Deuterium-containing film

Abstract

The films are modified to contain deuterium in an inductive high-density plasma chamber. The chamber hardware design allows for tuning of the uniformity of the deuterium concentration in the film across the substrate. The fabrication of solid-state electronic devices includes an integrated process flow for modifying films that are substantially free of hydrogen and deuterium to contain deuterium.

Description

[Technical field]

[0001]

[0001] The present disclosure relates generally to electronic devices. More specifically, embodiments of the present disclosure are directed to the use of deuterium-containing films to enhance the performance and reliability of electronic devices. [Background technology]

[0002]

[0002] Integrated circuits have evolved into complex devices that can contain millions of transistors, capacitors, and resistors on a single chip. During the evolution of integrated circuits, the functional density (i.e., the number of interconnected devices per chip area) has generally increased while the feature size (i.e., the smallest component (or line) that can be produced using a manufacturing process) has decreased.

[0003]

[0003] Reducing the size of integrated circuits (ICs) leads to improved performance, increased capacity, and / or reduced cost. Each reduction in size requires more advanced techniques to form the ICs. For example, reducing the size of transistors allows for an increased number of memory or logic devices on a chip, which aids in the production of products with higher capacity. However, the drive to ever-increasing capacity is not without problems. The need to optimize the performance of each device becomes increasingly important.

[0004]

[0004] Semiconductor manufacturers need processes and hardware that allow deposition or modification of films for more reliable passivation of solid state electronics, such as DRAMs. Additionally, tunability and within-wafer uniformity control are required to improve device die yields. Summary of the Invention

[0005]

[0005] One or more embodiments of the present disclosure relate to a method, in one embodiment, the method includes modifying a substrate having a substantially hydrogen and deuterium free film deposited thereon to include deuterium.

[0006]

[0006] In a further embodiment, the method includes exposing a substrate having a film substantially free of hydrogen and deuterium deposited thereon to a plasma containing a deuterium-containing precursor to form a modified deuterium-containing film on the substrate.

[0007]

[0007] One or more embodiments are directed to an apparatus. In one embodiment, the apparatus includes a chamber body including a top and at least one sidewall defining a plasma cavity; a first gas inlet centrally located in the top of the chamber body, the first gas inlet configured to deliver a flow of plasma comprising a deuterium-containing precursor to the plasma cavity; a second gas inlet centrally located in the at least one sidewall of the chamber body, the second gas inlet configured to deliver a flow of plasma comprising a deuterium-containing precursor to the plasma cavity; a top coil having an antenna on a top of the chamber body; at least one side coil on a side of the chamber body; and a multi-zone susceptor, each zone having independent temperature control.

[0008]

[0008] In order that the above-mentioned features of the present disclosure may be understood in detail, a more detailed description of the present disclosure briefly summarized above will be obtained by reference to embodiments, some of which are illustrated in the accompanying drawings. However, it should be noted that the accompanying drawings merely illustrate typical embodiments of the present disclosure, since the present disclosure may admit of other equally effective embodiments, and therefore should not be considered as limiting the scope of the present disclosure. The embodiments described herein are illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings, in which like reference numerals indicate similar elements. [Brief description of the drawings]

[0009] [Figure 1]

[0009] A flow process diagram of one embodiment of a method for modifying a thin film according to embodiments described herein is shown. [Diagram 2]

[0010] 1 illustrates a cross-sectional view of an electronic device according to one or more embodiments. [Diagram 3]

[0011] 1 illustrates a cross-sectional view of an electronic device according to one or more embodiments. [Figure 4]

[0012] 1 illustrates a cross-sectional view of an electronic device according to one or more embodiments. [Diagram 5]

[0013] 1 illustrates a cross-sectional view of an electronic device according to one or more embodiments. [Figure 6]

[0014] 1 shows a schematic diagram of an apparatus according to one or more embodiments. [Figure 7]

[0015] 1 illustrates a multi-zone susceptor according to one or more embodiments of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010]

[0016] Before describing certain exemplary embodiments of the present disclosure, it is to be understood that the disclosure is not limited to the details of structure or process steps set forth in the following description, as the disclosure is capable of other embodiments and of being practiced or carried out in various ways.

[0011]

[0017] The term "about" as used herein means "approximately" or "nearly" and refers to a variation of no more than ±15% of a numerical value in relation to a stated numerical value or range. For example, values ​​that differ by ±14%, ±10%, ±5%, ±2%, or ±1% would meet the definition of about.

[0012]

[0018] The term "substrate" or "wafer" as used herein and in the appended claims refers to a surface or a portion of a surface on which a process acts. Also, when reference is made to a substrate, those skilled in the art will understand that it may refer to only a portion of the substrate unless the context clearly indicates otherwise. Additionally, when reference is made to deposition on a substrate, it may refer to both a bare substrate and a substrate on which one or more films or features have been deposited or formed.

[0013]

[0019] As used herein, "substrate" refers to any substrate or material surface formed on a substrate on which a film treatment is performed during a manufacturing process. For example, substrate surfaces on which treatment may be performed include 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, depending on the application. Substrates include, but are not limited to, glass, metal, or semiconductor wafers. Substrates may also be exposed to pretreatment processes to polish, etch, reduce, oxidize, hydroxylate (or otherwise create or graft targeted chemical moieties to impart chemical functionality), anneal, and / or bake the substrate surface. In addition to treatments directly on the substrate surface itself, in this disclosure, any of the disclosed film treatment steps may also be performed on an underlayer formed on the substrate, as described in more detail below. The term "substrate surface" is intended to include such underlayers, as the context indicates. Thus, for example, if a film / layer or partial film / layer is deposited on a substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface. What a given substrate surface includes depends on the particular chemistry used as well as what material is deposited.

[0014]

[0020] As used in this specification and the appended claims, the terms "precursor," "reactant," "reactive gas," and the like are used interchangeably to refer to any gas species capable of reacting with the substrate surface.

[0015]

[0021] In one or more embodiments, deuterium (D) advantageously provides an improved method for stabilizing and increasing the reliability of films on substrates. Without intending to be bound by theory, it is believed that films containing deuterium and / or hydrogen allow for chemical passivation of unsatisfied valence bonds on immobilized atoms in a solid matrix.

[0016]

[0022] Deuterium advantageously allows stronger and more stable chemical passivation of many atoms compared to chemical passivation with hydrogen.For example, in solid materials and solid interfaces made of common silicon-based solid materials such as crystalline silicon, polycrystalline silicon, amorphous silicon, silicon oxide, silicon nitride, and silicon carbide, deuterium bonds stronger to silicon atoms compared to the chemical bond of hydrogen to silicon atoms.Compared to silicon materials and interfaces passivated with hydrogen, silicon materials and interfaces passivated with deuterium are more electrically stable and reliable at higher applied voltages, higher applied currents, shorter wavelengths and higher intensity electromagnetic radiation exposure, and higher temperatures.

[0017]

[0023] In one or more embodiments, improved reliability of deuterium chemically passivated materials and interfaces is possible in other common material systems, including, but not limited to, III-V and II-VI semiconductors: gallium arsenide, aluminum arsenide, aluminum-gallium arsenide, gallium nitride, aluminum nitride, aluminum-gallium nitride, zinc oxide, cadmium oxide, cadmium telluride, cadmium selenide, magnesium oxide, and oxide and nitride derivatives of III-V and II-VI semiconductors.

[0018]

[0024] In one or more embodiments, a film originally deposited on a substrate surface that does not contain deuterium or hydrogen is modified to contain deuterium and / or hydrogen. In one or more embodiments, the modification to form a deuterium-containing film occurs by exposing the hydrogen- and deuterium-free film in a plasma to a chemical precursor that contains deuterium.

[0019]

[0025] In one or more embodiments, the film is deposited on a substrate surface. In one or more embodiments, the film is substantially free of hydrogen and substantially free of deuterium. As used herein, the term "substantially free" means that less than 5% hydrogen and deuterium are present in the film, including less than 4%, less than 3%, less than 2%, less than 1%, and less than 0.5%.

[0020]

[0026] In one or more embodiments, the substantially hydrogen and deuterium free film is a film having a thickness in the range of about 0.5 nm to about 1000 nm (including about 0.5 nm to about 800 nm, about 0.5 nm to about 700 nm, about 0.5 nm to about 600 nm, about 0.5 nm to about 500 nm, about 0.5 to about 400 nm, about 0.5 to about 300 nm, and about 0.5 to about 200 nm). In some embodiments, the film has a thickness of less than about 1000 nm (including a thickness of less than about 900 nm, less than about 800 nm, less than about 700 nm, less than about 600 nm, less than about 500 nm, less than about 400 nm, less than about 300 nm, and less than about 200 nm). In some embodiments, the film has a thickness of about 0.5 nm, about 10 nm, about 15 nm, about 20 nm, about 25 nm, about 30 nm, about 35 nm, about 40 nm, about 45 nm, about 50 nm, about 55 nm, about 60 nm, about 65 nm, about 70 nm, about 75 nm, about 80 nm, about 85 nm, about 90 nm, about 95 nm, about 100 nm, about 150 nm, about 200 nm, about 250 nm, about 300 nm, about 350 nm, about 400 nm, about 450 nm, about 500 nm, about 550 nm, about 600 nm, about 650 nm, about 700 nm, about 750 nm, about 800 nm, about 850 nm, about 900 nm, about 950 nm, or about 1000 nm.

[0021]

[0027] In one or more embodiments, the substantially hydrogen and deuterium free film comprises a dielectric material. As used herein, the term "dielectric" refers to an electrically insulating material that can be polarized by an applied electric field. In one or more embodiments, the dielectric material includes, but is not limited to, oxides such as SiO2, Ta2O5, Al2O3, nitrides such as Si3N4, and barium strontium titanate (BST). In one or more embodiments, the dielectric material is silicon dioxide (SiO 2) In some embodiments, the film composition is non-stoichiometric relative to an ideal molecular formula. For example, in some embodiments, the dielectric material includes, but is not limited to, oxides (e.g., silicon oxide, titanium oxide, aluminum oxide), nitrides (e.g., silicon nitride (SiN)), carbides (e.g., silicon carbide (SiC)), silicon carbonitride (SiCN), oxycarbides (e.g., silicon oxycarbide (SiOC)), oxynitrocarbides (e.g., silicon oxycarbonitride (SiNCO)), and barium strontium titanate (BST).

[0022]

[0028] In one or more embodiments, the term "high-k dielectric" refers to a material having a high dielectric constant (e.g., compared to silicon dioxide). In one or more embodiments, the film comprises a high-k material selected from one or more of HfO2, ZrO2, VO2, TiO2, SnO2, Al2O3, or ZnO. In one or more particular embodiments, the film comprises a high-k material comprising or consisting essentially of Al2O3. As used herein, the term "consisting essentially of" means that the composition of the bulk film comprises the specified elements at 95%, 98%, 99%, or 99.5% of the total elemental composition by weight. In some embodiments, the film is a high-k material comprising or consisting essentially of aluminum atoms.

[0023]

[0029] 1 shows a flow diagram of a method 10 for modifying a film in accordance with one or more embodiments of the present disclosure. With reference to FIG. 1, the method 10 begins in operation 20 by positioning a substrate in a processing chamber.

[0024]

[0030] The substrate can be any substrate known to those skilled in the art. In one or more embodiments, the substrate comprises one or more semiconductor materials, such as silicon (Si), silicon oxide (SiO2), germanium (Ge), silicon germanium (SiGe), gallium arsenide (GaAs), indium phosphide (InP), indium gallium arsenide (InGaAs), indium aluminum arsenide (InAlAs), molybdenum disulfide (MoS2), molybdenum diselenide (MoSe2), tungsten disulfide (WS2), tungsten diselenide (WSe2), titanium nitride (TiN), tantalum nitride (TaN), tungsten (W), platinum (Pt), or iridium (Ir). In some embodiments, the substrate may include a spacer, a metal gate, a contact, or the like. Thus, in one or more embodiments, the substrate may comprise a semiconductor material including, but not limited to, copper (Cu), cobalt (Co), tungsten (W), titanium (Ti), molybdenum (Mo), nickel (Ni), ruthenium (Ru), silver (Ag), gold (Au), iridium (Ir), platinum (Pt), phosphorous (P), germanium (Ge), silicon (Si), aluminum (Al), zirconium (Zr), silicon carbonitride (SiCN), silicon oxycarbide (SiOC), silicon nitride (SiN), tungsten carbide (WC), tungsten oxide (WO), silicon oxycarbonitride (SiONC), or any semiconductor substrate material known to one of skill in the art.

[0025]

[0031] In operation 30, the substrate having the film deposited thereon is modified to include deuterium. In one or more embodiments, the film deposited on the substrate is substantially free of hydrogen and substantially free of deuterium. In one or more embodiments, modifying the film includes exposing the substantially hydrogen and deuterium free film to a plasma including a deuterium-containing precursor. In one or more embodiments, the deuterium-containing precursor may be pulsed or co-flowed into the process chamber with a flow gas or carrier gas. In other embodiments, the deuterium-containing precursor is pulsed into the process chamber in the absence of a carrier gas. As used herein, the term "carrier gas" refers to a fluid (gas or liquid) capable of moving precursor molecules from one location to another. For example, the carrier gas may be a liquid that moves the molecules from the solid precursor in the ampoule to the atomizer. In some embodiments, the carrier gas is an inert gas. In one or more embodiments, the carrier gas is one or more of argon (Ar), helium (He), xenon (Xe), or nitrogen (N2).

[0026]

[0032] In one or more embodiments, the deuterium-containing precursor comprises one or more of molecular deuterium (D2), heavy water (D2O), DH (deuterium-hydrogen), or HDO (deuterium-hydrogen oxide).

[0027]

[0033] In one or more embodiments, the plasma further comprises one or more of argon (Ar), helium (He), hydrogen (H2), deuterium (D2), nitrogen (N2), oxygen (O2), ammonia (NH3), or nitrogen trifluoride (NF3).

[0028]

[0034] In one or more embodiments, the substrate has a temperature in the range of about 20° C. to 800° C. (including about 150° C. to about 450° C.), and in one or more embodiments, the plasma has a pressure in the range of about 0.1 to about 500 mTorr (including about 1 to about 100 mTorr). In one or more embodiments, the plasma has a power in the range of about 500 to about 20,000 Watts (including about 1000 to about 10,000 Watts). In one or more embodiments, the plasma has a gas flow rate in the range of about 1 to about 5000 sccm (including about 50 to about 1000 sccm).

[0029]

[0035] 2 and 3, in one or more embodiments, the film is part of a CMOS device. In FIG. 2, the device 100 includes a film stack on a semiconductor substrate 102. An oxide layer 104 is deposited or formed on the semiconductor substrate 102, and a first metal 106 is formed in a dielectric layer 108 on the oxide layer 104. A second metal layer 110 (X) is deposited on the dielectric layer 108. An interlayer dielectric 112 is deposited on the second metal layer 110, followed by a third metal layer 114 (X+1) deposited on the interlayer dielectric. A post-metal dielectric layer 116 is deposited on the third metal layer 114. In one or more embodiments, the post-metal dielectric layer 116 is substantially free of hydrogen and substantially free of deuterium.

[0030]

[0036] The interlayer dielectric (ILD) 112 may be deposited using one or more deposition techniques known to those skilled in the art of microelectronic device fabrication. In one or more embodiments, the interlayer dielectric (ILD) 112 is deposited using one of the deposition techniques, such as, but not limited to, ALD, CVD, PVD, MBE, MOCVD, spin-on, or other insulating layer deposition techniques known to those skilled in the art. In one or more embodiments, the interlayer dielectric (ILD) 112 comprises a low-k dielectric. In some implementations, the low-k dielectric may be selected from one or more of silicon, silicon oxide, silicon nitride, silicon oxynitride, doped silicon, doped silicon oxide, doped silicon nitride, doped silicon oxynitride, or a spin-on dielectric. In one or more embodiments, the interlayer dielectric (ILD) 112 comprises silicon oxide.

[0031]

[0037] Referring to FIG. 3, the post-metal dielectric layer 116 is modified to form a post-metal deuterium-containing dielectric layer 118. In one or more embodiments, the post-metal dielectric layer 116 is modified by exposure to a plasma including a deuterium-containing precursor. In one or more embodiments, the deuterium-containing precursor includes one or more of molecular deuterium (D2), heavy water (D2O), DH (deuterium-hydrogen), or HDO (deuterium-hydrogen oxide). In one or more embodiments, the plasma further includes one or more of argon (Ar), helium (He), hydrogen (H2), deuterium (D2), nitrogen (N2), oxygen (O2), ammonia (NH3), or nitrogen fluoride (NF3). In one or more embodiments, the deuterium-containing precursor may be pulsed or co-flowed into the process chamber with a flow gas or carrier gas. In other embodiments, the deuterium-containing precursor is pulsed into the process chamber in the absence of a carrier gas. In some embodiments, the carrier gas is an inert gas. In one or more embodiments, the carrier gas is one or more of argon (Ar), helium (He), xenon (Xe), or nitrogen (N2).

[0032]

[0038] As used herein, "chemical vapor deposition" refers to a process in which a substrate surface is exposed to precursors and / or co-reagents simultaneously or substantially simultaneously. As used herein, "substantially simultaneously" refers to either co-flow or where there is an overlap for the majority of the exposure of the precursors.

[0033]

[0039] Plasma enhanced chemical vapor deposition (PECVD) is widely used to deposit thin films due to its cost-effectiveness and versatility in film properties. In a PECVD process, a hydrocarbon source, such as a gas-phase or liquid-phase hydrocarbon vapor entrained in a carrier gas, is introduced into a PECVD chamber. A plasma initiating gas is also introduced into the chamber. A plasma is then initiated in the chamber, generating excited CH radicals. The excited CH radicals chemically combine with a surface of a substrate disposed in the chamber to form a desired film thereon. The embodiments described herein in connection with a PECVD process may be practiced using any suitable thin film deposition system. Any apparatus descriptions described herein are exemplary and should not be understood or construed as limiting the scope of the embodiments described herein.

[0034]

[0040] The method according to one or more embodiments includes a plasma modification process, in which a plasma containing a deuterium-containing precursor is used to modify a film that is substantially free of hydrogen and deuterium to form a film with deuterium. Without intending to be bound by theory, it is believed that the deuterium dopes the starting film. The plasma doping and modification process works by generating a high density of ion radicals containing deuterium. The deuterium migrates from the plasma to the film on the substrate surface by thermal diffusion or by drift due to the force applied by the electric field generated through the film and substrate. After the plasma doping and modification process, the final film will have a concentration of ion radicals containing deuterium, and the total density of atoms will be different.

[0035]

[0041] Other embodiments are directed to optical devices having deuterium-containing films. Such optical devices may include solar panels or LEDs.

[0036]

[0042] In a further embodiment, in the manufacture of solid-state electronic devices, an integrated process flow can be used to transfer deuterium from a deuterium-containing film to adjacent or nearby other film materials. For example, in complementary metal oxide semiconductor (CMOS) or dynamic random access memory (DRAM) solid-state electronics, a pre-metal, inter-metal, or post-metal dielectric film layer can be deposited containing deuterium. A post-thermal process or annealing can then be performed to transfer the deuterium into the embedded transistor or capacitor structure.

[0037]

[0043] 4 and 5, in one or more embodiments, in optical solid state devices such as, but not limited to, light emitting diodes (LEDs) or photovoltaic solar cells, a dielectric thin film may be deposited or modified to contain deuterium, after which a post-thermal process or annealing may be performed to transfer the deuterium to the embedded active optical layers.

[0038]

[0044] 4 illustrates a cross-sectional view of a solar cell device 200 prior to annealing. In one or more embodiments, a first dielectric layer 202 has a second dielectric layer 204 and a light absorbing layer 206 formed thereon. A third dielectric layer 208 is formed on the second dielectric layer 206, the third dielectric layer 208 comprising deuterium. The first dielectric layer 202 is on top of the deuterium-containing dielectric layer 208.

[0039]

[0045] 5 illustrates a cross-sectional view of the solar cell 200 after high temperature annealing at a temperature range of about 100° C. to about 700° C., inclusive, from about 200° C. to about 450° C. As shown, deuterium from the deuterium-containing third dielectric layer 208 migrates to the second dielectric layer 204 and the light absorbing layer 206 forming the fourth dielectric layer 210 and modified light absorbing layer 212, where both the dielectric layer 210 and the light absorbing layer 212 contain deuterium.

[0040]

[0046] 6, one or more embodiments of the present disclosure are directed to a processing chamber that includes a high density plasma (HDP) chemical vapor deposition (CVD) chamber 300. For example, in one or more embodiments, the processing chamber may be an Ultima CVD chamber available from Applied Materials. TM 6 includes a HDP-CVD chamber. The chamber 300 shown in FIG. 6 includes a top 301, a bottom 302, and a sidewall 303 surrounding an interior 305. The chamber shown includes a multi-zone plasma coil including a top coil 310 and a side coil 320 to allow for adjustment of the power delivered to the chamber 300 and to enhance uniformity of the plasma formed in the chamber interior 305. The top coil 310 includes a coiled antenna 315, and the side coil 320 includes a coiled antenna 325 for generating a plasma in the interior 305. Although not specifically shown, one of ordinary skill in the art will recognize the components and connections used to generate a plasma in the interior 305 of the chamber 300.

[0041]

[0047] The chamber 300 has a multi-zone gas injector. A top gas injector 330 is at the top 301 of the chamber 300, and a side gas injector 340 is at the sidewall 303 of the chamber 300. Reactive gas 332 can be introduced into the interior 305 of the chamber through the top gas injector 330 or through the side gas injector 340, either simultaneously or separately. In some embodiments, the top gas injector 330 does not flow reactive gas at the same time as the side gas injector 330.

[0042]

[0048] In one or more embodiments, the process chamber is a chemical vapor deposition chamber or a film modification chamber equipped with an inductive high density plasma source (30 kHz-30 GHz) and is designed with hardware features to adjust the deuterium concentration uniformity and hydrogen concentration uniformity of the film deposited or modified on the substrate. One embodiment allows for tunability of the radial ion plasma density across the substrate surface by varying separate power settings to the top and side coiled antennas or by varying separate gas and precursor flows to the top and side gas injectors.

[0043]

[0049] The chamber 300 includes a susceptor 400 for supporting the substrate 360 ​​during processing. FIG. 7 illustrates a multi-zone susceptor 400 according to one or more embodiments of the present disclosure. In one or more embodiments, the processing chamber includes a multi-zone susceptor for adjusting temperature and deposition uniformity and deuterium and hydrogen concentration uniformity in a film deposited or modified on a substrate. The susceptor 400 shown has eight zones 411a, 411b, 412a, 412b, 413a, 413b, 414a, 414b separated into an inner ring 402 and an outer ring 404. Each of the outer zones 411a, 412a, 413a, 414a is angularly spaced about the center of the susceptor, and each of the inner zones 411b, 412b, 413b, 414b is angularly spaced about the center of the susceptor and the inner zones.

[0044]

[0050] In the embodiment shown, the inner ring 402 and the outer ring 404 each have four zones. In some embodiments, there are more or less than four zones. In some embodiments, the inner ring 402 and the outer ring 404 each independently include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 zones.

[0045]

[0051] The inner ring 402 and the outer ring 404 are radially spaced rings relative to the center of the susceptor. The term "radially spaced" means that the innermost edges of the rings are located at different radial distances from the center of the susceptor. In the embodiment shown, there are two radial zones defined by the inner ring 402 and the outer ring 404. In some embodiments, there are 1, 3, 4, 5, 6, 7, or 8 radial zones. Each of the radial zones can be independently controlled.

[0046]

[0052] In some embodiments, the inner zone is (angularly) aligned with the outer zone, as shown, hi some embodiments, the inner zone is offset from the outer zone.

[0047]

[0053] In another embodiment, the processing chamber includes independent multi-zone plasma coils with plasma power controls to adjust the uniformity of plasma density inside the deposition chamber and the uniformity of deuterium and hydrogen concentrations in the deposited or modified film on the substrate.

[0048]

[0054] In a further embodiment, the processing chamber includes a multi-zone substrate susceptor with independent zone temperature control to adjust substrate temperature uniformity and deuterium and hydrogen concentration uniformity in a deposited or modified film on the substrate.

[0049]

[0055] In one or more embodiments, the substrate is positioned on a multi-zone susceptor, each zone having independent temperature control. In one or more embodiments, the multi-zone susceptor has at least two zones. In some embodiments, the multi-zone susceptor includes an inner zone and an outer zone. In other embodiments, the multi-zone susceptor has radially spaced zones. In still further embodiments, the multi-zone susceptor includes an inner zone and an outer zone, each of the inner zone and the outer zone including radially spaced zones.

[0050]

[0056] In one or more embodiments, more hydrogen is incorporated into the modified membrane in the higher temperature zone than in the lower temperature zone.

[0051]

[0057] In one or more embodiments, the apparatus is directed to a chamber body including a top and at least one sidewall defining a plasma cavity; a first gas inlet located at a center of the top of the chamber body, the first gas inlet configured to deliver a flow of plasma including a deuterium-containing precursor to the plasma cavity; a second gas inlet located at least one sidewall of the chamber body, the second gas inlet configured to deliver a flow of plasma including a deuterium-containing precursor to the plasma cavity; an top coil having an antenna at a top of the chamber body; at least one side coil at a side of the chamber body; and a multi-zone susceptor, each zone having independent temperature control.

[0052]

[0058] Another embodiment is directed to a method including modifying a solid state electronic device including at least one buried layer containing deuterium and thermally annealing the solid state electronic device to transfer deuterium to one or more adjacent layers that are substantially free of deuterium.

[0053]

[0059] In other embodiments, the deuterium and silicon containing films are deposited by chemical vapor deposition (CVD) or atomic layer deposition (ALD) using chemical precursors and inert gases. In one or more embodiments, the deposition method passivates dangling silicon bonds by introducing deuterium into the film. For example, but not limited to, in one or more embodiments, SiH Y D Z , SiO X1 H Y D Z , SiN X2 H Y D Z , SiC X3 H Y D Z , SiO X1 N X2 CX3 H Y A film containing D is deposited on the substrate surface. In one or more embodiments, the deuterium-containing precursor comprises one or more of D2, DO, SiD4, Si2D6. In one or more embodiments, the deuterium-containing precursor can be combined or co-flowed with one or more silicon precursors selected from one or more of SiH4, Si2H6, SiCl4, SiHCl3, SiH2Cl2, SiHCl3, Si2Cl6, SiF4, SiBr4, TEOS, TDMAS, BTBAS, BDEAS, etc. In one or more embodiments, the deuterium-containing precursor can be combined or co-flowed with one or more of oxygen (O2), ozone (O3), or water (H2O). In one or more embodiments, the deuterium-containing precursor can be combined or co-flowed with one or more of nitrogen (N2), or ammonia NH3 to form a deuterium-containing nitride film. In one or more embodiments, the deuterium-containing precursor may be combined or co-flowed with one or more of methane (CH4) or ethane (C2H2) to form a deuterium-containing carbon film. In one or more embodiments, the deuterium-containing precursor may be combined or co-flowed with hydrogen (H2). In one or more embodiments, the deuterium-containing precursor may be combined or co-flowed with one or more inert gases, including but not limited to argon (Ar) or helium (He), to form a deuterium-containing film. In one or more embodiments, the deposition process may include thermal, plasma, and / or optical sources to activate the precursors and control chemical reaction rates.

[0054]

[0060] As used herein, "atomic layer deposition" or "cyclic deposition" refers to the sequential exposure of two or more reactive precursors to deposit layers of material on a substrate surface. A substrate or a portion of a substrate is separately exposed to two or more reactive precursors that are introduced into a reaction zone of a processing chamber. In a time-domain ALD process, the exposure to each reactive compound is separated by a time delay, allowing each compound to adhere to and / or react on the substrate surface and then be purged from the processing chamber. These reactive compounds are said to be sequentially exposed to the substrate. In a spatial ALD process, different portions of the substrate surface, or materials on the substrate surface, are simultaneously exposed to two or more reactive compounds such that any given point on the substrate is not exposed to two or more reactive compounds at substantially the same time.

[0055]

[0061] In one or more embodiments, the deuterium concentration in the film deposited on the substrate can be controlled and adjusted by changing deposition process parameters including precursor flow rate, substrate temperature, chamber pressure, and plasma power / density.For example, in one or more embodiments, in a chemical vapor deposition process involving inductive high-density plasma, the atomic concentration of deuterium in the SiOXHYDZ film on a silicon substrate can be controlled by the flow rate of deuterium-containing precursor.

[0056]

[0062] Spatially relative terms, such as "beneath," "below," "lower," "above," "upper," and the like, may be used herein to readily describe the relationship of one element or feature to another element or feature as depicted in the drawings for ease of description. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the drawings. For example, if the device in the drawings is turned over, an element described as "below" or "beneath" the other element or feature would be oriented "above" the other element or feature. Thus, the exemplary term "below" can encompass both an above and below orientation. The device may be oriented other than as described (rotated 90 degrees or at other orientations) and the spatially relative descriptions used herein will be interpreted accordingly.

[0057]

[0063] The use of "a" and "an," "the," and similar referents in the context of describing the materials and methods discussed herein (particularly in the context of the claims that follow) should be construed to encompass both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The recitation of numerical ranges herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein may be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein is intended merely to better describe the materials and methods and does not limit the scope unless specifically claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosed materials and methods.

[0058]

[0064] Throughout this specification, references to "one embodiment," "a particular embodiment," "one or more embodiments," or "an embodiment" mean that a particular feature, structure, material, or characteristic described in connection with an embodiment is included in at least one embodiment of the disclosure. Thus, the appearances of "in one or more embodiments," "in a particular embodiment," "in one embodiment," or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment of the disclosure. In one or more embodiments, the particular features, structures, materials, or characteristics may be combined in any suitable manner.

[0059]

[0065] 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 disclosure. It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed method and apparatus without departing from the spirit and scope of the disclosure. Thus, the disclosure is intended to cover modifications and variations that come within the scope of the appended claims and their equivalents.

Claims

1. A method for modifying a membrane, comprising the steps of: modifying a first dielectric film deposited on a substrate by exposing the first dielectric film to a plasma comprising a deuterium-containing precursor to form a modified dielectric film comprising deuterium; the first dielectric film is substantially free of hydrogen and deuterium; the substrate is positioned on a multi-zone susceptor, each zone having independent temperature control; A method wherein more deuterium is incorporated into the film in the high temperature zone than in the low temperature zone.

2. The deuterium-containing precursor is D ２ , D ２ 2. The method of claim 1, comprising one or more of O, DH (deuterium-hydrogen) or HDO (deuterium-hydrogen oxide).

3. The plasma may be argon (Ar), helium (He), hydrogen (H ２ ), nitrogen (N ２ ), oxygen (O ２ ), ammonia (NH ３ ), or nitrogen fluoride (NF ３ 10. The method of claim 1, further comprising one or more of the following:

4. The method of claim 1 , wherein the film has a temperature in the range of about 20° C. to about 800° C.

5. The method of claim 1 , wherein the plasma has a pressure in the range of about 0.1 to about 500 mTorr.

6. The method of claim 1 , wherein the plasma has a power in the range of about 500 to about 20,000 Watts.

7. The method of claim 1 , wherein the plasma has a gas flow rate in the range of about 1 to about 5000 sccm.

8. The method of claim 1 , wherein the film is part of a CMOS device.

9. The method of claim 1 , wherein the film is part of an optical solid-state device.

10. The method of claim 9 , wherein the multi-zone susceptor has at least two zones.

11. The method of claim 10 , wherein the multi-zone susceptor comprises an inner zone and an outer zone.

12. The method of claim 10 , wherein the multi-zone susceptor has radially spaced zones.

13. The method of claim 10 , wherein the multi-zone susceptor comprises an inner zone and an outer zone, each of the inner zone and the outer zone comprising radially spaced zones.

14. A method for modifying a membrane, comprising the steps of: exposing a substrate having a first dielectric film deposited thereon, the first dielectric film being substantially free of hydrogen and deuterium, to a plasma comprising a deuterium-containing precursor to form a modified deuterium-containing dielectric film on the substrate; the substrate is positioned on a multi-zone susceptor, each zone having independent temperature control; A method wherein more deuterium is incorporated into the film in the high temperature zone than in the low temperature zone.

15. The deuterium-containing precursor is D ２ , D ２ 15. The method of claim 14, comprising one or more of O, DH (deuterium-hydrogen) or HDO (deuterium-hydrogen oxide).

16. The plasma may be argon (Ar), helium (He), hydrogen (H ２ ), nitrogen (N ２ ), oxygen (O ２ ), ammonia (NH ３ ), or nitrogen fluoride (NF ３ 15. The method of claim 14, further comprising one or more of the following:

17. 1. An apparatus comprising: a chamber body including a top and at least one sidewall defining a plasma cavity; a first gas inlet centrally located in the top of the chamber body, the first gas inlet configured to deliver a flow of plasma containing a deuterium-containing precursor to the plasma cavity; a second gas inlet located in the at least one sidewall of the chamber body, the second gas inlet configured to deliver the plasma flow containing the deuterium-containing precursor to the plasma cavity; an upper coil having an antenna on the upper portion of the chamber body; at least one side coil on a side of the chamber body; A multi-zone susceptor, each zone having independent temperature control; 13. An apparatus comprising:

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