Method and apparatus for depositing dielectric material

Abstract

Methods and apparatus for depositing dielectric material include providing a first gas mixture into a processing chamber; forming a first remote plasma including first radicals in a remote plasma source and delivering the first radicals to the processing chamber to form a dielectric material layer in an opening in a material layer disposed on a substrate in the presence of the first gas mixture and the first radicals; terminating the first remote plasma and applying a first RF bias power to the processing chamber to form a first bias plasma; contacting the dielectric material layer with the first bias plasma to form a first dielectric material processing layer; and subsequently forming a second remote plasma including second radicals in the remote plasma source and delivering the second radicals into the interior processing region in the presence of a second gas mixture while applying a second RF bias power to form a second bias plasma, wherein the second radicals and the second bias plasma contact the first dielectric material processing layer to increase a hydrophobicity or a flowability of the first dielectric material processing layer.

Description

Technical Field

[0001] Embodiments of this disclosure generally relate to methods and apparatus for depositing dielectric materials and modifying their hydrophobicity. Background Technology

[0002] Reliably generating sub-half-micron and smaller features is one of the key technological challenges for next-generation very large-scale integration (VLSI) and extremely large-scale integration (ULSI) semiconductor devices. However, as circuit technology pushes its limits, the size of VLSI and ULSI interconnect technologies continues to shrink, placing higher demands on processing power. Reliably forming gate structures on the substrate is crucial for the success of VLSI and ULSI, as well as for ongoing efforts to improve circuit density and the quality of individual substrates and dies.

[0003] To enable the fabrication of next-generation devices and structures, three-dimensional (3D) stacking of semiconductor chips is often utilized to improve transistor performance. By arranging transistors in three dimensions instead of the conventional two-dimensional arrangement, multiple transistors can be placed very close to each other in an integrated circuit (IC). 3D stacking of semiconductor chips reduces wire lengths and maintains low wiring delays. As the width of features such as trenches continues to shrink, the aspect ratio (depth divided by width) for semiconductor chip stacking continues to increase. One challenge in fabricating high aspect ratio features such as trenches is avoiding the formation of voids or gaps during the deposition of dielectric material in the trenches.

[0004] To fill the trench, a dielectric material layer, such as silicon oxide, is deposited. The dielectric layer typically covers the field, as well as the walls and bottom of features such as the trench. If the feature is wide and shallow, completely filling the feature is not difficult. However, as the feature aspect ratio increases, the trench opening will be "pinch-off," increasing the likelihood of voids or defects forming within the feature. The inventors have observed that if subsequently deposited metal fills these voids or gaps, the voids or gaps reduce the yield of the semiconductor product and alter the dielectric constant of the dielectric material.

[0005] To reduce the likelihood of voids or defects forming within features (e.g., gaps within trenches), various processing techniques have been developed to fill features with dielectric materials with minimal defects. Poor processing control during deposition can lead to premature closure of irregular structural profiles or features (e.g., trenches), resulting in voids or air gaps within the trenches as the dielectric material is filled.

[0006] Flowable chemical vapor deposition (FCVD) is a bottom-up filling method to avoid the formation of voids or defects. However, the inventors have observed that dielectric materials formed by FCVD methods can be unstable and may not improve the overall stability and quality of the dielectric film, leading to increased device resistance and poor yield. For example, the inventors have observed that biased plasma treatment can be used to compact the deposited flowable film material, but this method can problematically reduce the flowability of the film formed, resulting in conformal deposition and problematic void or gap formation. The inventors have also observed that biased plasma treatment of the flowable film material can reduce the hydrophobicity of the deposited flowable film.

[0007] Therefore, the inventors have provided improved methods and apparatus suitable for improving materials formed by the FCVD method. Summary of the Invention

[0008] This document provides methods and apparatus for depositing dielectric materials. In some embodiments, a method for depositing a dielectric material includes: (a) providing a first gas mixture to a processing chamber in which a substrate is disposed; (b) forming a first remote plasma comprising first free radicals in a remote plasma source and delivering the first free radicals to an internal processing region in the processing chamber to form a dielectric material layer in an opening in a material layer disposed on the substrate in the presence of the first gas mixture and the first free radicals; (c) terminating the first remote plasma and applying a first RF bias power to the processing chamber to form a first bias plasma; (d) contacting the dielectric material layer with the first bias plasma to form a first dielectric material processing layer; and (e) subsequently forming a second remote plasma comprising second free radicals in a remote plasma source and delivering the second free radicals to an internal processing region in the processing chamber in the presence of a second gas mixture while applying a second RF bias power to the processing chamber to form a second bias plasma, wherein the second free radicals and the second bias plasma contact the first dielectric material processing layer to increase the hydrophobicity or fluidity of the first dielectric material processing layer.

[0009] In some embodiments, a method for forming a dielectric material includes: filling an opening on a substrate having an aspect ratio greater than 5 with the dielectric material, the dielectric material being formed by sequentially applying a first remote plasma, a first bias plasma, and a second remote plasma combined with a second bias plasma to an internal processing region of a processing chamber on which the substrate is disposed; and at least increasing the fluidity or hydrophobicity of the dielectric material.

[0010] In some embodiments, this disclosure relates to a non-transitory computer-readable storage medium having instructions stored thereon that, when executed by a processor, cause a method to be performed, the method comprising: (a) providing a first gas mixture into a processing chamber in which a substrate is disposed; (b) forming a first remote plasma comprising first free radicals in a remote plasma source and delivering the first free radicals to an internal processing region in the processing chamber to form a dielectric material layer in an opening in a material layer disposed on the substrate in the presence of the first gas mixture and the first free radicals; and (c) terminating the first remote plasma. (d) Applying a first RF bias power to the processing chamber to form a first bias plasma; (e) bringing the dielectric material layer into contact with the first bias plasma to form a first dielectric material processing layer; and (f) subsequently forming a second remote plasma comprising a second free radical in a remote plasma source, and delivering the second free radical to an internal processing region in the processing chamber in the presence of a second gas mixture, while applying a second RF bias power to the processing chamber to form a second bias plasma, wherein the second free radical and the second bias plasma contact the first dielectric material processing layer to increase the hydrophobicity or fluidity of the first dielectric material processing layer.

[0011] Other and further implementations of this disclosure are described below. Attached Figure Description

[0012] The embodiments of this disclosure, which have been briefly summarized above and discussed in more detail below, can be understood by referring to the illustrative embodiments depicted in the accompanying drawings. However, the drawings depict only typical embodiments of this disclosure and are therefore not to be considered as limiting the scope, as other equivalent embodiments of this disclosure may be permitted.

[0013] Figure 1 A schematic cross-sectional side view of an apparatus for performing a deposition process according to some embodiments of the present disclosure is depicted;

[0014] Figure 2 It shows including Figure 1 A top view of one embodiment of the processing tool of the device;

[0015] Figure 3 This is a process flow diagram illustrating one embodiment of a method for forming a dielectric material incorporating the present disclosure;

[0016] Figures 4A to 4B The stages for filling high aspect ratio openings according to some embodiments of this disclosure are depicted; and

[0017] Figure 5 This is a process flow diagram illustrating another method for forming dielectric materials according to the present disclosure.

[0018] For ease of understanding, the same reference numerals have been used as much as possible to denote common elements in the figures. These figures are not drawn to scale and may be simplified for clarity. Elements and features of one embodiment may be advantageously incorporated into other embodiments without further description. Detailed Implementation

[0019] This disclosure relates to apparatus and methods for depositing dielectric materials in one or more features, such as trenches with high aspect ratios, for semiconductor devices, particularly for three-dimensional (3D) stacking of semiconductor chips. In some embodiments, the deposition process may sequentially use remote plasma, RF bias power, and combinations of remote plasma and RF bias power supplied to a substrate support assembly on which a substrate is placed to process the deposited material and maintain or increase the material's fluidity and / or hydrophobicity to advantageously reduce or eliminate the formation of voids or gaps. In some embodiments, remote plasma, RF bias power, and combinations of remote plasma and RF bias power are sequentially and cyclically supplied to an internal processing region of a processing chamber to provide good gap-filling capability for dielectric material filling in features such as trenches from the substrate. In some embodiments, the dielectric material is processed with a first remote plasma, a first RF bias power, and a combination of a second remote plasma and a second RF bias power to modify one or more properties of the dielectric material, such as density, fluidity, and / or hydrophobicity. In some embodiments, the hydrophobicity of the dielectric layer material is maintained or increased such that the dielectric material has a contact angle between 90 and 110 degrees when in contact with water. This maintains the fluidity of the dielectric material, thereby improving bottom-up gap filling, which in turn advantageously increases device yield and maintains the dielectric constant of the deposited material.

[0020] Therefore, this disclosure includes depositing dielectric materials into features such as trenches or vias for use in semiconductor devices, particularly for three-dimensional (3D) stacking of semiconductor chips, to provide good gap-filling capability for dielectric material filling of features. Figure 1 This is a cross-sectional view of a deposition processing chamber 100 for performing deposition processes of dielectric materials suitable for semiconductor applications, according to the present disclosure. Suitable, non-limiting processing chambers applicable herein include, for example, HDP-type materials available from Applied Materials Inc., Santa Clara, California. or Processing chambers. Other processing chambers, including those available from other manufacturers, may also be used appropriately in conjunction with the teachings provided herein.

[0021] Reference Figure 1The processing chamber 100 includes a processing chamber body 102 and a remote plasma source 104 coupled to the processing chamber body 102. The remote plasma source 104 can be any suitable source capable of generating free radicals. The remote plasma source 104 can be a remote plasma source, such as a radio frequency (RF) or ultra-high radio frequency (VHRF) capacitively coupled plasma (CCP) source, an inductively coupled plasma (ICP) source, a microwave induced (MW) plasma source, an electron cyclotron resonance (ECR) chamber, or a high-density plasma (HDP) chamber. In some embodiments, the remote plasma source 104 may include one or more gas sources 106, and the remote plasma source 104 may be coupled to the processing chamber 100 via a free radical conduit 108. One or more processing gases, which may be free radical forming gases, may enter the remote plasma source 104 via one or more gas sources 106. The one or more processing gases may include chlorine-containing gases, fluorine-containing gases, inert gases, oxygen-containing gases, nitrogen-containing gases, hydrogen-containing gases, or any combination thereof. In some embodiments, the processing gas includes a plasma gas selected from ammonia (NH3), nitrogen (N2), hydrogen (H2), and combinations thereof. Free radicals generated in the remote plasma source 104 travel through a free radical conduit 108 coupled to the processing chamber 100 into the processing chamber 100, reaching an internal processing region 151 defined within the processing chamber 100.

[0022] In some embodiments, the radical conduit 108 is part of a cap assembly 112, which also includes a radical cavity 110, a top plate 114, a cap edge 116, and a nozzle 118. The radical conduit 108 may include a material that is substantially non-reactive to radicals. For example, the radical conduit 108 may include aluminum nitride (AlN), silicon dioxide (SiO2), yttrium oxide (Y2O3), magnesium oxide (MgO), anodized Al2O3, sapphire, ceramics comprising one or more of Al2O3, sapphire, aluminum nitride (AlN), yttrium oxide (Y2O3), and magnesium oxide (MgO), or plastics. A representative example of a suitable silicon dioxide (SiO2) material is quartz. The radical conduit 108 may be disposed within and supported by a radical conduit support member 120. The radical conduit support member 120 may be disposed on a top plate 114, which rests on the cap edge 116.

[0023] In some embodiments, a radical cavity 110 is located below and coupled to a radical conduit 108, and radicals generated in a remote plasma source 104 travel through the radical conduit 108 to the radical cavity 110. The radical cavity 110 is defined by a top plate 114, a cover 116, and a nozzle 118. Optionally, the radical cavity 110 may include a liner 122. The liner 122 may cover the surfaces of the top plate 114 and the cover 116 exposed to the radical cavity 110. Radiations from the remote plasma source 104 enter an internal processing region 151 through a plurality of tubes 124 disposed in the nozzle 118. The nozzle 118 further includes a plurality of openings 126 with a diameter smaller than that of the plurality of tubes 124. The plurality of openings 126 are connected to an internal volume (not shown) not in fluid communication with the plurality of tubes 124. One or more fluid sources 119 may be coupled to the nozzle 118 for introducing a fluid mixture into the internal processing region 151 of the processing chamber 100. The fluid mixture may include a precursor and / or a carrier fluid. The fluid mixture may be a mixture of gas and liquid. In embodiments, non-limiting examples of suitable precursors include those suitable for forming silicon nitride (SiN). x Membrane precursors, such as trimethylsilylamine (TSA).

[0024] Processing chamber 100 may include a cover assembly 112, a chamber body 130, and a substrate support assembly 132. The substrate support assembly 132 may be at least partially disposed within the chamber body 130. The chamber body 130 may include a slit valve 135 to provide access to the interior of the processing chamber 100. The chamber body 130 may include a liner 134 covering an inner surface of the chamber body 130. The liner 134 may include one or more orifices 136 and a pump passage 138 formed therein in fluid communication with a vacuum system 140. The orifices 136 provide a flow path for gas to enter the pump passage 138, which provides an outlet for gas within the processing chamber 100.

[0025] Vacuum system 140 may include vacuum port 142, valve 144, and vacuum pump 146. Vacuum pump 146 is fluidly connected to pump channel 138 via vacuum port 142. Hole 136 allows pump channel 138 to fluidly communicate with internal processing region 151 within chamber body 130. Internal processing region 151 is defined by lower surface 148 of nozzle 118 and upper surface of substrate support assembly 132, and is surrounded by liner 134.

[0026] The substrate support assembly 132 may include a substrate support member 152 to support a substrate (not shown) for processing within the chamber body 130. The substrate can be any standard wafer size, for example, 300 mm. Alternatively, the substrate can be larger than 300 mm, for example, 450 mm or larger. Depending on the operating temperature, the substrate support member 152 may include aluminum nitride (AlN) or aluminum. The substrate support member 152 may be configured to clamp the substrate to the substrate support member 152. For example, the substrate support member 152 may be an electrostatic chuck or a vacuum chuck.

[0027] The substrate support member 152 is coupled to the lifting mechanism 154 via a shaft 156 extending through a central opening 158 formed in the bottom surface of the chamber body 130. The lifting mechanism 154 is flexibly sealed to the chamber body 130 via a bellows 160, which prevents vacuum leakage from around the shaft 156. The lifting mechanism 154 allows the substrate support member 152 to move vertically within the chamber body 130 between a processing position and a lower conveying position. The conveying position is slightly below the opening of the slit valve 135. During operation, the gap between the substrate 301 and the nozzle 118 can be minimized to maximize the free radical flux on the substrate surface. For example, the gap can be between about 100 mm and about 5,000 mm. The lifting mechanism 154 can be able to rotate the shaft 156, which in turn rotates the substrate support member 152, thereby causing the substrate disposed on the substrate support member 152 to rotate during operation.

[0028] One or more heating elements 162 and cooling channels 164 may be embedded in the substrate support member 152. The heating elements 162 and cooling channels 164 can be used to control the temperature of the substrate during operation. The heating element 162 can be any suitable heating element, such as one or more resistance heating elements. The heating element 162 can be connected to one or more power sources (not shown). The heating element 162 can be individually controlled to have independent heating and / or cooling control for multi-zone heating or cooling. The ability to independently control multi-zone heating and cooling can enhance the substrate temperature profile under any given processing conditions. Coolant can flow through the cooling channels 164 to cool the substrate. The substrate support member 152 may further include a gas channel extending to the upper surface 150 for allowing cooling gas to flow to the back side of the substrate.

[0029] RF source power 143 can be coupled to nozzle 118 via RF source power matching box 147. RF source power 143 can be low-frequency, high-frequency, or ultra-high-frequency. In one embodiment, RF source power 143 is a high-frequency RF generator that can generate high-density plasma for depositing high-density films. In one example, RF source power 143 can be used as an inductively coupled RF energy transfer device that can generate and control inductively coupled plasma (ICP) generated in the internal processing region 351 above the substrate support member 152. Dynamic impedance matching from RF source power matching box 147 can be provided when inductively coupled plasma (ICP) is generated.

[0030] In addition to the RF source power 143, the RF bias power supply 145 can be coupled to the substrate support member 152. The substrate support member 152 is configured as a cathode and includes an electrode 163 coupled to the RF bias power supply 145. The RF bias power supply 145 is coupled between the electrode 163 disposed in the substrate support member 152 and another electrode, such as the nozzle 118 or the ceiling (e.g., top plate 114) of the chamber body 130. The RF bias power generated from the RF bias power supply 145 excites and sustains a plasma discharge formed by a gas disposed in the internal processing region 151 of the chamber body 130.

[0031] In one operating mode, substrate 301 is disposed on substrate support member 152 in processing chamber 100. Processing gas and / or gas mixture is introduced from gas source 106 into chamber body 130 through nozzle 118. Vacuum pump 146 maintains pressure inside chamber body 130 while removing deposited byproducts.

[0032] Controller 170 is coupled to processing chamber 100 to control its operation. Controller 170 includes a central processing unit (CPU) 172, memory 174, and support circuitry 176 for controlling the processing sequence and regulating airflow from gas source 106. CPU 172 can be any type of general-purpose computer processor that can be used in an industrial setting. Software programs can be stored in memory 174, such as random access memory, read-only memory, floppy disk or hard disk drives, or other forms of digital storage. Support circuitry 176 is conventionally coupled to CPU 172 and may include cache, clock circuitry, input / output systems, power supply, etc. Bidirectional communication between controller 170 and the various components of processing chamber 100 is handled via a network of signal cables.

[0033] Figure 2 This is a schematic top plan view of an exemplary processing system 200, which includes one or more processes incorporated therein. Figure 1The processing chamber 100 is depicted. In one embodiment, the processing system 200 may be... The integrated processing system is commercially available from Applied Materials, located in Santa Clara, California. However, other processing systems, including those from other manufacturers, may also be suitable for benefiting from this disclosure.

[0034] In some embodiments, the processing system 200 includes a vacuum-sealed processing platform, such as processing platform 204, a plant interface 202, and a system controller 244. Processing platform 204 includes at least one processing chamber 100 (e.g., Figure 1 The diagram shows a processing chamber 100, multiple processing chambers 201, 228, 220, 210, and at least one loading and locking chamber 222, which is coupled to a vacuum substrate transfer chamber 236. Figure 2 Two loading locking chambers 222 are shown. The plant interface 202 is coupled to the transfer chamber 236 via the loading locking chambers 222.

[0035] In one embodiment, the factory interface 202 includes at least one docking station (such as docking station 208) and at least one factory interface robot 214 to facilitate substrate transfer. Docking station 208 is configured to receive one or more front-opening unified pods (FOUPs). Figure 2 The embodiment illustrates two FOUPs 206A-206B. A factory interface robot 214, having blades 216 disposed at one end, is configured to transfer substrates from the factory interface 202 to a processing platform 204 for processing via a loading locking chamber 222. Optionally, one or more metering stations 218 may be connected to the end 226 of the factory interface 202 to facilitate measurement of substrates from FOUPs 206A-206B.

[0036] Each loading lock chamber 222 has a first port coupled to the factory interface 202 and a second port coupled to the transfer chamber 236. The loading lock chamber 222 is coupled to a pressure control system (not shown) that evacuates and exhausts the loading lock chamber 222 to facilitate the passage of the substrate between the vacuum environment of the transfer chamber 236 and the physical surrounding environment (e.g., the atmosphere) of the factory interface 202.

[0037] The transfer chamber 236 has a vacuum robot 230 disposed therein. The vacuum robot 230 has blades 234 capable of transferring the substrate 301 between the loading locking chamber 222, the processing chamber 100, the processing chamber 201, and the processing chambers 201, 210, 220, 228.

[0038] In one embodiment of the processing system 200, the processing system 200 may include Figure 1 The processing chamber 100 shown (e.g., a high-density plasma (HDP) chamber) and other processing chambers 201, 210, 220, 228 may be deposition chambers, etching chambers, thermal processing chambers, or other similar types of semiconductor processing chambers, which can help form dielectric materials with good gap-filling capabilities to fill trenches in semiconductor devices or provide further downstream processing.

[0039] System controller 244 is very similar to controller 170 described above, and typically includes a central processing unit (CPU) 238, memory 240, and support circuitry 242. CPU 238 can be any form of general-purpose computer processor that can be used in an industrial setting. Support circuitry 242 is conventionally coupled to CPU 238 and may include cache, clock circuitry, input / output subsystems, power supply, etc. Software programs transform CPU 238 into a dedicated computer (controller) 244. The software programs may also be stored and / or executed by a second controller (not shown) located remotely from processing system 200.

[0040] Figure 3 This is a flowchart of one embodiment of a process 300 that can be carried out in a processing chamber 100 or other suitable processing chamber. Figures 4A to 4B This is a schematic cross-sectional view of a portion of the composite substrate 450 corresponding to the various stages of process 300. Process 300 can be used to fill features, such as features with a high aspect ratio, for example, for structures, for semiconductor devices, particularly for three-dimensional (3D) stacks of semiconductor memories, greater than 3:1, or between 3:1 and 15:1. Alternatively, process 300 can be advantageously used to fill other types of structures.

[0041] In some embodiments, processing 300 can be performed by transferring or providing a substrate, such as the substrate 301 depicted in FIG. 4, to a substrate such as... Figure 1 The process begins with a deposition processing chamber such as the processing chamber 100 depicted. The substrate 301 may have a substantially flat surface, a non-flat surface, or a substantially flat surface with structures formed thereon. Figure 4AIn the illustrated embodiment, substrate 301 has a material layer 404 disposed on interface layer 402. In one embodiment, material layer 404 includes openings 408 formed therein. Material layer 404 can be used to form gate structures, contact structures, interconnect structures, or any suitable structures as needed in front-end or back-end processing. In one embodiment, processing 300 can be performed on material layer 404 to form contact structures therein. Substrate 301 can be a material such as crystalline silicon (e.g., Si<100> or Si<111>), silicon oxide, strained silicon, silicon germanium, doped or undoped polycrystalline silicon, doped or undoped silicon wafers, patterned or unpatterned wafers, silicon on insulator (SOI), carbon-doped silicon oxide, silicon nitride, doped silicon, germanium, gallium arsenide, glass, or sapphire. Substrate 301 can have various sizes, such as wafers of 200 mm, 300 mm, 450 mm, or other diameters, and rectangular or square panels. Unless otherwise stated, the embodiments and examples described herein are carried out on substrates having a diameter of 200 mm, 300 mm, or 450 mm. In embodiments where an SOI structure is utilized on substrate 301, substrate 301 may include a buried dielectric layer disposed on a silicon crystalline substrate. In the embodiments depicted herein, substrate 301 may be a crystalline silicon substrate.

[0042] In one embodiment, interface layer 402 may be a dielectric layer. Material layer 404 has an opening 408 that exposes a portion 410 of interface layer 402 for depositing dielectric material therein. The opening 408 described herein may include trenches, vias, openings, etc. In one embodiment, material layer 404 may be a metallic material, a silicon-containing material, a carbon-containing material, or other suitable material. Suitable examples of metallic materials include copper-containing materials, aluminum-containing materials, nickel-containing materials, tungsten-containing materials, or other metallic materials. Suitable silicon-containing materials include silicon, silicon oxide, silicon nitride, silicon oxynitride, and combinations thereof. Suitable carbon-containing materials include silicon carbide, amorphous carbon, or similar materials. In the exemplary embodiments depicted herein, material layer 404, such as a patterned material layer, is a metallic layer. In some embodiments, material layer 404, such as a patterned material layer, may include one or more pad layers 401 or one or more barrier layers 403 deposited on the top surface of material layer 404, such as a patterned material layer.

[0043] In some embodiments, the interface layer 402 may be a dielectric layer, such as a dielectric oxide layer or a dielectric nitride layer, as needed. The interface layer 402 may include a multilayer, a composite layer, or a single layer. Other suitable materials for the dielectric layer include undoped silicon glass (USG), such as silicon oxide or TEOS, borosilicate glass (BSG), phosphosilicate glass (PSG), borophosphosilicate glass (BPSG), silicon nitride, amorphous silicon, and combinations thereof.

[0044] In some embodiments, the material layer 404 may be patterned to a predetermined depth to expose a portion 410 of the interface layer 402, such as Figure 4A As shown. The material layer 404 can be etched or patterned using any suitable patterning process. The material layer 404 can be patterned by supplying a gas mixture to the processing chamber along with a predetermined RF power level applied to the processing chamber.

[0045] In operation 302, a first gas mixture is provided into a processing chamber in which a substrate is disposed. For example, a first gas mixture, such as a deposition gas mixture, can be supplied to a process chamber such as... Figure 1 The processing chamber 100 is used to perform a deposition process to form dielectric material 406 in the opening 408. Figure 4B (As shown). The first gas mixture supplied to the processing chamber 100 can be varied depending on the type of material to be formed and filled in the opening 408. In one example, when the dielectric material 406 to be formed is expected to be a silicon nitride layer, the supplied first gas mixture may include one or more silicon-containing gases, nitrogen-containing gases, and inert gases (e.g., argon). In another example, when the dielectric material 406 to be formed is expected to be a silicon oxide layer, the supplied deposition gas mixture includes silicon-containing gases, oxygen-containing gases, and selectively inert gases. In yet another example, when the dielectric material 406 to be formed is expected to be a silicon carbide layer, the supplied deposition gas mixture may include silicon-containing gases, carbon-containing gases, and selectively inert gases. In yet another example, when the dielectric material 406 to be formed is expected to be a carbide layer, the supplied deposition gas mixture includes at least one carbon-containing gas and selectively inert gases.

[0046] Non-limiting examples of silicon-containing gases include silanes (SiH4), tetraethoxysilanes, disilanes (Si2H6), and the like. Suitable examples of nitrogen-containing gases include nitrogen (N2), ammonia (NH3), nitrous oxide (N2O), nitrogen dioxide (NO2), and the like. Suitable examples of oxygen-containing gases include hydrogen peroxide (H2O2), water (H2O), oxygen (O2), ozone (O3), and the like. Suitable examples of carbon-containing gases include carbon dioxide (CO2), hydrocarbon gases (e.g., CH4 and C2H6), and the like. Suitable examples of inert gases include helium (He), argon (Ar), and the like.

[0047] In some embodiments, additional carrier gases, such as nitrogen (N2), hydrogen (H2), and the like, may be supplied to the deposition gas mixture as needed.

[0048] In some embodiments, the first gas mixture includes a silicon-containing gas, a nitrogen- or carbon-containing gas, and argon or hydrogen. In one particular example, the deposition gas mixture includes silane (SiH4), argon (Ar), helium (He), ammonia (NH3), hydrogen (H2), and nitrogen (N2) for depositing a silicon nitride layer as dielectric material 406. In another particular example, the first gas mixture includes trimethylsilylamine (TSA), argon (Ar), helium (He), and ammonia (NH3) for depositing a silicon nitride layer as dielectric material 406. In yet another particular example, the first gas mixture includes silane (SiH4), argon (Ar), helium (He), methane (CH4), carbon dioxide (CO2), hydrogen (H2), and / or nitrogen (N2) for depositing a silicon carbide layer as dielectric material 406. In yet another specific example, the first gas mixture includes silane (SiH4), argon (Ar), helium (He), and oxygen (O2) or nitrogen dioxide (NO2) for depositing a silicon oxide layer as dielectric material 406.

[0049] In some embodiments, the silicon-containing gas is controlled at a flow rate between about 30 sccm and about 500 sccm, or between 50 sccm and 275 sccm. The oxygen, carbon, or nitrogen-containing gas is controlled at a flow rate between about 50 sccm and about 2000 sccm. In some embodiments, argon (Ar), ammonia (NH3), or helium (He) is controlled at a flow rate between about 500 sccm and about 3000 sccm. In some embodiments, helium (He) is supplied at a flow rate of 1000 sccm. In some embodiments, ammonia (NH3) is supplied at a flow rate of 525 sccm. In some embodiments, argon (Ar) is supplied at a flow rate of 2850 sccm.

[0050] In some embodiments, some gases from the first gas mixture may be supplied from gas source 106 through remote plasma source 104 to the internal processing region 151, while some gases may be supplied through one side of the processing chamber 100 (e.g., a fluid source 119 laterally formed around nozzle 118) to be delivered to the internal processing region 151. In some examples, a first gas (e.g., a reactive precursor) (such as a silicon-containing gas like TSA) from the first gas mixture is supplied from the side of the processing chamber 100 (e.g., fluid source 119), while a second gas (e.g., a carrier gas, an inert gas, a carbon or nitrogen-containing gas, or other gas) from the first gas mixture is supplied from gas source 106 via remote plasma source 104 to the internal processing region 151. In some embodiments, the first gas is SiH4 gas supplied to the processing chamber from fluid source 119, while the second gas is at least one of Ar, He, NH3, H2, N2, or combinations thereof supplied from gas source 106 via remote plasma source 104 to the internal processing region 151. In some embodiments, the first gas is TSA gas supplied to the processing chamber from fluid source 119, while the second gas is at least one of Ar, He, NH3, H2, N2, or combinations thereof supplied from gas source 106 via remote plasma source 104 to the internal processing region 151.

[0051] In operation 304, after a first gas mixture, such as a deposition gas mixture, is supplied to the processing chamber, a first remote plasma comprising first free radicals is formed in a remote plasma source, and the first free radicals are delivered to the inner processing region 151 within the processing chamber to form a dielectric material layer in an opening in a material layer disposed on a substrate in the presence of the first gas mixture and the first free radicals. In some embodiments, a first remote plasma source power is applied to a remote plasma source 104 to generate a first remote plasma to be delivered from the remote plasma source 104 to the inner processing region 151. In embodiments, the remotely dissociated gas and / or other gas provides a high density and low energy atomic species compared to the conventional chamber RF source power applied to the nozzle, which could provide high-energy but relatively low-density gas free radicals. In this embodiment, a high-density gas species with relatively low-energy atomic species is then transported to the internal processing region 151 using a remote plasma source with certain active gas species and gas supplied from the side (e.g., from fluid source 119) to form a dielectric material 406 on the substrate 301. Figure 4BAs shown. In this embodiment, the atomic gas species from a remote plasma source have a higher degree of reactivity, which can react more effectively, slowly, and thoroughly with reactive gas precursors supplied from the side (e.g., from fluid source 119), thereby providing good gap-filling capability to fill the dielectric material 406 into the openings 408 defined in the material layer 404.

[0052] In some embodiments, the amount of each gas introduced into the processing chamber can be varied and adjusted to accommodate, for example, the thickness of the dielectric material 406 to be formed in the opening 408 (e.g., the height or geometry of the opening 408). In one or more embodiments, the gases supplied from the remote plasma source 104 can be in a specific ratio. For example, the volume ratio of nitrogen- or carbon-containing gas to Ar gas can be controlled between about 0.2:1 and about 2:1.

[0053] In some embodiments, free radicals from a remote plasma are supplied to the substrate support member 152 to deposit dielectric material to a desired or predetermined thickness in the dielectric material 406 filling the openings 408 in the material layer 404. For example, in embodiments, the dielectric material is deposited to a thickness of about 30 nanometers, 60 nanometers, 90 nanometers, or 120 nanometers, or between about 20 nanometers and 150 nanometers. As explained below, the deposition can be periodic, such that the dielectric material layer is deposited according to this disclosure.

[0054] In some embodiments, a remote RF source power between about 1,000 watts and about 10,000 watts, for example, between about 2,000 watts and about 4,000 watts, is supplied to a remote plasma source 104 to generate remote plasma and free radicals to be delivered to the internal processing region 151. The frequency at which power is applied to the remote plasma source 104 is about 400 kHz. The frequency can range from about 50 kHz to about 2.45 GHz. The substrate temperature is maintained between about -20 degrees Celsius and about 200 degrees Celsius, for example, between about 20 degrees Celsius and about 90 degrees Celsius.

[0055] In some embodiments, during operation 306, while terminating the remote plasma from the remote plasma source 104 to the internal processing region 151, RF bias power can be applied to the substrate support member 152 to generate RF bias plasma reaching the substrate 301 disposed on the substrate support member 152. In some embodiments, the RF bias power generated to the substrate support member 152 is used during the deposition process to help provide directionality to the plasma in the internal processing region 151. In one embodiment, the RF bias power can be provided at 60 MHz and / or 2 MHz as needed. In a particular embodiment, the RF bias power is provided at 60 MHz, 2 MHz, or 400 kHz.

[0056] In some embodiments, RF bias power can be provided to the substrate support member 152 in a pulsed mode. In this embodiment, the pulsed RF bias power can provide a relatively mild RF power level to the substrate 301 disposed on the substrate support member, thereby accelerating reactive species toward the substrate 301 at a relatively mild energy level. The RF bias power provided to the substrate support member 152 can be applied sequentially after remote plasma power provided from the remote plasma source 104.

[0057] In some embodiments, remote plasma is supplied from remote plasma source 104 from a first time point to a second time point. Subsequently, after the power applied to remote plasma source 104 is terminated at the second time point (e.g., the remote plasma supplied from remote plasma source 104 is turned off), RF bias power is then supplied to substrate support member 152 in a pulsed mode from the second time point to a third time point. The RF bias power supplied to substrate support member 152 in a pulsed mode can be terminated (e.g., turned off) when dielectric material 406 of a predetermined or desired thickness fills the openings 408 in material layer 404. In some embodiments, the dielectric material 406 formed in material layer 404 may be silicon nitride.

[0058] In some embodiments, the RF bias power supplied to the substrate support member 152 can form a bias plasma, which is used to process or densify the dielectric material in the openings 408 in the material layer 404 to a desired or predetermined density. For example, in operation 308, the dielectric material layer can be contacted with a first bias plasma to form a first dielectric material processing layer. In embodiments, the dielectric material is processed to increase the density of the material.

[0059] In some embodiments, the RF bias power supplied to the substrate support member 152 may be accompanied by the process gas mixture described herein. In some embodiments, the process gas mixture does not contain silicon-containing gas. In some embodiments, oxygen-, carbon-, or nitrogen-containing gases are controlled at a flow rate between about 50 sccm and about 2000 sccm by volume. In some embodiments, argon (Ar), ammonia (NH3), or helium (He) is controlled at a flow rate between about 500 sccm and about 3000 sccm by volume. In some embodiments, helium (He) is supplied at a flow rate of 1000 sccm by volume. In some embodiments, ammonia (NH3) is supplied at a flow rate of 525 sccm by volume. In some embodiments, argon (Ar) is supplied at a flow rate of 2850 sccm by volume.

[0060] In some embodiments, the inventors have observed that the dielectric material 406 may problematically lose its ability to flow and / or maintain its hydrophobic properties after RF bias power is applied. For example, the viscosity of the dielectric material may increase, causing the material to lose its flowability. Furthermore, the first-treated dielectric film may problematically possess hydrophilic properties, or be hydrophilic enough to have a water contact angle of less than 85 degrees.

[0061] In processing sequence 310, after contacting the dielectric material layer with a first bias plasma to form a first dielectric material processing layer, a second remote plasma may be formed. The second remote plasma includes a second free radical in a remote plasma source and includes delivering the second free radical to an internal processing region in a processing chamber in the presence of a second gas mixture, while applying a second RF bias power to the processing chamber to form the second bias plasma. The second free radical and the second bias plasma contact the first dielectric material processing layer to increase the hydrophobicity or fluidity of the first dielectric material processing layer (e.g., reduce viscosity).

[0062] In some embodiments, at processing sequence 310, a second remote plasma or free radicals from the second remote plasma can be supplied from the remote plasma source 104 to the substrate 301 simultaneously with the RF bias power supplied to the substrate support member 152 during a predetermined time period from a first time point to a second time point. In some embodiments, the remote plasma from the remote plasma source 104 is supplied in a continuous mode, and the RF bias power supplied to the substrate support member 152 is also in a continuous mode. In some embodiments, when the desired viscosity and / or hydrophobicity of the dielectric material 406 is achieved (e.g., in the openings 408 in the material layer 404), the second remote plasma from the remote plasma source 104 and the RF bias power supplied to the substrate support member 152 can be terminated simultaneously at the second time point. In some embodiments, the dielectric material 406 formed in the material layer 404 may be silicon nitride.

[0063] At processing sequence 310, in some embodiments, the second gas mixture supplied to processing chamber 100 may be varied based on the type of material of the first dielectric material processing layer in opening 408. In one example, when dielectric material 406 is a silicon nitride layer, the supplied second gas mixture includes at least one silicon-containing gas, a nitrogen-containing gas, or a selectively inert gas. In another example, when the first dielectric material processing layer is a silicon oxide layer, the second gas mixture may include at least one silicon-containing gas, an oxygen-containing gas, or a selectively inert gas. In yet another example, when the first dielectric material processing layer is a silicon carbide layer, the supplied second gas mixture includes at least one silicon-containing gas, a carbon-containing gas, or a selectively inert gas. In yet another example, when the first dielectric material processing layer is a carbide layer, the second gas mixture may include at least one carbon-containing gas or a selectively inert gas.

[0064] Non-limiting examples of silicon-containing gases include silanes (SiH4), tetraethoxysilanes, disilanes (Si2H6), and the like. Suitable examples of nitrogen-containing gases include nitrogen (N2), ammonia (NH3), nitrous oxide (N2O), nitrogen dioxide (NO2), and the like. Suitable examples of oxygen-containing gases include hydrogen peroxide (H2O2), water (H2O), oxygen (O2), ozone (O3), and the like. Suitable examples of carbon-containing gases include carbon dioxide (CO2), hydrocarbon gases (e.g., CH4 and C2H6), and the like. Suitable examples of inert gases include helium (He), argon (Ar), and the like. In some embodiments, a carrier gas, such as nitrogen (N2), hydrogen (H2), and the like, may also be supplied to the second gas mixture as needed.

[0065] In some embodiments, the second gas mixture includes a silicon-containing gas, a nitrogen- or carbon-containing gas, and argon or hydrogen. In one particular example, the second gas mixture includes silane (SiH4), argon (Ar) or helium (He), ammonia (NH3), hydrogen (H2) or nitrogen (N2), or combinations thereof, for use on the silicon nitride layer as a first dielectric material treatment layer. In another particular example, the second gas mixture includes trimethylsilylamine (TSA), argon (Ar), helium (He), or ammonia (NH3), or combinations thereof, for use on the silicon nitride layer as a first dielectric material treatment layer. In yet another particular example, the deposition gas mixture includes silane (SiH4), argon (Ar), helium (He), methane (CH4), carbon dioxide (CO2), hydrogen (H2), or nitrogen (N2), for use on the silicon carbide layer as a first dielectric material treatment layer. In yet another specific example, the second gas mixture includes (SiH4), argon (Ar), helium (He), or oxygen (O2) or nitrogen dioxide (NO2) for use as a first dielectric material treatment layer on the silicon oxide layer.

[0066] In some embodiments, the silicon-containing gas is controlled at a flow rate between about 30 sccm and about 500 sccm, or between 50 sccm and 275 sccm. The oxygen, carbon, or nitrogen-containing gas is controlled at a flow rate between about 50 sccm and about 2000 sccm. In some embodiments, argon (Ar), ammonia (NH3), or helium (He) is controlled at a flow rate between about 500 sccm and about 3000 sccm. In some embodiments, helium (He) is supplied at a flow rate of 1000 sccm. In some embodiments, ammonia (NH3) is supplied at a flow rate of 525 sccm. In some embodiments, argon (Ar) is supplied at a flow rate of 2850 sccm.

[0067] In some embodiments, some gases from the second gas mixture may be supplied from gas source 106 to the internal processing region 151 via remote plasma source 104, while some gases may be supplied through one side of the processing chamber 100 (such as a fluid source 119 laterally formed around nozzle 118) to be delivered to the internal processing region 151. In some examples, the first gas is the same as the first gas described above (e.g., a reactive precursor), such as a silicon-containing gas like TSA supplied from the side of the processing chamber 100 (e.g., fluid source 119), while the second gas (e.g., a carrier gas, an inert gas, a carbon or nitrogen-containing gas, or other gas) is supplied from gas source 106 to the internal processing region 151 via remote plasma source 104. In some embodiments, the first gas is SiH4 gas supplied from fluid source 119 to the processing chamber, while the second gas is at least one of Ar, He, NH3, H2, N2, or combinations thereof supplied from gas source 106 to the internal processing region 151 via remote plasma source 104. In some embodiments, the first gas is TSA gas supplied to the processing chamber from fluid source 119, while the second gas is at least one of Ar, He, NH3, H2, N2, or combinations thereof supplied from gas source 106 via remote plasma source 104 to the internal processing region 151.

[0068] In processing sequence 310, while the second gas mixture is supplied to the processing chamber, a second remote plasma comprising second free radicals is formed in a remote plasma source. In embodiments, the second free radicals are adapted to be delivered to the inner processing region 151 within the processing chamber in the presence of the second gas mixture and the second free radicals. In some embodiments, the second remote plasma source power is applied to the remote plasma source 104 to generate the second remote plasma to be delivered from the remote plasma source 104 to the inner processing region 151. In embodiments, the remotely dissociated gas and / or other gases provide high-density and low-energy atomic species compared to the conventional chamber RF source power applied to the nozzle, which can provide high-energy but relatively low-density gas free radicals. In embodiments, a high-density gas species with relatively low-energy atomic species is then delivered to the inner processing region 151 using a remote plasma source having certain active gas species and gas supplied from the side (e.g., from fluid source 119) to form a dielectric material 406 on the substrate 301, such as... Figure 4B As shown. In this embodiment, the atomic gas species from a remote plasma source have a higher degree of reactivity, which can react more effectively, slowly, and thoroughly with reactive gas precursors supplied from the side (e.g., from fluid source 119), thereby providing good gap-filling capability to fill the dielectric material 406 into the openings 408 defined in the material layer 404.

[0069] In some implementations, the amount of each gas introduced into the processing chamber can be changed and adjusted to accommodate, for example, the viscosity and hydrophobicity of the first dielectric material processing layer.

[0070] In some embodiments, a remote RF source power between about 1,000 watts and about 10,000 watts, for example, between about 2,000 watts and about 4,000 watts, is supplied to a remote plasma source 104 to generate a second remote plasma to be delivered to the internal processing region 151. The frequency at which power is applied to the second remote plasma source may be the same as that of the remote plasma source 104 and is about 400 kHz. The frequency may be in the range of about 50 kHz to about 2.45 GHz. The substrate temperature is maintained between about -20 degrees Celsius and about 200 degrees Celsius, for example, between about 20 degrees Celsius and about 90 degrees Celsius.

[0071] In some embodiments, at processing sequence 310, while maintaining a second remote plasma from remote plasma source 104 to internal processing region 151, a second RF bias power may be simultaneously applied to substrate support member 152 to generate a second RF bias plasma reaching substrate 301 disposed on substrate support member 152. In some embodiments, the second RF bias power may be provided at 60 MHz and / or 2 MHz as needed. In a particular embodiment, the second RF bias power is provided at 60 MHz, 2 MHz, or 400 kHz.

[0072] In some embodiments, a second remote plasma is supplied from a remote plasma source 104, and a second RF bias power is supplied to the substrate support member 152 for a predetermined time, such as 10 to 30 seconds. In some embodiments, the first dielectric material treatment layer may be silicon nitride.

[0073] In some embodiments, the second RF bias power provided to the substrate support member 152 can form a second bias plasma for treating the first dielectric material treatment layer in the opening 408 of the material layer 404 to a desired or predetermined viscosity or hydrophobicity. For example, after processing sequence 310, the first dielectric material treatment layer may have hydrophobic properties or be sufficiently hydrophobic to have a water contact angle of about 90 degrees to about 110 degrees. Hydrophobicity and hydrophobicity refer to the wettability of a surface (e.g., a coated surface or a smooth surface) having a water contact angle of about 85° or greater. Typically, on a hydrophobic surface, for example, a water droplet with a diameter of 2 mm will bead up but will not flow off the surface when the surface is not excessively tilted. As the surface tilts, the wetting angle increases on the downslope side of the droplet and decreases on the upslope side. Because the advancing (downslope) interface has difficulty pushing forward to the next increment of the solid surface and the retreating (upslope) interface has difficulty releasing the portion of the solid surface where the droplet is located, the droplet tends to remain stationary or fixed in place. In this embodiment, the contact angle is measured by methods known in the art, such as using a goniometer.

[0074] In one embodiment, the first dielectric material treatment layer or its top surface is treated to increase its contact angle by at least 10 degrees, at least 20 degrees, at least 30 degrees, or at least 50 degrees upon contact with water. In another embodiment, the first dielectric material treatment layer is modified to have a contact angle of 90 to 110 degrees upon contact with water. In yet another embodiment, after treatment sequence 310, when in contact with water, the first dielectric material treatment layer includes a contact angle of at least 100 degrees, at least 102 degrees, at least 104 degrees, at least 106 degrees, at least 108 degrees, or at least 110 degrees.

[0075] In some embodiments, this disclosure relates to a method for depositing a dielectric material. In one embodiment, the method includes: (a) providing a first gas mixture to a processing chamber in which a substrate is disposed; (b) forming a first remote plasma comprising first free radicals in a remote plasma source and delivering the first free radicals to an internal processing region within the processing chamber to form a dielectric material layer in an opening in a material layer disposed on the substrate in the presence of the first gas mixture and the first free radicals; (c) terminating the first remote plasma and applying a first RF bias power to the processing chamber to form a first bias plasma; (d) contacting the dielectric material layer with the first bias plasma to form a first dielectric material processing layer; and (e) subsequently forming a second remote plasma comprising second free radicals in a remote plasma source and delivering the second free radicals to an internal processing region within the processing chamber in the presence of a second gas mixture, while simultaneously applying a second RF bias power to the processing chamber to form a second bias plasma, wherein the second free radicals and the second bias plasma contact the first dielectric material processing layer to increase the hydrophobicity or flowability (e.g., reduce viscosity) of the first dielectric material processing layer. In some embodiments, the method includes repeating (a) through (e) until the first dielectric material treatment layer has a predetermined thickness, for example, 90 to 160 nanometers. In some embodiments, the method includes contacting the dielectric material layer with a first bias plasma to form the first dielectric material treatment layer, thereby reducing the hydrophobicity of the first dielectric material treatment layer, wherein the first dielectric material treatment layer has a contact angle of less than 90 degrees when in contact with water. In some embodiments, contacting the first dielectric material treatment layer with a second free radical and a second bias plasma increases the hydrophobicity of the first dielectric material treatment layer, wherein the first surface of the first dielectric material treatment layer has a contact angle of 90 to 110 degrees when in contact with water. In some embodiments, the first gas mixture and the second gas mixture comprise silicon-containing gases, argon, helium, and ammonia at temperatures ranging from -20 degrees Celsius to 90 degrees Celsius. In some embodiments, (e) includes contacting the first dielectric material treatment layer with the second free radical and the second RF bias plasma for approximately 5 seconds. In some embodiments, the second gas mixture comprises argon, helium, ammonia, and trisilaneamine (TSA) at temperatures ranging from -20°C to 90°C. In some embodiments, a second remote plasma is formed before a second RF bias power is applied to the processing chamber. In some embodiments, forming the first remote plasma further comprises: forming the first remote plasma for a predetermined time period; and terminating the first remote plasma before applying the first RF bias power. In some embodiments, the first gas mixture and the second gas mixture comprise a precursor gas supplied to the internal processing area through one side of the processing chamber.In some embodiments, the first gas mixture and the second gas mixture comprise a second gas supplied to the internal processing region via a remote plasma source. In some embodiments, the first gas mixture and the second gas mixture comprise one or more gases selected from the group consisting of silicon-containing gases, nitrogen-containing gases, inert gases, carbon-containing gases, and oxygen-containing gases. In some embodiments, the first gas mixture and the second gas mixture comprise at least argon (Ar), helium (He), ammonia (NH3), hydrogen (H2), and nitrogen (N2). In some embodiments, the first dielectric material processing layer is a silicon nitride layer or a silicon carbide layer. In some embodiments, the method includes maintaining a substrate temperature between about -20 degrees Celsius and about 90 degrees Celsius.

[0076] Now for reference Figure 5 Method 500 includes a method for forming a dielectric material according to the present disclosure. In one embodiment, method 500 includes filling an opening having an aspect ratio greater than 5 on a substrate with a dielectric material at a processing sequence 502, the dielectric material being formed by sequentially applying a first remote plasma, a first bias plasma, and a second remote plasma combined with a second bias plasma to an internal processing region of a processing chamber on which the substrate is disposed. In a processing sequence 504, method 500 includes at least increasing the fluidity or hydrophobicity of the dielectric material. In some embodiments, the method includes a dielectric material, wherein the dielectric material is a silicon nitride layer or a silicon carbide layer. In one embodiment, the opening is filled with a dielectric material from bottom to top. In some embodiments, the opening is filled with multiple dielectric material layers to a predetermined thickness.

[0077] In some embodiments, this disclosure relates to a processing chamber and / or integrated system configured to (a) provide a first gas mixture into a processing chamber in which a substrate is disposed; (b) form a first remote plasma comprising first free radicals in a remote plasma source and deliver the first free radicals to an internal processing region in the processing chamber to form a dielectric material layer in an opening in a material layer disposed on the substrate in the presence of the first gas mixture and the first free radicals; (c) terminate the first remote plasma and apply a first RF bias power to the processing chamber to form a first bias plasma; (d) contact the dielectric material layer with the first bias plasma to form a first dielectric material processing layer; and (e) subsequently form a second remote plasma comprising second free radicals in a remote plasma source and deliver the second free radicals to an internal processing region in the processing chamber in the presence of a second gas mixture, while applying a second RF bias power to the processing chamber to form a second bias plasma, wherein the second free radicals and the second bias plasma contact the first dielectric material processing layer to increase the hydrophobicity or fluidity (e.g., reduce viscosity) of the first dielectric material processing layer.

[0078] In some embodiments, this disclosure relates to a non-transitory computer-readable storage medium having instructions stored thereon that, when executed by a processor, cause a method to be performed, the method comprising: (a) providing a first gas mixture into a processing chamber in which a substrate is disposed; (b) forming a first remote plasma comprising first free radicals in a remote plasma source and delivering the first free radicals to an internal processing region in the processing chamber to form a dielectric material layer in an opening in a material layer disposed on the substrate in the presence of the first gas mixture and the first free radicals; and (c) terminating the first remote plasma and directing the first remote plasma into the processing chamber. (d) Applying a first RF bias power to the chamber to form a first bias plasma; (e) contacting the dielectric material layer with the first bias plasma to form a first dielectric material processing layer; and (f) subsequently forming a second remote plasma comprising a second free radical in a remote plasma source, and delivering the second free radical to an internal processing region in the processing chamber in the presence of a second gas mixture, while applying a second RF bias power to the processing chamber to form a second bias plasma, wherein the second free radical and the second bias plasma contact the first dielectric material processing layer to increase the hydrophobicity or fluidity (e.g., reduce viscosity) of the first dielectric material processing layer.

[0079] While the foregoing describes implementations of this disclosure, other and further implementations of this disclosure are conceivable without departing from its basic scope.

Claims

1. A method of forming a dielectric material, comprising: filling an opening on a substrate having an aspect ratio greater than 5 with a dielectric material formed by sequentially applying a first remote plasma, a first bias plasma, a second remote plasma, and a second bias plasma to an interior processing region of a processing chamber provided with the substrate, thereby at least increasing a flowability or a hydrophobicity of the dielectric material.

2. The method of claim 1, wherein filling the opening further comprises: (a) providing a first gas mixture into a processing chamber in which the substrate is disposed; (b) forming the first remote plasma comprising first radicals in a remote plasma source and delivering the first radicals to an interior processing region in the processing chamber to form a dielectric material layer in an opening in a material layer disposed on the substrate in the presence of the first gas mixture and the first radicals; (c) terminating the first remote plasma and applying a first RF bias power to the processing chamber to form the first bias plasma; (d) contacting the dielectric material layer with the first bias plasma to form a first dielectric material processing layer; and (e) subsequently forming the second remote plasma comprising second radicals in the remote plasma source and delivering the second radicals to the interior processing region in the processing chamber in the presence of a second gas mixture while applying a second RF bias power to the processing chamber to form the second bias plasma, wherein the second radicals and second bias plasma contact the first dielectric material processing layer to increase the hydrophobicity or the flowability of the first dielectric material processing layer.

3. The method of claim 2, further comprising: repeating (a) through (e) until the first dielectric material processing layer has a predetermined thickness.

4. The method of any of claims 2 through 3, wherein contacting the dielectric material layer with the first bias plasma to form a first dielectric material processing layer decreases a hydrophobicity of the first dielectric material processing layer, wherein the first dielectric material processing layer has a contact angle less than 90 degrees when in contact with water.

5. The method of any of claims 2 through 3, wherein contacting the second radicals and second bias plasma with the first dielectric material processing layer increases a hydrophobicity of the first dielectric material processing layer, wherein the hydrophobicity of a first surface of the first dielectric material processing layer has a contact angle of 90 to 110 degrees when in contact with water.

6. The method of any of claims 2 through 3, wherein the first gas mixture and the second gas mixture comprise a silicon-containing gas, argon, helium, and ammonia at a temperature of negative 20 degrees Celsius to 90 degrees Celsius.

7. The method of any of claims 2 through 3, wherein (e) comprises contacting the first dielectric material processing layer with the second radicals and second RF bias plasma for 5 seconds.

8. The method, as recited in any of claims 2-3, wherein the second gas mixture comprises argon, helium, ammonia, and trisilylamine (TSA) at a temperature of negative 20 degrees Celsius to 90 degrees Celsius.

9. The method, as recited in any of claims 2-3, wherein the second remote plasma is formed prior to applying a second RF bias power to the processing chamber.

10. The method of any of claims 2-3, wherein forming the first remote plasma further comprises: the first remote plasma is terminated prior to applying the first RF bias power.

11. The method, as recited in any of claims 2-3, wherein the first and second gas mixtures comprise a precursor gas supplied through a side of the processing chamber to the interior processing region.

12. The method, as recited in any of claims 2-3, wherein the first and second gas mixtures comprise a second gas supplied to the interior processing region by the remote plasma source.

13. The method, as recited in any of claims 2-3, wherein the first and second gas mixtures comprise one or more gases selected from the group consisting of a silicon-containing gas, a nitrogen-containing gas, an inert gas, a carbon-containing gas, and an oxygen-containing gas.

14. The method, as recited in any of claims 2-3, wherein the first and second gas mixtures comprise at least argon (Ar), helium (He), ammonia (NH3), hydrogen (H2), and nitrogen (N2).

15. The method, as recited in any of claims 2-3, wherein the first dielectric material processing layer is a silicon nitride layer or a silicon carbide layer.

16. The method, as recited in any of claims 2-3, further comprising: maintaining a substrate temperature at negative 20 degrees Celsius to 90 degrees Celsius.

17. The method, as recited in any of claims 1-3, wherein the opening is filled from bottom to top.

18. The method, as recited in any of claims 1-3, wherein the opening is filled to a predetermined thickness in a plurality of dielectric material layers.

19. A non-transitory computer readable storage medium having stored thereon instructions which, when executed by a processor, cause a method to be performed, the method as recited in any of claims 1-3.

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