Formation of a film having an upward-facing film quality

Abstract

The method comprises depositing a flowable film on a substrate by supplying a first input stream, the first input stream including a plasma emission of a first precursor; removing a portion of the flowable film from sidewalls of features defined in the substrate by supplying a second input stream to obtain a remaining portion of the flowable film, the second input stream including a plasma emission of a second precursor; reducing a hydrogen content of the remaining portion of the flowable film by supplying a third input stream to obtain a densified film, the third input stream including a plasma emission of a third precursor; and processing the densified film according to a film processing process.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims the benefits and priority of U.S. Patent Application No. 17 / 873,597, filed on July 26, 2022, entitled "FORMING FILMS WITH IMPROVED FILM QUALITY", which is hereby incorporated by reference in its entirety.

[0002] This technology relates to semiconductor processing. More specifically, this technology relates to forming films with improved film quality.

Background Art

[0003] An electronic device manufacturing system may include one or more process chambers in which a substrate is processed to fabricate an electronic device (e.g., an integrated circuit and / or a flat panel display) on the substrate. The process chambers may be operated at a vacuum level (e.g., in the range of about 0.01 Torr to about 80 Torr) and a high temperature (e.g., in the range of about 100 °C to about 700 °C). The same or different substrate processes may be performed in each process chamber of the electronic device manufacturing system. Substrate processing may be performed in the load lock of some electronic device manufacturing systems. The load lock is a chamber in which the substrate is transferred between the process chamber and the factory interface for transport to other parts of the electronic device manufacturing system.

Summary of the Invention

[0004] According to yet another aspect, a method is provided. The method includes depositing a flowable film on a substrate by supplying a first input stream, where the first input stream includes a plasma emission of a first precursor; removing a portion of the flowable film from sidewalls of features defined within the substrate by supplying a second input stream to obtain a remaining portion of the flowable film, where the second input stream includes a plasma emission of a second precursor; reducing a hydrogen content of the remaining portion of the flowable film by supplying a third input stream to obtain a densified film, where the third input stream includes a plasma emission of a third precursor; and processing the densified film according to a film processing process.

[0005] According to another aspect, a system is provided. The system includes at least one system controller including a processor operably coupled to a memory. The at least one system controller is configured to deposit a flowable film on a substrate by causing a first input stream to be supplied, where the first input stream includes a plasma emission of a first precursor; remove a portion of the flowable film from sidewalls of features defined within the substrate by causing a second input stream to be supplied to obtain a remaining portion of the flowable film, where the second input stream includes a plasma emission of a second precursor; reduce a hydrogen content of the remaining portion of the flowable film by causing a third input stream to be supplied to obtain a densified film, where the third input stream includes a plasma emission of a third precursor; and cause the densified film to be processed using a film processing process.

[0006] According to yet another aspect, a system is provided, comprising: a process chamber including a first substrate support, a film treatment chamber including a second substrate support, and a transfer chamber coupled to the process chamber and the film treatment chamber, the transfer chamber housing a transfer robot, and at least one system controller operably coupled to the process chamber, the film treatment chamber, and the transfer robot. The at least one system controller is configured to: cause the transfer robot to load a substrate onto a first substrate support in a process chamber, the substrate including a feature defined therein; deposit a flowable film on the substrate in the process chamber by supplying a first input flow into a processing volume of the process chamber, the first input flow including a plasma effluent of a first precursor; cause the transfer robot to remove a portion of the flowable film from sidewalls of the feature in the process chamber to obtain a remainder of the flowable film, the second input flow including a plasma effluent of a second precursor; and cause the transfer robot to reduce a hydrogen content of the remainder of the flowable film in the process chamber by supplying a third input flow into the processing volume, the third input flow including a plasma effluent of the third precursor, to obtain a densified film; cause the transfer robot to transfer the substrate from the process chamber to a film treatment chamber and onto the second substrate support; and cause the transfer robot to treat the densified film in the film treatment chamber using the film treatment process.

[0007] Still other aspects, features, and advantages of these and other embodiments of the present disclosure may become readily apparent from the following detailed description, the appended claims, and the accompanying drawings, which, accordingly, are to be regarded as illustrative in nature and not as restrictive.

[0008] The drawings described below are provided for illustrative purposes only and are not necessarily drawn to scale. The drawings are not intended to limit the scope of the present disclosure in any way. [Brief explanation of the drawings]

[0009]

Figure 1

Figure 2

Figure 3

Figures 4A - 4C

Figure 5

Figure 6

Figure 7

Best Mode for Carrying Out the Invention

[0010] Aspects of the present disclosure are directed to forming a film (e.g., a thin silicon film) having improved film quality. Electronic devices such as integrated circuits are realized by a process of generating a complexly patterned material layer on a substrate surface. Generating a patterned material on a substrate requires a controlled method of forming and removing the exposed material. As device sizes continue to shrink, the formation of the material may affect subsequent operations. For example, in a gap filling operation, material may be formed or deposited to fill trenches or other features formed in a semiconductor substrate. These filling operations can be challenging because the features may be characterized by a higher aspect ratio and reduced critical dimensions. For example, deposition may occur at the top of the feature and along the sidewalls, so continued deposition may cause pinch-off of the feature, including between the sidewalls within the feature, and may generate voids within the feature. This can affect device performance and subsequent processing operations.

[0011] Amorphous silicon may be used as a sacrificial material in a number of structures and processes in semiconductor device manufacturing, for example, as a dummy gate material or as a trench fill material. In a gap filling operation, some processes may utilize a flowing film formed under process conditions to limit the conformality of the deposition, thereby allowing the deposited material to better fill the features on the substrate. The flowing silicon material may be characterized by a relatively large amount of hydrogen and may be less dense than other formed films. As a result, subsequent processing operations may be performed to cure the generated film. In some embodiments, a UV curing process may be utilized to remove hydrogen and process the film. However, UV curing may result in significant film shrinkage, which can cause stress in the features and may generate voids within the structure.

[0012] As the feature size continues to shrink, the flowable film may pose a problem for narrow features that may further feature a higher aspect ratio. For example, due to deposition on the sidewalls of the feature, pinching of the feature may be more likely to occur, which may further limit the flow to additional features and may create voids at small feature sizes. Additionally, in processes where the conversion of amorphous silicon can occur, the expansion of the sidewall material during conversion may further limit access into the feature.

[0013] Aspects of the present disclosure address the above and other deficiencies by forming a film having improved film quality. Embodiments described herein may selectively form a film (e.g., a thin film). More specifically, selectively forming a film may include depositing a flowable film using a suitable deposition process and removing a portion of the flowable film from the sidewalls using a dry etching process to obtain the remaining portion of the flowable film within the feature. The dry etching process can maintain a higher density material within the feature while removing a lower quality material from the sidewalls. In some embodiments, the dry etching process is a plasma etching process (e.g., a hydrogen (H2) etching process). This may limit or prevent sidewall coating during trench filling, thereby enabling an improved filling operation. Thus, during a selective deposition process, material can be formed in features that may not occur for the material deposited on the sidewalls.

[0014] In some embodiments, the film includes silicon (Si). For example, the film may be a Si film. The Si film may have a nitrogen (N) concentration of about 0%, a Si concentration of about 99%, and an oxygen (O) concentration of about 1%. Additionally, the Si film may have a wet etching rate of less than about 8 angstroms (Å) per minute, assuming a 1:500 dilute hydrofluoric acid (DHF) etchant for 60 seconds. The remaining portion of the Si film may have a thickness between about 5 nm and about 10 nm and a sidewall thickness of less than about 2 nm.

[0015] The deposition process may be performed using any suitable process window parameters. In some embodiments, the deposition process is performed at a temperature between about 25°C and about 100°C. More specifically, the temperature may be about 80°C. In some embodiments, the deposition process is performed at a source power between about 60 watts (W) and about 250 W. In some embodiments, the selective deposition process is performed at a bias power between about 100 W and about 200 W. In some embodiments, the deposition process is performed with a plasma pulse having a duty cycle between about 1% and about 99% and a frequency between about 1 hertz (Hz) and about 20 Hz. In some embodiments, the deposition process is performed at a pressure between about 0.5 Torr and about 5 Torr. In some embodiments, the deposition process is performed over a time range of about 5 seconds to about 15 seconds. More specifically, the deposition process may be performed over about 13 seconds.

[0016] The embodiments described herein may further process the film according to a film treatment process. The film treatment process may be used to incorporate materials into the film (e.g., the upper surface of the film). The treated film may have, for example, an improved wet etching rate relative to the wet etching rate of the film. The selective deposition process and the film treatment process may be performed in respective process chambers (e.g., the film treatment process may be an ex-situ process).

[0017] In some embodiments, the film treatment chamber is a plasma film treatment chamber for performing a plasma film treatment process. For example, the plasma film treatment process may be an inductively coupled plasma (ICP) plasma film treatment process. In some embodiments, the film treatment chamber is a nitridation chamber for performing a nitridation process. For example, the film treatment chamber may be a discrete plasma nitridation (DPN) chamber for performing a DPN process, although the plasma used need not be "discrete". For example, the film treatment chamber may be the DPN chamber of a 300 mm DPN Centura® system available from Applied Materials, Inc. of Santa Clara, California.

[0018] During the DPN process, the film may be treated by injecting nitrogen into the film using a low-energy pulsed plasma to form a desired nitrogen concentration at each interface to maintain a high channel mobility. The direct high-temperature wafer heating performed during the DPN process can generate a higher dose amount of nitrogen required for the oxynitride gates at 3X and 2X nm nodes while simultaneously achieving improved leakage voltage and threshold voltage performance. Other nitridation processes may be limited in achieving the required leakage voltage and threshold voltage.

[0019] For example, the DPN process forms a silicon nitride material (e.g., Si x N y) may be used to form. The silicon nitride material formed using the DPN process described herein may have an improved wet etching rate with respect to the Si film. For example, the silicon nitride material may have a wet etching rate of less than about 4 Å per minute, assuming a 1:500 DHF etchant for 60 seconds. In some embodiments, the silicon nitride material has a wet etching rate of less than about 1 Å per minute, assuming a 1:500 DHF etchant for 60 seconds. In some embodiments, the silicon nitride material has a wet etching rate of about 0.6 Å per minute, assuming a 1:500 DHF etchant for 60 seconds. The silicon nitride material may have an N concentration of about 55%, an Si concentration of about 45%, and an O concentration of about 0%.

[0020] The film treatment process may be performed using any suitable process window parameters. Exemplarily, in some embodiments, the DPN process may be performed at a temperature between about 200°C and about 500°C. More specifically, the temperature may be about 450°C. In some embodiments, the DPN process is performed with a source power between about 100 W and about 250 W. More specifically, the source power may be about 150 W. In some embodiments, the DPN process is performed with a bias power between about 100 W and about 600 W. More specifically, the bias power may be about 400 W. In some embodiments, the DPN process is performed at a pressure between about 5 mTorr and about 100 mTorr. In some embodiments, the DPN process is performed over a time range of about 5 seconds to about 15 seconds. More specifically, the DPN process may be performed over about 10 seconds.

[0021] The concentration of a substance (e.g., nitrogen) used to treat the film may decrease over time after the treatment. To counteract this effect, high-temperature annealing may be performed immediately after the film treatment process. The high-temperature annealing may be performed in a chamber separate from the film treatment process. For example, the high-temperature annealing performed immediately after the film treatment process may be referred to as post-nitridation annealing (PNA). PNA can also eliminate unstable bonding phases that can cause fluctuations in the threshold voltage from the nitridation process. By reducing or removing this unstable bonding phase, PNA can contribute to improved device performance.

[0022] FIG. 1 shows an electronic device manufacturing system 100 according to one or more embodiments. The electronic device manufacturing system 100 may perform one or more processes on a substrate 102. The substrate 102 may be any suitably rigid, fixed-dimension planar article suitable for fabricating an electronic device or circuit component, such as, for example, a silicon-containing disk or wafer, a patterned wafer, a glass plate, etc. In some embodiments, the substrate may be a semiconductor wafer having a diameter of, for example, 200 mm, 300 mm, or 450 mm.

[0023] The electronic device manufacturing system 100 may include a process tool 104 and a factory interface 106 coupled to the process tool 104. The process tool 104 may include a housing 108 having a transfer chamber 110 therein, and the transfer chamber 110 may have a transfer robot 112 housed therein. A plurality of process chambers 114, 116, and 118 may be coupled to the housing 108 and the transfer chamber 110. A load lock 120 may be coupled to the housing 108 and the transfer chamber 110. The transfer chamber 110, the process chambers 114, 116, and 118, and the load lock 120 may be maintained at a vacuum level. The vacuum level for the transfer chamber 110 may be in the range of, for example, about 0.01 Torr to about 80 Torr. Other vacuum levels may be used.

[0024] The transfer robot 112 may include a plurality of arms and one or more end effectors configured to transfer the substrate 102 to and from any process chamber and load lock physically coupled to the transfer chamber 110. (Note that the substrate 102 and the substrate placement positions are indicated by circles in FIG. 1.)

[0025] The same or different substrate processes may be performed on one or more substrates in each of the process chambers 114, 116, and 118. Examples of substrate processes include selective film deposition (e.g., using atomic layer deposition (ALD), physical vapor deposition (PVD), chemical vapor deposition (CVD)), nitridation, etching, annealing, curing, pre-cleaning, removal of metals or metal oxides, etc. Further details regarding selective film deposition and nitridation that may be performed to improve film quality are described herein below with respect to FIGS. 2 - 6.

[0026] The load lock 120 may be configured to connect and couple the transfer chamber 110 on one side and the factory interface 106 on the opposite side. The load lock 120 may have an environmentally controlled atmosphere that can be changed from a vacuum environment (where the substrate can be transferred to and from the transfer chamber 110) to an atmospheric pressure inert gas environment (where the substrate can be transferred to and from the factory interface 106).

[0027] In some embodiments, the load lock 120 may be a stacked load lock having a pair of upper internal chambers and a pair of lower internal chambers disposed at different vertical levels (e.g., one above the other). In some embodiments, the pair of upper internal chambers may be configured to receive a processed substrate from the transfer chamber 110 for removal from the process tool 104, while the pair of lower internal chambers may be configured to receive a substrate from the factory interface 106 for processing in the process tool 104. In some embodiments, the load lock 120 may be configured to perform a substrate process (e.g., etching and / or pre-cleaning) on one or more substrates 102 received therein.

[0028] The factory interface 106 may be any suitable housing, such as, for example, an equipment front end module or EFEM. The factory interface 106 may be configured to receive the substrate 102 from a substrate carrier 122 (which may be, for example, a front opening unified pod or FOUP) docked at various load ports 124 of the factory interface 106. A factory interface robot 126 (shown in dashed lines) may be used to transfer the substrate 102 between the substrate carrier 122 and the load lock 120. Any suitable robot type may be used for the factory interface robot 126. The transfer may be performed in any order or direction. The factory interface 106 may be maintained, for example, in a slightly positive pressure non-reactive gas environment (using nitrogen as the non-reactive gas, for example).

[0029] The movement of the transfer robot 112 and the factory interface robot 126, and the transfer of the substrate 102 within and / or between the process chambers 114, 116, and 118, the load lock 120, the factory interface 106, and the substrate carrier 122 may be controlled by a motor drive system (not shown in FIG. 1) that may include a plurality of servo motors or stepper motors.

[0030] The electronic device manufacturing system 100 may include at least one system controller 128. The system controller 128 may be coupled to each of the active hardware components and control their operation. The system controller 128 may include a programmable processor, memory for storing processor-executable instructions / software programs / firmware, various support circuits, and input / output circuits. The system controller 128 may be configured to allow for input and display of data, operational commands, etc. by a human operator.

[0031] Electronic device manufacturing system 100 may further include motion controller 130. Motion controller 130 may include a programmable processor, memory for storing processor-executable instructions / software programs / firmware, various support circuits, and input / output circuits. Motion controller 130 may operate in a closed-loop position control system, which may be referred to as a servo control system, to collect and process data from actuator (motion) equipment in electronic device manufacturing system 100 by using various devices that may be coupled to a network both internal and external to the actuator (motion) drivers of the actuator (motion) equipment for higher-level monitoring tasks beyond motor commutation. Motion controller 130 may operate independently of system controller 128, may provide information to system controller 128, and / or may be controlled by system controller 128. Alternatively, system controller 128 may perform the functions of motion controller 130, and motion controller 130 may be omitted from electronic device manufacturing system 100.

[0032] Although process variation tolerances in the semiconductor industry continue to decrease as semiconductor device sizes shrink, tightly controlled differences between process components must be maintained during substrate processing (e.g., deposition, annealing, curing, etching, and other processing of films on substrates in a process chamber or load lock).

[0033] The process components may include a substrate support and a process delivery apparatus. The substrate support apparatus may include a single-axis or multi-axis actuator (e.g., a motor) and may have a single-slot or multi-slot (two or more vertical) stacked substrate with a lift, elevator, or indexer for transporting and supporting the substrate. Various embodiments of the process delivery apparatus may have an actuator that can be used to place a process delivery assembly (e.g., a pattern mask and / or a plasma, gas, or heat distribution assembly) inside a process chamber or a load lock. Examples of such assemblies include a cathode assembly in an etching process chamber or load lock, a heater pedestal assembly and a gas distribution showerhead assembly in a chemical vapor deposition and atomic layer deposition process chamber, and a substrate pattern masking assembly in a bevel etching process chamber or load lock. Bevel edge etching may be used to remove unwanted portions of the deposited film in the edge region of the substrate.

[0034] FIG. 2 is a schematic cross-sectional view of an exemplary process chamber (“chamber”) 200 for selectively forming a film on a substrate, according to some embodiments. For example, chamber 200 may be one of process chambers 114-118 described above with respect to FIG. 1. Chamber 200 may be utilized to form a film layer according to some embodiments of the present technology, but it should be understood that the method may be similarly implemented in any chamber in which film formation can be performed internally. Chamber 200 may be utilized in a method that may include the formation, processing, etching, or conversion of materials for a semiconductor structure, in some embodiments. It should be understood that the chamber described is not to be considered limiting, and any chamber configured to perform the operations described may be similarly used.

[0035] As shown in FIG. 2, the chamber 200 may include a chamber body 202, a substrate support 204 disposed inside the chamber body 202, and a lid assembly 206 coupled to the chamber body 202 and sealing the substrate support 204 in the processing volume 220. The substrate 203 may be provided in the processing volume 220 through an opening 226 that can be sealed for processing using a slit valve or a door. The substrate 203 may seat on the surface 205 of the substrate support 204 during processing. The substrate support 204 may be rotatable along an axis 247 where a shaft 244 of the substrate support 204 can be disposed, as indicated by the arrow 245. Alternatively, the substrate support 204 may be raised to rotate as needed during the deposition process.

[0036] A plasma profile modulator 211 may be disposed in the chamber 200 to control the plasma distribution over the substrate 203 disposed on the substrate support 204. The plasma profile modulator 211 may include a first electrode 208 that may be disposed adjacent to the chamber body 202, and may separate the chamber body 202 from other components of the lid assembly 206. The first electrode 208 may be part of the lid assembly 206 or may be a separate sidewall electrode. The first electrode 208 may be an annular or ring-shaped member and may be a ring electrode. The first electrode 208 may be a continuous loop around the perimeter of the process chamber 200 surrounding the processing volume 220, or may be discontinuous at selected locations if necessary. The first electrode 208 may be a perforated electrode such as a perforated ring or a mesh electrode, or may be a plate electrode such as a secondary gas distributor for example.

[0037] One or more isolators 210 a, 210 b, which may be a dielectric material such as ceramic or a metal oxide (e.g., aluminum oxide and / or aluminum nitride), may contact the first electrode 208 and electrically and thermally isolate the first electrode 208 from the gas distributor 212 and the chamber body 202. The gas distributor 212 may define apertures 218 for distributing process precursors to the processing volume 220. The gas distributor 212 may be coupled to a first power source 242, such as an RF generator, an RF power supply, a DC power supply, a pulsed DC power supply, a pulsed RF power supply, or any other power source that may be coupled to the process chamber 200. In some embodiments, the first power source 242 may be an RF power supply.

[0038] The gas distributor 212 may be a conductive gas distributor or a non-conductive gas distributor. The gas distributor 212 may be formed from conductive and non-conductive components. For example, the body of the gas distributor 212 may be conductive, while the faceplate of the gas distributor 212 may be non-conductive. The gas distributor 212 may be powered by a first power source 242, for example, as shown in FIG. 2, or the gas distributor 212 may be coupled to ground in some embodiments.

[0039] The first electrode 208 may be coupled to a first adjustment circuit 228 that can control the ground path of the chamber 200. The first adjustment circuit 228 may include a first electronic sensor 230 and a first electronic controller 234. The first electronic controller 234 may be or include a variable capacitor or other circuit element. The first adjustment circuit 228 may be or include one or more inductors 232. The first adjustment circuit 228 may be any circuit that realizes a variable or controllable impedance under the plasma conditions present in the processing volume 220 during processing. In some of the illustrated embodiments, the first adjustment circuit 228 may include a first circuit leg and a second circuit leg coupled in parallel between the ground and the first electronic sensor 230. The first circuit leg may include a first inductor 232A. The second circuit leg may include a second inductor 232B coupled in series with the first electronic controller 234. The second inductor 232B may be disposed between the first electronic controller 234 and a node that connects both the first circuit leg and the second circuit leg to the first electronic sensor 230. The first electronic sensor 230 may be a voltage or current sensor and may be coupled to the first electronic controller 234, which may provide some degree of closed-loop control of the plasma conditions inside the processing volume 220.

[0040] The second electrode 222 may be coupled to the substrate support 204. The second electrode 222 may be embedded within the substrate support 204 or coupled to the surface of the substrate support 204. The second electrode 222 may be a plate, perforated plate, mesh, wire screen, or any other distributed arrangement of conductive elements. The second electrode 222 may be an adjustment electrode and may be coupled to the second adjustment circuit 236, for example by a cable, to a condit 246 having a selected resistance, such as 50 ohms, disposed on the shaft 244 of the substrate support 204. The second adjustment circuit 236 may include a second electronic sensor 238 and a second electronic controller 240 which may be a second variable capacitor. The second electronic sensor 238 may be a voltage or current sensor and may be coupled to the second electronic controller 240 to provide further control over the plasma conditions in the processing volume 220.

[0041] A third electrode 224, which may be a bias electrode and / or an electrostatic chuck electrode, may be coupled to the substrate support 204. The third electrode may be coupled to a second power source 250 through a filter 248 which may be an impedance matching circuit. The second power source 250 may be DC power, pulsed DC power, RF bias power, a pulsed RF source or bias power, or a combination thereof or other power source. In some embodiments, the second power source 250 may be RF bias power.

[0042] The lid assembly 206 and the substrate support 204 of FIG. 2 may be used with any process chamber for plasma or heat treatment. During operation, the process chamber 200 may provide real-time control of plasma conditions in the processing volume 220. The substrate 203 may be disposed on the substrate support 204, and process gas may flow through the lid assembly 206 using the inlet 214 according to any desired flow plan. The inlet 114 may include a remote plasma source unit 216 that may be fluidly coupled to the chamber, and in some embodiments, delivery from a bypass 217 for process gas delivery that may not flow through the remote plasma source unit 216. The gas may exit the chamber 200 through the outlet 252. Power may be coupled to the gas distributor 212 to establish plasma in the processing volume 220. In some embodiments, an electrical bias may be applied to the substrate using a third electrode 224.

[0043] When energy is imparted to the plasma in the processing volume 220, a potential difference may be established between the plasma and the first electrode 208. A potential difference may also be established between the plasma and the second electrode 222. The electronic controllers 234, 240 may then be used to adjust the flow characteristics of the ground path represented by the two adjustment circuits 228 and 236. Setpoints may be provided to the first adjustment circuit 228 and the second adjustment circuit 236 to provide independent control of the deposition rate and plasma density uniformity from the center to the edge. In embodiments where both of those electronic controllers may be variable capacitors, an electronic sensor may adjust the variable capacitors to independently maximize the deposition rate and minimize thickness non-uniformity.

[0044] Each of the tuning circuits 228, 236 may have a variable impedance that can be adjusted using respective electronic controllers 234, 240. When the electronic controllers 234, 240 are variable capacitors, the capacitance range of each variable capacitor, as well as the inductance of the first inductor 232A and the second inductor 232B, may be selected to provide an impedance range. This range may depend on the frequency and voltage characteristics of the plasma, which may have a minimum value within the capacitance range of each variable capacitor. Thus, when the capacitance of the first electronic controller 234 is at a minimum or maximum value, the impedance of the first tuning circuit 228 may be high, and as a result, a plasma shape with a minimum aerial or lateral coverage rate on the substrate support is obtained. As the capacitance of the first electronic controller 234 approaches a value that minimizes the impedance of the first tuning circuit 228, the aerial coverage rate of the plasma may increase to a maximum value, effectively covering the entire working area of the substrate support 204. As the capacitance of the first electronic controller 234 moves away from the minimum impedance setting, the plasma shape may contract from the chamber wall, and the aerial coverage rate of the substrate support may decrease. The second electronic controller 240 may have a similar effect, and as the capacitance of the second electronic controller 240 can be varied, the aerial coverage rate of the plasma across the substrate support may increase or decrease.

[0045] The electronic sensors 230, 238 may be used to adjust the respective circuits 228, 236 in a closed loop. Depending on the type of sensor used, a current or voltage setpoint may be installed in each sensor, and the sensor may be provided with control software that determines the adjustment for each respective electronic controller 234, 240 to minimize the deviation from the setpoint. As a result, the plasma shape may be selected and dynamically controlled during processing. It should be understood that the above discussion is based on the electronic controllers 234, 240 that can be variable capacitors, but any electronic component with adjustable characteristics may be used to provide the tuning circuits 228 and 236 with adjustable impedance.

[0046] FIG. 3 is a flowchart of a method 300 for selectively forming a film on a substrate according to some embodiments. The method 300 may include a plurality of optional operations that may or may not be specifically associated with some embodiments of the methods according to the present technology. For example, many of those operations are described to provide a wider range of structure formation, but are not decisive for the present technology and may be performed by alternative methodologies that will be readily understood. The method 300 may describe the operations schematically shown in FIGS. 4A-4C, and those illustrations will be described in relation to the operations of the method 300. It should be understood that each figure shows only a partial schematic diagram, and the substrate may include any number of additional materials and features having various characteristics and aspects as shown in each figure.

[0047] The method 300 may include additional operations before the start of the operations listed. For example, the additional processing operations may include forming a structure on a semiconductor substrate, which may include both the formation and removal of materials. For example, a transistor structure, a memory structure, or any other structure may be formed. The preprocessing operations may be performed in a chamber in which the method 300 can be executed, or the processing may be executed in one or more other process chambers before delivering the substrate to a semiconductor process chamber or a chamber in which the method 300 can be performed. Nevertheless, the method 300 may include loading the substrate into a process chamber such as chamber 200 of FIG. 2, or another chamber that may include components as described above. The substrate may be placed on a substrate support, which may be a pedestal such as substrate support 204 of FIG. 2 and may be present in the processing region of a process chamber such as processing volume 220 of FIG. 2.

[0048] The substrate on which several operations may have been performed may be substrate 405 of structure 400, which may show a partial view of a substrate on which semiconductor processing may be performed. It should be understood that structure 400 may show only a few upper layers during processing for purposes of exemplifying aspects of the present technology. Substrate 405 may include a material in which one or more features 410 may be formed. Substrate 405 may be any number of materials used in semiconductor processing. The substrate material may be, or may include, or may be a combination of any number of, silicon, germanium, a dielectric material including silicon oxide or silicon nitride, a metallic material, and these may be substrate 405 or may be materials formed in structure 400. Feature 410 may be characterized by any shape or configuration according to the present technology. In some embodiments, the feature may be, or may include, a trench structure or an aperture formed within substrate 405.

[0049] Feature 410 may be characterized by any shape or size, but in some embodiments, Feature 410 may be characterized by a higher aspect ratio, i.e., the ratio of the depth of the feature to the width of the feature. For example, in some embodiments, Feature 310 may be characterized by an aspect ratio greater than or around 5:1, greater than or around 10:1, greater than or around 15:1, greater than or around 20:1, greater than or around 25:1, greater than or around 30:1, greater than or around 40:1, greater than or around 50:1, or greater than that. Additionally, the feature may be characterized by a narrow width or diameter of the feature including between two sidewalls, such as a dimension less than or around 20 nm, less than or around 15 nm, less than or around 12 nm, less than or around 10 nm, less than or around 9 nm, less than or around 8 nm, less than or around 7 nm, less than or around 6 nm, less than or around 5 nm, or less than that of the feature.

[0050] In some embodiments, Method 300 may include optional processing operations such as a pre - treatment that may be performed to prepare the surface of substrate 405 for deposition. Once prepared, Method 300 may include delivering one or more precursors to a processing region of a semiconductor process chamber that houses Structure 400. The precursors may include one or more silicon - containing precursors, in addition to one or more diluents or carrier gases such as an inert gas or other gas delivered with the silicon - containing precursor. In operation 310, a plasma may be formed from the deposition precursor (e.g., a silicon - containing precursor). The plasma may be formed within the processing region, thereby enabling the deposition material to be deposited on the substrate. For example, in some embodiments, a capacitively - coupled plasma may be formed within the processing region by applying a plasma output to the aforementioned faceplate.

[0051] In operation 320, a flowable film may be deposited on the substrate. The deposition material of the flowable film may at least partially flow into the features on the substrate so as to provide bottom-up type gap filling. As shown in FIG. 4A, material 415 may be deposited on substrate 405 and may flow into trench or feature 410. As shown, material 415 may flow into the bottom of the feature, but as shown by material 417, some amount of material may remain on the sidewalls of the substrate, and in addition, as shown by material 419, material may remain on the top of the feature or in between. The amount deposited may be relatively small, but the residual material on the sidewalls may limit subsequent flow. In addition, when the deposited material is converted, such as conversion to silicon nitride, this conversion will be accompanied by film expansion. In features with reduced dimensions, the residual material formed on the sidewalls may be converted and expand outward toward the opposite sidewall. This may result in pinch-off of the feature that may form voids within the feature.

[0052] In some embodiments, the film comprises a silicon material (e.g., amorphous Si). The silicon material may be formed from the plasma emissions of a silicon-containing precursor. For example, the film may be a Si film. The Si film deposited using the selective deposition process described herein may have a nitrogen (N) concentration of about 0%, a Si concentration of about 99%, and an oxygen (O) concentration of about 1%. In addition, the Si film deposited using the selective deposition process described herein may have a wet etching rate of less than about 8 angstroms (Å) per minute, assuming a 1:500 DHF etchant for 60 seconds. The Si film deposited using the selective deposition process may have a bottom layer thickness between about 5 nm and about 10 nm, and a sidewall thickness of less than about 2 nm.

[0053] The selective deposition process may be performed using any suitable process window parameters. In some embodiments, the selective deposition process is performed at a temperature between about 25°C and about 80°C. In some embodiments, the selective deposition process is performed at a source power between about 60 W and about 250 W. In some embodiments, the selective deposition process is performed at a bias power between about 100 W and about 200 W. In some embodiments, the selective deposition process is performed with a plasma pulse having a duty cycle between about 1% and about 99% and a frequency between about 1 hertz (Hz) and about 20 Hz. In some embodiments, the selective deposition process is performed at a pressure between about 0.5 Torr and about 5 Torr.

[0054] The power applied during deposition may be a lower power plasma, which may limit dissociation and may maintain some amount of hydrogen incorporation in the deposited material. This incorporated hydrogen may contribute to the fluidity of the deposited material. Additionally, the technology may incorporate a bias process that can cause treatment to the deposited film during the deposition operation. The process may include utilizing, in addition to source power coupled to, for example, a faceplate or showerhead as described above, bias power applied through, for example, a substrate support as discussed above. The source power may be used to effect controlled dissociation of a silicon-containing precursor, which may limit dissociation and may allow for the formation of longer material chains. When these materials contact the substrate, the longer chain silicon-containing materials may have increased fluidity, which may improve bottom-up filling.

[0055] In some embodiments, to facilitate dissociation and deposition, the deposition precursor may include one or more inert gases such as argon and / or helium, which may help improve dissociation. Additionally, in some embodiments, the deposition precursor may include diatomic hydrogen, which may be flowed to facilitate the processing during deposition and may be assisted by the application of bias power. For example, hydrogen may be delivered with the silicon-containing precursor at a flow rate ratio of hydrogen to silicon-containing precursor greater than 0.5:1 or around that, greater than 1:1 or around that, greater than 1.5:1 or around that, greater than 2:1 or around that, greater than 2.5:1 or around that, greater than 3.0:1 or around that, greater than 3.5:1 or around that, greater than 4.0:1 or around that, or greater than that.

[0056] These radical species of hydrogen and inert gas may transfer energy to the materials along the bottom and top of the feature, e.g., materials such as 415 and 419, along the plane perpendicular to the direction of travel. The energy may help release excess hydrogen, which may densify the film at these locations. As shown in FIG. 4B, the material 417 along the sidewall may be unaffected or may undergo limited changes, while the materials 415 and 419 may be densified, which may improve the quality of the material. As a result, in some embodiments, the materials along the top and bottom of the structure may be characterized by higher quality, including an increased density, relative to the materials that may be deposited along the sidewalls of the feature.

[0057] However, by utilizing bias power, the deposition plasma is often characterized by increased power, which may further dissociate the silicon-containing precursor and reduce fluidity. Therefore, to limit this effect, the bias power may be pulse output at a pulse frequency less than or around 10 kHz, less than or around 5 kHz, less than or around 1 kHz, less than or around 500 Hz, less than or around 100 Hz, less than or around 50 Hz, less than or around 10 Hz, or less than that frequency. Additionally, the duty cycle may be operated at less than or around 50%, less than or around 40%, less than or around 30%, less than or around 20%, less than or around 10%, less than or around 5%, or around 1%, which may further reduce the influence of the bias power. By operating the bias power at a very low pulse frequency and duty cycle, the bias power may be utilized to improve the film quality at the top of the structure and the bottom of the feature while limiting the impact on any other deposition characteristics. Additionally, by utilizing low power, there may not be enough energy given to hydrogen to cause etching of the deposited material or to result in sputtering of the material based on the implantation of inert gas emissions.

[0058] After a certain amount of deposition, in some embodiments, an etching process configured to selectively etch back the formed material may be performed. This process may be performed in the same chamber as the deposition and may be performed in a cyclic process to fill the features. In some embodiments, the flow of the silicon-containing precursor may be stopped and the processing area may be purged. The flow of an inert gas such as argon and / or helium may also be stopped. After purging, a hydrogen-containing precursor may be flowed into the processing area of the process chamber. In some embodiments, the etching process may include only a hydrogen-containing precursor which may be diatomic hydrogen in some embodiments. In operation 330, a modified plasma (e.g., an etching plasma) may be formed, which may be a capacitively coupled plasma formed within the processing area, although in some embodiments an inductively coupled plasma may be equally applicable.

[0059] Similar to the deposition process, during the etching operation, an additional power source may be connected and coupled to the substrate support as described above to bias the plasma generated above the substrate. Thus, the etching process may include both source power and bias power. This may attract the plasma emissions to the substrate, which may collide with the film and cause densification of the deposited material, especially the material that has already been at least partially improved by the processes performed during deposition. Any hydrogen-containing material may be used, although in some embodiments, diatomic hydrogen may be used as the hydrogen-containing precursor to generate the etching plasma. Hydrogen radicals and ions may easily penetrate the material formed within the trench, release the incorporated hydrogen from the film, and cause densification. The applied bias power may be relatively low to limit sputtering of the generated film and any potential damage to the structure. Additionally, by adjusting the applied source power and bias power, the etching operation may be performed, which may limit the effect on the previously processed material while reducing the sidewall coverage of the deposited material.

[0060] To generate plasma in the processing region by delivering power from a plasma output source to the faceplate, diatomic hydrogen, or any other hydrogen-containing material may be utilized. The plasma output in some embodiments may be greater than the plasma output used during deposition, from both the source power and the bias power. For example, the delivered plasma source power may be greater than or around 100 W, greater than or around 200 W, greater than or around 300 W, greater than or around 400 W, greater than or around 500 W, or greater than that. By increasing the plasma output during processing plasma formation, a greater amount of plasma emissions may be generated. However, as the plasma output increases, the amount of material etched from the bottom of the structure may also increase. Thus, in some embodiments, the plasma source power may be maintained at a value less than or around 500 W, less than or around 400 W, less than or around 300 W, or less than that. Additionally, the manner of the bias power may be adjusted. For example, in some processing operations, the bias power may be higher than the plasma source power, which may provide sufficient power to the plasma to ensure that etching of lower quality materials, such as materials along sidewalls that may not be processed during deposition operations, occurs.

[0061] By applying a larger bias power, the ability of hydrogen to etch the deposited material may be increased. The bias power during deposition may be reduced to limit the etching effect, but during the etching operation, the bias power, which may be at any of the frequencies shown above, may be increased to greater than 500 W or values around it, greater than 800 W or around it, greater than 1000 W or around it, greater than 1200 W or around it, greater than 1400 W or around it, greater than 1600 W or around it, greater than 1800 W or around it, or to even greater values. However, since the bias power may impart directivity, the bias power may be pulse-output as discussed below, which may serve to maintain the previously processed material while achieving etching of lower quality materials. In operation 340, the plasma emissions may then modify (e.g., etch) the fluidity film and may remove a portion of the fluidity film from the sidewalls of the feature.

[0062] At the same time and beneficially, the more directionally delivered plasma emissions may penetrate well through the remaining fluid film formed at the bottom of the feature and may reduce hydrogen mixing to densify the fluid film in optional operation 350. As shown in FIG. 4C, material 417 may be removed from the sidewalls and overhang regions of substrate 405, which may maintain the deposited material at the bottom region of the feature and also along the top region of the structure. As an additional advantage, the densified material 419 at the top of the structure may protect the underlying material from damage by limiting any effects on the material. The process may achieve a reduced hydrogen mixing in the remaining material, such as a hydrogen mixing of less than or around 40 atomic percent (at.%), less than or around 35 at.%, less than or around 30 at.%, less than or around 25 at.%, less than or around 20 at.%, less than or around 15 at.%, less than or around 10 at.%, less than or around 5 at.%, or less than that.

[0063] Additional adjustments may be made to further increase the etching of the deposited material along the sidewalls of the feature by adjusting one or more characteristics of the supplied plasma output or bias power. For example, in some embodiments, both the plasma output source and the bias power source may be operated in continuous wave mode. Additionally, one or both of these power sources may be operated in pulse mode. In some embodiments, the bias power may be operated in pulse mode while the source power may be operated in continuous wave mode. The pulse frequency of the bias power may be any of the pulse frequencies described above. The duty cycle of the bias power may be less than 75% or around it, and the bias power may be less than 70% or around it, less than 60% or around it, less than 50% or around it, less than 40% or around it, less than 30% or around it, less than 20% or around it, less than 10% or around it, less than 5% or around it, or less than that and may be operated with a reduced duty cycle such as an on-time duty less than 50% or around it. Operating the bias power with a reduced duty cycle, such as an on-time duty less than 50% or around it, may allow for more isotropic etching within the feature for a longer time per cycle, for example during the off-time, which may better remove material from the sidewalls.

[0064] Additional power configurations may include some degree of synchronization of the source power and bias power in a master / slave relationship. For example, both power sources may be operated in a pulsed orientation, with the bias power synchronized to turn on after the source power turns on in each pulse. An inter-level pulse scheme may also be applied. For example, during the bias power on-duty, the source power may be operated at a first plasma power. During the remaining cycle when the bias power is off, the source power may be operated at a second plasma power, which may be greater than the first plasma power. This may both enhance isotropic etching by eliminating bias-induced directionality and may enhance the etching characteristics of the isotropic etch. The deposition and etching process may be repeated cyclically any number of times to fill a feature in embodiments of the present technology, which may fill a feature with amorphous silicon.

[0065] Additionally, in some embodiments where conversion of silicon within a feature may be desired, the cycling may include a conversion operation. By performing the conversion during each cycle, feature penetration issues may be completely resolved. Also, by performing the conversion operation after curing and etching, deposited material may be removed from the sidewalls before conversion, which may limit lateral film expansion within the trench or feature between the sidewalls as described above. While the conversion may be performed in a different chamber from the deposition and processing, in some embodiments, two or more operations, including all operations, may be performed in a single process chamber. This may reduce queue times relative to conventional processes.

[0066] Method 300 may optionally include conversion of the fluidity film in operation 360. For example, after etching and densification, one or more conversion precursors may be delivered to the processing region of the chamber. For example, a nitrogen-containing precursor, an oxygen-containing precursor, and / or a carbon-containing precursor may be delivered to the processing region of the chamber along with any carrier gas or dilution gas. Plasma may be formed from the conversion precursor, which may then contact the amorphous silicon material within the feature. The plasma emissions of the conversion precursor interact with the amorphous silicon material within the trench and convert the material to silicon nitride, silicon oxide, silicon carbide, silicon oxynitride, silicon oxycarbide, silicon carbonitride, or silicon oxycarbonitride, along with any other material that may be used to convert the amorphous silicon film. The plasma output may be similar to the power described above. For example, the plasma output may be from about 100 W to a maximum of about 1,000 W or more in a capacitively coupled system, or up to 10 kW or more in an inductively coupled plasma system, although any type of conversion may be performed.

[0067] Deposits can be formed up to several nanometers or more, but by performing the etching process as described above, the thickness of the densified material may be controlled to be less than 500 Å or around that thickness, less than 450 Å or around it, less than 400 Å or around it, less than 350 Å or around it, less than 300 Å or around it, less than 250 Å or around it, less than 200 Å or around it, less than 150 Å or around it, less than 100 Å or around it, less than 50 Å or around it, or less than that. By controlling the thickness of the deposited material, conversion throughout the thickness may be more easily performed, and the penetration problems common to conventional processes may be solved. After conversion of the deposited material, the process may then be completely repeated to continue generating the converted material throughout the feature.

[0068] Regarding the deposition precursors used during any of the forming operations, any number of precursors may be used in the present technology. The silicon-containing precursors that may be used during any silicon formation, silicon oxide formation, or silicon nitride formation include, but are not limited to, silane (SiH4), disilane (Si2H6), trisilane, or other organosilanes including cyclohexasilane, silicon tetrafluoride (SiF4), silicon tetrachloride (SiCl4), dichlorosilane (SiH2Cl2), tetraethyl orthosilicate (TEOS), and any other silicon-containing precursors that may be used for forming silicon-containing films. By utilizing higher-order silanes, longer material chains may be generated, thereby increasing fluidity in some embodiments. The silicon-containing material may be nitrogen-free, oxygen-free, and / or carbon-free in some embodiments. The oxygen-containing precursors used in any of the operations described throughout the present technology may include O2, N2O, NO2, O3, H2O, and any other oxygen-containing precursors that may be used for forming silicon oxide films or other films. The nitrogen-containing precursors used in any of the operations may include N2, N2O, NO2, NH3, N2H2, and any other nitrogen-containing precursors that may be used for forming silicon nitride films. The carbon-containing precursors may be or include any carbon-containing material such as any hydrocarbon, or any other precursor containing carbon. During any of the operations, an inert precursor that may include Ar, He, Xe, Kr, or one or more additional precursors such as other materials like nitrogen, ammonia, hydrogen, or other precursors may be included.

[0069] FIG. 5 is a schematic diagram of a membrane treatment system 500 according to some embodiments. The membrane treatment system 500 includes a membrane treatment chamber 502 for performing a membrane treatment process. The membrane treatment chamber 502 may include a chamber housing 506 adapted to surround a process kit portion including a first electrode 508 disposed above a susceptor 510 that supports a substrate 512 during processing. The chamber housing 502 may include various inlets and outlets (not shown) provided for flowing a process gas and / or a coolant. The membrane treatment system 500 may further include a system controller 504 coupled to the nitriding chamber (wirelessly, etc., via one or more wires or cables). The system controller 504 may include one or more microprocessors, microcontrollers, dedicated hardware, combinations thereof, etc. In some embodiments, the system controller 504 is configured (e.g., programmed) to cause a high-reactivity plasma process to be performed in the membrane treatment chamber 502 before the substrate is loaded into the membrane treatment chamber 502 in order to perform a membrane treatment on the substrate. Such a high-reactivity plasma step may be performed before each substrate is processed (e.g., plasma for each substrate), or after some other number of substrates have been processed in the chamber. The system controller 504 may be adapted to control other processes, for example, according to the membrane treatment process performed in the membrane treatment chamber 502.

[0070] The membrane treatment chamber 502 may include any suitable membrane treatment chamber. In some embodiments, the membrane treatment chamber 502 is a plasma membrane treatment chamber, and the system controller 504 is configured to cause a plasma membrane treatment process to be performed within the membrane treatment chamber 502. For example, the plasma membrane treatment process may be an inductively coupled plasma (ICP) plasma membrane treatment process. In some embodiments, the membrane treatment chamber 502 is a nitridation chamber, and the system controller 504 is configured to cause a nitridation process to be performed within the membrane treatment chamber 502. For example, the membrane treatment chamber 502 may be a discrete plasma nitridation (DPN) chamber, and the nitridation process may be a DPN process, although the plasma used need not be "discrete". For example, the membrane treatment chamber 502 may be the DPN chamber of a 300 mm DPN Centura® system available from Applied Materials, Inc. of Santa Clara, California. Further details regarding the membrane treatment process performed within the membrane treatment chamber 502 are described below with respect to FIG. 6.

[0071] FIG. 6 is a flowchart of a method 600 for forming a membrane having improved membrane quality, according to some embodiments. The method 600 may include a plurality of optional operations that may or may not be specifically associated with some embodiments of the methods according to the present technology. For example, many of those operations are described to provide a broader range of structure formation, but are not decisive for the present technology and may be performed by alternative methodologies that will be readily understood.

[0072] In operation 610, a substrate is loaded into a process chamber of an electronic device manufacturing system. For example, at least one system controller may cause the substrate to be loaded into the process chamber. More specifically, at least one system controller may cause the transfer robot to load the substrate onto a substrate support within the process chamber. For example, the electronic device manufacturing system may be the electronic device manufacturing system 100 of FIG. 1, the process chamber may be one of process chambers 114, 116, 118 (e.g., chamber 200 of FIG. 2), the transfer robot may be the transfer robot 112 of FIG. 1, and at least one system controller may include the system controller 128 of FIG. 1.

[0073] In operation 620, a film is selectively formed on the substrate within the process chamber. For example, at least one system controller may cause a film to be selectively formed on the substrate within the process chamber. More specifically, at least one system controller may cause a first input stream to be supplied into a processing volume of the process chamber to deposit a fluid film (e.g., a Si film) on the substrate, and cause a second input stream to be supplied into the processing volume to remove (e.g., etch) a portion of the fluid film from sidewalls of features of the substrate to obtain a remaining portion of the fluid film. The first input stream may include a plasma emission of a first precursor, and the second input stream may include a plasma emission of a second precursor. In some embodiments, the first precursor is a silicon-containing precursor and the second precursor is a hydrogen-containing precursor.

[0074] The deposition process may be performed using any suitable process window parameters. In some embodiments, the deposition process is performed at a temperature between about 25°C and about 100°C. More specifically, the temperature may be about 80°C. In some embodiments, the deposition process is performed at a source power between about 60 W and about 250 W. In some embodiments, the selective deposition process is performed at a bias power between about 100 W and about 200 W. In some embodiments, the deposition process is performed with a plasma pulse having a duty cycle between about 1% and about 99% and a frequency between about 1 Hertz (Hz) and about 20 Hz. In some embodiments, the deposition process is performed at a pressure between about 0.5 Torr and about 5 Torr. In some embodiments, the deposition process is performed over a time range of about 5 seconds to about 15 seconds. More specifically, the deposition process may be performed over about 13 seconds.

[0075] Selectively forming the film may further include densifying the film. For example, at least one system controller may densify the remaining portion of the fluid membrane. More specifically, at least one system controller may reduce the hydrogen content of the remaining portion of the fluid membrane by feeding a third input stream into the processing volume to obtain a densified film. The third input stream may include a plasma emission of a third precursor. In some embodiments, the third precursor is a hydrogen-containing precursor. Further details regarding the selective membrane deposition process are described above with respect to FIGS. 1-4.

[0076] In operation 630, the substrate is transferred from the process chamber to the film processing chamber. For example, at least one system controller may cause the substrate to be transferred from the process chamber to the film processing chamber. More specifically, at least one system controller may cause the transfer robot to remove the substrate from the process chamber, rotate it to be aligned with the film processing chamber, and place the substrate on a substrate support within the film processing chamber. For example, the film processing chamber may be one of the process chambers 114, 116, 118 of FIG. 1 (e.g., the film processing chamber 502 of FIG. 5).

[0077] In operation 640, the film is processed within the film processing chamber. For example, at least one system controller may cause the film to be processed within the film processing chamber according to a film processing process. More specifically, at least one system controller may cause the remaining portion of the fluid film to be processed within the film processing chamber according to a film processing process. In some embodiments, a highly reactive plasma process is performed within the film processing chamber before the film processing process is carried out.

[0078] The film processing process may include a plasma film processing process. For example, the plasma film processing process may be an ICP plasma film processing process. In some embodiments, the film processing chamber is a nitriding chamber, and the film processing process includes a nitriding process. In some embodiments, the film processing process may be a DPN process.

[0079] For example, the DPN process is from a Si film to a silicon nitride material (e.g., Si x N y) may be used to form. The silicon nitride material formed using the DPN process described herein may have a wet etching rate of less than about 4 Å per minute, assuming a 1:500 DHF etchant for 60 seconds. In some embodiments, the silicon nitride material has a wet etching rate of less than about 1 Å per minute, assuming a 1:500 DHF etchant for 60 seconds. In some embodiments, the silicon nitride material has a wet etching rate of about 0.6 Å per minute, assuming a 1:500 DHF etchant for 60 seconds. The silicon nitride material may have a N concentration of about 55%, a Si concentration of about 45% and an O concentration of about 0%.

[0080] During the DPN process, nitrogen may be implanted into the film. For example, at least one system controller may introduce a low-energy pulsed plasma into the DPN chamber to form a desired nitrogen concentration at each interface to maintain high channel mobility. The at least one system controller may further cause direct high-temperature heating to produce a higher dose amount of nitrogen for oxynitride gates at 3X and 2X nm nodes while simultaneously achieving improved leakage voltage and threshold voltage performance. Other nitridation processes may be limited in achieving the required leakage voltage and threshold voltage.

[0081] The membrane treatment process may be performed using any suitable process window parameters. Exemplarily, to perform the DPN process, at least one system controller may set the temperature of the DPN chamber in the range between about 200°C and about 500°C. More specifically, the temperature may be about 450°C. At least one system controller may set the source power in the range between about 100 W and about 250 W. At least one system controller may set the bias power in the range between about 100 W and about 600 W. At least one system controller may set the pressure of the DPN chamber in the range between about 5 milliTorr and about 100 milliTorr. At least one system controller may cause the DPN process to be performed over a time range between about 5 seconds and about 15 seconds. More specifically, the DPN process may be performed over about 10 seconds.

[0082] Any additional post-treatment steps (e.g., deposition, etching, annealing) may be used. For example, the concentration of a substance (e.g., nitrogen) used to treat the membrane may decrease over time after treatment. To counteract this effect, at least one system controller may cause a high-temperature anneal to be performed immediately after the membrane treatment process. The high-temperature anneal may be performed in a chamber separate from the membrane treatment process. For example, the high-temperature anneal may be a PNA process performed after nitridation to eliminate unstable bonding phases that can cause fluctuations in the threshold voltage. By reducing or removing this unstable bonding phase, the PNA can contribute to improved device performance.

[0083] In operation 650, the substrate is removed from the membrane treatment chamber. For example, at least one system controller may cause the substrate to be removed from the membrane treatment chamber. More specifically, at least one system controller may cause the transfer robot to remove the substrate from the membrane treatment chamber.

[0084] In some embodiments, the substrate may then be placed in another process chamber for further post - processing. For example, at least one system controller may cause the substrate to be placed in another process chamber. More specifically, at least one system controller may cause the transfer robot to place the substrate in another process chamber.

[0085] In some embodiments, the substrate may then be placed in a load lock (e.g., load lock 120 of FIG. 1). For example, at least one system controller may cause the substrate to be placed in the load lock. More specifically, at least one system controller may cause the transfer robot to place the substrate in the load lock. Further details regarding operations 610 - 650 were described above with respect to FIGS. 1 - 5 and will be described below with respect to FIG. 7.

[0086] FIG. 7 is a diagram 700 of a schematic cross - section during a method for forming a film having improved film quality according to some embodiments. Diagram 700 shows a deposition step 710 and a film removal step 720. Steps 710 and 720 may be performed during operation 620 described above with respect to FIG. 6. Step 720 may be performed in - situ after step 710 (e.g., without exposing the substrate to air between step 710 and step 720). For example, during deposition step 710, a flowable film 712 is deposited on a substrate including features 714 - 1 and 714 - 2 and a bottom surface 716. During film removal step 720, an etching process may be performed to remove a portion of the flowable film 712 and obtain a remaining portion 722 of the flowable film. Removal of the said portion of the flowable film 712 further exposes the sidewalls of features 714 - 1 and 714 - 2 including sidewall 724 of feature 714 - 1. The etching process may be a dry etching process (e.g., an H2 plasma etching process). In some embodiments, the remaining portion 722 of the flowable film may be densified as described in more detail above.

[0087] FIG. 700 further illustrates the membrane treatment step 730. Step 730 may be performed during operation 640 described above with respect to FIG. 6. Step 730 may be performed ex-situ after step 720. During the membrane treatment step 710, the remaining portion 722 of the fluid membrane (e.g., the densified membrane) is treated to obtain a treated membrane 732. For example, the remaining portion 722 of the fluid membrane may be treated using a DPN process. Further details regarding steps 710-730 are described above with respect to FIGS. 1-6.

[0088] In the foregoing description, for purposes of explanation, numerous details have been set forth in order to provide an understanding of various embodiments of the present technology. However, it will be apparent to one skilled in the art that certain embodiments may be practiced without some of these details or with additional details.

[0089] Although several embodiments have been disclosed, it will be recognized by those skilled in the art that various modifications, alternative structures, and equivalents may be used without departing from the spirit of the embodiments. In addition, numerous well-known processes and elements have not been described in order to avoid unnecessarily obscuring the present technology. Accordingly, the foregoing description should not be construed as limiting the scope of the present technology. In addition, although methods or processes may be described sequentially or stepwise, it should be understood that those operations may be performed simultaneously or in an order different from that recited.

[0090] When a range of values is provided, unless a context dictates otherwise, each intermediate value between the upper and lower limits of that range is also specifically disclosed, to the smallest fraction of the unit of the lower limit. Any narrower range between any of the stated values or unstated intermediate values in the stated range and any other stated value or intermediate value in that stated range is encompassed. The upper and lower limits of those smaller ranges may independently be included in or excluded from the range, and each range that includes any one of the limits, excludes any one of the limits, or includes both limits is included in the technology, subject to any specifically excluded limits in the stated range. When the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.

[0091] As used in this specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a precursor" includes a plurality of such precursors, reference to "a layer" includes one or more layers and equivalents thereof known to those skilled in the art, and the like.

[0092] Also, the terms "comprises," "comprising," "includes," "including," "contains," and "containing" as used in this specification and the following claims are intended to specify the presence of the stated feature, integer, component, or operation, but do not preclude the presence or addition of one or more other features, integers, components, operations, acts, or groups.

Claims

1. Depositing a film on a substrate by supplying a first input stream, wherein the first input stream includes a plasma emission of a first precursor; Reducing the hydrogen content of the remaining portion of the film by supplying a second input stream to obtain a densified film, wherein the second input stream includes a plasma emission of a second precursor; Removing a portion of the densified film from sidewalls of features defined within the substrate by supplying a third input stream to obtain the remaining portion of the film, wherein the third input stream includes a plasma emission of a third precursor; Processing the remaining portion of the film according to a film processing process A method comprising.

2. The method according to claim 1, wherein the deposition, the removal, and the reduction are performed in a process chamber, and the processing is performed in a film processing chamber different from the process chamber.

3. The method according to claim 1, wherein at least one of the second precursor or the third precursor includes a hydrogen-containing precursor.

4. The method according to claim 1, wherein the first precursor includes a silicon-containing precursor, and the film includes silicon.

5. The deposition is performed using a set of process window parameters, and the set of process window parameters includes A temperature between about 25 °C and about 100 °C, A source power between about 60 watts (W) and about 250 W, A bias power between about 100 W and about 2000 W, A plasma pulse having a duty cycle between about 1% and about 99% and a frequency between about 1 hertz (Hz) and about 20 Hz, A pressure between about 0.5 Torr and about 100 Torr, or A time between about 5 seconds and about 15 seconds The method according to claim 1, including at least one of.

6. The method according to claim 1, wherein the film processing process is a separated plasma nitridation (DPN) process performed using a set of process window parameters to achieve a wet etching rate of less than about 4 angstroms per minute.

7. The set of process window parameters includes A temperature between about 200 °C and about 500 °C, A source power between about 100 watts (W) and about 250 W, A bias power between about 100 W and about 600 W, A pressure between about 5 milli Torr and about 100 milli Torr, or A time between about 5 seconds and about 15 seconds The method according to claim 6, comprising at least one of them.

8. Operably coupled to a memory, Depositing a film on a substrate by supplying a first input stream, wherein the first input stream comprises a plasma emission of a first precursor, Reducing the hydrogen content of the remaining portion of the film by supplying a second input stream to obtain a densified film, wherein the second input stream comprises a plasma emission of a second precursor, Removing a portion of the densified film from sidewalls of features defined in the substrate by supplying a third input stream to obtain the remaining portion of the film, wherein the third input stream comprises a plasma emission of a third precursor, Processing the remaining portion of the film according to a film processing process At least one system controller comprising a processor configured to perform A system comprising

9. The at least one system controller is Depositing the film on the substrate in a process chamber, Reducing the hydrogen content of the film in the process chamber to obtain the densified film, Removing the portion of the densified film from the sidewalls of the features in the process chamber, Processing the remaining portion of the film according to a film processing process in a film processing chamber different from the process chamber The system according to claim 8, configured to perform

10. The system according to claim 8, wherein at least one of the second precursor or the third precursor comprises a hydrogen-containing precursor.

11. The system according to claim 8, wherein the first precursor comprises a silicon-containing precursor and the film comprises silicon.

12. The film is deposited using a set of process window parameters, the set of process window parameters comprising A temperature between about 25 °C and about 100 °C, A source power between about 60 watts (W) and about 250 W, A bias power between about 100 W and about 2000 W, A plasma pulse having a duty cycle between about 1% and about 99% and a frequency between about 1 hertz (Hz) and about 20 Hz, A pressure between about 0.5 Torr and about 100 Torr, or A time between about 5 seconds and about 15 seconds The system according to claim 8, comprising at least one of them.

13. The system according to claim 8, wherein the film treatment process is a separated plasma nitriding (DPN) process performed using a set of process window parameters to achieve a wet etching rate of less than about 4 angstroms per minute.

14. The set of process window parameters includes a temperature between about 200 °C and about 500 °C, a source power between about 100 watts (W) and about 250 W, a bias power between about 100 W and about 600 W, a pressure between about 5 milli Torr and about 100 milli Torr, or a time between about 5 seconds and about 15 seconds The system according to claim 13, comprising at least one of them.

15. A process chamber comprising a first substrate support, a film treatment chamber comprising a second substrate support, a transfer chamber coupled to the process chamber and the film treatment chamber, the transfer chamber accommodating a transfer robot, at least one system controller operably coupled to the process chamber, the film treatment chamber, and the transfer robot, loading a substrate onto the first substrate support in the process chamber by the transfer robot, the substrate comprising features defined within the substrate, [[ID=1'6]]depositing a film on the substrate in the process chamber by supplying a first input flow into a processing volume of the process chamber, the first input flow comprising a plasma emission of a first precursor, reducing a hydrogen content of the film in the process chamber to obtain a densified film by supplying a second input flow into the processing volume, the second input flow comprising a plasma emission of a second precursor, removing a portion of the densified film from sidewalls of the features in the process chamber to obtain a remaining portion of the film by supplying a third input flow into the processing volume, the third input flow comprising a plasma emission of a third precursor, transferring the substrate from the process chamber to the film treatment chamber by the transfer robot and onto the second substrate support, and processing the densified film in the film treatment chamber according to a film treatment process At least one system controller configured to perform An electronic device manufacturing system comprising

16. The system according to claim 15, wherein the first precursor includes a silicon-containing precursor, and the film includes silicon.

17. The system according to claim 15, wherein at least one of the second precursor or the third precursor includes a hydrogen-containing precursor.

18. The film is deposited using a set of process window parameters, and the set of process window parameters includes a temperature between about 25°C and about 100°C, a source power between about 60 watts (W) and about 250 W, a bias power between about 100 W and about 2000 W, a plasma pulse having a duty cycle between about 1% and about 99%, and a frequency between about 1 hertz (Hz) and about 20 Hz, a pressure between about 0.5 Torr and about 100 Torr, or a time between about 5 seconds and about 15 seconds The system according to claim 15, including at least one of them.

19. The system according to claim 15, wherein the film treatment process is a DPN process performed using a set of process window parameters to achieve a wet etching rate of less than about 4 angstroms per minute.

20. The set of process window parameters includes a temperature between about 200°C and about 500°C, a source power between about 100 watts (W) and about 250 W, a bias power between about 100 W and about 600 W, a pressure between about 5 milli-Torr and about 100 milli-Torr, or a time between about 5 seconds and about 15 seconds The system according to claim 19, including at least one of them.

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