Plasma treatment with adjustable nitriding

Abstract

In one embodiment, a method for nitriding a substrate is provided, the method including flowing a nitrogen-containing source and a carrier gas into a plasma processing source connected to a processing chamber such that the nitrogen-containing source has a flow rate of about 3% to about 20% of the carrier gas flow rate, generating an inductively coupled plasma (ICP) in the plasma processing source by operating an ICP source, the ICP including radical species formed from the nitrogen-containing source, the carrier gas, or both, nitriding the substrate in the chamber, the ICP including operating a heat source in the chamber at a temperature of about 150° C. to about 650° C. to heat the substrate, maintaining a chamber pressure of about 50 mTorr to about 2 Torr, introducing the ICP into the chamber, and adjusting a property of the substrate by exposing the substrate to the radical species.

Description

[Technical Field]

[0001] TECHNICAL FIELD

[0001] Embodiments of the present disclosure relate generally to plasma processing methods, and more particularly to nitriding radical species using plasma processing. [Background technology]

[0002]

[0002] Plasma processing is used in the semiconductor industry for deposition, etching, resist removal, and related processing of semiconductor and other substrates. Plasma sources are often used in plasma processing to generate high-density plasma and reactive species for processing substrates. The formation of plasma breaks down molecules into radicals (generating ions), which can be used to achieve substrate processing within the chamber. Typically, a gas mixture is fed into the plasma generation region (active zone) of an inductively coupled plasma (ICP) source, where electrons accelerated by a high electric field region ionize and dissociate the mixture, creating a new gas (plasma) with radicals and ions.

[0003]

[0003] Conventional methods for nitridation include thermal and plasma-based methods. Conventional thermal methods for nitridation are typically performed at temperatures that can be harmful to the substrate being processed. Conventional plasma-based nitridation also suffers from the drawback of poor conformality of the nitride layer to high aspect ratio structures and the difficulty of conformal nitridation of silicon oxide films.

[0004] There is a need for new and improved plasma processing methods for nitriding substrates. Summary of the Invention

[0005]

[0005] Embodiments of the present disclosure generally relate to plasma processing methods, and more particularly to nitriding radical species using plasma processing.

[0006] In one embodiment, a method for nitriding a substrate is provided. The method includes positioning the substrate on a substrate support within a processing space of a processing chamber and flowing a nitrogen-containing source and a carrier gas into a plasma processing source connected to the processing chamber such that a flow rate of the nitrogen-containing source is about 3% to about 20% of a flow rate of the carrier gas. The method further includes generating an inductively coupled plasma in the plasma processing source by operating the inductively coupled plasma source at a power of about 2,000 W to about 10,000 W, wherein the inductively coupled plasma comprises radical species formed from the nitrogen-containing source, the carrier gas, or both. The method further includes nitriding the substrate in a processing chamber, the method including operating a heat source in the processing chamber at a temperature of about 150° C. to about 650° C. to heat the substrate, maintaining a processing chamber pressure of about 50 mTorr to about 2 Torr, introducing an inductively coupled plasma into the processing chamber, and exposing the substrate to radical species to adjust the nitrogen content, number of nitrogen atoms per unit area, nitride thickness, or a combination thereof, of the substrate.

[0007]

[0007] Embodiments may include one or more of the following: H2 may be co-flowed with a nitrogen-containing source, the inductively coupled plasma may further include radical species formed from H2, or a combination thereof. The plasma processing source may include a gas injection channel defined between a gas injection insert and a sidewall of the plasma processing source. The inductive coil may be positioned proximate to the sidewall and horizontally overlapping the gas injection channel. Flowing the nitrogen source and carrier gas into the plasma processing source may include flowing the nitrogen source and carrier gas into the gas injection channel. The nitrogen-containing source may include NH3, N2, hydrazine (N2H4), or a combination thereof. The carrier gas may include Ar, He, Ne, Kr, Xe, or a combination thereof. The heat source may include a lamp positioned above the substrate, a lamp positioned below the substrate, a heater embedded in the substrate support, or a combination thereof. The heat source may have a plasma source output of about 2 inches to about 15 inches in diameter. The substrate may comprise crystalline silicon, amorphous silicon, polycrystalline silicon, crystalline SiGe, amorphous SiGe, polycrystalline SiGe, silicon oxide, silicon nitride, hafnium oxide, hafnium zirconium oxide, or a combination thereof. The method may further comprise performing an oxygen radical treatment before or after nitriding the substrate, performing a hydrogen radical treatment before or after nitriding the substrate, or a combination thereof. The oxygen radical treatment, the hydrogen radical treatment, or both may be performed in the same process chamber as nitriding the substrate.

[0008] In another embodiment, a method for nitriding a substrate is provided, the method including: positioning the substrate on a substrate support within a processing space of a processing chamber; generating an inductively coupled plasma in a plasma processing source connected to the processing chamber, the inductively coupled plasma source operating at a power of about 2,000 W to about 10,000 W; flowing hydrazine and a carrier gas into the plasma processing source such that the hydrazine flow rate is about 3% to about 100% of the carrier gas flow rate, the carrier gas comprising Ar, He, Ne, Kr, Xe, or a combination thereof; and forming an inductively coupled plasma comprising radical species comprising N, NH, or a combination thereof. and generating an inductively coupled plasma comprising: a) forming a nitride layer on the substrate in a process chamber, the process chamber comprising: operating a heat source in the process chamber at a temperature of about 150° C. to about 650° C. to heat the substrate; maintaining a pressure in the process chamber of about 50 mTorr to about 2 Torr; introducing the inductively coupled plasma into the process chamber; and exposing the substrate to the inductively coupled plasma comprising radical species to adjust the nitrogen content, number of nitrogen atoms per unit area, nitride thickness, or a combination thereof, of the substrate.

[0009]

[0009] Embodiments may include one or more of the following: The flow rate of the hydrazine may be about 5% to about 15% of the flow rate of the carrier gas; The pressure may be about 200 mTorr to about 1 Torr, the temperature may be about 500°C to about 650°C, and nitriding the substrate may be performed for about 5 minutes or less, or a combination thereof; The heat source may have a plasma source power of about 2 inches to about 15 inches in diameter; H2 may be co-flowed with the hydrazine, and the inductively coupled plasma may further include radical species generated from the H2; NH3, N2, or a combination thereof may be co-flowed with the hydrazine, and the inductively coupled plasma may further include radical species formed from NH3, N2, or a combination thereof, or a combination thereof.

[0010] In another embodiment, a method for nitriding a substrate is provided, the method including: positioning a substrate comprising silicon on a substrate support within a processing space of a processing chamber; generating an inductively coupled plasma in a plasma processing source connected to the processing chamber, the inductively coupled plasma source operating at a power of about 2,000 W to about 10,000 W; flowing a nitrogen-containing source and a carrier gas into the plasma processing source such that a flow rate of the nitrogen-containing source is about 3% to about 100% of a flow rate of the carrier gas, the carrier gas comprising Ar, He, Ne, Kr, Xe, or a combination thereof; and forming an inductively coupled plasma comprising radical species comprising N, NH, or a combination thereof. The method further includes nitriding the substrate in a processing chamber, the method including operating a heat source in the processing chamber at a temperature of about 150° C. to about 650° C. to heat the substrate, maintaining a pressure in the processing chamber of about 50 mTorr to about 2 Torr, introducing an inductively coupled plasma into the processing chamber, and exposing the substrate to the inductively coupled plasma comprising radical species to adjust the nitrogen content, number of nitrogen atoms per unit area, nitride thickness, or a combination thereof, of the substrate.

[0011]

[0011] Embodiments may include one or more of the following: The substrate may include silicon germanium (SiGe). The flow rate of the nitrogen-containing source may be about 5% to about 15% of the flow rate of the carrier gas. The pressure may be about 200 mTorr to about 1 Torr. The temperature may be about 500°C to about 650°C. Nitriding the substrate may be performed for about 10 minutes or less. H2 may be co-flowed with the nitrogen-containing source. The inductively coupled plasma further includes radical species formed from H2. The plasma processing source may be integrated into the processing chamber.

[0012]

[0012] So that the features of the present disclosure described above can be understood in detail, a more particular description of the present disclosure briefly summarized above will be had by reference to embodiments, some of which are illustrated in the accompanying drawings. It should be noted, however, that the accompanying drawings illustrate only exemplary embodiments and therefore should not be considered as limiting the scope of the present disclosure, as other equally effective embodiments may be tolerated. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a schematic diagram of an exemplary plasma processing apparatus in accordance with at least one embodiment of the present disclosure. [Figure 2]

[0014] FIG. 1 is a schematic diagram of an exemplary plasma processing apparatus in accordance with at least one embodiment of the present disclosure. [Figure 3]

[0015] FIG. 1 is a schematic diagram of an exemplary plasma processing apparatus in accordance with at least one embodiment of the present disclosure. [Figure 4]

[0016] FIG. 1 is a schematic diagram of an exemplary plasma processing apparatus in accordance with at least one embodiment of the present disclosure. [Figure 5]

[0017] FIG. 1 is a schematic diagram of an exemplary plasma processing apparatus in accordance with at least one embodiment of the present disclosure. [Figure 6A]

[0018] FIG. 1 is an isometric view of an exemplary separation grid in accordance with at least one embodiment of the present disclosure. [Figure 6B]

[0019] FIG. 6B is a cross-sectional view (along line 6B) of the separation grid of FIG. 6A, in accordance with at least one embodiment of the present disclosure. [Figure 7]

[0020] 1 is an exemplary induction coil that may be used with an exemplary plasma source in accordance with at least one embodiment of the present disclosure. [Figure 8]

[0021] 1 is a flowchart illustrating steps in an exemplary method for nitriding a substrate in accordance with at least one embodiment of the present disclosure. [Figure 9]

[0022] 1 is a flowchart illustrating steps in an exemplary method for nitriding a substrate in accordance with at least one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0014]

[0023] For ease of understanding, where possible, identical reference numerals have been used to designate identical elements common to the figures. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.

[0015]

[0024] Embodiments of the present disclosure relate generally to plasma processing methods, and more specifically, to radical species nitridation using plasma processing. Process embodiments described herein may enable higher nitrogen doses and nitride thicknesses for processed substrates with lower thermal budgets compared to conventional nitridation methods, for example. Furthermore, the methods described herein may be highly conformal to high aspect ratio structures present on semiconductor device substrates. Furthermore, the processes described herein may be cyclical, combined with hydrogen radical treatments, and / or combined with oxygen radical treatments to achieve desired results. The nitridation methods may be performed in a single chamber with other processes, such as other radical treatment processes.

[0016]

[0025] For purposes of this disclosure, nitridation and nitriding are used interchangeably. For example, nitriding a substrate also refers to nitriding the substrate. Aspects of the present disclosure are discussed with reference to a "substrate" or semiconductor wafer for purposes of explanation and discussion. Those skilled in the art, using the disclosure provided herein, will understand that exemplary aspects of the present disclosure can be used in connection with any suitable semiconductor substrate or other suitable substrate. "Substrate support" refers to any structure that can be used to support a substrate.

[0017] Device example

[0026] Referring now to the figures, exemplary embodiments of the present disclosure will now be described. FIG. 1 illustrates a plasma processing apparatus 100. The plasma processing apparatus 100 includes a processing chamber 110 and a plasma source 120 connected to the processing chamber 110. The processing chamber 110 includes a substrate support 112 operable to hold a substrate 114. In some embodiments, the substrate has a thickness of less than about 1 mm. The substrate support 112 may be proximate to one or more heat sources (e.g., a plurality of lamps 176) that provide heat to the substrate during processing of the substrate in the processing chamber 110. Heat may be provided via any suitable heat source, for example, one or more lamps, e.g., one or more rapid thermal processing lamps, or a heated pedestal (e.g., a pedestal having a resistive heating element embedded therein or connected thereto). During operation, the heat sources enable independent temperature control of the substrate, as described in more detail below.

[0018]

[0027] 1 , the processing chamber 110 includes a window 162, such as a dome, and a plurality of lamps 176. The plurality of lamps 176 is disposed between the window 162 and a bottom wall of the processing chamber 110. The plurality of lamps 176 is positioned in an array. The plurality of lamps 176 may be arranged in a plurality of concentric circles surrounding the center of the processing chamber 110. The plurality of lamps 176 may include 100 or more lamps (e.g., 200 or more lamps, e.g., 200 to 500 lamps, e.g., 200 to 300 lamps, e.g., 240 lamps, e.g., 300 to 400 lamps, e.g., 400 to 500 lamps, e.g., 400 lamps). The power of each of the plurality of lamps 176 is between 400 W and 1000 W, for example, between 500 W and 800 W, for example, between 500 W and 600 W, for example, between 600 W and 700 W, for example, 645 W, for example, between 700 W and 800 W. The distance from the plurality of lamps 176 to the substrate is about 50 mm or less, for example, between about 5 mm and about 50 mm, for example, between about 5 mm and about 20 mm, for example, about 12.5 mm, for example, between about 20 mm and about 50 mm, for example, about 36.5 mm.

[0019]

[0028] A controller (not shown) may be connected to the processing chamber 110 and used to control the chamber processes described herein, including controlling the plurality of lamps 176. The substrate support 112 is disposed between the separation grating 116 and the window 162. To measure the temperature within the processing chamber 110, a plurality of sensors (not shown) may be disposed proximate one or more of the lamps 176 and / or the substrate support 112. The plurality of sensors may include one or more infrared pyrometers or miniature pyrometers. In certain embodiments, the one or more pyrometers include two, three, or four pyrometers. In certain embodiments, the pyrometer wavelength is 3.3 μm, although the wavelength of commonly available pyrometers typically ranges from about 0.5 μm to about 14 μm. In some embodiments, the pyrometer is a bottom pyrometer, i.e., the pyrometer is positioned below the substrate so as to be proximate to the plurality of lamps 176.

[0020]

[0029] The substrate support 112 is connected to a shaft 165. The shaft is connected to an actuator 178, which provides rotational movement (about axis A) of the shaft and substrate support. The actuator 178 may additionally or alternatively provide height adjustment of the shaft 165 during processing.

[0021]

[0030] The substrate support 112 includes lift pin holes 166 disposed therein. The lift pin holes 166 are sized to accommodate lift pins 164 for lifting the substrate 114 from the substrate support 112 either before or after a deposition process is performed. The lift pins 164 may rest on lift pin stops 168 when the substrate 114 is lowered from a processing position to a transfer position.

[0022]

[0031] A plasma can be generated within the plasma source 120 (e.g., within the plasma generation region) by an inductive coil 130, and desired particles flow from the plasma source 120 to the surface of the substrate 114 through holes 126 in a separation grid 116 that separates the plasma source 120 from the processing chamber 110 (downstream region).

[0023]

[0032] The plasma source 120 includes a dielectric sidewall 122. The plasma source 120 includes a top plate 124. The dielectric sidewall 122 and the top plate 124, integrated with a gas injection insert 140, define a plasma source interior 125. The dielectric sidewall 122 may comprise any suitable dielectric material, such as quartz. The inductive coil 130 is positioned proximate (e.g., adjacent) to the dielectric sidewall 122 around the plasma source 120. The inductive coil 130 is connected to an RF power generator 134 through any suitable matching network 132. A feed gas is introduced into the plasma source interior from a gas supply 150. A plasma is generated in the plasma source 120 when the inductive coil 130 is energized with RF power from the RF power generator 134. In some embodiments, RF power is supplied to the inductive coil 130 at between about 1 kW and about 15 kW, e.g., between about 3 kW and about 10 kW. The inductive coil 130 can ignite and sustain a plasma over a wide range of pressures and flow rates. In some embodiments, the plasma processing apparatus 100 includes a grounded Faraday shield 128 to reduce capacitive coupling of the inductive coil 130 to the plasma.

[0024]

[0033] To enhance efficiency, the plasma processing apparatus 100 includes a gas injection insert 140 disposed within the plasma source interior 125. The gas injection channel 151 supplies process gas to the plasma source interior 125 through an active zone 172, where enhanced confinement of hot electrons allows reactions to occur between the hot electrons and the supplied gas. The enhanced electron confinement region, or active zone 172, is defined radially by the gas injection insert and the sidewall of the vacuum tube, and vertically by the edge of the insert's surface 180 from below. The active zone 172 provides an electron confinement region within the plasma source interior 125 for efficient plasma generation and maintenance. The gas injection channel 151 can be narrow to prevent the plasma from spreading from the chamber interior into the gas injection channel 151. The gas injection channel 151 can have a diameter of about 1 mm or more, e.g., about 10 mm or more, e.g., about 1 mm to about 10 mm. The gas injection insert 140 passes the process gas through the active zone 172, where the plasma is formed.

[0025]

[0034] The ability of gas injection insert 140 to improve the efficiency of plasma processing apparatus 100 is independent of the material of gas injection insert 140, as long as the walls in direct contact with radicals are made of a material with a low radical recombination rate. For example, in some embodiments, gas injection insert 140 can be made of a metal, such as an aluminum material, with a coating configured to reduce surface recombination. Alternatively, gas injection insert 140 can be a dielectric material, such as a quartz material, or an insulating material.

[0026]

[0035] The induction coil 130 is aligned with the active region such that the upper turn of the coil is above the surface 180 of the gas injection insert 140 and operates substantially within the active region of the interior space, and the lower turn of the coil is below the surface 180 and operates substantially outside the active region. The center of the coil is substantially aligned with the surface 180. Within this boundary, the coil position can be adjusted to achieve desired performance. Aligning the coil with the surface 180 improves source efficiency, i.e., controls the generation of chemical species required for plasma processing and delivers them to the substrate while reducing or eliminating losses. For example, plasma sustaining conditions (balance between local ion generation and loss) may not be optimal for generating species for the plasma process. With regard to delivery of species to the substrate, efficiency may depend on the volume and wall recombination of these particular species. Therefore, controlling the alignment of the coil with the surface 180 controls the source efficiency of the plasma process.

[0027]

[0036] In some embodiments, the coil has a short transition region near the lead wire, with the remainder of the coil turns parallel to surface 180. In other embodiments, the coil is helical, but can always define a top turn and a bottom turn of the coil. In some embodiments, the coil can have 2-5 turns.

[0028]

[0037] In some embodiments, surface 180 is aligned with a portion of inductive coil 130 (e.g., coil loop 182) along axis 184 by utilizing an appropriately sized gas inject insert 140 (and top plate 124, which may be a pre-formed portion of gas inject insert 140) to form plasma source 120. Alternatively, surface 180 may be movable along a vertical direction V1 relative to plasma source 120 to align surface 180 with a portion of inductive coil 130 while the remainder of gas inject insert 140 remains stationary (e.g., fixed) as part of plasma source 120. For example, mechanism 170 may be connected to any appropriate portion of gas inject insert 140 to adjust the position of surface 180 such that a portion of gas inject insert 140 having a first length (L1) is adjusted to a second length (L2). Mechanism 170 may be any appropriate mechanism, such as an actuator, for example, a motor, an electric motor, a stepper motor, a pneumatic actuator, or the like. In some embodiments, the difference in length from L1 to L2 is from about 0.1 cm to about 4 cm, for example, from about 1 cm to about 2 cm.

[0029]

[0038] Additionally or alternatively, gas injection insert 140 may be connected to a mechanism (such as mechanism 170) configured to move the entire gas injection insert 140 vertically (e.g., along a vertical direction V1 relative to plasma source 120) to align surface 180 with a portion of inductive coil 130. A spacer (not shown) may be used to fill a gap between gas injection insert 140 and another portion of plasma source 120 (e.g., between top plate 124 and dielectric sidewall 122) formed by moving the insert vertically. The spacer may be formed from a ceramic material such as quartz.

[0030]

[0039] Generally, positioning the center of the induction coil 130 above the surface 180 will improve ionization and dissociation efficiency, but reduce the efficiency of transport of these species to the substrate, as many of these species may recombine at the walls of the narrow active region. Positioning the induction coil 130 below the surface 180 can improve plasma delivery efficiency, but may reduce plasma generation efficiency.

[0031]

[0040] The separation grid 116 is configured to separate the processing chamber 110 region from plasma charged particles (ions and electrons) that recombine on the grid, allowing only neutral plasma species to pass through the grid and enter the processing chamber 110. The holes in the bottom portion of the separation grid 116 can have different patterns (e.g., uniform), as shown in FIGS. 6A and 6B. In some embodiments, the separation grid 600 is formed of aluminum, anodized aluminum, quartz, aluminum nitride, aluminum oxide, tantalum, tantalum nitride, titanium, titanium nitride, or one or more combinations thereof. For example, AlN can be effective in fluxing nitrogen radicals, while conventional separation grids are prone to recombination of nitrogen radicals. Similarly, aluminum oxide can provide a flux of oxygen radicals or hydrogen radicals, while conventional separation grids are prone to recombination of these radicals. In some embodiments, the separation grid 600 has a plurality of holes 602. As shown in FIG. 6B, the plurality of holes 602 are disposed throughout the separation grid (e.g., the holes 602 traverse the thickness of the separation grid). The plurality of holes 602 may have an average diameter of about 4 mm to about 6 mm. In some embodiments, each hole of the plurality of holes 602 has a diameter (D1) of about 4 mm to about 6 mm. In some embodiments, the separation grid 600 of FIGS. 6A and 6B has a thickness of about 5 mm to about 10 mm, defining a length (L1) of the holes. The thickness (length ( L The ratio of 1) to the average diameter of the plurality of pores may be greater than about 1, for example, from about 1 to about 3.

[0032]

[0041] The exhaust port 192 is connected to a sidewall of the processing chamber 110. In some embodiments, the exhaust port 192 is connected to the bottom wall of the processing chamber 110, which can provide azimuthal independence (e.g., in the absence of a rotating pedestal). If the lamp is rotating, the exhaust port 192 can be connected to the sidewall because the rotation mitigates azimuthal dependency.

[0033]

[0042] Various features of the ICP source and plasma processing apparatus will now be described with reference to Figures 2, 3, 4, and 5. Figures 2, 3, 4, and 5 are schematic diagrams of plasma processing apparatuses according to some embodiments of the present disclosure. The plasma processing apparatuses of Figures 2, 3, 4, and 5 are configured in a manner similar to plasma processing apparatus 100 (Figure 1) and may operate in the manner described above for plasma processing apparatus 100. It will be understood that the components of the plasma processing apparatuses of Figures 2, 3, 4, and 5 may also be incorporated into any other suitable plasma processing apparatus in alternative exemplary embodiments.

[0034]

[0043] As shown in FIG. 2, the plasma processing apparatus 200 includes a processing chamber 220 having an isolation grid (not shown) disposed therein. The plasma processing apparatus 200 includes a plasma source 222 along a vertical direction V. A substrate may be positioned within the processing chamber directly below the grid and at some distance from the grid. Neutral particles from the plasma source interior 230 may flow downward through the isolation grid toward the substrate within the processing chamber 220. The neutral particles may contact the substrate to perform a process, such as a surface treatment process.

[0035]

[0044] The multiple induction coils 250 are disposed at different positions along the vertical direction V on the plasma source 222, for example, such that the induction coils (e.g., 252 and 254) are spaced apart from one another along the vertical direction V along the plasma source 222. For example, the induction coils 250 may include a first induction coil (peripheral induction coil 252) and a second induction coil (central induction coil 254). The first induction coil (peripheral induction coil 252) may be positioned at a first vertical position along the vertical surface of the dielectric sidewall 232. The second induction coil (central induction coil 254) may be positioned at a second vertical position along the vertical surface of the dielectric sidewall 232. The first vertical position may be different from the second vertical position. For example, the first vertical position may be above the second vertical position. In some embodiments, a portion of the first induction coil (peripheral induction coil 252) is substantially aligned with the surface 180 of the insert, as described above. A second induction coil (central induction coil 254) is positioned at the bottom (e.g., lower) portion of the plasma source. The second induction coil can include one or more magnetic field concentrators 280, and the coil can be positioned at the bottom of the plasma source as shown in FIG. 2. The use of one or more magnetic field concentrators 280 increases the efficiency of plasma generation at the bottom of the source and significantly increases radial control near the substrate (compared to without the magnetic field concentrators). In some embodiments, the central induction coil 254 is positioned at the bottom third of the height, e.g., the bottom quarter of the height, of the plasma source 222.

[0036]

[0045] The induction coils 250 (252, 254) may be operable to generate (or modify) an inductive plasma within the plasma source interior 230. For example, the plasma processing apparatus 200 may include a first high frequency power generator 262 (e.g., an RF generator and a matching network) connected to the peripheral induction coil 252. The central induction coil 254 is connected to a second high frequency power generator 264 (e.g., an RF generator and a matching network). The frequency and / or power of the RF energy applied by the first high frequency power generator 262 to the first induction coil (peripheral induction coil 252) and the second high frequency power generator 264 to the second induction coil (central induction coil 254) may be independent to better control process parameters of the surface treatment process.

[0037]

[0046] For example, the frequency and / or power of the RF energy applied by the second radio frequency power generator 264 may be lower than the frequency and / or power of the RF energy applied by the first radio frequency power generator 262. The first radio frequency power generator 262 is operable to energize the peripheral induction coil 252 to generate an inductive plasma in the plasma source interior 230. In particular, the first radio frequency power generator 262 energizes the peripheral induction coil 252 with radio frequency (RF) alternating current (AC) such that the AC induces alternating magnetic and electric fields within a space adjacent the peripheral induction coil 252 that heats electrons to generate the inductive plasma. In some embodiments, RF power is supplied to the peripheral induction coil 252 at about 1 kW to about 15 kW, e.g., about 3 kW to about 15 kW. The peripheral induction coil 252 can ignite and sustain plasma over a wide range of pressures and flow rates. The second radio frequency power generator 264 is operable to energize the central induction coil 254 to generate and / or modify a plasma in the plasma source interior 230. In particular, the second radio frequency power generator 264 may energize the central induction coil 254 with alternating current (AC) radio frequency (RF) such that an induced RF electric field in the space adjacent to the central induction coil 254 accelerates electrons to generate the plasma. In some embodiments, RF power is supplied to the central induction coil 254 at about 0.5 kW to about 6 kW, e.g., about 0.5 kW to about 3 kW. The central induction coil 254 may modify the plasma density within the plasma processing apparatus 200. For example, the central induction coil 254 may adjust the radial profile of the plasma to promote more uniformity of the plasma moving toward the substrate within the processing chamber 220. Because the peripheral induction coil 252 is further away from the substrate than the central induction coil 254 during use, the plasma and radicals generated by the peripheral induction coil 252 can promote a dome-shaped profile near the substrate, and the central induction coil 254 can flatten (or even raise the edges of) the dome-shaped plasma profile as the plasma approaches the substrate.

[0038]

[0047] A dielectric sidewall 232 is positioned between the inductive coil 250 and the plasma source 222. The dielectric sidewall 232 has a generally cylindrical shape. An electrically grounded Faraday shield 234 can be made of metal and / or is positioned between the inductive coil 250 and the dielectric sidewall 232. The Faraday shield 234 has a cylindrical shape and is disposed around the dielectric sidewall 232. The grounded Faraday shield 234 extends the length of the plasma source 222. The dielectric sidewall 232 contains the plasma in the plasma source interior 230, allowing an RF field to penetrate from the inductive coil 250 to the plasma source interior 230, and the grounded Faraday shield 234 reduces capacitive coupling of the inductive coil 250 to the plasma in the plasma source interior 230. In some embodiments, the Faraday shield 234 can be a metal cylinder with slots perpendicular to the coil direction. The vertical slot is in the region of the coil (e.g., adjacent to the coil), and at least one vertical end of the coil (above or below the coil) has a complete current path around the circumference of the cylinder. The Faraday shield can have any suitable thickness and / or the slot can have any suitable shape. Near the coil, the slot can be relatively narrow (e.g., about 0.5 cm to about 2 cm) and can be substantially vertical, even when a helical coil is utilized.

[0039]

[0048] As described above, each inductive coil 250 is positioned at a different location along the vertical direction V on the plasma source 222 adjacent a vertical portion of the dielectric sidewall of the plasma source 222. In this manner, each inductive coil 250 may be operable to generate (or modify) a plasma in a region adjacent to the coil along the vertical surface of the dielectric sidewall 232 of the plasma source 222.

[0040]

[0049] In some embodiments, the plasma processing apparatus 200 includes one or more peripheral gas injection ports 270 disposed radially outward of the gas injection insert 240 of the plasma source 222. The peripheral gas injection ports 270 and the insert's profile configuration are operable to inject process gas directly into the active plasma generation region adjacent the vertical surface of the dielectric sidewall 232 at the periphery of the plasma source interior 230. For example, there may be more than 20 (e.g., 70-200) vertical injection holes disposed through the gas injection insert 240. For example, the first induction coil (peripheral induction coil 252) may be operable to generate plasma in a region 272 adjacent to the vertical surface of the dielectric sidewall 232. The second induction coil (central induction coil 254) may be operable to generate or modify plasma present in a region 275 adjacent to the vertical surface of the dielectric sidewall 232. Gas injection insert 240, in some embodiments, can further define an active region for generation of plasma in plasma source interior 230 adjacent the vertical surface of dielectric sidewall 232. The top of a gas injection insert of the present disclosure can have a diameter of about 10 cm to about 15 cm. The bottom of a gas injection insert of the present disclosure can have a diameter of about 7 cm to about 10 cm.

[0041]

[0050] The plasma processing apparatus 200 may include an edge gas injection port 290 configured to introduce the same or a different gas into the volume 210 as the peripheral gas injection port 270 provides to the plasma source interior 230. The edge gas injection port 290 is connected to the processing chamber 220 and serves as the top plate of the processing chamber 220. The edge gas injection port 290 includes a plenum 292 (which may be circular) into which gas is introduced through an inlet 294. The gas flows from the plenum 292 through one or more openings 296 into the volume 210. The edge gas injection port 290 can fine-tune the plasma chemistry near the edge of the substrate and / or improve plasma uniformity at the substrate. For example, the edge gas injection port 290 can provide a change in flow (same gas) and / or a change in chemistry (chemical reaction between plasma radicals and a new feed gas or a different gas).

[0042]

[0051] The plasma processing apparatus 200 provides improved source tunability compared to known plasma processing apparatuses. For example, the induction coils 250 can be positioned at two locations along the vertical plane of the dielectric sidewall 232, such that the peripheral induction coil 252, located near the active plasma generation region, functions to ignite and sustain the plasma in the plasma source interior 230, while the central induction coil 254, located at the bottom of the source, provides advantageous source tunability. The lower location of the second coil is achieved through the use of one or more magnetic field concentrators 280, which couple the coil to the plasma rather than to the surrounding metal (e.g., 290). In this manner, processing processes performed on substrates using the plasma processing apparatus 200 can be made more uniform.

[0043]

[0052] FIG. 3 is a schematic diagram of a plasma processing apparatus 300. The plasma processing apparatus 300 includes a plasma source 322 and a processing chamber 220. The plasma source 322 includes a gas inject insert 302 having a peripheral gas inject port 270 and a central gas inject port 310. The central gas inject port 310 is formed by a top plate 318 and a bottom plate 340, which form a plenum 316. The bottom plate 340 has a plurality of holes (through-holes) 312 so that the central gas inject port 310 / gas inject insert 302 can have a plurality of holes (through-holes) 312 for supplying process gases into a central process region 314. The dimensions of the central process region 314 are determined by portions of the gas inject insert 302, namely, the central gas inject port 310 and a sidewall 320. The sidewall 320 has a cylindrical shape and is made of a dielectric material. For example, the sidewall 320 may be made of quartz or alumina. The dimensions of region 272 are determined by dielectric sidewall 232 and gas inject insert 302, i.e., peripheral gas inject port 270 and sidewall 324. Sidewall 324 (and gas inject insert 302 generally) can have a cylindrical shape. The surface material of sidewall 324 can be a dielectric material or a metal. For example, sidewall 324 can be formed of aluminum and covered with quartz or alumina, or the aluminum surface can be bare or anodized. Additionally, a first Faraday shield (not shown) can be disposed between peripheral inductive coil 252 and dielectric sidewall 232. Similarly, a second Faraday shield (not shown) can be disposed between central inductive coil 254 and sidewall 320. In some embodiments, sidewall 320 is quartz or ceramic and / or has a thickness of about 2.5 mm to about 5 mm.

[0044]

[0053] The flow rate of process gas supplied by peripheral gas injection port 270 through conduit 326 to region 272 can be greater than the flow rate of process gas supplied by central gas injection port 310 to central process region 314. In some embodiments, the ratio of the flow rate of process gas supplied by peripheral gas injection port 270 to the flow rate of process gas supplied by central gas injection port 310 is from about 2:1 to about 20:1, for example, from about 5:1 to about 10:1. Providing a higher flow rate to region 272 than to central process region 314 improves the center-edge uniformity of the plasma across the substrate surface of a substrate present in processing chamber 220.

[0045]

[0054] The plasma processing apparatus 300 further includes a peripheral induction coil 252 and a central induction coil 254. The RF power supplied by the peripheral induction coil 252 can be greater than the RF power supplied by the central induction coil 254. In some embodiments, the ratio of the RF power supplied by the peripheral induction coil 252 to the RF power supplied by the central induction coil 254 is about 2:1 to about 20:1, for example, about 3:1 to about 10:1, for example, about 5:1. When the central coil is not energized, the secondary plasma source acts as an auxiliary gas injection that reduces the flux of radicals and ions / electrons generated by the peripheral induction coil 252 toward the center of the substrate. During conventional plasma processes, plasma density is typically higher at the center of the substrate; therefore, supplying greater RF power to the central induction coil 254 than to the peripheral induction coil 252 facilitates an increase in plasma density at one or more edges of the substrate, improving plasma uniformity. One or more plasma separators 304 (cylindrical protrusions) are located between the center and edge areas to enhance the ability for independent center-to-edge plasma control.

[0046]

[0055] The peripheral induction coil 252 and the central induction coil 254 may be operable to generate (or modify) an inductive plasma within the plasma source interior 330. For example, the plasma processing apparatus 300 may include a first radio frequency power generator 262 (e.g., an RF generator and a matching network) connected to the peripheral induction coil 252. The central induction coil 254 is connected to a second radio frequency power generator 264 (e.g., an RF generator and a matching network). The frequency and / or power of the RF energy applied to the peripheral induction coil 252 by the first radio frequency power generator 262 and to the central induction coil 254 by the second radio frequency power generator 264, respectively, may be adjusted to be the same or different to control process parameters of the substrate processing process.

[0047]

[0056] For example, the frequency and / or power of the RF energy applied by the second radio frequency power generator 264 may be lower than the frequency and / or power of the RF energy applied by the first radio frequency power generator 262. The first radio frequency power generator 262 is operable to energize the peripheral induction coil 252 to generate an inductive plasma in the plasma source interior 330. In particular, the first radio frequency power generator 262 energizes the peripheral induction coil 252 with radio frequency (RF) alternating current (AC) such that the AC induces an alternating magnetic field inside the peripheral induction coil 252 that heats the gas to generate the inductive plasma. In some embodiments, RF power is supplied to the peripheral induction coil 252 at about 1 kW to about 15 kW, e.g., about 3 kW to about 10 kW.

[0048]

[0057] The second radio frequency power generator 264 is operable to energize the central induction coil 254 to generate and / or modify an inductive plasma in the central process region 314 of the plasma source 322. In particular, the second radio frequency power generator 264 energizes the central induction coil 254 with radio frequency (RF) alternating current (AC) such that the AC induces an alternating magnetic field within the central induction coil 254 that heats the gas to modify the inductive plasma. In some embodiments, RF power is supplied to the central induction coil 254 at about 0.3 kW to about 3 kW, e.g., about 0.5 kW to about 2 kW. The central induction coil 254 can modify the plasma in the plasma processing apparatus 300. For example, the central induction coil 254 can adjust the radial profile of the plasma to promote more uniformity of the plasma moving toward the substrate in the processing chamber 220.

[0049]

[0058] In some embodiments, the plasma processing apparatus 300 includes peripheral gas injection ports 270 operable to inject process gas into a periphery of a region 272 along the vertical surface of the dielectric sidewall 232, which defines one or more active plasma generation regions adjacent the vertical surface of the dielectric sidewall 232. For example, the peripheral induction coil 252 may be operable to generate a plasma in the region 272 adjacent the vertical surface of the dielectric sidewall 232. The central induction coil 254 may be operable to create and / or modify a plasma present in the central process region 314 adjacent the vertical surface of the sidewall 320. The gas injection insert 302, in some embodiments, may further define an active region for generation of plasma within the plasma source adjacent the vertical surface of the dielectric sidewall 232 and the vertical surface of the sidewall 320.

[0050]

[0059] In practice, the substrate may be provided with some overlap of the process plasma formed in the central process region 314 with the process plasma formed in region 272. Overall, the peripheral gas injection ports 270 / central gas injection ports 310 and the peripheral induction coil 252 / central induction coil 254 may improve plasma and process uniformity (center-to-edge plasma control) for treating a substrate with plasma. To enhance center-to-edge process control, the gas injection insert 302 includes one or more plasma separators 304. The one or more plasma separators 304 may be uniform cylindrical separators connected to (e.g., disposed along) the surface 180.

[0051]

[0060] Furthermore, in embodiments in which the process gas supplied by the central gas injection port 310 is different from the process gas supplied by the peripheral gas injection port 270, new plasma chemistries may be obtained compared to conventional plasma processes using conventional plasma sources. For example, advantageous processing of substrates may be provided that is not obtainable with conventional plasma processing. For example, unique mixtures of plasmas may be generated when mixing a plasma-generated flow of radicals and excited species (e.g., in some embodiments of region 272) with a different plasma flow enriched in a different type of plasma species (e.g., different radicals). In addition, the formation of these unique plasma chemistries may be obtained, for example, in embodiments utilizing alignment of the surface 180 with a portion of the peripheral inductive coil 252, as described above.

[0052]

[0061] FIG. 4 is a schematic diagram of a plasma processing apparatus 400. The plasma processing apparatus 400 includes a plasma source 422. The plasma source 422 includes a gas inject insert 402, which may be integrated with the top cover, a peripheral gas inject port 270, and a central gas inject port 410. The central gas inject port 410 is disposed within the gas inject insert 402 and fluidly connects the central gas inject port 410 to a gas supply plenum 416 of the gas inject insert 402. The gas supply plenum 416 provides an increased diameter (compared to the diameter of the central gas inject port 410) to ensure that the process gas is evenly distributed before entering the exhaust region between the bottom of the gas inject insert 402 and the platform 414. Once the gas is delivered through the holes 412, the platform 414 provides a second gas supply plenum to facilitate an outward flow of the gas to the periphery of the plasma source 422 (e.g., within region 272). In some embodiments of the present disclosure, no material is present to form the holes 412, and a larger plenum is formed. The platform 414 can be connected to the gas injection insert 402 via multiple screws or bolts (not shown). The platform 414 can be made of quartz or ceramic. The platform 414 can have any suitable design and accommodate different materials. The outward / lateral flow of gas promoted by the platform 414 can affect the gas / plasma flow profile relative to the substrate being processed, improving center-to-edge uniformity compared to conventional plasma processing devices. Furthermore, this outward flow of gas to a region adjacent to the plasma generation region (e.g., region 272) of the plasma source 422 provides advantages. Because a high plasma density can be created in region 272 adjacent to the top of the induction coil 130, the electric field does not penetrate far from the coil. Therefore, gas from the central inlets 410-416-414 does not experience significant ionization or dissociation, but the gas can chemically interact with the high density of radicals and ions generated in region 272. Both radicals and ions become chemically activated and interact with fresh feed gas from the central inlet 410-416-414.The new feed gases, radicals, and ions can create new plasma chemistries compared to conventional plasma sources using plasma processing chambers. For example, when mixing a plasma-generated flow of radicals and excited species (e.g., some embodiments of region 272) with a new flow of gas that does not pass through region 272 with hot electrons (e.g., process gas supplied by central gas injection port 410 and platform 414 / region 418), a unique mixture of plasmas can be created. For example, H obtained in the plasma from a H feed gas. + The flow of H- and H-radicals (e.g., from gas supplied by peripheral gas injection port 270) can be mixed with the flow of oxygen O2 (e.g., from gas supplied by central gas injection port 410), thereby significantly increasing the fraction of HO2, HO, HO2, and other non-equilibrium molecules in the region adjacent to region 272 associated with induction coil 130. Additionally, the formation of these unique plasma chemistries can be achieved in embodiments utilizing, for example, alignment of the edge of surface 180 with a portion of induction coil 130, as described above.

[0053]

[0062] In some embodiments, the ratio of the flow rate of the process gas supplied by the peripheral gas injection port 270 to the flow rate of the process gas supplied by the central gas injection port 410 is from about 20:1 to about 1:20, such as from about 10:1 to about 1:10, such as from about 2:1 to about 1:2, such as from about 1.2:1 to about 1:1.2, such as about 1:1. Such flow rates may provide stoichiometries (e.g., substantially equimolar amounts) of the different process gases to provide desired densities of chemical species in the plasma formed in region 272.

[0054]

[0063] Additionally, the outward / lateral flow provided by the central gas injection port 410 and platform 414 / region 418 can modify the flow pattern within the plasma source 422, which affects the delivery profile of radicals to the substrate. For example, in embodiments where the process gas supplied by the central gas injection port 410 is substantially the same as the process gas supplied by the peripheral gas injection ports 270, more plasma flow is promoted toward the edge of the substrate, improving the center-to-edge plasma profile (e.g., uniformity of the plasma delivered to the substrate).

[0055]

[0064] Furthermore, in embodiments in which the process gas supplied by the central gas injection port 410 is different from the process gas supplied by the peripheral gas injection port 270, new plasma chemistries may be achieved compared to conventional plasma processes using conventional plasma sources. For example, advantageous processing of substrates may be provided that is not obtainable with conventional plasma processing. For example, unique plasma mixtures may be created when the plasma-generated flow of radicals and excited species (e.g., in some embodiments of region 272) is mixed with a new flow of gas that does not pass through the plasma region with hot electrons. For example, the flow of N-radicals obtained in the plasma from an N2 feed gas can be mixed with a flow of nitrogen (N2), hydrazine, and / or NH3. Here, a number of different radicals, such as NH, NH2 molecules, etc., can be generated in regions of the plasma processing device 400 downstream of region 272. Furthermore, the formation of these unique plasma chemistries may be achieved, for example, in embodiments utilizing the alignment of surface 180 with a portion of peripheral inductive coil 252, as described above.

[0056]

[0065] FIG. 5 is a schematic diagram of a plasma processing apparatus 500. The plasma processing apparatus 500 includes a plasma source 522 and a processing chamber 220. The plasma source 522 includes a gas injection insert 240, peripheral gas injection ports 270, a central gas injection port 510, and a top plate 124. The central gas injection port 510 can be located proximate (e.g., adjacent) to a wall 550. The central gas injection includes the central gas injection port 510 with a generally cylindrical plenum / manifold and multiple angled outlets 512 uniformly spread along the plenum. The gas injection insert 240 can also have a generally cylindrical shape. The central gas injection port 510 has angled outlets 512 to promote outward / lateral flow of process gas delivered by the central gas injection port 510 and angled outlets 512. The angled outlet 512 may have an angle relative to a vertical axis (such as the vertical axis 186 parallel to the axial centerline of the plasma processing apparatus 500 and / or the axial centerline of the plasma source 522) that is between about 0 degrees and about 90 degrees, for example, between about 30 degrees and about 60 degrees, for example, about 45 degrees.

[0057]

[0066] The outward / lateral gas flow promoted by the angled outlet 512 may affect the gas / plasma flow profile relative to the substrate being processed, improving center-to-edge uniformity compared to conventional plasma processing equipment. Furthermore, because a high plasma density can be generated in the region adjacent to the inductive coil 130 (the electric field does not penetrate far from the coil), new plasma chemistries may be achieved compared to conventional plasma processing using a plasma processing chamber. For example, unique plasma mixtures can be created when the plasma-generated flow of radicals and excited species (e.g., in some embodiments of region 272) is mixed with a new flow of gas that does not pass through the plasma region with hot electrons (e.g., process gas supplied by the central gas injection port 510 and angled outlet 512). For example, a flow of N-radicals obtained within the plasma from the N2 supply gas (e.g., from gas supplied by the peripheral gas injection port 270) can be mixed with a flow of N2, hydrazine, and / or NH3 (e.g., from gas supplied by the central gas injection port 510). Here, molecular radicals such as NH, NH molecules, etc. can be generated in the region 272 adjacent to the inductive coil 130. Additionally, the formation of these unique plasma chemistries can be achieved in embodiments that utilize the alignment of the inductive coil 130 with the surface 180, as described above.

[0058]

[0067] In some embodiments, the ratio of the flow rate of the process gas supplied by the peripheral gas injection port 270 to the flow rate of the process gas supplied by the central gas injection port 510 is from about 2:1 to about 1:2, such as from about 1.2:1 to about 1:1.2, such as about 1:1. Such flow rates may provide stoichiometries (e.g., substantially equimolar amounts) of the different process gases to provide desired densities of chemical species in the plasma formed in region 272.

[0059]

[0068] Additionally, the outward / sideward flow provided by the central gas injection port 510 and angled outlet 512 can modify the flow pattern within the plasma source 522, which affects the delivery profile of radicals to the substrate. For example, in embodiments where the process gas supplied by the central gas injection port 510 is substantially the same as the process gas supplied by the peripheral gas injection ports 270, more plasma flow is promoted toward the edge of the substrate, improving the center-to-edge plasma profile (e.g., uniformity of the plasma delivered to the substrate).

[0060]

[0069] Furthermore, the gas injection insert 240 of FIG. 5 has a fixed edge at the surface 180, defining an active area that indicates the axis 184 (or alignment level) of the induction coil 130. The induction coil 130 is substantially aligned with the surface 180 so that the upper turns of the coil are positioned above the axis 184 (surface 180) and the lower turns are positioned below the edge. Furthermore, the coil position can be adjusted within this range based on process results. Aligning the vertical center of the coil with the surface 180 improves source efficiency. That is, the generation of chemical species required for the plasma process is controlled and delivered to the substrate with minimal loss. For example, plasma sustaining conditions (balance of local ion generation and loss) may not work well to generate species for the plasma process. With regard to the delivery of species to the substrate, efficiency may depend on the volume and wall recombination of these specific species. Therefore, controlling the alignment of the induction coil 130 with the surface 180 (edge) results in control of the source efficiency of the plasma process.

[0061]

[0070] In some embodiments, by utilizing an appropriately sized gas inject insert 240 to form plasma source 120, the bottom surface of gas inject insert 240 is aligned with insert surface 180, which defines the active area for the coil (this alignment level is shown as axis 184). Alternatively, the bottom surface of gas inject insert 240 can be flexible using a movable central portion of gas inject insert 240, as shown in FIG. 5, while the remainder of gas inject insert 240 is fixed as part of plasma source 120. For example, mechanism 170 can be electronically connected to the central portion of gas inject insert 240 to adjust the central portion such that the central portion has a first position relative to a second position. In some embodiments, the difference in position from the first position to the second position is about 0.1 cm to about 10 cm, e.g., about 1 cm to about 2 cm. Mechanism 170 can be any suitable mechanism, such as an actuator, for example, a motor, an electric motor, a stepper motor, or a pneumatic actuator. Movement of the central portion of gas inject insert 240 by mechanism 170 increases or decreases the space between the central portion and top plate 124 .

[0062]

[0071] Generally, moving the center of the gas injection insert 240 downward along the vertical direction V reduces the flow of activated species toward the center of the substrate, thereby decreasing the center-to-edge process rate, while moving the center upward increases the center-to-edge process rate.

[0063]

[0072] Although the figures are described independently, it should be understood that one or more embodiments from one figure may be beneficially combined with one or more embodiments from a different figure. For example, gas inject insert 140 of Figure 1 or gas inject insert 240 of Figure 2 may be configured with gas inject insert 302 of Figure 3, gas inject insert 402 of Figure 4, or gas inject insert 240 of Figure 5 and center gas inject port 510. As another non-limiting example, edge gas inject port 290 may be included as an embodiment with plasma processing apparatus 300 of Figure 3, plasma processing apparatus 400 of Figure 4, and plasma processing apparatus 500 of Figure 5.

[0064]

[0073] 7 is an inductive coil 130 that can be used with a plasma source. The inductive coil 130 includes multiple coil loops, including coil loop 182. The inductive coil 130 includes three complete coils, although more or fewer coils are contemplated. For example, the inductive coil can have two to six complete turns for an RF frequency of 13.56 MHz. For lower RF frequencies, more turns may be utilized.

[0065] Example

[0074] The present disclosure also relates to plasma processing of substrates using the plasma processing apparatus of the present disclosure. In some embodiments, the plasma processing is, for example, a nitridation method that increases the amount of nitrogen in the processed substrate. The nitridation method is radical species nitridation using plasma processing. Method embodiments described herein may enable higher nitrogen doses and nitride thicknesses in processed substrates with lower thermal budgets, for example, compared to conventional nitridation methods. Furthermore, the methods described herein may be highly conformal in high aspect ratio structures. Furthermore, the methods described herein may be cyclical, combined with hydrogen radical treatments, and / or combined with oxygen radical treatments to achieve desired results. The nitridation methods described herein may be performed in a single chamber with other processes, such as other radical treatment processes. The nitridation method embodiments described herein may be selective, for example, depending on the substrate and nitrogen-containing source.

[0066]

[0075] 8 is a flowchart illustrating exemplary steps of a method 800 for plasma processing a substrate using the plasma processing apparatus of the present disclosure. The embodiments of the plasma processing apparatus shown in FIGS. 1 through 7 can be utilized with method 800, but the method is not limited to such embodiments.

[0067]

[0076] The method 800 includes introducing a process gas into a plasma processing source in step 810. The process gas and its flow rate are selected based on the particular substrate processing application. Generally, the process gas may include at least one of N, NH, hydrazine (N, H), O, H, a noble gas (He, Ar, Ne, Kr, Xe), or a combination thereof. The noble gas may function as a carrier gas. The flow rate of the process gas and / or carrier gas may be from about 50 sccm to about 20,000 sccm, as further described below. Other process gases and / or carrier gases and their flow rates are also contemplated.

[0068]

[0077] Illustrative, but non-limiting examples of substrates that can be utilized in the methods described herein include silicon-containing substrates such as crystalline Si (c-Si), amorphous Si (a-Si), and polycrystalline Si (poly-Si); silicon- and germanium-containing substrates such as SiGe, amorphous SiGe (a-SiGe), polycrystalline SiGe (poly-SiGe); and silicon oxides (SiO ) such as SiO . x ) and silicon nitrides such as Si3N4 (SiN x ) and hafnium oxide such as HfO2 (HfO x ) and hafnium zirconium oxide (Hf x Zr y O z ) and combinations thereof. Other substrates are also contemplated.

[0069]

[0078] The substrate can be a logic CMOS structure such as a planar FET, FinFET, and gate-all-around structure, a dynamic random access memory (DRAM) structure, a 3D NAND structure, and a high aspect ratio structure having an aspect ratio of about 20:1 or greater, for example, from about 20:1 to about 200:1, for example, from about 100:1 to about 200:1.

[0070]

[0079] The method 800 further includes, in step 820, providing radio frequency power to generate an inductively coupled plasma in the plasma source. The radio frequency power can be controlled based on the particular substrate processing application. Generally, the radio frequency power can be from about 1 kW to about 10 kW, although other power levels are contemplated. From the interior region of the plasma source, neutral particles and / or radicals of the inductive plasma flow through a separation grid to the substrate in the processing chamber. Although a separation grid is shown in FIG. 1, the method 800 can be performed without a separation grid.

[0071]

[0080] The method 800 further includes processing the substrate in a processing chamber in step 830. The temperature and pressure of the processing chamber can be controlled based on the particular substrate processing application. Generally, in some embodiments, the processing chamber can be operated at a temperature from about 100° C. to about 1200° C., e.g., from about 150° C. to about 650° C., and / or a pressure from about 0.025 Torr (25 milliTorr (mTorr)) to about 5 Torr, e.g., from about 0.050 Torr (50 mTorr) to about 2 Torr. However, other temperatures and pressures are also contemplated.

[0072]

[0081] The heat source used to control the temperature of the processing chamber may include a lamp 176 (or lamps) positioned above the substrate, a lamp (or lamps) positioned below the substrate, a heater embedded within the substrate support, or a combination thereof. When heating is performed using a lamp source positioned above the substrate, plasma injection will occur from the side of the processing chamber. Other heat sources are also contemplated. These or other heat sources may be operated at the temperatures described herein. In some examples, the substrate is heated using a ceramic resistive heater and / or an array of lamps.

[0073]

[0082] A substrate in a processing chamber can be exposed to neutral particles and / or radicals generated in an inductive plasma that passes through a separation grid. The plasma, including the neutral particles and / or radicals contained therein, can contact a first side of the substrate facing the plasma source. In some embodiments, the substrate is heated using a heat source (e.g., multiple lamps) positioned opposite the first side of the substrate. The neutral particles and / or radicals can be used, for example, as part of a surface treatment process for the substrate. In practice, gas flow rates and / or gas ratios can be selected such that the surface of the substrate is saturated with a reactant supply of neutral particles and / or radicals. The ability of the apparatus disclosed herein to provide surface saturation of reactive species can be attributed to the very high density of the source and the short distance between the plasma source and the substrate.

[0074]

[0083] In plasma processing processes without surface saturation, the arrival rate of reactive species at the substrate surface determines the reaction rate and / or incorporation rate of the reactive species. However, using the apparatus and / or methods disclosed herein, reactive species are saturated on the surface with a high species flux such that diffusion of the reactive species becomes the dominant factor. Because temperature determines the diffusion of reactive species and drives the reaction, the reaction is temperature dependent. Because thermal energy is inherently conformal and substantially uniform in three dimensions, the temperature-based controlled methods disclosed herein result in more conformal surface processing compared to plasma processing processes where the arrival rate of reactive species determines the rate.

[0075]

[0084] Generally, the processing time for step 830 can be from about 10 seconds to about 10 minutes depending on the particular substrate processing application, although other processing times are contemplated. It will be understood that method 800 can be performed using any of the plasma processing apparatuses of the present disclosure.

[0076]

[0085] The plasma can be generated by supplying RF energy to one or more inductive coils proximate to the plasma source to generate a plasma using a process gas introduced into the plasma source. For example, the process gas can be received in the plasma source from a gas source. RF energy from one or more RF sources can be applied to the inductive coils to generate a plasma in the plasma source.

[0077]

[0086] Generally, method 800 can be used for an array of different substrate processing applications, including, but not limited to, nitrogen radical processing (e.g., nitridation), oxygen radical processing (e.g., oxidation), hydrogen radical processing, helium radical processing, and various pre- and post-processing processes.

[0078]

[0087] 9 is a flow diagram of a method 900 for plasma processing a substrate using a plasma processing apparatus of the present disclosure. Embodiments and implementations of method 800 can be utilized with method 900. The embodiments of the plasma processing apparatus shown in FIGS. 1 through 7 can be utilized with method 900, although the method is not limited to such embodiments.

[0079]

[0088] The method 900 begins with positioning a substrate in a processing chamber at step 910. For example, the substrate 114 may be positioned on a substrate support 112 in a processing region / volume of the processing chamber 110. As described herein, the processing chamber may have a plasma processing source integrated within the processing chamber and / or positioned above the processing chamber (or positioned above the processing region / volume of the processing chamber). The plasma processing source includes an inductively coupled plasma source, described further below, that can be operated at a desired power level.

[0080]

[0089] Illustrative, but non-limiting examples of substrates that can be utilized in the method 900 described herein include silicon-containing substrates such as crystalline Si (c-Si), amorphous Si (a-Si), and polycrystalline Si (poly-Si); silicon- and germanium-containing substrates such as SiGe, crystalline SiGe, amorphous SiGe (a-SiGe), polycrystalline SiGe (poly-SiGe); and silicon oxides (SiO ) such as SiO . x ) and silicon nitrides such as Si3N4 (SiN x ) and hafnium oxide such as HfO2 (HfO x ) and hafnium zirconium oxide (Hf x Zr y O z ) and combinations thereof. Other substrates are also contemplated.

[0081]

[0090] The substrate can be a logic CMOS structure such as a planar FET, FinFET, and gate-all-around structure, a DRAM structure, a 3D NAND structure, and a high aspect ratio structure having an aspect ratio of about 20:1 or greater, for example, from about 20:1 to about 200:1, for example, from about 100:1 to about 200:1.

[0082]

[0091] The method 900 further includes flowing a process gas into the plasma processing source in step 920. For example, the process gas may be flowed into a gas injection channel defined between a gas injection insert and a sidewall of the plasma source. The process gas may include a nitrogen-containing source(s) and a carrier gas(es). Illustrative, but non-limiting, examples of nitrogen-containing sources include NH3, N2, hydrazine (N2H4), and combinations thereof. Illustrative, but non-limiting, examples of carrier gases include noble gases such as Ar, He, Ne, Kr, Xe, and combinations thereof.

[0083]

[0092] The flow rate of the nitrogen-containing source into the plasma processing source can be from about 50 sccm to about 5,000 sccm, for example, from about 100 sccm to about 700 sccm, for example, from about 150 sccm to about 650 sccm, for example, from about 200 sccm to about 600 sccm, for example, from about 250 sccm to about 550 sccm, for example, from about 300 sccm to about 500 sccm, for example, from about 350 sccm to about 450 sccm. Higher or lower flow rates of the nitrogen-containing source are contemplated.

[0084]

[0093] The flow rate of the carrier gas into the plasma processing source can be from about 1000 sccm to about 20,000 sccm, for example, from about 1500 sccm to about 4500 sccm, for example, from about 2000 sccm to about 4000 sccm, for example, from about 2500 sccm to about 3500 sccm, for example, from about 2500 sccm to about 3000 sccm, or from about 3000 sccm to about 3500 sccm. Higher or lower flow rates of the carrier gas are contemplated.

[0085]

[0094] In some embodiments, the flow rate of the nitrogen-containing source can be set relative to the flow rate of the carrier gas. For example, the flow rate of the nitrogen-containing source can be about 1% to about 25% of the flow rate of the carrier gas, e.g., about 2% to about 22%, e.g., about 3% to about 20%, e.g., about 5% to about 15%, e.g., about 8% to about 12%, e.g., about 5% to about 10%, or about 10% to about 15% of the flow rate of the carrier gas. In some embodiments, the flow rate of the nitrogen-containing source can be about 3% to about 100%, e.g., about 3% to about 20%, e.g., about 5% to about 15% of the flow rate of the carrier gas. Higher or lower ratios are contemplated. As a non-limiting example, if the flow rate of the nitrogen-containing source is about 300 sccm and the flow rate of the carrier gas is about 3000 sccm, the flow rate of the nitrogen-containing source is about 10% of the flow rate of the carrier gas. Higher or lower relative flow rates are contemplated.

[0086]

[0095] The method 900 may further include generating an inductive plasma (or inductively coupled plasma) in a plasma source in step 930. The inductively coupled plasma includes radical species formed from the process gas, such as radical species formed from one or more nitrogen-containing sources and / or radical species formed from one or more carrier gases. Such radical species may include N and / or NH, e.g., N * and / or NH * The RF power of the ICP source can be operated at a power of about 1,000 W to about 12,000 W, e.g., about 2,000 W to about 10,000 W, e.g., about 3,000 W to about 9,000 W, e.g., about 4,000 W to about 8,000 W, e.g., about 5,000 W to about 7,000 W, although higher or lower powers are contemplated. Here, the RF power generates an inductive plasma (or inductively coupled plasma) adjacent to the plasma source. Radicals and / or neutrals of the inductive plasma can flow through the separation grid to the substrate 114 in the processing chamber. While a separation grid is shown in FIG. 1, the method 900 can also be performed without a separation grid.

[0087]

[0096] In some embodiments, which can be combined with other embodiments, the heat source includes a lamp having a plasma source power that can be adjusted depending on the desired application. The plasma source power can be from about 2 inches in diameter to about 15 inches in diameter, e.g., from about 2 inches in diameter to about 14 inches in diameter, e.g., from about 4 inches in diameter to about 12 inches in diameter, e.g., from about 6 inches in diameter to about 10 inches in diameter. In at least one embodiment, the heat source includes a lamp having a plasma source power of from about 2 inches in diameter to about 12 inches in diameter, or from about 4 inches in diameter to about 12 inches in diameter. These diameters are the diameters of the plasma cavity exit where radical species leave the plasma cavity and travel toward the substrate.

[0088]

[0097] The method 900 may further include treating the substrate (or a layer of the substrate) with a plasma comprising one or more radical species in step 940. The substrate treatment may include nitriding the substrate (or a layer of the substrate). Step 940 may include operating the processing chamber at a selected temperature and pressure. The heat source may be operated at a temperature ranging from about 100° C. to about 1200° C., e.g., from about 150° C. to about 650° C., e.g., from about 200° C. to about 600° C., e.g., from about 250° C. to about 550° C., e.g., from about 300° C. to about 500° C., e.g., from about 350° C. to about 450° C., e.g., from about 350° C. to about 400° C., or from about 400° C. to about 450° C. In some embodiments, the heat source used to control the temperature of the processing chamber may include lamps positioned above the substrate, lamps positioned below the substrate, a heater embedded in the substrate support (e.g., a pedestal having a resistive heating element embedded therein or connected thereto), or a combination thereof. Other heat sources are also contemplated. In some examples, the substrate is heated using ceramic resistive heaters and / or an array of lamps.

[0089]

[0098] The pressure of the processing chamber for step 940 can be set or maintained at a pressure of from about 25 mTorr to about 5 Torr, for example, from about 50 mTorr to about 2 Torr, for example, from about 100 mTorr to about 1.25 Torr, for example, from about 200 mTorr to about 1 Torr, for example, from about 300 mTorr to about 900 mTorr, for example, from about 400 mTorr to about 800 mTorr, for example, from about 500 mTorr to about 700 mTorr, for example, from about 500 mTorr to about 600 mTorr, or from about 600 mTorr to about 700 mTorr. Other temperatures and pressures are contemplated.

[0090]

[0099] The processing time for step 940 can be about 5 seconds or more and / or about 10 minutes or less, e.g., from about 15 seconds to about 10 minutes, e.g., from about 30 seconds to about 5 minutes, e.g., from about 1 minute to about 4 minutes, e.g., from about 2 minutes to about 3 minutes, although longer or shorter processing times are also contemplated.

[0091]

[0100] During step 940, a plasma containing one or more radical species can be introduced into the processing chamber. If necessary, the plasma can be passed through a separation grid. The plasma can contact one or more sides of the substrate while the other side is being heated. For example, the plasma can contact a first side of the substrate while the substrate is heated using a heat source located on a second side of the substrate. The first and second sides can be the same or different sides of the substrate. If a separation grid is used, the first side of the substrate can be the side facing the separation grid.

[0092]

[0101] In step 940, exposing the substrate to a plasma containing one or more radical species can, for example, allow for tailoring of the nitrogen content and other properties of the substrate or substrate layer being processed. For example, the nitride thickness of the substrate can be tailored. That is, the substrate (or substrate layer) can be made more nitrogen dense according to embodiments described herein. After processing the substrate in step 940, the substrate (or substrate layer) can have one or more properties, as described below.

[0093]

[0102] The nitride thickness of the substrate (or a layer of the substrate) can be from about 25 angstroms (Å) to about 50 Å, for example, from about 30 Å to about 40 Å, although greater or lesser nitride thicknesses are contemplated. The nitride thickness is measured by X-ray photoelectron spectroscopy.

[0094]

[0103] The nitride thickness variation of the substrate (or layer of the substrate) can be from about 5 Å to about 50 Å, e.g., from about 10 Å to about 40 Å, e.g., from about 20 Å to about 30 Å. Greater or smaller variations in nitride thickness are contemplated. The nitride thickness variation is measured by X-ray photoelectron spectroscopy.

[0095]

[0104] The number of nitrogen atoms per unit area of ​​the substrate (or layer of the substrate) (nitrogen dosage) is about 5×10 15 atoms / cm 2 From about 50 x 10 15 atoms / cm 2 , e.g., about 10 x 10 15 atoms / cm 2 From about 40 x 10 15 atoms / cm 2 , e.g., about 15 x 10 15 atoms / cm 2 From about 35 x 10 15 atoms / cm 2 , e.g., about 20 × 10 15 atoms / cm 2 From about 30 x 10 15 atoms / cm 2 In at least one embodiment, the number of nitrogen atoms per unit area of ​​the substrate (or layer of the substrate) (nitrogen dosage) can be about 10×10 15 atoms / cm 2 From about 25 x 10 15 atom / cm 2 , for example, about 12 × 10 15 atoms / cm 2 From about 20 x 10 15 atoms / cm 2 , for example, about 14 × 10 15 atoms / cm 2 From about 18 x 10 15 atoms / cm 2, although larger or smaller values ​​are contemplated. The number of nitrogen atoms per unit area is measured by X-ray photoelectron spectroscopy.

[0096]

[0105] The change in the number of nitrogen atoms per unit area (nitrogen dosage) of the substrate (or layer of the substrate) is about, e.g., 1×10 15 atoms / cm 2 From about 50 x 10 15 atoms / cm 2 , 5×10 15 atoms / cm 2 From about 45 x 10 15 atoms / cm 2 , e.g., about 10 x 10 15 atoms / cm 2 From about 40 x 10 15 atoms / cm 2 , e.g., about 15 x 10 15 atoms / cm 2 From about 35 x 10 15 atoms / cm 2 , e.g., about 20 × 10 15 atoms / cm 2 From about 30 x 10 15 atoms / cm 2 In at least one embodiment, the change in the number of nitrogen atoms per unit area (nitrogen dosage) of the substrate (or layer of the substrate) can be about 1×10 15 atoms / cm 2 From about 30x10 15 atoms / cm 2 , 10x10 15 atoms / cm 2 From about 25x10 15 atoms / cm 2 , for example, about 12x10 15 atoms / cm 2 From about 20x10 15 atoms / cm 2 , for example, about 14x10 15 atoms / cm 2 From approximately 18x10 15 atoms / cm 2 , although larger or smaller values ​​are contemplated. The change in the number of nitrogen atoms per unit area is measured by X-ray photoelectron spectroscopy.

[0097]

[0106] The nitrogen content (in atomic percent) in a layer of a substrate (or a layer of a substrate) can be about 1% or more and / or about 45% or less, based on the total amount of material in the layer or substrate, e.g., about 3% to about 40%, e.g., about 5% to about 35%, e.g., about 10% to about 30%, e.g., about 15% to about 25%, e.g., about 10% to about 20%. Higher and lower atomic percent nitrogen values ​​are contemplated. Nitrogen content is measured by X-ray photoelectron spectroscopy.

[0098]

[0107] The change in nitrogen content in a layer of a substrate (or a layer of a substrate) can be about 1% or more and / or about 500% or more, e.g., about 50% to about 400%, e.g., about 75% to about 200%, e.g., about 100% to about 150%. Larger or smaller changes in nitrogen content are contemplated. The change in nitrogen content is measured by X-ray photoelectron spectroscopy. For example, the nitrogen content can increase by about 1% or more and / or 50% or less, e.g., about 5% to about 45%, e.g., about 10% to about 40%, e.g., about 15% to about 35%, e.g., about 20% to about 30%, based on the total amount of material in the layer or substrate.

[0099]

[0108] In a particular example, a substrate undergoing a nitridation process may include a silicon oxide layer having a thickness of about 10 angstroms to about 100 angstroms. During the nitridation of silicon oxide, at least one of diatomic nitrogen (N), ammonia (NH), hydrazine, other nitrogen-containing sources, or mixtures thereof, is introduced into the plasma processing source to form N * and / or NH * Silicon oxide nitridation performed using the plasma processing apparatus and method of the present disclosure can increase the nitrogen content in silicon oxide compared to rapid thermal nitridation processes at approximately the same level of nitrogen conformality. This is because nitrogen radicals (e.g., N * and / or NH * This may be because the NH radical is more reactive than the NH molecule. Furthermore, the silicon oxide nitridation process described herein also improves the conformality of nitrogen in silicon oxide compared to ion-driven separation plasma nitridation processes. The silicon oxide nitridation described herein promotes the transfer of N from the surface to the interface.* and / or NH * Radical diffusion can result in the formation of nitrogen peaks at both the silicon-silicon oxide interface and the silicon oxide surface. Furthermore, the nitridation of silicon oxide described herein can enhance the conformality of gate-all-around (GAA) semiconductor structures. In some examples, when the method is performed using, for example, a larger amount of N than the amount of NH or hydrazine, the nitridation of SiO results in higher nitrogen content, more nitrogen atoms per unit area, thicker nitride, and other properties. In some examples, when the method is performed using, for example, a larger amount of NH or hydrazine than the amount of N, the nitridation of hafnium oxide results in higher nitrogen content, more nitrogen atoms per unit area, thicker nitride, and other properties.

[0100]

[0109] In another example, the plasma processing apparatus of the present disclosure can be used for nitridation of silicon (Si). In a particular example, a substrate subjected to a nitridation method can include a layer of silicon that can be treated with nitrogen radicals to form a conformal layer of silicon nitride (e.g., SiN).

[0101]

[0110] Silicon nitridation performed using the disclosed plasma processing apparatus and methods can form a conformal layer of silicon nitride having a thickness of about 10 angstroms to about 60 angstroms. As an example, the silicon nitridation described herein can form a substantially conformal nitrogen content on the top and bottom sidewalls of the polysilicon in 3D NAND channel polysilicon (stacks with aspect ratios of 10:1 to 200:1).

[0102]

[0111] Before, during, and / or after the nitridation of methods 800 and 900, a cleaning step can be included to pre-clean the substrate (or a layer of the substrate) to remove contaminants, such as surface oxides, from the layer being nitrided as described herein. Surface cleaning can be performed using wet chemicals such as dilute HF, ammonium hydroxide / peroxide, sulfuric acid / peroxide, and combinations thereof. Cleaning can be performed in the same process chamber as the plasma treatment described herein using plasma-generated species such as hydrogen radicals and / or oxygen radicals. Additionally or alternatively, before, during, and / or after nitridation, the substrate can undergo a hydrogen radical treatment and / or an oxygen radical treatment. The cleaning, hydrogen radical treatment, and / or oxygen radical treatment can be performed in the same process chamber as the nitrogen radical treatment (nitridation) or in a separate process chamber. The cleaning, nitrogen radical treatment, hydrogen radical treatment, and / or oxygen radical treatment can be performed in a cyclical process.

[0103]

[0112] The methods described herein can be used to nitride silicon (e.g., nitridation of bare Si). In addition, the methods described herein can be used to nitride amorphous silicon (a-Si). Here, the inventors have found that the embodiments described herein enable similar nitridation rates for both crystalline and amorphous silicon, for example. The nitridation processes described herein can be used with or without a separation lattice.

[0104]

[0113] Nitridation using different plasma source power densities was also compared. It was found that plasma source powers with smaller diameters (e.g., plasma source interior 125) provided similar or even better nitride thickness and nitrogen atoms per unit area compared to plasma source powers with larger diameters. Here, the inventors have found that the methods described herein can increase, for example, the thickness of the nitrogen.

[0105]

[0114] Nitridation of SiO films, such as PECVD oxide films and thermally grown oxide films, has also been investigated. The inventors have found that embodiments of the nitridation methods described herein can be used to increase the nitrogen content of these and other SiO films. Furthermore, transmission electron microscopy (TEM) measurements were performed to measure the nitride thickness of 3D NAND memory holes. TEM measurements indicated that the nitridation described herein can be greater than 90% conformal, with the nitride thickness at the top of the memory hole being very close to the nitride thickness at the bottom of the memory hole. Therefore, the nitridation methods described herein can be performed on advanced semiconductor structures, such as DRAM structures, 3D NAND structures, and high aspect ratio structures (e.g., about 100:1 to about 200:1).

[0106]

[0115] Overall, the methods described herein enable the nitridation of a variety of substrates. Embodiments of the methods described herein can achieve, for example, higher nitrogen doses (more nitrogen atoms per area of ​​substrate), greater nitride thicknesses, greater nitride depths, and improved conformality than existing processes.

[0107]

[0116] As is apparent from the foregoing general description and specific embodiments, while forms of the present embodiment have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited to the forms of the present disclosure shown and described. Similarly, the term "comprising" is considered synonymous with the term "including." Similarly, whenever a composition, element, or group of elements is preceded by the transitional phrase "comprising," it is understood that the same composition or group of elements having the transitional phrase "consisting essentially of," "consisting of," "selected from the group of consisting of," or "is" preceding the list of one or more elements is also contemplated, and vice versa. For example, the terms "comprising," "consisting essentially of," and "consisting of" include any combination of the elements listed after the term.

[0108]

[0117] For purposes of this disclosure, unless otherwise specified, all numerical values ​​in the detailed description and claims herein are modified by "about" or "approximately" relative to the stated value, taking into account experimental error and variations that would be expected by one of ordinary skill in the art. For purposes of brevity, only certain ranges are expressly disclosed herein. However, a range from any lower limit may be combined with any upper limit to describe a range not expressly recited. Similarly, a range from any lower limit may be combined with any other lower limit to describe a range not expressly recited. Similarly, a range from any upper limit may be combined with any other upper limit to describe a range not expressly recited. Furthermore, a range includes every point or individual value between its endpoints, even if not expressly recited. Thus, to describe a range not expressly recited, every point or individual value may serve as its own lower or upper limit in combination with any other point or individual value, or any other lower or upper limit. As used herein, the term "approximately" or "about" refers to being within at least ±5% of a reference value.

[0109]

[0118] As used herein, the indefinite article "a" or "an" means "at least one" unless specifically stated to the contrary or the context clearly indicates otherwise. For example, an embodiment including a "nanotube" includes embodiments including one, two, or more nanotubes unless specifically stated to the contrary or the context clearly indicates that only one nanotube is included.

[0110]

[0119] As used herein, terms such as "inner" and "outer," "up" and "down," "top" and "bottom," "vertical" and "horizontal," "upward" and "downward," "above" and "below," and other similar terms used herein refer to relative positions with respect to each other and are not intended to indicate a particular direction or spatial orientation of the overall source / device.

[0111]

[0120] While the forgoing is directed to embodiments of the present disclosure, other and further embodiments of the present disclosure may be devised without departing from the basic scope thereof.

Claims

1. 1. A method for nitriding a substrate, comprising: positioning the substrate on a substrate support within a processing space of a processing chamber; flowing a nitrogen-containing source and a carrier gas into a plasma processing source connected to the processing chamber such that the flow rate of the nitrogen-containing source is between 3% and 20% of the flow rate of the carrier gas; generating an inductively coupled plasma in the plasma processing source by operating an inductively coupled plasma source at a power of 2,000 W to 10,000 W, wherein the inductively coupled plasma comprises radical species formed from the nitrogen-containing source, the carrier gas, or both; nitriding the substrate in the processing chamber, operating a heat source within the processing chamber at a temperature between 150° C. and 650° C. to heat the substrate; maintaining the pressure of the processing chamber at 50 mTorr to 2 Torr; introducing the inductively coupled plasma into the processing chamber; and adjusting the nitrogen content, the number of nitrogen atoms per unit area, the nitride thickness, or a combination thereof, of the substrate by exposing the substrate to the radical species; nitriding the substrate; Including, the plasma processing source a gas injection channel defined between a gas injection insert and a sidewall of the plasma processing source; an induction coil positioned proximate to the sidewall and horizontally overlapping the gas injection channel; Equipped with The method, wherein flowing the nitrogen-containing source and the carrier gas into the plasma processing source comprises flowing the nitrogen-containing source and the carrier gas into the gas injection channel.

2. H ２ is co-flowed with the nitrogen-containing source, and the inductively coupled plasma is ２ 10. The method of claim 1, further comprising forming a radical species from

3. The nitrogen-containing source is NH ３ , N ２ , hydrazine (N ２ H ４ ), or a combination thereof.

4. The method of claim 1 , wherein the carrier gas comprises Ar, He, Ne, Kr, Xe, or a combination thereof.

5. The method of claim 1 , wherein the heat source comprises lamps positioned above the substrate, lamps positioned below the substrate, a heater embedded within the substrate support, or a combination thereof.

6. The method of claim 1 , wherein the heat source has a plasma source output of from 2 inches in diameter to 15 inches in diameter.

7. 10. The method of claim 1, wherein the substrate comprises crystalline silicon, amorphous silicon, polycrystalline silicon, crystalline SiGe, amorphous SiGe, polycrystalline SiGe, silicon oxide, silicon nitride, hafnium oxide, hafnium zirconium oxide, or a combination thereof.

8. Furthermore, performing an oxygen radical treatment before or after nitriding the substrate; performing a hydrogen radical treatment before or after nitriding the substrate; or A combination of these The method of claim 1 , comprising:

9. 9. The method of claim 8, wherein the oxygen radical treatment, the hydrogen radical treatment, or both, are performed in the same processing chamber as the substrate nitridation.

10. 1. A method for nitriding a substrate, comprising: positioning the substrate on a substrate support within a processing space of a processing chamber; generating an inductively coupled plasma in a plasma processing source connected to the processing chamber; operating the inductively coupled plasma source at a power of 2,000 W to 10,000 W; flowing hydrazine and a carrier gas into the plasma processing source such that the flow rate of the hydrazine is between 3% and 100% of the flow rate of the carrier gas, wherein the carrier gas comprises Ar, He, Ne, Kr, Xe, or a combination thereof; and forming the inductively coupled plasma containing radical species including N, NH, or a combination thereof; generating an inductively coupled plasma, nitriding the substrate in the processing chamber, operating a heat source within the processing chamber at a temperature between 150° C. and 650° C. to heat the substrate; maintaining the pressure of the processing chamber at 50 mTorr to 2 Torr; introducing the inductively coupled plasma into the processing chamber; and adjusting the nitrogen content, the number of nitrogen atoms per unit area, the nitride thickness, or a combination thereof, of the substrate by exposing the substrate to the inductively coupled plasma containing the radical species. nitriding the substrate; Including, the plasma processing source a gas injection channel defined between a gas injection insert and a sidewall of the plasma processing source; an induction coil positioned proximate to the sidewall and horizontally overlapping the gas injection channel; Equipped with The method, wherein flowing the hydrazine and the carrier gas into the plasma processing source comprises flowing the hydrazine and the carrier gas into the gas injection channel.

11. 11. The method of claim 10, wherein the flow rate of the hydrazine is 5% to 15% of the flow rate of the carrier gas.

12. the pressure is between 200 mTorr and 1 Torr; the temperature is between 500°C and 650°C; nitriding the substrate is performed in 5 minutes or less; or It is a combination of these, The method of claim 10.

13. The method of claim 10 , wherein the heat source has a plasma source output of 4 inches to 15 inches in diameter.

14. H ２ is co-flowed with the hydrazine, and the inductively coupled plasma is ２ and further comprising a radical species generated from NH ３ , N ２ or a combination thereof is co-flowed with the hydrazine, and the inductively coupled plasma is ３ , N ２ or a combination thereof, or It is a combination of these, The method of claim 10.

15. 1. A method for nitriding a substrate, comprising: positioning a substrate comprising silicon on a substrate support within a processing space of a processing chamber; generating an inductively coupled plasma in a plasma processing source connected to the processing chamber; operating the inductively coupled plasma source at a power of 2,000 W to 10,000 W; flowing a nitrogen-containing source and a carrier gas into the plasma processing source such that the flow rate of the nitrogen-containing source is between 3% and 100% of the flow rate of the carrier gas, wherein the carrier gas comprises Ar, He, Ne, Kr, Xe, or a combination thereof; and forming the inductively coupled plasma containing radical species including N, NH, or a combination thereof; generating an inductively coupled plasma, nitriding the substrate in the processing chamber, operating a heat source within the processing chamber at a temperature between 150° C. and 650° C. to heat the substrate; maintaining the pressure of the processing chamber at 50 mTorr to 2 Torr; introducing the inductively coupled plasma into the processing chamber; and adjusting the nitrogen content, the number of nitrogen atoms per unit area, the nitride thickness, or a combination thereof, of the substrate by exposing the substrate to the inductively coupled plasma containing the radical species. nitriding the substrate; Including, the plasma processing source a gas injection channel defined between a gas injection insert and a sidewall of the plasma processing source; an induction coil positioned proximate to the sidewall and horizontally overlapping the gas injection channel; Equipped with The method, wherein flowing the nitrogen-containing source and the carrier gas into the plasma processing source comprises flowing the nitrogen-containing source and the carrier gas into the gas injection channel.

16. The method of claim 15 , wherein the substrate comprises silicon germanium (SiGe).

17. the flow rate of the nitrogen-containing source is 5% to 15% of the flow rate of the carrier gas; the pressure is between 200 mTorr and 1 Torr; the temperature is between 500°C and 650°C; nitriding the substrate is carried out for 10 minutes or less; or It is a combination of these, 16. The method of claim 15.

18. H ２ is co-flowed with the nitrogen-containing source, and the inductively coupled plasma is ２ and further comprising a radical species formed from the plasma processing source is integrated within the processing chamber; or It is a combination of these, 16. The method of claim 15.

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