Vapor cleaning of substrate surfaces

Abstract

A method of cleaning a substrate includes: arranging the substrate in a processing chamber; controlling a pressure of the processing chamber within a predetermined pressure range; controlling a temperature of the processing chamber within a predetermined temperature range; continuously supplying a vapor mixture including a metal chelate vapor for a first period of time to remove metal contaminants from a surface of the substrate.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application No. 62 / 865,647, filed June 24, 2019. The entire disclosure of the above-referenced application is incorporated herein by reference. TECHNICAL FIELD

[0003] The present disclosure relates generally to substrate processing systems, and more particularly, the present disclosure relates to substrate processing systems for vapor cleaning of substrates such as semiconductor wafers. BACKGROUND

[0004] The background description provided herein is for the purpose of generally presenting the context of the disclosure. The work of the presently named inventors, to the extent the work is described in this background section, as well as aspects of the description that can not otherwise qualify as prior art at the time of filing, are neither expressly nor impliedly admitted as prior art against the present disclosure.

[0005] Substrate processing systems can be used to process films on substrates such as semiconductor wafers. Examples of processing include etching, deposition, ashing, and other kinds of processing. During substrate processing, multiple processes can be performed in one or more processing chambers. Substrates are often cleaned between processes to remove contaminants from an upstream processing chamber before further processing in a downstream processing chamber.

[0006] Wet cleaning can be performed to clean a substrate. For example, a substrate can be mounted on a chuck. As the chuck is rotated, fluid nozzles can be used to dispense a fluid such as a liquid and / or heat can be applied to process the substrate.

[0007] Some substrates include high aspect ratio (HAR) structures. For example, HAR structures can include nanorods, trenches, or vias. The width (parallel to the surface of the substrate) of a HAR structure is significantly less than the depth (perpendicular to the surface of the substrate) of the feature. HAR structures with a depth-to-width ratio greater than 5: 1 are quite common. More advanced processes include HAR structures with higher depth-to-width ratios.

[0008] Pattern collapse occurs when one or more HAR structures collapse, move laterally relative to the substrate surface, and / or directly contact an adjacent HAR structure. Pattern collapse often occurs during drying after wet cleaning. Pattern collapse can cause performance issues and defects. SUMMARY

[0009] A method of cleaning a substrate includes: arranging the substrate in a processing chamber; controlling a pressure of the processing chamber to be within a predetermined pressure range; controlling a temperature of the processing chamber to be within a predetermined temperature range; continuously supplying a vapor mixture including a metal chelate vapor during a first period to remove metal contaminants from a surface of the substrate.

[0010] In other features, at least one of: a component located within the processing chamber is made of a non-metallic material; and / or an exposed surface of the component located within the processing chamber is coated with a non-metallic coating.

[0011] In other features, the metal chelate vapor includes a beta-diketone and a beta-diketone derivative. The metal chelate vapor is selected from the group consisting of: acetylacetone (acac), trifluoroacetylacetone (tfa), hexafluoroacetylacetone (hfacH), pivaloyltrifluoroacetone, tetramethylheptanedione, and heptafluoro-dimethyl octanedione (fod).

[0012] In other features, the metal chelate vapor includes trifluoroacetic acid and ethylenediamine.

[0013] In other features, the vapor mixture further includes a hydrogen halide containing vapor.

[0014] The method includes: after the first period, removing reactants from the processing chamber; supplying an oxidizing gas mixture to the processing chamber during a second period; and after the second period, removing reactants from the processing chamber.

[0015] In other features, before supplying the vapor mixture to the processing chamber, the method further includes: supplying an oxidizing gas mixture to the processing chamber during a second period; and after the second period, removing reactants from the processing chamber.

[0016] In other features, the predetermined pressure range is from 0.1 Torr to 100 Torr. The predetermined temperature range is from 50 °C to 300 °C.

[0017] A substrate processing system for cleaning a substrate includes: a processing chamber including a top surface, a bottom surface, and a sidewall, the sidewall being at least one of made of a non-metallic material and / or coated with a non-metallic material. A substrate support supports a substrate. A heater heats the substrate to a temperature within a predetermined range. A vapor delivery system supplies a vapor mixture containing a metal chelate vapor to the processing chamber during a first period to remove metal contaminants from a surface of the substrate.

[0018] In other features, the metal chelating vapor includes beta-diketones and beta-diketone derivatives. The metal chelating vapor includes acetylacetone (acac), trifluoroacetylacetone (tfa), pivaloyltrifluoroacetone, tetramethylheptanedione, hexafluoroacetylacetone (hfacH), and heptafluoro-dimethyl octanedione (fod). The metal chelating vapor includes trifluoroacetic acid and ethylenediamine.

[0019] In other features, the vapor mixture further includes a halogen-containing species. The gas delivery system delivers an oxidizing gas mixture to the processing chamber during a second period after the first period. The gas delivery system delivers the oxidizing gas mixture to the processing chamber prior to the vapor delivery system supplying the vapor mixture to the processing chamber.

[0020] In other features, the processing chamber is maintained at a pressure within a predetermined pressure range of 0.1 Torr to 100 Torr. The predetermined temperature range is 50 °C to 300 °C.

[0021] The processing chamber includes a transparent window. The heater is disposed outside of the processing chamber adjacent to the transparent window. The heater includes a plurality of light emitting diodes.

[0022] In other features, the heater is disposed inside of the processing chamber. An exposed surface of the heater is made of a non-metallic material and / or coated with a non-metallic coating. The heater includes at least one of an embedded heater and a coolant channel.

[0023] Further scope of the applicability of the present disclosure will become apparent from the detailed description, claims, and drawings. The detailed description and specific examples are given for purposes of illustration only and are not intended to limit the scope of the present disclosure. BRIEF DESCRIPTION OF DRAWINGS

[0024] The present disclosure will become more fully understood from the detailed description and drawings, wherein:

[0025] Figure 1A is a cross-sectional view of an example of a substrate with high aspect ratio features before cleaning;

[0026] Figure 1B is a cross-sectional view of an example of a substrate with high aspect ratio features that has pattern collapse after wet cleaning;

[0027] Figure 1C is a cross-sectional view of an example of a substrate with high aspect ratio features that has no pattern collapse after cleaning using a vapor mixture according to the present disclosure;

[0028] Figure 2A and 2B is a functional block diagram illustrating an example of a substrate processing system for cleaning a substrate in accordance with the present disclosure; and

[0029] Figure 3 is a flow chart illustrating an example of a method for cleaning a substrate using a vapor in accordance with the present disclosure.

[0030] In the drawings, reference numbers can be reused to identify similar and / or identical elements. DETAILED DESCRIPTION

[0031] Metal contamination of a substrate can be caused by upstream processing chamber metals (UPCM) (e.g., stainless steel (iron (Fe), chromium (Cr), nickel (Ni), and molybdenum (Mo))), processing chamber coatings such as yttrium (Y), and / or chamber body materials such as aluminum (Al). Contamination can also occur due to the presence of other metals: transition metals (e.g., titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), molybdenum (Mo), and tungsten (W)), alkaline earth metals (e.g., magnesium (Mg) and calcium (Ca)), and alkali metals (e.g., sodium (Na) and potassium (K)).

[0032] Substrate cleaning systems and methods in accordance with the present disclosure use a vapor mixture to clean a substrate and remove metal contaminants without leaving residues or causing collapse of HAR structures. As will be described further below, the vapor mixture converts the metals into volatile metal compounds.

[0033] In some examples, the vapor mixture includes a metal chelating vapor. In some examples, the metal chelating vapor includes a beta-diketone and derivatives thereof. Examples of beta-diketones include acetylacetone (acac), trifluoroacetylacetone (tfa), hexafluoroacetylacetone (hfacH), pivaloyltrifluoroacetone, tetramethylheptanedione, and heptafluoro-dimethyl octanedione (fod). In other examples, the metal chelating vapor includes trifluoroacetic acid (C2HF302) and ethylenediamine. Examples of derivatives of beta-diketones include halogenated derivatives (e.g., fluorinated derivatives such as trifluoroacetylacetone, hexafluoroacetylacetone, etc.).

[0034] Some metal chelating vapors (e.g., hfacH) are reactive to metals (e.g., stainless steel). In some examples, the surfaces of the substrate cleaning system that are exposed to the metal chelating vapor are made of a non-metal material or are coated with a non-metal coating. For example, all of the components located within the processing chamber can be made of a non-metal material, or the exposed surfaces of the components that contain metal are coated with a non-metal coating such as Teflon, silicon carbide, silicon, or other suitable coating.

[0035] In some examples, during cleaning, the substrate is heated to a predetermined temperature greater than 50 °C and less than 500 °C. In some examples, during cleaning, the substrate is heated to a predetermined temperature greater than 50 °C and less than 300 °C. In some examples, a heater is used to heat the substrate. In some examples, the heater is located outside of the processing chamber adjacent to the transparent window and optionally includes a light emitting diode (LED) heater. In some examples, the heater is located inside of the processing chamber and is optionally zoned. In some examples, during cleaning, the chamber pressure is controlled to be within a predetermined pressure range from 0.1 Torr to 100 Torr.

[0036] In some examples, the vapor mixture can further include another vapor including a halogen species such as hydrogen fluoride (HF) vapor, hydrogen chloride (HC1) vapor, hydrogen bromide (HBr) vapor, hydrogen iodide (HI) vapor, and the like. The halogen species vapor can be delivered with the metal chelating vapor as they are generally chemically compatible. However, the metal chelating vapor and the halogen species vapor can be delivered separately to and / or used in the processing chamber during different periods.

[0037] In some examples, the substrate is treated using an oxidizing gas (e.g., ozone (O3) gas, molecular oxygen (O2) gas, nitrogen oxide (NO) gas, and the like). The oxidizing gas can be used to remove organic contaminants. In some examples, the oxidizing gas is delivered before or after the vapor mixture is delivered to and / or used in the processing chamber to prevent decomposition of the metal chelating vapor and / or the halogen species vapor.

[0038] In some examples, the present cleaning system and method provides a vapor that reacts with a metal (which can also be in the form of a metal oxide or metal fluoride) to form a volatile metal compound at appropriate processing temperatures (<300 °C). In some examples, the vapor and the metal compound are relatively stable at these processing temperatures. In some examples, the cleaning process is selective to silicon-based materials.

[0039] Beta-diketones contain a ketone group at the beta-carbon position (e.g., acac, tfa, hfacH, and fed). Beta-diketones exist primarily in enol form. Beta-diketones can act as bidentate ligands to form volatile metal chelate complexes. The complexation between beta-diketones and transition metals is derived from the availability of d-orbitals in these metals. Metal diketonates, especially those formed from fluorinated beta-diketones, have high vapor pressures.

[0040] Reference is now made to Figures 1A to 1C , which shows a substrate 120 having high aspect ratio (HAR) features. Prior to cleaning, the substrate 120 includes one or more underlying layers 124 and 126, as shown in Figure 1A . The HAR features 122 are disposed in spaced relation on the underlying layer 124. The exposed layer of the substrate 120 (shown as reference numeral 134) can be contaminated with metal and can need to be cleaned prior to performing downstream processing.

[0041] In Figure 1B , the substrate 120 is shown after cleaning using a wet cleaning process. As can be seen, some of the HAR features 122 can have experienced pattern collapse (shown as 160) after cleaning. In Figure 1C , the substrate 120 is shown after cleaning using a vapor mixture (and optionally an oxidizing gas mixture) as described herein. The exposed layer 134 is removed without causing pattern collapse of the HAR features 122. As can be appreciated, while the HAR features 122 are shown as being cleaned, other types of surfaces and / or features can also be cleaned.

[0042] Reference is now made to Figure 2A and Figure 2B , which show a substrate processing system 200 for cleaning a substrate. In Figure 2A , the substrate processing system 200 includes a processing chamber 210, and the processing chamber 210 includes a top surface 214, a bottom surface 216, and sidewalls 218. During vapor cleaning, a substrate 222 is disposed inside the processing chamber 210. In some examples, the substrate 222 can be disposed on a support 224 that supports the radially outer edge of the substrate 222. A window 226 is disposed along the surface of the processing chamber adjacent to the surface of the substrate 222. In some examples, the window 226 is optically transparent. In some examples, the window 226 is made of quartz. In some examples, the exposed surfaces of components located within the processing chamber 210 and exposed to the metal chelate vapor are made of a non-metallic material. In some examples, the components are made of a non-metallic material, or are made of a metal and are coated with a non-metallic coating material such as Teflon, silicon, silicon carbide, etc.

[0043] Showerhead 230 includes a plenum 234 and through-holes 238. A vapor mixture flows into plenum 234 and is dispensed by through-holes 238. A heater 240 is disposed inside or outside of processing chamber 210. Heater 240 heats substrate 222 to a desired temperature for processing. For example, a heated substrate support such as an electrostatic chuck, a susceptor, or a mechanical chuck is disposed inside of processing chamber 210. Alternatively, an infrared heater, a laser, a flash lamp, an LED heater, or other type of light-based heater can be disposed outside of processing chamber 210 and window 226 can be used.

[0044] A gas delivery system 250 can be used to supply one or more gases to showerhead 230. For example, gas delivery system 250 can be used to supply a carrier gas, an inert gas, an oxidizing gas, etc. Gas delivery system 250 includes gas sources 252-1, 252-2,... and 252-N (collectively, gas sources 252), valves 254-1, 254-2,... and 254-N (collectively, valves 254), and mass flow controllers 256-1, 256-2,... and 256-N (collectively, mass flow controllers 252). A manifold 260 receives the output of mass flow controllers 256. Manifold 260 is connected to showerhead 230.

[0045] Vapor sources 260-1, 260-2, and 260-V (collectively, vapor sources 260) supply vapor to showerhead 230 via valves 262-1, 262-2, and 262-V. In some examples, vapor sources 260 include ampoules, bubbler, or other vapor generators.

[0046] Valves 270 and a pump 272 can be used to remove reactants from processing chamber 210 and / or to control the pressure in processing chamber 210.

[0047] A controller 280 can be used to control the timing of the delivery of gases from gas delivery system 250, the heating of substrate 222 by heater 240, the delivery of a vapor mixture from vapor sources 260, the regulation of the pressure inside of processing chamber 210 (e.g., by feedback from pressure sensor 281), and / or the removal of reactants by purging or evacuation.

[0048] As can be appreciated, when a vapor mixture includes more than one vapor, the vapor mixture can be mixed prior to delivery and then delivered to the processing chamber. Alternatively, vapors in a vapor mixture can be delivered separately and mixed in the chamber. In other examples, vapors are delivered separately to the processing chamber without mixing. In some examples, an oxidizing gas mixture is delivered separately from a metal chelating vapor mixture.

[0049] In Figure 2BIn some examples, the heater 290 is located outside of the processing chamber 210. In some examples, the heater 290 is located inside of the processing chamber 210. In some examples, the heater 290 is located outside of the processing chamber 210 and the processing chamber 210 is heated by a heater located inside of the processing chamber 210. In some examples, the heater 290 is located inside of the processing chamber 210. The heater 290 can include a single zone or multiple zones. In some examples, the heater 290 is made of a non-metallic material or a metallic material coated with a non-metallic material as described herein. The heater 290 can include coolant channels 294 and / or embedded heaters such as thermal control elements (TCEs), resistive heaters, Peltier heaters, etc.

[0050] Reference is now made to Figure 3 which shows a method 300 of cleaning a substrate using vapor. At 310, a substrate is arranged in a processing chamber. At 314, the chamber pressure is set to a pressure within a predetermined pressure range. At 318, the substrate is heated to a temperature within a predetermined temperature range. At 322, a vapor mixture including a metal-chelating vapor is continuously supplied to the processing chamber for a first period of time. In some examples, a halogen species vapor is supplied with or separately from the metal-chelating vapor. At 324, after the first period of time, the reactants are removed from the processing chamber by purging or evacuating.

[0051] At 326, a gas mixture including an oxidizing gas is continuously supplied to the processing chamber for a second period of time. At 328, after the second period of time, the reactants are removed from the processing chamber by purging or evacuating.

[0052] At 330, the substrate is removed from the processing chamber. At 332, the method determines whether another substrate is to be processed. If 332 is true, the method returns to 310. Otherwise, the method ends.

[0053] The foregoing description is merely illustrative in nature and is in no way intended to limit the disclosure, its application, or uses. The broad teachings of the disclosure can be implemented in a variety of forms. Therefore, while this disclosure includes particular examples, the true scope of the disclosure should not be so limited since other modifications will become apparent upon a study of the drawings, specification, and appended claims. It should be understood that no single feature is solely responsible for the desirable attributes of the disclosure. Rather, any one feature can be used alone or in combination with other features in various combinations to produce the desired results. Thus, the disclosure is not limited to only those aspects that can be described in the detailed description and / or claims. In addition, each of the features and objects described herein can be used to enable both the methods and devices of the disclosure. Thus, the breadth and scope of the present disclosure should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.

[0054] Various terminology is used to describe spatial and functional relationships between elements (for example, between modules, circuit elements, semiconductor layers, etc.) as well as relationships between elements. The terms "connected," "coupled," "adjacent," "next to," "on top of," "above," and "below" are used broadly and encompass both direct and indirect spatial and functional relationships. Unless the context clearly dictates otherwise, the relationship between first and second elements described in the above disclosure can be a direct relationship, in which no other intervening elements are present between the first and second elements, but can also be an indirect relationship, in which one or more intervening elements are present between the first and second elements (spatially or functionally). As used herein, the phrase "at least one of A, B, and C" should be interpreted to mean a logical (OR) using non-exclusive logical OR (A or B or C), and should not be interpreted to mean "at least one of A, and at least one of B, and at least one of C."

[0055] In some implementations, a controller is part of a system, which can be part of the above-described examples. Such systems can include semiconductor processing equipment, including one or more processing tools, one or more chambers, one or more platforms for processing, and / or specific processing components (wafer pedestals, gas flow systems, etc.). These systems can be integrated with electronics for controlling the operations of the systems before, during, and after processing of semiconductor wafers or substrates. The electronics can be referred to as the "controller," which can control various components or subparts of the system or systems. Depending on the process requirements and / or system type, the controller can be programmed to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., of heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, positional and operation settings, wafer transfer into and out of the tool and other transfer tools and / or load locks connected to or interfaced with the specific system.

[0056] Generally, a controller can be defined as electronics having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operation, enable cleaning operations, enable endpoint measurements, and the like. The integrated circuits can include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and / or one or more microprocessors, or microcontrollers that execute program instructions (e.g., software). Program instructions can be instructions or

[0057] In some implementations, a controller can be part of, or coupled to, a computer that is integrated with, coupled to the system, otherwise networked to the system, or a combination thereof. For example, a controller can be in the "cloud" or all or a part of a fab host computer system, which can allow for remote access of wafer processing. Computer can enable remote access to the system to monitor current progress of fabrication operations, examine a history of past fabrication operations, examine trends or performance metrics from a plurality of fabrication operations, change parameters of current processing, set processing steps to follow for current wafers, or start new processes. In some examples, a remote computer (e.g., a server) can provide process recipes to a system over a network, which can include a local network or the Internet. The remote computer can include a user interface that enables entry or programming of parameters and / or settings, which are then transmitted over the network to the system. In some examples, a controller receives instructions in the form of data, which specify parameters for each of the processing steps during one or more operations. It should be understood that the parameters can be specific to a type of process to be performed by the tool and a type of tool that the controller is configured to interface with or control. Thus as described above, a controller can be distributed across several separate components, e.g., by including one or more discrete controllers that are networked together and working towards a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes includes one or more integrated circuits on a chamber in communication with one or more integrated circuits located off the chamber, e.g., in a remote location, such as at a platform level or as part of a remote computer, that work together to control processes on the chamber.

[0058] Example systems can include, but are not limited to, plasma etch chambers or modules, deposition chambers or modules, spin rinse chambers or modules, metal plating chambers or modules, clean chambers or modules, bevel edge etch chambers or modules, physical vapor deposition (PVD) chambers or modules, chemical vapor deposition (CVD) chambers or modules, atomic layer deposition (ALD) chambers or modules, atomic layer etch (ALE) chambers or modules, ion implantation chambers or modules, track chambers or modules, and any other semiconductor processing systems that can be associated or used in the manufacturing and / or production of semiconductor wafers.

[0059] As noted above, depending on the process step or steps to be performed by the tool, the controller might communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout a factory, a main computer, another controller, or tools used in material transport that bring wafers containers to and from the tool locations and / or ports in a semiconductor manufacturing factory.

Claims

1. A method of cleaning a substrate, comprising: arranging the substrate in a processing chamber; controlling a pressure of the processing chamber within a predetermined pressure range; controlling a temperature of the processing chamber within a predetermined temperature range; continuously supplying a vapor mixture comprising a metal chelating vapor during a first period to remove metal contaminants from a surface of the substrate; after the first period, removing reactants from the processing chamber; supplying an oxidizing gas mixture to the processing chamber during a second period; and after the second period, removing reactants from the processing chamber, wherein cleaning the substrate by supplying the vapor mixture and the oxidizing gas mixture prevents collapse of high aspect ratio structures on the substrate.

2. The method of claim 1, comprising at least one of: components within the processing chamber are made of a non-metallic material; and / or exposed surfaces of the components within the processing chamber are coated with a non-metallic coating.

3. The method of claim 2, wherein the metal chelating vapor comprises a β-diketone and a β-diketone derivative.

4. The method of claim 1, wherein the metal chelating vapor is selected from the group consisting of acetylacetone (acac), trifluoroacetylacetone (tfa), hexafluoroacetylacetone (hfacH), pivaloyltrifluoroacetone, tetramethylheptanedione, and heptafluoro-dimethyl octanedione (fod).

5. The method of claim 1, wherein the metal chelating vapor comprises trifluoroacetic acid and ethylenediamine.

6. The method of claim 3, wherein the vapor mixture further comprises a vapor containing a hydrohalide.

7. The method of claim 1, further comprising: prior to supplying the vapor mixture to the processing chamber, supplying an oxidizing gas mixture to the processing chamber during a second period; and after the second period, removing reactants from the processing chamber.

8. The method of claim 1, wherein the predetermined pressure range is from 0.1 Torr to 100 Torr.

9. The method of claim 1, wherein the predetermined temperature range is from 50 °C to 300 °C.

10. The method of claim 1, further comprising controlling the temperature of the processing chamber using a heater arranged outside the processing chamber.

11. The method of claim 1, wherein cleaning the substrate by supplying the vapor mixture and the oxidizing gas mixture is selective to silicon-based materials on the substrate.

12. The method of claim 1, wherein the substrate is not moved during the cleaning process.

13. A substrate processing system for cleaning a substrate, comprising: a processing chamber comprising a top surface, a bottom surface, and sidewalls, the sidewalls being at least one of made of a non-metallic material and coated with a non-metallic material; a substrate support for supporting a substrate; a heater for heating the substrate to a temperature within a predetermined temperature range; ​ a vapor delivery system for supplying a vapor mixture containing a metal chelating vapor to the processing chamber during a first period to remove metal contaminants from a surface of the substrate; and a gas delivery system for delivering an oxidizing gas mixture to the processing chamber during a second period after the first period, wherein the supplying of the vapor mixture and the oxidizing gas mixture prevents collapse of high aspect ratio structures on the substrate.

14. The substrate processing system of claim 13, wherein the metal chelating vapor comprises a β-diketone and a β-diketone derivative.

15. The substrate processing system of claim 13, wherein the metal chelating vapor comprises acetylacetone (acac), trifluoroacetylacetone (tfa), pivaloyltrifluoroacetone, tetramethylheptanedione, hexafluoroacetylacetone (hfacH), and heptafluoro-dimethyl octanedione (fod).

16. The substrate processing system of claim 13, wherein the metal chelating vapor comprises trifluoroacetic acid and ethylenediamine.

17. The substrate processing system of claim 13, wherein the vapor mixture further comprises a vapor containing a halogen species.

18. The substrate processing system of claim 13, further comprising a gas delivery system for delivering an oxidizing gas mixture to the processing chamber during a second period, wherein the gas delivery system delivers the oxidizing gas mixture to the processing chamber prior to the vapor delivery system supplying the vapor mixture.

19. The substrate processing system of claim 13, wherein the processing chamber is maintained at a pressure within a predetermined pressure range of between 0.1 Torr and 100 Torr.

20. The substrate processing system of claim 13, wherein the predetermined temperature range is from 50 °C to 300 °C.

21. The substrate processing system of claim 13, wherein: the processing chamber comprises a transparent window; and the heater is disposed outside of the processing chamber adjacent to the transparent window.

22. The substrate processing system of claim 13, wherein the heater comprises a plurality of light emitting diodes.

23. The substrate processing system of claim 13, wherein: the heater is disposed inside of the processing chamber; an exposed surface of the heater is made of a non-metallic material and / or coated with a non-metallic coating; and the heater comprises at least one of an embedded heater and a coolant channel.

24. The system of claim 13, wherein the substrate is not moved during the cleaning process.

25. The system of claim 13, wherein the supplying of the vapor mixture and the oxidizing gas mixture is selective to silicon-based materials on the substrate.

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