TITLE OF THE INVENTION

MULTI-SOURCE METHOD AND SYSTEM FOR FORMING AN OXIDE LAYER

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is based on and derives the benefit of the filing date of United States Patent Application No. 11/231,336, filed September 21, 2005. The entire contents of this application is herein incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

Field of the Invention

[0001] The present invention generally relates to methods and systems suitable for producing electric devices and materials used for electronic devices.

BRIEF SUMMARY OF THE INVENTION

[0002] This invention generally relates to a method for preparing an oxide film on a substrate. A surface of a substrate is oxidized to form an oxide film. The surface is exposed to oxygen radicals formed by ultraviolet (UV) radiation induced dissociation and plasma induced dissociation of a first process gas comprising at least one molecular composition comprising oxygen.

BRIEF DESCRIPTION OF THE FIGURES

[0003] FIG, 1 illustrates one embodiment of a treatment system for forming an oxide layer on a substrate.

[0004] FIG. 2 illustrates one embodiment of schematic diagram of a processing system for performing an oxidation process.

[0005] FIG. 3 illustrates one embodiment of an alternative processing system.

[0006] FIG. 4 illustrates one embodiment of a plasma processing system containing a

slot plane antenna (SPA) plasma source for forming an oxide layer on a substrate or for processing a gate stack.

DETAILED DESCRIPTION OF SEVERAL EMBODIMENTS

UVO? and Plasma Oxidation

[0007] FIG. 1 illustrates a treatment system 1 for forming an oxide and/or oxynitride layer on a substrate. For example, the substrate can comprise a silicon substrate, and the oxide layer can comprise a silicon oxide layer formed via oxidation of the substrate. The substrate surface can be a silicon surface, an oxide surface, or a silicon oxide surface.

[0008] The treatment system 1 comprises an oxidation system 10 configured to introduce an oxygen containing molecular composition to the substrate, and an oxidation and/or nitridation system 20 configured to introduce an oxygen and/or nitrogen containing molecular composition to the substrate in the case of subsequent oxidation, nitridation or oxynitridation. Additionally, treatment system 1 further comprises a controller 30 coupled to the oxidation system 10 and the oxidation and/or nitridation system 20, and configured to perform at least one of monitoring, adjusting, or controlling the process(es) performed in the oxidation system 10 and the oxidation and/or nitridation system 20. Although the oxidation system 10 and the oxidation and/or nitridation system 20 are illustrated as separate modules in FIG. 1 , they may comprise the same module.

[0009] According to one embodiment, FIG. 2 presents a schematic diagram of a processing system for performing an oxidation process. The processing system 101 comprises a process chamber 110 having a substrate holder 120 configured to support a substrate 125 having a silicon (Si) surface. The process chamber 110 further contains an electromagnetic radiation assembly 130 for exposing the processing gas in chamber 110 to electromagnetic radiation. Additionally, the processing system 101 contains a power source

150 coupled to the electromagnetic radiation assembly 130, and a substrate temperature control system 160 coupled to substrate holder 120 and configured to elevate and control the temperature of substrate 125. A gas supply system 140 is coupled to the process chamber 110, and is configured to introduce a process gas to process chamber 110. For example, in an oxidation process, the process gas can include an oxygen containing gas, such as, for example, O ₂ , NO, NO ₂ or N ₂ O. The process gas can be introduced at a flow rate of about 30 seem to about 5 slm, which includes 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 250, 275, 300, 400, 500, 600, 700, 800, 900, or 1000 (seem), 2, 3, 4, or 5 (slm), or any combination thereof. Additionally (not shown), a purge gas can be introduced to process chamber 110. The purge gas may comprise an inert gas, such nitrogen or a noble gas (i.e., helium, neon, argon, xenon, or krypton). The flow rate of the purge gas can be about 0 slm to about 5 slm, which includes 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 250, 275, 300, 400, 500, 600, 700, 800, 900, or 1000 (seem), 2, 3, 4, or 5 (slm), or any combination thereof.

[0010] The gas supply system 140 is located opposite the exhaust line 138 for flowing a process gas over the substrate 125. The process gas crosses the substrate 125 in a processing space 145 in a laminar flow and is evacuated from the process chamber 110 by the exhaust line 138. However, other configurations for introducing and evaluating process gas may be utilized.

[0011] Referring to FIG. 2, the processing system can comprise an upstream or remote plasma source 142 configured for plasma induced dissociation of a process gas upstream or remote from the substrate 125. For example, in an oxidation process, the process gas can include an oxygen containing gas, such as, for example, O ₂ , NO, NO ₂ or N ₂ O. The process gas can be introduced at a flow rate of about 30 seem to about 5 slm, which includes 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 250, 275, 300, 400, 500, 600, 700, 800,

900, or 1000 (seem), 2, 3, 4, or 5 (slm), or any combination thereof. Oxygen radicals are produced as the gas passes through remote plasma source 142 and are then introduced into process chamber 110. The oxygen radicals associate with the surface of substrate 125 to oxidize the surface of the substrate. The composition of the surface can be SiO ₂ .

[0012] Any plasma source may be used for the remote and/or upstream plasma source, 142. Suitable plasma sources include Radio Frequency (RF) plasma, inductively coupled plasma, plasma torch, capacitively coupled plasma, microwave plasma, capacitive microwave plasma, microwave induced plasma, slot plane antenna plasma, surface wave plasma, or helium wave plasma, or combinations thereof, or the like. One or more than one source may be used. Examples of commercial remote plasma sources include the ASTRON® sources commercially available from MKS Instruments, Inc., ASTeX® Products (90 Industrial Way, Wilmington, MA 01887), and TRIAS™ SPA processing systems commercially available from Tokyo Electron Limited, Akasaka, Japan.

[0013] The electromagnetic radiation assembly 130 can dissociate the process gas, e.g., containing oxygen, in process chamber 110 from gas-supply system 142 and/or remote plasma source 142. The electromagnetic radiation source 130 can, for example, comprise an ultraviolet (UV) radiation source. The UV source may be monochromatic or polychromatic. Additionally, the UV source can be configured to produce radiation at a wavelength sufficient for dissociating the process gas, e.g., O ₂ . In one embodiment, the ultraviolet radiation can have a wavelength from about 145 nm to about 192 nm, which includes 145, 147, 150, 155, 171, 172, 173, 175, 180, 185, 190, or 192 nm as appropriate for the binding energy of the molecule which is dissociated. The electromagnetic radiation assembly 130 can operate at a power of about 5 W/cm ² to about 100 mW/cm ² , which includes 5, 6, 7, 8, 9, 10, 11, 13, 15, 17, 19, 20, 30, 40, 50, 60, 70, 80, 90, or 100 mW/cm ² , or any combination thereof. The electromagnetic radiation assembly 130 can include one, two, three, four, or more radiation

sources. The sources can include lamps or lasers or a combination thereof.

[0014] Referring still to FIG. 2, the processing system 101 may be configured to process 200 mm substrates, 300 mm substrates, or larger-sized substrates. In fact, it is contemplated that the processing system may be configured to process substrates, wafers, or LCDs regardless of their size, as would be appreciated by those skilled in the art. Therefore, while aspects of the invention will be described in connection with the processing of a semiconductor substrate, the invention is not limited solely thereto.

[0015] Referring again to FIG. 2, processing system 101 comprises substrate temperature control system 160 coupled to the substrate holder 120 and configured to elevate and control the temperature of substrate 125. Substrate temperature control system 160 comprises temperature control elements, such as a heating system that may comprise resistive heating elements, or thermo-electric heaters/coolers. Additionally, substrate temperature control system 160 may comprise a cooling system including a re-circulating coolant flow that receives heat from substrate holder 120 and transfers heat to a heat exchanger system (not shown), or when heating, transfers heat from the heat exchanger system. Furthermore, the substrate temperature control system 160 may include temperature control elements disposed in the chamber wall of the process chamber 110 and any other component within the processing system 101.

[0016] In order to improve the thermal transfer between substrate 125 and substrate holder 120, the substrate holder 120 can include a mechanical clamping system, or an electrical clamping system, such as an electrostatic clamping system, to affix substrate 125 to an upper surface of substrate holder 120. Furthermore, substrate holder 120 can further include a substrate backside gas delivery system configured to introduce gas to the back-side of substrate 125 in order to improve the gas-gap thermal conductance between substrate 125 and substrate holder 120. Such a system can be utilized when temperature control of the

substrate is required at elevated or reduced temperatures. For example, the substrate backside gas system can comprise a two-zone gas distribution system, wherein the helium gas gap pressure can be independently varied between the center and the edge of substrate 125.

[0017] Furthermore, the process chamber 110 is further coupled to a pressure control system 132, including a vacuum pumping system 134 and a valve 136, through a duct 138, wherein the pressure control system 134 is configured to controllably evacuate the process chamber 110 to a pressure suitable for forming the thin film on substrate 125, and suitable for use of the process materials.

[0018] The vacuum pumping system 134 can include a turbo-molecular vacuum pump (TMP) capable of a pumping speed up to about 5000 liters per second (and greater) and valve 136 can include a gate valve for throttling the chamber pressure. In conventional plasma processing devices, a about 500 to about 3000 liter per second TMP is generally ^• employed. Moreover, a device for monitoring chamber pressure (not shown) can be coupled to the processing chamber 10. The pressure measuring device can be, for example, a Type 628B Baratron absolute capacitance manometer commercially available from MKS Instruments, Inc. (Andover, MA).

[0019] Additionally, the processing system 101 contains a controller 170 coupled to the process chamber 110, substrate holder 120, electromagnetic radiation assembly 130, power source 150, gas-supply system 140, remote plasma source 142, pressure control system 132, and substrate temperature control system 160. Alternately, or in addition, controller 170 can be coupled to a one or more additional controllers/computers (not shown), and controller 170 can obtain setup and/or configuration information from an additional controller/computer.

[0020] In FIG. 2, singular processing elements (110, 120, 130, 132, 140, 142, 150,

160, and 170) are shown, but this is not required for the invention. The processing system 101 can comprise any number of processing elements having any number of controllers associated with them in addition to independent processing elements.

[0021] The controller 170 can be used to configure any number of processing elements (110, 120, 130, 132, 140, 142, 150, and 160), and the controller 170 can collect, provide, process, store, and display data from processing elements. The controller 170 can comprise a number of applications for controlling one or more of the processing elements. For example, controller 170 can include a graphic user interface (GUI) component (not shown) that can provide easy to use interfaces that enable a user to monitor and/or control one or more processing elements.

[0022] Still referring to FIG. 2, controller 170 can comprise a microprocessor, memory, and a digital I/O port capable of generating control voltages sufficient to communicate and activate inputs to processing system 101 as well as monitor outputs from processing system 101. For example, a program stored in the memory may be utilized to activate the inputs to the aforementioned components of the processing system 101 according to a process recipe in order to perform process. One example of the controller 170 is a DELL PRECISION WORKSTATION 610™, available from Dell Corporation, Austin, Texas.

[0023] The controller 170 may be locally located relative to the processing system

101, or it may be remotely located relative to the processing system 101. For example, the controller 170 may exchange data with the processing system 101 using at least one of a direct connection, an intranet, the Internet and a wireless connection. The controller 170 may be coupled to an intranet at, for example, a customer site (i.e., a device maker, etc.), or it may be coupled to an intranet at, for example, a vendor site (i.e., an equipment manufacturer). Additionally, for example, the controller 160 may be coupled to the Internet. Furthermore, another computer (i.e., controller, server, etc.) may access, for example, the controller 170 to

exchange data via at least one of a direct connection, an intranet, and the Internet. As also would be appreciated by those skilled in the art, the controller 170 may exchange data with the processing system 101 via a wireless connection.

[0024] The processing conditions can further include a substrate temperature between about 0° C and about 1000° C. Alternately, the substrate temperature can be between about 200° C and about 700° C. Thus, the oxidizing can be carried out at a substrate temperature of 200, 225, 250, 275, 300, 325, 350, 375, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or 1000° C, or any combination thereof.

[0025] The pressure in the process chamber 110 can, for example, be maintained between about 1 mTorr and about 30,000 mTorr. Alternately, the pressure can be maintained between about 20 mTorr and about 1000 mTorr. Yet alternately, the pressure can be maintained between about 50 mTorr and about 500 mTorr. Thus, the oxidizing may be carried out at a pressure of about 1 mTorr to about 30,000 mTorr, which includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 250, 500, 750, 1,000, 10,000, 20,000, or 30,000 mTorr, or any combination thereof.

[0026] FIG. 3 is a schematic diagram of a processing system according to another embodiment of the invention. The processing system 200 includes a process chamber 210 accommodating therein a substrate holder 220 equipped with a heater 224 that can be a resistive heater configured to elevate the temperature of substrate 225. Alternately, the heater 224 may be a lamp heater or any other type of heater. Furthermore the process chamber 210 contains an exhaust line 238 connected to the bottom portion of the process chamber 210 and to a vacuum pump 234. The substrate holder 220 can be rotated by a drive mechanism (not shown). The substrate can be rotated on the substrate holder 220 in the plane of the substrate surface at a rate of about 1 rpm to about 60 rpm, which includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 30, 40, 50, or 60 rpm, or any combination thereof.

[0027] The process chamber 210 contains a process space 245 above the substrate

125. The inner surface of the process chamber 210 contains an inner liner 212 made of quartz in order to suppress metal contamination of the substrate 225 to be processed.

[0028] The process chamber 210 contains a gas line 240 with a nozzle 242 located opposite the exhaust line 238 for flowing a process gas over the substrate 225. The process gas crosses the substrate 225 in a processing space 245 in a laminar flow and is evacuated from the process chamber 210 by the exhaust line 238. A remote plasma source 252 is coupled to process chamber 210 via a gas inlet 250 and is configured to generate a plasma remotely and upstream of the substrate 225.

[0029] In one example, the processing space may be exposed to ultraviolet radiation from an ultraviolet radiation source 230 emitting light through a quartz window 232 into the processing space 245 between the nozzle 242 and the substrate 225. Alternately, the ultraviolet radiation source 230 and quartz window 232 can cover the whole substrate 225.

[0030] Still referring to FIG. 3, a controller 270 includes a microprocessor, a memory, and a digital I/O port capable of generating control voltages sufficient to communicate and activate inputs of the processing system 200 as well as monitor outputs from the plasma processing system 200. Moreover, the controller 270 is coupled to and exchanges information with process chamber 210, the gas supply system (not shown) for gas line 240, the gas supply system (not shown) for gas inlet 250 to remote plasma source 252, the remote plasma source 252, the substrate holder 200, the vacuum pump 234, the heater 224, and the ultraviolet radiation source 230. The controller 270 may be implemented as a UNIX-based workstation. Alternately, the controller 270 can be implemented as a general-purpose computer, digital signal processing system, etc.

[0031] Prior to oxidizing, it may be desirable to clean the substrate surface, or remove

a native oxide from the substrate surface. This may be accomplished using one or more cleaning steps including wet chemical cleaning, or forming a bare silicon surface on the substrate surface by cleaning followed by contacting the substrate surface with HF, or both.

[0032] The substrate 125 (FIG. 2) or 225 (FIG. 3) is then placed on substrate holder

120 (FIG. 2) or 220 (FIG. 3). Conditions in process chamber 110 or 210 (pressure, temperature, substrate rotation, etc.) are then brought to the desired values. Accordingly, an oxygen containing molecular composition is introduced into process chamber 110 or 210 via gas supply system 140 or nozzle 242. Electromagnetic radiation assembly 130 or 230 is energized to form oxygen radicals from the process gas. The population of oxygen radicals can be enhanced by supplying an oxygen containing molecular composition to remote plasma source 142 or inlet 250. Oxygen radicals are produced as the gas passes through remote plasma source 142 or 252 and are then introduced into process chamber 110 or 210.

[0033] The oxygen radicals associate with the surface of substrate 125 or 225 to oxidize the surface of the substrate. The composition of the surface can be SiO ₂ .

[0034] The oxidizing may be carried out for a time of about 5 seconds to about 25 minutes, which includes 5, 10, 15, 20, 25, 30, 35, 40, 50, 60 (seconds), 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, or 25 (minutes), or any combination thereof.

[0035] The oxide film can have a thickness of about 0.1 nm to about 3 nm, which range includes 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0,8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0 nm. The oxide film may have a thickness variation σ of about 0.7% to about 4%, which includes 0.7, 0.9, 1, 2, 3, or 4%.

[0036] The UV radiation induced dissociation and the plasma induced dissociation may be configured to generate radical species from the same or different process gas. The UV radiation induced dissociation and the plasma induced dissociation may be configured to

generate radical species concurrently, or in the order of UV radiation induced dissociation then plasma induced dissociation or plasma induced dissociation then UV radiation induced dissociation.

[0037] Any of the process conditions or features mentioned herein with regard to the embodiments of either FIG. 1, FIG. 2, FIG. 3, or FIG.4 may also be applied to any other embodiment. Indeed, as an alternative to the conditions discussed above, the following conditions may be employed:

UVO ₂ (Ultraviolet Oxidation)

RFO (Radical Flow Oxidation)

Parameter Typical Low High

Pressure 20OmT 1OmT 1OT

Temperature 400 ⁰ C 25 ⁰ C 1000 ⁰ C

Gas Ar lslm 500sccm lOslm

Gas O ₂ lOOsccm lOsccm lslm

RFQ (Radical Flow Oxidation)

[0038] Other suitable processing systems containing an ultraviolet (UV) radiation source and methods of using are described in European Patent Application EP 1453083 Al, filed December 5, 2002, the entire contents of which are hereby incorporated by reference.

Plasma Nitridation and/or Oxidation

[0039] FIG. 4 is a simplified block-diagram of a plasma processing system containing a slot plane antenna (SPA) plasma source for nitridation or oxidation process according to an embodiment of the invention. The plasma produced in the plasma processing system 400 is characterized by low electron temperature (less than about 1.5 eV) and high plasma density (e.g., >about lxlO ¹² /cm ³ ), that enables damage-free processing of gate stacks according to the invention. The plasma processing system 400 can, for example, be a TRIAS™ SPA processing system from Tokyo Electron Limited, Akasaka, Japan. The plasma processing system 400 contains a process chamber 450 having an opening portion 451 in the upper portion of the process chamber 450 that is larger than a substrate 125. A cylindrical dielectric top plate 454 made of quartz or aluminum nitride is provided to cover the opening portion 451. Gas lines 472 are located in the side wall of the upper portion of process chamber 450 below the top plate 454. In one example, the number of gas lines 472 can be 16 (only two are which are shown in FIG. 4). Alternately, a different number of gas feed lines 472 can be used. The gas lines 472 can be circumferentially arranged in the process chamber 450, but this is not required for the invention. A process gas can be evenly and uniformly supplied into the plasma region 459 in process chamber 450 from the gas lines 472. Alternatively, a

feed line 472 on the upstream side of the substrate relative to the exhaust may be configured as a remote radical flow plasma source suitable for nitridation or oxidation. One or more UV radiation sources 480 may be arranged in process chamber 450 to generate radical species by UV radiation induced dissociation to oxidize or nitridate the substrate 125.

[0040] In the plasma processing system 450, microwave power is provided to the process chamber 450 through the top plate 454 via a plane antenna member 460 having a plurality of slots 460A. The slot plane antenna 460 can be made from a metal plate, for example copper. In order to supply the microwave power to the slot plane antenna 460, a waveguide 463 is disposed on the top plate 454, where the waveguide 463 is connected to a microwave power supply 461 for generating microwaves with a frequency of about 2.45 GHz, for example. The waveguide 463 contains a flat circular waveguide 463A with a lower end connected to the slot plane antenna 460, a circular waveguide 463B connected to the upper surface side of the circular waveguide 463 A, and a coaxial waveguide converter 463C connected to the upper surface side of the circular waveguide 463B. Furthermore, a rectangular waveguide 463D is connected to the side surface of the coaxial waveguide converter 463C and the microwave power supply 461.

[0041] Inside the circular waveguide 463B, an axial portion 462 of an electroconductive material is coaxially provided, so that one end of the axial portion 462 is connected to the central (or nearly central) portion of the upper surface of slot plane antenna 460, and the other end of the axial portion 462 is connected to the upper surface of the circular waveguide 463B, thereby forming a coaxial structure. As a result, the circular waveguide 463B is constituted so as to function as a coaxial waveguide. The microwave power can, for example, be between about 0.5 W/cm ² and about 4 W/cm ² . Alternately, the microwave power can be between about 0.5 W/cm ² and about 3 W/cm ² .

[0042] In addition, in the vacuum process chamber 450, a substrate holder 452 is

provided opposite the top plate 454 for supporting and heating a substrate 125 (e.g., a wafer). The substrate holder 452 contains a heater 457 to heat the substrate 125, where the heater 457 can be a resistive heater. Alternately, the heater 457 may be a lamp heater or any other type of heater. Furthermore the process chamber 450 contains an exhaust line 453 connected to the bottom portion of the process chamber 450 and to a vacuum pump 455.

[0043] For nitridation or oxidation, a gas containing a molecular composition having nitrogen or oxygen may be introduced into any of system 20 (FIG. 1), process chambers 110 (FIG. 2), 210 (FIG. 3), and/or 450 (FIG. 4). Any nitrogen containing composition is suitable, e.g., any of O ₂ , N ₂ , NO, N ₂ O, NO ₂ , alone or in combination. Once introduced, the nitrogen or oxygen containing composition may be dissociated via either microwave radiation plasma induced dissociation based on microwave irradiation via a plane antenna having a plurality of slots or in-chamber plasma induced dissociation, or, alternatively, it may be dissociated by a remote plasma source located upstream of the substrate via, for example, the coupling of RF power to the oxygen or nitrogen containing composition.

[0044] Nitridation or oxidation may also be accomplished using a microwave induced plasma via slot plane antenna microwave source, such as shown in FIG. 4. In this embodiment, the nitrogen or oxygen containing molecular composition is dissociated by microwave induced plasma, which has a low electron temperature and high plasma density.

[0045] Any nitrogen or oxygen containing composition is suitable, e.g., any ofN ₂ ,

NO, N ₂ O, NO ₂ , or O ₂ alone or in combination. In one embodiment, the molecular composition in the nitriding or oxynitriding process gas may include O ₂ or N ₂ and optionally at least one gas selected from the group consisting of H ₂ , Ar, He, Ne, Xe, or KJ, or any combination thereof. In one embodiment, the molecular composition in the process gas comprises O ₂ or N ₂ and H ₂ and optionally at least one gas selected from the group consisting ofH ₂ , Ar, He, Ne, Xe, or Rr, or any combination thereof. The oxygen or nitrogen containing

molecular composition in the process gas may suitably comprise O ₂ or N ₂ , and the oxygen or nitrogen radicals are produced from plasma induced dissociation of the O ₂ and/or N ₂ .

[0046] The oxynitride film obtained under nitridation may have a thickness of about

0.1 nm to about 5 nm, which range includes 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3., 3.4, 3.5, 3.6, 3.8, 4, 4.1, 4.5, or 5 nm, or any combination thereof. The oxynitride film may have a thickness variation σ of about 0.7% to about 4%, which includes 0.7, 0.9, 1, 2, 3, or 4%.

[0047] The nitriding or oxidizing may be carried out at a substrate temperature of about 20° C to about 1000° C, which range includes 20, 30, 40, 50, 60, 70, 80, 90, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, or 1000° C ₅ or any combination thereof.

[0048] The nitriding or oxidizing may be carried out at a pressure of about 1 mTorr to about 30,000 mTorr, which includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 250, 500, 750, 1,000, 10,000, 20,000, or 30,000 mTorr, or any combination thereof.

[0049] The flow rate of the nitrogen containing molecular composition or oxygen containing molecular composition may range from about 2sccm to about 5slm. These ranges include 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 250, 275, 300, 400, 500, 600, 700, 800, 900, or 1000 (seem), 2, 3, 4, or 5 (slm), or any combination thereof.

[0050] The nitriding or oxidizing may be carried out for a time of about 5 seconds to about 25 minutes, which range includes 5, 10, 15, 20, 25, 30, 35, 40, 50, 60 (seconds), 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, or 25 (minutes), or any combination thereof.

[0051] The oxynitride film may have a surface nitrogen concentration of about 20%

or less, which includes 4, 6, 8, 10, 12, 14, 16, 18, and 20% or less.

[0052] The nitriding or oxidizing plasma may be generated by a microwave output of about 0.5 W/cm ² to about 5 W/cm ² , which includes 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.3, 1.5, 1.7, 1.9, 2, 3, 4, or 5 W/cm ² , or any combination thereof.

[0053] The microwave irradiation may comprise a microwave frequency of about 300

MHz to about 10 GHz, which includes 300, 400, 500, 600, 700, 800, 900, or 1000 (MHz), 1.5, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (GHz).

[0054] In this embodiment, the plasma may comprise an electron temperature of less than about 3 eV, which includes 0.1, 0.3, 0.5, 0.7, 0.9, 1, 1.5, 2, 2.5, or 3 eV, or any combination thereof. The plasma may have a density of about 1 x 10 ^u /cm ³ to about 1 x 10 ¹³ /cm ³ or higher, and a density uniformity of about ± 3% or less, which includes ± 1 , ± 2, and ± 3%.

[0055] The plane antenna member may have a surface area on a surface thereof greater than the area of the substrate surface on which the film is deposited.

[0056] The oxynitride film may suitably have the formula SiON. The oxide film may have the formula SiO ₂ .

[0057] Still referring to FIG. 4, a controller 499 includes a microprocessor, a memory, and a digital I/O port capable of generating control voltages sufficient to communicate and activate inputs of the plasma processing system 400 as well as monitor outputs from the plasma processing system 400. Moreover, the controller 499 is coupled to and exchanges information with process chamber 450, the pump 455, the heater 457, and the microwave power supply 461. A program stored in the memory is utilized to control the aforementioned components of plasma processing system 400 according to a stored process recipe. One example of processing system controller 499 is a UNIX-based workstation. Alternately, the

controller 499 can be implemented as a general-purpose computer, digital signal processing system, etc.

[0058] The controller 499 may be locally located relative to the plasma processing system 400 or it may be remotely located relative to the plasma processing system 400 via an internet or intranet. Thus, the controller 499 can exchange data with the plasma processing system 99 using at least one of a direct connection, an intranet, or the internet. The controller 499 may be coupled to an intranet at a customer site (i.e., a device maker, etc.), or coupled to an intranet at a vendor site (i.e., an equipment manufacturer). Furthermore, another computer (i.e., controller, server, etc.) can access the controller 499 to exchange data via at least one of a direct connection, an intranet, or the internet.

[0059] As an alternative to the nitridation process parameters set forth above, the following parameters can be employed in slot plane antenna nitridation (SPAN):

SPAN

[0060] Other suitable plasma processing systems containing a slot plane antenna plasma source and methods of using are described in European Patent Application EP 1361605 Al, filed January 22, 2002, the entire contents of which are hereby incorporated by

reference.

[0061] Radical flow nitriding or oxidizing may be employed concurrently with or after the UVO ₂ oxidizing, SPA oxidizing, or SPA nitriding processes. In radical flow nitriding (RFN), the oxide film (or oxynitride film) may be exposed to nitrogen radicals formed by an upstream plasma induced dissociation of an upstream process gas comprising an upstream molecular composition comprising nitrogen. The upstream plasma induced dissociation can use plasma generated via the coupling of radio frequency (RF) power to said upstream process gas.

[0062] In radical flow oxidizing, the oxide film may be exposed to oxygen radicals formed by an upstream plasma induced dissociation of an upstream process gas comprising an upstream molecular composition comprising oxygen. The upstream plasma induced dissociation can use plasma generated via the coupling of radio frequency (RF) power to said upstream process gas.

[0063] RFN (radical flow nitridation) and RFO (radical flow oxidation) remote plasma systems are illustrated in FIGs. 2, 3 and 4. The processing system illustrated in FIG. 3 includes a remote plasma source 252 with a gas inlet 250, which is suitable for generating plasma remotely and upstream of substrate 225. Nitrogen or oxygen radicals produced in remote plasma source 252 are caused to flow downstream and over the surface of substrate 225 to the exhaust line 238 and pump 234. The substrate can be rotated (as shown by the circular arrow) in the process system of FIG. 3. In this way, uniformity in oxidation, nitridation, oxynitridation, or annealing under nitrogen is improved.

[0064] Alternatively, a remote plasma source may be provided in feed line 472 connected to the process chamber 450 in FIG. 4 on an upstream side of the substrate 458 relative to the exhaust, and would be suitable as a remote RF plasma source for nitridation or

plasma oxidation. The UV source(s) 480 may be configured for UV radiation induced dissociation of the process gas.

[0065] An example of some process parameters for RFN nitridation is given below:

RFN

[0066] The plasma oxidation conditions discussed herein in combination with the

UVO ₂ oxidation, which plasma oxidation processes may include any of the following, alone or in combination:

[0067] exposing the oxide film to oxygen radicals formed by plasma induced dissociation of a process gas comprising at least one molecular composition comprising oxygen;

[0068] exposing the oxide film to oxygen radicals formed by plasma induced dissociation of a process gas comprising at least one molecular composition comprising oxygen, wherein the plasma induced dissociation of the process gas comprises using plasma based on microwave irradiation via a plane antenna member having a plurality of slots; and/or

[0069] exposing the oxide film to oxygen radicals formed by plasma induced dissociation of a process gas comprising at least one molecular composition comprising oxygen, wherein the plasma induced dissociation of the process gas comprises using plasma based on upstream radical generation.

[0070] Alternative SPA Oxidation (SPAO) conditions are set out below:

SPAO

Simple Annealing

[0071] After the subject film is prepared, it may be annealed. The anneal suitably anneals the oxynitride film, the oxide film, or the nitride film. Annealing the resultant film can assist in the formation of a stable film by removing film defects, such as oxygen and/or nitrogen vacancies, for example. Film annealing may be performed concurrently with the oxidation, nitridation, or oxynitridation process, or following the respective process.

[0072] The annealing may be carried out at a pressure of about 5 mTorr to about 800

Torr, which includes 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 250, 500, 750, 1,000,

10,000, 20,000, 30,000, 50,000, 100,000, 200,000, 400,000, or 800,000 mTorr, or any combination thereof.

[0073] The annealing may be carried out at a temperature of about 500° C to about

1200° C, which includes 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, or 1200° C, or any combination thereof.

[0074] The annealing may be carried out under an annealing gas comprising at least one molecular composition comprising oxygen, nitrogen, H ₂ , Ar, He, Ne, Xe, or Kr, or any combination thereof at a flow rate of 0 to 2OsIm. In one embodiment, annealing is effected under N ₂ at an N ₂ flow rate of about 0 slm to about 20 slm, which includes 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 250, 275, 300, 400, 500, 600, 700, 800, 900, or 1000 (seem), 2, 3, 4, 5, 10, 15, or 20 (slm), or any combination thereof.

[0075] The annealing may be carried out for a time of about 1 second to about 10 minutes, which range includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 50, 60 (seconds), 2, 3, 4, 5, 6, 7, 8, 9, or 10 (minutes), or any combination thereof.

[0076] The annealing and the oxidizing or nitriding may be carried out in the same process chamber, in which case it is possible to carry out at least one purging step after the nitriding or oxidizing and prior to the annealing. Of course, it is also possible to carry out nitriding or oxidizing and the annealing in different process chambers. In this embodiment, it is possible to transfer the film-bearing substrate from one chamber to another without contacting ambient atmosphere, air, etc.

[0077] Alternatively, the following conditions may be employed for an anneal:

Anneal

Parameter Low High

Anneal

[0078] As an alternative after the subject film is prepared, UVO ₂ /N ₂ anneal optionally suitably anneals the oxide/nitride/oxynitride film by exposing the oxide/nitride/oxynitride film to oxygen radicals and nitrogen radicals formed by ultraviolet (UV) radiation induced dissociation of an annealing gas comprising at least one molecular composition comprising oxygen and nitrogen. The oxygen and nitrogen radicals are dissociated from an annealing gas comprising at least one molecular composition comprising oxygen and nitrogen selected from the group consisting of O ₂ , N ₂ , NO, NO ₂ , and N ₂ O, or any combination thereof. Other gases may be present for example one or more OfH ₂ , Ar, He, Ne, Xe, or Kr, or any combination thereof.

[0079] In one embodiment of this anneal, the annealing gas flows across the oxynitride surface such that the oxygen and nitrogen radicals are comprised within a laminar flow of the annealing gas across the surface.

[0080] The annealing may be carried out at a pressure of about 1 mTorr to about

80,000 mTorr, which includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 250, 500, 750, 1,000, 10,000, 20,000, 30,000, 50,000, 100,000, 200,000, 400,000, or 800,000

mTorr, or any combination thereof.

[0081] The annealing may be carried out at a temperature of about 400° C to about

1200° C ₅ which includes 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, or 1200° C, or any combination thereof.

[0082] The annealing gas may have a flow rate of about 0 slm to about 20 slm, which includes 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 250, 275, 300, 400, 500, 600, 700, 800, 900, or 1000 (seem), 2, 3, 4, 5, 10, 15, or 20 (slm), or any combination thereof.

[0083] The annealing may be carried out for a time of about 1 second to about 10 minutes, which range includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 50, 60 (seconds), 2, 3, 4, 5, 6, 7, 8, 9, or 10 (minutes), or any combination thereof.

[0084] The ultraviolet radiation during this anneal may include wavelengths of about

145 nm to about 192 nm, which includes 145, 147, 150, 155, 171, 172, 173, 175, 180, 185, 190, and 192 nm as appropriate for the binding energy of the molecule which is dissociated. The radiation may be monochromatic or polychromatic.

[0085] It may originate from an ultraviolet radiation source operating at a power of about 5 mW/cm ² to about 50 mW/cm ² , which includes 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.3, 1.5, 1.7, 1.9, 2, 3, 4, or 5 W/cm ² , or any combination thereof. One or more ultraviolet sources may be used.

[0086] The annealing and the oxidizing/nitriding may be carried out in the same process chamber, in which case it is possible to carry out at least one purging step after the oxidizing/nitriding and prior to the annealing. Of course, it is also possible to carry out oxidizing/nitriding and the annealing in different process chambers. In this embodiment, it is possible to transfer the film-bearing substrate from one chamber to another without

contacting ambient atmosphere, air, etc.

RFN Anneal

[0087] As an alternative after the subject film is prepared, RFN anneal optionally suitably anneals the oxide/nitride//oxynitride film by exposing the oxide/nitride/oxynitride film to nitrogen radicals formed by an upstream plasma induced dissociation of an upstream annealing gas comprising an upstream molecular composition comprising nitrogen, and wherein the nitrogen radicals flow across the surface in a laminar manner. The radicals can be generated by coupling radio frequency (RF) power to the upstream annealing gas.

[0088] The annealing may be suitably carried out at a pressure of about 1 mTorr to about 20,000 mTorr, which includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 250, 500, 750, 1,000, 10,000, 20,000 mTorr, or any combination thereof.

[0089] The annealing may be suitably carried out at a substrate temperature of about

20° C to about 1200° C, which includes 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1100, or 1200° C, or any combination thereof.

[0090] The annealing may be carried out is carried out for a time of about 1 second to about 25 min, which range includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 50, 60 (seconds), 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20 (minutes), or any combination thereof.

[0091] The annealing may be carried out under N ₂ at an N ₂ flow rate of about 2 seem to about 20 slm, which includes 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 250, 275, 300, 400, 500, 600, 700, 800, 900, or 1000 (seem), 2, 3, 4, 5, 10, 15, or 20 (slm), or any combination thereof.

[0092] The annealing may also be carried out in the presence of other gases, for example, H ₂ , Ar, He, Ne, Xe, or Rr, or any combination thereof. The flow rate of these other

gases may be about 100 seem to about 20 slm, which includes 100, 250, 275, 300, 400, 500, 600, 700, 800, 900, or 1000 (seem), 2, 3, 4, 5, 10, 15, or 20 (slm), or any combination thereof.

[0093] The annealing may be carried out using plasma remotely generated via the coupling of radio frequency (RF) power having a frequency of about 40 kHz to about 4 MHz with the upstream annealing gas, which includes 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, or 1000 (IcHz), 1.5, 2, 3, or 4 (MHz), or any combination thereof.

Device

[0094] One embodiment includes forming a semiconductor device including a poly- silicon, amorphous-silicon, or SiGe layer, or any combination thereof, on the oxide film, the oxynitride film, or both.

[0095] Another embodiment includes making a semiconductor or electronic device with the present method and system.

[0096] The processes can be performed on a thin oxide formed during a wet chemical clean, e.g., chemical oxide, or on a bare Si surface formed by a clean in which the last step is a HF dip to remove all oxide.

[0097] Other suitable systems and methods are described in the following references, the entire contents of each of which are independently incorporated by reference:

[0098] JP 2001-012917, filed January 22, 2001;

[0099] JP 2001-374631, filed December 7, 2001;

[0100] JP 2001-374632, filed December 7, 2001;

[0101] JP 2001-374633, filed December 7, 2001;

[0102] JP 2001-401210, filed December 28, 2001;

[0103] JP 2002-118477, filed April 19, 2002;

[0104] US 2004/0142577 Al, filed January 22, 2002; and

[0105] US 2003/0170945 Al, filed December 6, 2002.

[0106] The present invention is not limited to the above embodiments and may be practiced or embodied in still other ways without departing from the scope and spirit thereof.