component on which a process acts. Those skilled in the art will also understand that unless the context clearly indicates otherwise, reference to a substrate may also refer to only a portion of a substrate. In addition, reference to depositing on a substrate may refer to both a bare substrate and a substrate having one or more films or features deposited or formed thereon.

[0021] As used herein, "substrate" refers to any substrate or material surface formed on a substrate on which film processing is performed during a manufacturing process. For example, depending on the application, the substrate surface on which processing can be performed includes materials such as silicon, silicon oxide, strained silicon, silicon on insulator (SOI), carbon-doped silicon oxide, amorphous silicon, doped silicon, germanium, gallium arsenide, glass, sapphire, and any other materials such as metals, metal nitrides, metal alloys and other conductive materials. Substrates include, but are not limited to, semiconductor wafers. The substrate can be exposed to a pretreatment process to polish, etch, reduce, oxidize, hydroxylate, anneal, ultraviolet cure, electron beam cure and / or bake the substrate surface. In addition to performing film processing directly on the surface of the substrate itself, in the present disclosure, any of the disclosed film processing steps can also be performed on a bottom layer formed on the substrate, as disclosed in more detail below, and the term "substrate surface" is intended to include such bottom layers as shown in the context. Therefore, for example, when a film / layer or a portion of a film / layer has been deposited on a substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface.

[0022] Figure 1 Illustrated is a side cross-sectional view of an interconnect formed in a substrate 110 and a dielectric layer 130 in which one or more embodiments of the present disclosure may be implemented.

[0023] As shown, a first set of metal fill layers 120 may be formed in a substrate 110. A dielectric layer 130 may be deposited over the substrate 110 and the metal fill layers 120, and a second set of metal fill layers 140 may be formed in the dielectric layer 130. As shown, the second set of metal fill layers 140 may be aligned such that the second set of metal fill layers 140 are directly over and in contact with the first set of metal fill layers 120.

[0024] In some embodiments, selective metal fill layers are sometimes used in mid-stage process vias. For example, the second group of metal fill layers 140 can be selective metal fill layers. The selective metal fill layer can be, for example, tungsten (W), aluminum (Al), molybdenum (Mo), cobalt (Co), titanium (Ti), tantalum (Ta), zirconium (Zr), platinum (Pt), zinc (Zn), hafnium (Hf), lead (Pb), nickel (Ni), iron (Fe), niobium (Ni), vanadium (V), or silicon (Si). In some embodiments, the selective metal fill layer contains a metal with a desired Pilling-Bedworth ratio (such as a high Pilling-Bedworth ratio greater than 1). The selective metal fill layers can be referred to as linerless fill layers because they do not require conformal liners. Linerless fill layers typically have lower resistance than fill layers with liners and therefore may be preferred in some devices. However, sometimes the unlined fill layer may have adhesion issues with the surrounding dielectric, which results in the presence of via pores (e.g., gaps) at the interface between the metal fill layer and the dielectric layer. The gaps may cause defects in other areas of the circuit. For example, due to the diffusion and / or presence of residual wet etch chemistry components, plasma etch chemistry components, polishing slurry components and / or cleaning chemicals, the gaps may cause defectivity issues in the formed circuit, which then attack the metal interconnect structure and / or the underlying film in subsequent processing steps. Therefore, there is a need for methods to prevent or repair gaps at the interface between the metal fill layer and the dielectric layer.

[0025] Figure 2 A method for forming a semiconductor device according to one or more embodiments of the present disclosure is illustrated.

[0026] Method 200 may begin at activity 210 by forming a dielectric layer (e.g., dielectric layer 130) over a surface of a substrate. In some embodiments, the dielectric material may be formed by depositing a stoichiometric dielectric film on the substrate. The process of forming the dielectric layer may be accomplished using an atomic layer deposition (ALD) process, a chemical vapor deposition (CVD) process, a physical vapor deposition (PVD) process, or other useful deposition processes. Method 200 may involve, at activity 220, forming one or more openings in the dielectric layer. The one or more openings may be formed by etching one or more openings in the stoichiometric dielectric film.

[0027] At activity 230, method 200 may involve filling one or more openings with a metal (e.g., any of the metals listed above), wherein the metal is disposed on a surface of each of the one or more openings. Filling the one or more openings with the metal may form a set of metal fill layers, such as the second set of metal fill layers 140. The process of forming the metal fill layers may be accomplished using an atomic layer deposition (ALD) process, a chemical vapor deposition (CVD) process, a physical vapor deposition (PVD) process, or other useful deposition processes. It is desirable that the deposition process performed during activity 230 is formed by a selective deposition process that does not form a capping material layer on the field region of the substrate (i.e., the region of the substrate surface between the openings) to avoid the need to perform a chemical mechanical polishing (CMP) process to remove the capping layer. Figure 1 The ideally formed metal layers are shown excluding the capping layers.

[0028] However, in some embodiments, the method 200 may optionally include removing any overburden formed on or over the "field region" of the substrate during activity 230. In one example, the overburden removal process may include using a slurry-less chemical mechanical polishing (CMP) process. If overburden removal is performed, the substrate will need to be cleaned and dried.

[0029] At activity 240, if Figure 3As shown, method 200 includes implanting an oxygen-containing species into the dielectric layer to provide a dose of the oxygen-containing species to the surface of each of the one or more openings and the metal layer disposed therein (e.g., metal fill layer 140). The implantation process may result in the formation (e.g., growth) of a localized metal oxide layer on the exposed surface of the metal fill layer at the interface with the surface of the opening formed in the dielectric layer.

[0030] In some embodiments, implanting the oxygen-containing species involves using a tilted beam implantation process. In some embodiments, implanting the oxygen-containing species involves annealing the dielectric layer 130 and the metal fill layer 140 to promote the formation of a metal oxide. In some cases, activity 240 may also include heating the patterned dielectric layer after implanting the oxygen-containing species to oxidize the surface of each of the one or more openings exposed to the dose of the oxygen-containing species and the metal fill layer. In one embodiment, the implantation process includes a high temperature tilted implant beam implantation process that includes the oxygen species in the beam. The implantation process may also be performed using thermionic thermal implantation or any other suitable means of oxidizing the dielectric layer.

[0031] In one example, the process of implanting the oxygen-containing species into the dielectric layer 130 and the metal fill layer 140 may include implanting the oxygen-containing species while maintaining the substrate at a temperature between 20° C. and 500° C. In some examples, the implantation energy between <0.5 eV and >25 eV may be used to implant the oxygen-containing species at a dose of 10 14 with 10 17 The oxygen-containing species may be injected at a tilt angle between 0° and 75°. During the injection, the substrate may be rotated in increments (e.g., 90 degrees, 180 degrees) so that all exposed surfaces of the metal fill layer 140 may be injected with the oxygen-containing species. After performing the injection process, the substrate may also be annealed at a temperature between 300° C. and 600° C. for a period of time between 5 seconds and 120 seconds.

[0032] In certain embodiments, implanting oxygen-containing species into the dielectric layer and the metal fill layer may cause a metal oxide layer to grow on an exposed surface of the metal fill layer, thereby closing any gaps formed between the metal fill layer and the dielectric layer due to poor adhesion of the metal fill layer and the dielectric layer.

[0033] Figure 3 The diagram shows Figure 22 is a cross-sectional view of the dielectric layer 130 and the metal fill layer 140 before and after activity 240 in the method 200 of FIG. In some embodiments, as shown, the intervening dielectric layer 310 can be disposed below the dielectric layer 130. In some embodiments, the intervening dielectric layer 310 can be considered to be a part of the dielectric layer 130. As shown, openings can be formed in both the dielectric layer 130 and the intervening dielectric layer 310, and the metal fill layer 140 can be disposed on the surface of the openings in both the dielectric layer 130 and the intervening dielectric layer 310.

[0034] Figure 3 The cross-sectional view to the left of the arrow shows Figure 2 of the dielectric layer 130 and the metal fill layer 140 prior to activity 240. As shown, a gap 320 resulting from adhesion issues exists between the metal fill layer 140 and the dielectric layer 130. During activity 240, an oxygen-containing substance 330 is injected into the dielectric layer to provide a dose of the oxygen-containing substance 330 to the surface of each of the one or more openings and the metal fill layer 140 disposed therein. In some embodiments, as shown, injecting the oxygen-containing substance 330 may involve using a thermal oxygen tilted injection process. In some embodiments, the process of injecting the oxygen-containing substance into the dielectric layer includes performing an ultra-shallow injection so that the depth of the injected oxygen-containing substance will substantially reach the surface of the one or more openings and at least one of the metals disposed thereon. In general, it is desirable to perform an ultra-shallow injection process so that the injected substance does not significantly damage the surface of the metal fill layer 140 positioned adjacent to the surface of the opening. The dose of the oxygen-containing substance may be greater than 1×10 20 atoms / cm 2 .

[0035] Figure 3 The cross-sectional view to the right of the arrow shows Figure 2 The dielectric layer 130 and the metal fill layer 140 after activity 240 (eg, the dielectric layer 130 and the metal fill layer 140 are implanted with oxygen-containing species 330 ).

[0036] After trench patterning, filling, and CMP planarization, the dielectric layer 130 and the metal fill layer 140 may be implanted with an oxygen-containing compound (eg, using hot ion implantation). Figure 3As shown in the right cross-sectional view in FIG. 2 , metal oxide layer 340 has grown on the exposed surface of metal fill layer 140 due to the implantation process performed during activity 240. In some embodiments, the implantation causes metal oxide layer 340 to form (e.g., grow) on the exposed surface of metal fill layer 140. Metal oxide layer 340 thereby closes any gaps (e.g., gaps 320) at the interface between metal fill layer 140 and dielectric layer 130. In one example, metal fill layer 140 can be tungsten, and metal oxide layer 340 can be localized tungsten oxide (e.g., WO x , W2O3, WO5, etc.).

[0037] In some embodiments, the metal fill layer 140 can be any suitable metal having a high Pylin-Bedworth ratio (e.g., having a Pylin-Bedworth ratio greater than 1). It is believed that utilizing a metal layer having a high Pylin-Bedworth ratio can be used to ensure that the metal fill layer 140 will form a metal oxide layer 340 with sufficient volume expansion to fill the gap at the interface between the metal fill layer 140 and the dielectric layer 130. Such metals can be, for example, tungsten (W), aluminum (Al), molybdenum (Mo), cobalt (Co), titanium (Ti), tantalum (Ta), zirconium (Zr), platinum (Pt), zinc (Zn), hafnium (Hf), lead (Pb), nickel (Ni), iron (Fe), niobium (Ni), vanadium (V), or silicon (Si).

[0038] In some embodiments, at least the surface of the metal fill layer adjacent to the surface of the opening is exposed to a dose of implanted hydrogen species. The surface of the metal fill layer can then be exposed to a process of implanting germanium. The hydrogen content can be increased by: 1) adding H2 gas to the process; 2) reducing the deposition temperature; 3) reducing the plasma power; and 4) reducing the oxidant concentration. The typical hydrogen content in the film is within 3% to 50%, and the benefits of increasing the hydrogen content are higher etch rates, lower etch selectivity, lower film stress, lower density, and higher transparency.

[0039] In some embodiments, the dielectric layer 130 and / or the metal filling layer 140 may be implanted with heavy impurities (e.g., germanium (Ge) or argon (Ar)). The heavy impurities are implanted into the dielectric layer 130 and / or the metal filling layer 140 to cause mechanical volume expansion. Thus, the gap at the interface between the metal filling layer 140 and the dielectric layer 130 may be filled without using a chemical reaction (e.g., without oxidation).

[0040] The methods described herein may have additional beneficial uses beyond via void repair. For example, the methods described herein may also be used to create compressive stress on or within various components (e.g., metal fill layer 140) of an IC device to be formed. The generated compressive stress may be used to change the electrical conductivity and / or contact resistance of various portions of the interconnect structure within the formed IC device.

[0041] Figure 4 A multi-chamber processing system 400 is illustrated. The processing system 400 may include load lock chambers 402, 404, a robot 406, a transfer chamber 408, processing chambers 410, 412, 414, 416, 418, 428, and a controller 420. The load lock chambers 402, 404 allow substrates (such as substrate 110, not shown) to be transferred into and out of the processing system 400. The load lock chambers 402, 404 may pump down the substrates introduced into the processing system 400 to maintain a vacuum seal. The robot 406 may transfer substrates between the load lock chambers 402, 404 and the processing chambers 410, 412, 414, 416, 418, and 428. The robot 406 may also transfer substrates between the load lock chambers 402, 404 and the transfer chamber 408.

[0042] Each processing chamber 410, 412, 414, 416, 418, and 428 may be equipped to perform a number of substrate operations, such as atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), dry etching, pre-cleaning, degassing, thermal treatment (e.g., annealing), orientation, or other substrate processes. In addition, each processing chamber 410, 412, 414, 416, 418, and 428 may be equipped to deposit a dielectric barrier layer, deposit a dielectric layer, form one or more vias and / or trenches in a stack, perform one or more pre-cleaning processes, deposit a first metal material layer, and deposit a second metal material layer.

[0043] Controller 420 may be configured to operate all aspects of processing system 400, such as Figure 2 For example, the controller 420 may be configured to control a method of forming a dielectric layer (e.g., dielectric layer 130) on a substrate, forming one or more openings in the dielectric layer, filling the one or more openings with a metal (e.g., metal-filled layer 140), and injecting an oxygen-containing substance into the dielectric layer to provide a dose of the oxygen-containing substance to a surface of each of the one or more openings and a metal disposed therein.

[0044] Each processing chamber 410, 412, 414, 416, 418, and 428 may be capable of rotating the substrate so that the sidewalls on each side of the metal fill may be treated with an angled oxygen implant. For example, the substrate may be rotated in 90 degree or 180 degree increments.

[0045] The controller 420 includes a programmable central processing unit (CPU) 422 operable with a memory 424 and mass storage devices, an input control unit, and a display unit (not shown), such as power supplies, clocks, caches, input / output (I / O) circuits, and pads, which are coupled to various components of the processing system to facilitate control of substrate processing. The controller 420 also includes hardware for monitoring substrate processing via sensors in the processing system 400, including sensors that monitor precursor, process gas, and purge gas flow rates. Other sensors that measure system parameters such as substrate temperature, chamber atmosphere pressure, etc. may also provide information to the controller 420.

[0046] To facilitate control of the above-described processing system 400, the CPU 422 may be one of any form of general purpose computer processor that may be used in an industrial environment, such as a programmable logic controller (PLC) for controlling various chambers and subprocessors. A memory 424 is coupled to the CPU 422 and the memory 424 is non-temporary and may be one or more of readily available memory (such as random access memory (RAM), read only memory (ROM)), a floppy disk drive, a hard disk, or any other form of local or remote digital storage device. Support circuits 426 are coupled to the CPU 422 for supporting the processor in a conventional manner. Charged species generation, heating, and other processes are typically stored in the memory 424, typically as software routines. The software routines may also be stored and / or executed by a second CPU (not shown) located away from the hardware controlled by the CPU 422.

[0047] The memory 424 is in the form of a computer-readable storage medium containing instructions that, when executed by the CPU 422, facilitate the operation of the processing system 400. The instructions in the memory 424 are in the form of a program product, such as a program that implements the method of the present disclosure. The program code may conform to any of a variety of different programming languages. In one example, the present disclosure may be implemented as a program product stored on a computer-readable storage medium for use by a computer system. The program of the program product defines the functions of each embodiment (including the method described herein). Illustrative computer-readable storage media include, but are not limited to: (i) a non-writable storage medium (e.g., a read-only memory device within a computer, such as a CD-ROM disk, flash memory, ROM chip, or any type of solid-state non-volatile semiconductor memory that can be read by a CD-ROM drive), on which information is permanently stored; and (ii) a writable storage medium (e.g., a floppy disk or hard disk drive in a disk drive or any type of solid-state random access semiconductor memory), on which variable information is stored. Such computer-readable storage media, when carrying computer-readable instructions that direct the functions of the method described herein, are embodiments of the present disclosure.

[0048] The method 200 discussed above may not be limited to only the processing system 400. For example, one or more steps of the method 200 may be performed in a processing chamber external to the processing system 400.

[0049] While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof, and the scope of the disclosure is determined by the claims that follow.

Claims

1. A method for manufacturing a semiconductor device, comprising the following steps: forming a dielectric layer over a surface of the substrate; forming one or more openings in the dielectric layer; filling the one or more openings with a metal, wherein the metal is disposed on a surface of each of the one or more openings; and An oxygen-containing species is implanted into the dielectric layer to provide a dose of the oxygen-containing species to the surface of each of the one or more openings and the metal disposed thereon.

2. The method of claim 1, wherein the step of injecting the oxygen-containing species comprises using a tilted injection process.

3. The method of claim 2, wherein the tilted implantation process comprises a hot oxygen tilted implantation process, and the method further comprises the following steps: The substrate is annealed after providing the dosage of the oxygen-containing species to the surface of each of the openings and the metal.

4. The method of claim 2, wherein the step of annealing the substrate is performed at a temperature between 300°C and 600°C.

5. The method of claim 2, wherein the step of annealing the substrate is performed for a period of time between 5 seconds and 120 seconds.

6. The method of claim 1, wherein: The step of forming the dielectric layer comprises the steps of: depositing a stoichiometric dielectric film; and The step of forming the one or more openings comprises the step of etching the one or more openings in the stoichiometric dielectric film.

7. The method of claim 1, wherein: The one or more openings in the dielectric layer are formed in a surface of the dielectric layer, The step of filling the one or more openings with the metal further comprises the steps of: forming a layer of the metal on the surface of the dielectric layer, and The method further comprises the following steps: Prior to implanting the oxygen-containing species into the dielectric layer, the layer of the metal is removed from the surface of the dielectric layer.

8. The method of claim 1, wherein the metal has a Pilling-Bedworth ratio greater than 1.

9. The method of claim 8, wherein the metal comprises at least one of tungsten, aluminum, molybdenum, cobalt, titanium, tantalum, zirconium, platinum, zinc, hafnium, lead, nickel, iron, niobium, vanadium, or silicon.

10. The method of claim 9, wherein: The metal comprises tungsten; and The oxygen-containing species causes a tungsten oxide layer to form on one or more surfaces of the metal.

11. The method of claim 1, wherein the step of implanting the oxygen-containing species into the dielectric layer comprises the step of performing an ultra-shallow implantation such that the implanted oxygen-containing species has a depth that substantially reaches the surface of the one or more openings and at least one of the metal disposed thereon, wherein the dose of the oxygen-containing species is greater than 1×1020.

12. A method for manufacturing a semiconductor device, comprising the steps of: An oxygen-containing species is implanted into a patterned dielectric layer disposed on a substrate, wherein: The patterned dielectric layer includes a dielectric layer including a plurality of openings, each opening including a metal layer disposed on a surface of the opening, and The step of injecting the oxygen-containing species into the dielectric layer provides a dose of the oxygen-containing species to the surface of each of the plurality of openings and the metal layer disposed thereon, and The patterned dielectric layer is heated after implanting the oxygen-containing species to oxidize the surface of each of the plurality of openings exposed to the dose of the oxygen-containing species and the metal layer.

13. The method of claim 12, wherein the step of oxidizing the metal layer exposed to the dose of the oxygen-containing species results in the formation of a metal oxide layer on one or more surfaces of the metal layer.

14. The method of claim 12, wherein the step of injecting the oxygen-containing species comprises using a hot oxygen tilted injection process.

15. The method of claim 13, wherein the metal in the metal layer has a Pilling-Bedworth ratio greater than 1.

16. The method of claim 15, wherein the metal in the metal layer comprises at least one of tungsten, aluminum, molybdenum, cobalt, titanium, tantalum, zirconium, platinum, zinc, hafnium, lead, nickel, iron, niobium, vanadium, or silicon.

17. The method of claim 16, wherein the metal layer comprises tungsten and the metal oxide layer comprises tungsten oxide.

18. The method of claim 12, wherein the step of implanting the oxygen-containing species into the dielectric layer comprises the step of performing an ultra-shallow implantation such that the implanted oxygen-containing species has a depth that substantially reaches the surface of the one or more openings and at least one of the metals disposed thereon, wherein the dose of the oxygen-containing species is greater than 1×1020.

19. A semiconductor device comprising: substrate; a patterned dielectric layer disposed above the substrate, the patterned dielectric layer comprising a plurality of openings; a metal layer disposed on the surfaces of the plurality of openings; and A metal oxide layer is provided at an interface between the metal layer and surfaces of the plurality of openings.

20. The method of claim 19, wherein the metal in the metal layer comprises at least one of tungsten, aluminum, molybdenum, cobalt, titanium, tantalum, zirconium, platinum, zinc, hafnium, lead, nickel, iron, niobium, vanadium, or silicon.

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