Method and apparatus for processing a semiconductor substrate

Abstract

The present invention relates to a gas delivery system and method suitable for repairing or avoiding friction of high aspect ratio structures on a semiconductor substrate. The gas delivery system and method deliver a mixture of hydrogen halide, vaporized solvent, and carrier gas to the substrate via a heated supply line (201) to avoid droplet formation during the conveyance of the gas mixture. The gas mixture supply line is preferably maintained within a conduit (202) that includes a purge gas supply line (204) such that any hydrogen halide leaking through the gas mixture supply line (201) can be carried away by the purge gas flow within the conduit. In such an embodiment, the purge gas is also preferably heated and used as a measure to heat the distribution outlet of the gas mixture supply line.

Description

TECHNICAL FIELD

[0001] The present invention relates to a substrate processing method, in particular a method for repairing high aspect ratio structures on a semiconductor substrate or avoiding friction thereof. The present invention also relates to a method and an apparatus for performing such a method, in particular a method and an apparatus for delivering hydrogen halide in surface treatment. BACKGROUND ART

[0002] A substrate processing system can be used to deposit a film on a substrate (such as a semiconductor wafer) or to etch, clean, and / or otherwise process the surface of the substrate. In some processes, the substrate may be subjected to wet processing. In these processes, the substrate is fixed to a rotating chuck. When the rotating chuck rotates, fluid nozzles can be used to dispense fluids, such as liquids or gases, and / or heat can be applied to process the substrate.

[0003] Some substrates contain high aspect ratio (HAR) structures, such as nanocolumns, trenches, or vias. HAR structures have a width (parallel to the substrate surface) that is much smaller than the height (perpendicular to the substrate surface). HAR structures with an aspect ratio greater than 5:1 (trench depth: trench width) are common. Many advanced processes involve HAR structures with even higher aspect ratios.

[0004] Pattern collapse occurs when one or more HAR structures collapse, move laterally relative to the substrate surface, and / or come into direct contact with adjacent HAR structures. Pattern collapse typically occurs during drying after a wet cleaning process. In particular, the capillary force generated by the surface tension of the drying rinse liquid between HAR structures causes the surfaces of adjacent structures to experience friction - i.e., stick together.

[0005] Several processes are used to reduce pattern collapse when drying the substrate. For example, the substrate can be dried using supercritical CO2. Supercritical CO2 with a low surface tension can displace the rinse fluid and sublimate when heated, avoiding capillary action that would cause friction. However, supercritical CO2 is relatively expensive and has implementation problems. The surface of the substrate can be modified with a layer to avoid friction. However, since surface modification requires the use of additional chemicals, it is usually expensive. Since the modified layer needs to be removed, surface modification also results in material loss. The substrate can also be dried using IPA delivered to the substrate surface at a temperature close to the boiling point of IPA. However, some aspect ratios cannot be dried with boiling IPA without causing pattern collapse.

[0006] In the prior application WO2019 / 083735 of the applicant of the present invention, the inventors disclosed a method for treating HAR structures involving the use of gaseous hydrogen fluoride (HF). In particular, the method involves: (a) spin-rinsing the surface of a substrate with a first rinse liquid; (b) spin-removing the first rinse liquid from the substrate surface; and (c) directing a gas mixture containing HF onto the substrate surface after dispensing the first rinse liquid. HF can solve the friction problem by assisting in breaking the bridging oxide bonds between HAR structures or preventing their formation.

[0007] However, there is still a need for improved equipment and methods for treating substrates, and in particular, equipment and methods that can avoid or repair pattern collapse. Summary of the Invention

[0008] The method disclosed in the prior application WO2019 / 083735 provides a particularly effective method for avoiding and repairing pattern collapse of HAR structures. However, the inventors of the present invention have found that this method can lead to non-uniformities across the surface of the treated substrate. In particular, upon detailed examination, it was found that non-uniform treatment can occur due to the formation and coalescence of HF droplets during gas delivery and subsequent random deposition onto the substrate surface. The random delivery of droplets can cause random spots on the surface due to local etching, which can have a serious impact on the quality of the finished product. In extreme cases, condensation can cause droplets to form on the nozzles used to deliver the HF gas, which then drip onto the substrate.

[0009] Accordingly, the inventors of the present invention have developed equipment and methods that can solve this problem. In particular, to solve this problem, the present invention provides a method for treating a substrate, which comprises:

[0010] - combining a vaporized solvent and a hydrogen halide to form a gas mixture;

[0011] - passing the gas mixture through a gas mixture supply line; and

[0012] - dispensing the gas mixture onto the surface of the substrate;

[0013] wherein the gas mixture supply line is heated to limit condensation of the gas mixture during transport. Importantly, using a heated supply line can limit or even avoid the delivery of undesired droplets (such as droplets containing HF) onto the substrate surface by keeping the hydrogen halide in the gas phase. This can be achieved by limiting condensation of the gas mixture and selectively re-vaporizing any droplets that have formed.

[0014] The temperature to which the gas mixture supply line is heated depends on the type of gas mixture used. In particular, the type of hydrogen halide, the partial pressure of the hydrogen halide used, and the overall pressure. However, generally, the gas mixture supply line is heated to at least about 40 °C, or at least about 50 °C, preferably at least about 60 °C. The upper limit of the temperature is not particularly limited, but can be, for example, about 150 °C, or about 120 °C, or about 100 °C. The temperature mentioned corresponds to the temperature of the inner surface of the gas mixture supply line. When the heater and the gas mixture are in proximity to each other, the temperature of the heater can be the same as the temperature of the inner surface of the gas mixture supply line.

[0015] Suitably, the substrate is a semiconductor substrate, such as a silicon substrate, like a wafer (i.e., a slice or sheet of material (substantially thin)). For example, the substrate can be an integrated circuit. The substrate can be flat.

[0016] Suitably, the substrate is a patterned substrate. In other words, the substrate includes a surface structure. The surface structure can include pillars or be composed of pillars. Additionally or alternatively, the surface structure can include trenches or be composed of trenches. Additionally or alternatively, the surface structure can include vias or be composed of vias. Preferably, the method is applied to a semiconductor substrate having a high aspect ratio (HAR) structure, such as a substrate having one or more (optionally all) structures with an aspect ratio (trench depth: trench width) of at least about 5:1, at least about 8:1, or at least about 10:1. In this specification, "aspect ratio" refers to the ratio of height to width. Advantageously, the method of the present invention can be particularly effective in repairing and / or avoiding friction of surface structures, especially HAR structures.

[0017] The width of one or more surface structures can be, for example, 100 nm or less, 80 nm or less, 60 nm or less, 50 nm or less, 40 nm or less, 30 nm or less, or 20 nm or less. The pitch between features can be, for example, 200 nm or less, 150 nm or less, 100 nm or less, 80 nm or less, 60 nm or less, 50 nm or less, 40 nm or less, or 30 nm or less. The height can be, for example, 100 nm or greater, 200 nm or greater, 300 nm or greater, 400 nm or greater, 500 nm or greater, 600 nm or greater, 700 nm or greater, 800 nm or greater, or 1000 nm or greater.

[0018] For a substrate having an array of surface structures (optionally the same surface structures), the pitch between the structures (i.e., the distance between the centers of the structures) can be 500 nm or less, 400 nm or less, 300 nm or less, 200 nm or less, 100 nm or less, 50 nm or less, 40 nm or less, or 30 nm or less. The structure pitch, if expressed as a percentage of the structure height, can be, for example, 50% or less, 40% or less, 30% or less, 20% or less, or 10% or less. The structure pitch, if expressed as a percentage of the structure width, can be, for example, less than 500%, less than 400%, less than 300%, or less than 200%, or less than 150%.

[0019] The hydrogen halide used is preferably hydrogen fluoride (HF) or hydrogen chloride (HCl), preferably HF. Due to its high reactivity, HF can particularly effectively avoid or repair pattern collapse. However, due to the relatively high boiling point of HF (the boiling point of pure HF at atmospheric pressure is 19.5 °C), it is also most likely to form droplets, and its high boiling point is due to the interaction between highly negatively charged HF molecules and the tendency to form mixtures with higher boiling point ranges with other hydrogen-bond-forming compounds (such as water and alcohols). Such mixtures with hydrogen-bond-forming compounds (to some extent this exists for all hydrogen halides) have a much higher boiling point than pure hydrogen halides. Therefore, the inventors of the present invention have found that particularly good results can be obtained when using HF when the gas mixture supply line is heated to at least 40 °C, especially when using an HF / alcohol mixture, such as a mixture of HF and isopropyl alcohol (IPA).

[0020] The relative and absolute amounts of the hydrogen halide and the vaporized solvent depend on the specific application for which the gas mixture will be used.

[0021] Suitably, the gas mixture contains at least 0.1% by volume, at least 0.5% by volume, or at least 1% by volume of hydrogen halide (preferably HF). The upper limit of the amount of hydrogen halide in the gas mixture is, for example, 10% by volume or 5% by volume. For example, the amount of hydrogen halide can range from 0.5% by volume to 5% by volume.

[0022] The vaporized solvent can be water or preferably can be alcohols. For example, the alcohols can be methanol or IPA, preferably IPA. Advantageously, IPA can be obtained in a high-purity grade and does not undergo severe condensation at the above temperatures. Advantageously, when IPA is used in a method for surface drying, IPA displaces the rinsing liquid from the surface and then evaporates to obtain a surface free of water vapor.

[0023] The solvent is evaporated through a heated liquid ampoule, bubbler, or other evaporator. Suitably, the gas mixture contains at least 0.1 vol%, at least 0.5 vol%, or at least 1 vol% of the vaporized solvent. The upper limit of the amount of the vaporized solvent in the gas mixture can be, for example, 10 vol%, 5 vol%, or 2.5 vol%. For example, the range of the amount of the vaporized solvent can be in the range of 0.5 vol% to 2.5 vol%.

[0024] Preferably, the gas mixture contains a carrier gas. The carrier gas is preferably an inert gas, more preferably nitrogen (N2) for reasons of cost, availability, and lack of reactivity.

[0025] The combined amount of the hydrogen halide, vaporized solvent, and carrier gas can account for at least 95 vol%, at least 98 vol%, at least 99 vol%, or at least 99.5 vol% of the total gas mixture. Optionally, the gas mixture consists of the hydrogen halide, vaporized solvent, and carrier gas.

[0026] Preferably, the gas mixture contains 0.5 vol% to 5 vol% of a hydrogen halide (preferably HF), 0.5 to 2.5 vol% of the vaporized solvent (preferably IPA), and the remaining carrier gas (preferably nitrogen). Advantageously, this mixture can repair or avoid pattern collapse without causing excessive etching of the substrate surface.

[0027] Generally, the gas mixture substantially does not contain any oxidizing agent. For example, the gas mixture can have no more than 0.5 vol% or no more than 0.1 vol% of the oxidizing agent. For example, the total amount of oxygen, ozone, hydrogen peroxide, nitric acid, and sulfuric acid in the gas mixture can be no more than 0.5 vol% or no more than 0.1 vol%, or the gas mixture can contain no such compounds.

[0028] Preferably, the method is carried out using a gas delivery system having:

[0029] - a hydrogen halide (HH) supply line;

[0030] - a vaporized solvent (VS) supply line; and

[0031] - a carrier gas (CG) supply line, where these supply lines are combined to form an HH / VS / CG mixture supply line, and the HH / VS / CG mixture supply line is heated to limit condensation of the gas mixture during transportation.

[0032] The method can include, for example:

[0033] (i) evaporating the solvent and combining it with the carrier gas to form a VS / CG mixture supply line (e.g., by combining the VS and CG supply lines);

[0034] (ii) Combining the VS / CG mixture supply line with the HH supply line to form a HH / VS / CG mixture supply line:

[0035] (iii) optionally, diluting the HH / VS / CG mixture supply line with additional carrier gas, preferably with a pre-heated carrier gas (e.g., heating the carrier gas to the same temperature as the HH / VS / CG mixture); and

[0036] (iv) Dispensing the HH / VS / CG mixture from the HH / VS / CG mixture supply line.

[0037] Preferably, any or all of the HH supply line, VS supply line, CG supply line are also heated. Preferably, the CG supply line is heated. Preferably, the VS / CG mixture supply line is heated. In a particularly preferred method, both the HH supply line and the VS / CG mixture supply line are heated. Heating the individual supply lines further helps to limit condensation. In particular, heating the individual components in the gas mixture before they combine helps to avoid condensation at the point where the components mix.

[0038] Although optional, step (iii) when used together with the aforementioned dilution step (i) can help to accurately dilute HH and VS to the desired partial pressures.

[0039] The selectivity and preferred temperatures discussed above for heating the vaporized solvent and hydrogen halide gas mixture may also be applied to the other supply lines described above. In particular, any or all of the heated supply lines may be heated to at least about 40° C., or at least about 50° C., preferably at least about 60° C. The upper temperature limit is not particularly limited, but may be, for example, about 150° C., about 120° C., or about 100° C.

[0040] The method of the present invention may be used to repair structural collapse of a patterned semiconductor substrate, for example to repair structural collapse of a patterned semiconductor substrate having a HAR structure (as defined above).

[0041] Optionally, the gas mixture is used as part of a method for drying a patterned semiconductor substrate, for example a method for drying a patterned semiconductor substrate having a HAR structure (as defined above). Advantageously, the vaporized solvent is used to dry the substrate, while the hydrogen halide helps to avoid structural collapse (in particular, adhesion of adjacent surface structures). Preferably, such a method involves:

[0042] a) rinsing (preferably, spin rinsing) the surface of the substrate with a rinsing liquid (e.g., water or alcohol, such as IPA);

[0043] b) selectively removing at least a portion of the rinse liquid from the substrate surface (e.g., spinning the liquid away); and then

[0044] c) Treat the substrate surface with the gaseous mixture of the vaporized solvent and hydrogen halide using a heated gaseous mixture supply line as described above.

[0045] In such repair and drying methods, the conditions can be adjusted such that the hydrogen halide (preferably HF) is sufficient to help "unstick" or prevent adjacent structures on the substrate surface from sticking, without causing excessive etching. Thus, the conditions can be selected to limit the etching rate. For example, the supply line for the gaseous mixture of the vaporized solvent and hydrogen halide is preferably heated to a temperature in the range of between 40 °C and less than 100 °C to avoid excessive high temperatures that may cause an undesired degree of etching (since the reactivity of hydrogen halide increases with increasing temperature). Similarly, the partial pressure of the hydrogen halide can be selected to limit excessive etching.

[0046] Optionally, the time between step (c) and its previous step (step (a) or step (b)) is, for example, no more than 60 seconds, no more than 40 seconds, no more than 30 seconds, no more than 20 seconds, or no more than 10 seconds. Advantageously, a short time before delivering the gaseous mixture helps to achieve efficient drying but minimizes the number of collapsed structures.

[0047] Optionally, step (c) at least partially overlaps with step (a) and / or step (b). In other words, the gaseous mixture is delivered at the same time as the delivery of the rinse liquid and / or during the temporary drying step (b). Additionally, it has been found that this scheme can achieve efficient drying but minimizes the number of collapsed structures.

[0048] A chemical treatment step, such as an etching step, can be carried out before the above rinse step (a). For example, the method can include:

[0049] - Deliver an etching liquid to the surface of the substrate;

[0050] - Rinse the substrate surface with water (such as deionized water);

[0051] - Rinse the substrate surface with IPA to displace the water;

[0052] - Optionally, remove at least a portion of the IPA from the substrate surface;

[0053] - Treat the surface of the substrate with the gaseous mixture of the vaporized solvent and hydrogen halide using a heated gaseous mixture supply line as described above.

[0054] In the method of the present invention, the gas mixture can be dispensed from a dispensing outlet (such as a nozzle or a showerhead). Suitably, the position of the outlet can be adjacent to the substrate during dispensing the gas mixture onto the substrate surface. This allows the gas mixture to effectively impinge on the substrate surface. The distance between the outlet and the substrate surface during dispensing the gas mixture can be, for example, 2 to 20 mm, 2 to 15 mm, 2 to 10 mm, or 2 to 5 mm. Preferably, the dispensing outlet is moved (such as scanned) across the substrate surface during conveyance of the gas mixture of the vaporized solvent and hydrogen halide. For example, the dispensing outlet can be provided on a movable arm such as a rotatable arm, and the arm scans the entire substrate surface. This helps to ensure a uniform degree of treatment of the entire substrate surface.

[0055] The heating of the supply line can be carried out by any suitable means. For example, the heating can be carried out by one or more heaters extending along the gas supply line. The heater can be, for example, an electric heater (trace heater, such as a resistive heater) placed on or near the gas delivery pipe for conveying the gas, such as a heater strip, a heater cable, a heater tape, a heater pad, a heater coil, or a heater tape. The temperature of the heater is set to heat the gas conveyed through the gas supply line to a desired temperature.

[0056] The heater can extend along most of the length of a particular gas supply line (such as the HH, VS, CG, VS / CG, HH / VS / CG supply lines specified above). For example, the heater can extend along at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or all of the length of a particular gas supply line. For the HH / VS / CG mixture supply line, the above length calculation generally does not include the dispensing outlet (such as a nozzle) (the dispensing outlet generally constitutes a separate component), and the gas is ejected from the dispensing outlet. Advantageously, heating most of the length of the supply line contributes to efficient and consistent heating of the relevant gas.

[0057] Optionally, the substrate itself can be heated while dispensing the gas mixture. For example, the substrate can be heated to a temperature in the range from 20 °C to 400 °C, such as between 50 °C and 150 °C.

[0058] Various gases are transported through a gas delivery pipe. Preferably, a plastic pipe (such as a fluorine-based pipe, for example, a perfluoroalkoxy alkane polymer (PFA) pipe) is used to supply the gas (especially HF and a gas mixture containing HF). Generally, HF is transported using stainless steel components. However, the combination of HF and certain solvents (including IPA) is corrosive to stainless steel, thus limiting the lifespan of the equipment and can cause the deposition of undesired metal contaminants onto the substrate. Therefore, in the present invention, a plastic pipe is preferably used to supply the gas mixture of hydrogen halide and vaporized solvent. However, one of the disadvantages of using a plastic pipe is that the pipe is not substantially completely airtight with respect to HF. Thus, although the plastic pipe itself is not damaged by HF, the environment near the pipe may degrade due to the leaked HF. In particular, in the present invention, the leaked HF may potentially damage the heater used to heat the gas mixture supply line.

[0059] In view of this problem, the inventors of the present invention have developed a system that can limit the impact of the leaked HF. In particular, the inventors of the present invention have found that transporting the gas mixture of HF and vaporized solvent through a gas delivery pipe (preferably a delivery pipe made of PFA) and flowing a purge gas (preferably an inert gas, optimally nitrogen) over the outer surface of the pipe to purge the HF leaked through the pipe wall can limit or avoid the dilemmas associated with the leaked HF. This method can be implemented by the following means: placing the gas delivery pipe (such as a PFA pipe) inside a conduit (pipe), flowing the gas through the pipe, and flowing the purge gas through the conduit over the outer surface of the conduit. The inventors of the present invention refer to this method as "double limitation". The conduit is generally another pipe with a diameter larger than the gas mixture delivery pipe.

[0060] This double limitation scheme itself represents a useful addition to the prior art. Therefore, another aspect of the present invention provides a method for transporting a hydrogen halide (such as HF), which includes: flowing the hydrogen halide through a gas delivery pipe (preferably made of a plastic such as PFA); and flowing another gas over the outer surface of the gas delivery pipe to purge any hydrogen halide leaked through the wall of the gas delivery pipe. As described above, this can preferably be achieved by the following means: placing the gas delivery pipe inside a conduit, establishing a flow of hydrogen halide through the gas delivery pipe, and flowing another gas (preferably an inert gas, most preferably nitrogen) through the conduit over the outer surface of the gas delivery pipe.

[0061] The purge gas can be heated. For example, the purge gas can be heated by the same heater used to heat the gas mixture of vaporized solvent and hydrogen halide. In this embodiment, the purge gas itself can be used to heat additional components of the gas delivery system. Preferably, the heated purge gas is used to heat the distribution outlet for delivering the gas mixture, which will be described in more detail below.

[0062] In another aspect, the present invention provides a system suitable for performing the above method. Generally speaking, the present invention provides a gas delivery system that includes a supply line connected to a source of a gas mixture, the gas mixture comprising hydrogen halide and vaporized solvent, and means for heating the supply line in use. In particular, the present invention provides a gas delivery system that includes:

[0063] - A hydrogen halide (HH) supply line connected to an HH source;

[0064] - A vaporized solvent (VS) supply line connected to a solvent source; and

[0065] - A carrier gas (CG) supply line connected to a carrier gas source;

[0066] wherein:

[0067] - The VS supply line and the CG supply line are combined (e.g., connected) to form a VS / CG mixture supply line;

[0068] - The VS / CG mixture supply line and the HH supply line are combined (e.g., connected) to form an HH / VS / CG mixture supply line;

[0069] - The HH / VS / CG mixture supply line includes a dispensing outlet for dispensing the HH / VS / CG mixture onto a substrate; and

[0070] - The system includes a heater for heating the HH / VS / CG mixture supply line in use.

[0071] Preferably, the system further includes one or more heaters for heating the HH supply line and / or the VS / CG mixture supply line in use.

[0072] Preferably, the heater(s) extends along most of the length of the HH / VS / CG mixture supply line (as discussed above for the method).

[0073] Optionally, the dispensing outlet includes a housing that includes a nozzle tube extending to a nozzle outlet, wherein the nozzle tube and the nozzle outlet are for dispensing the HH / VS / CG mixture onto a substrate.

[0074] In such embodiments, the heater for heating the HH / VS / CG mixture supply line may extend into the housing to further limit the possibility of droplet formation.

[0075] Preferably, the dispensing outlet includes a gas mixture control valve to control the flow of the HH / VS / CG mixture to the nozzle outlet. Preferably, the gas mixture control valve is switchable between an open position and a closed position. Preferably, the distance (measured along the gas flow path) between the gas mixture control valve and the nozzle orifice is not more than 20 cm, preferably not more than 15 cm, and most preferably not more than 10 cm. Advantageously, ensuring a relatively short distance between the gas mixture control valve and the nozzle orifice minimizes the time delay between opening the valve and delivering gas from the nozzle orifice. Further, it minimizes the gas volume between the gas mixture control valve and the nozzle orifice, which can reduce the likelihood of contaminants accumulating in this volume when the valve is closed. On the other hand, if the distance between the gas mixture control valve and the nozzle orifice is too small, this can interfere with the gas flow through the nozzle due to the generation of turbulence. Thus, preferably, the distance is at least 2 cm, more preferably at least 3 cm, more preferably at least 4 cm, and most preferably at least 5 cm. The preferred range of the distance between the gas mixture control valve and the nozzle orifice is from 2 to 20 cm, more preferably from 5 to 10 cm.

[0076] Preferably, the dispensing outlet further includes a flush line controlled by a flush line control valve. The flush line provides a means to divert the flow of the HH / VS / CG mixture to a discharge device rather than delivering it to the substrate. The flush line control valve is preferably switchable between an open position and a closed position.

[0077] The gas mixture control valve and the flush line control valve are preferably gas-operated (such as air-operated) valves. Advantageously, this can avoid the need for external moving parts (i.e., moving parts not contained within the valve) or metal parts associated with the valve, which may generate debris that can contaminate and / or damage the equipment and the substrate.

[0078] Particularly preferably, the gas delivery system further includes both a gas mixture control valve and a flush line control valve to control the delivery of the HH / VS / CG mixture to the substrate or the flush line. In such an embodiment, preferably, the controls of the gas mixture control valve and the flush line control valve are linked such that when one is open, the other is closed. This ensures that a flow path is always provided for the HH / VS / CG mixture, thus avoiding pressure buildup in the system. In such a system, preferably, in the rest state of the system, the flush line control valve is open and the gas mixture control valve is closed. For example, the flush line control valve and the gas mixture control valve can be gas-operated (such as air-operated valves), the flush line control valve is open in the rest state (normally open valve), and the gas mixture control valve is closed in the rest state (normally closed valve), and when using gas-actuated valves, the flush line control valve is closed and the gas mixture control valve is open.

[0079] In a particularly preferred embodiment, the dispensing outlet comprises a housing that includes:

[0080] - a nozzle tube that extends to a nozzle outlet;

[0081] - a gas mixture control valve as described above; and

[0082] - a flushing line controlled by a flushing line control valve as described above.

[0083] Preferably, when using an HH / VS / CG mixture, the HH / VS / CG mixture is continuously supplied to the dispensing outlet and the HH / VS / CG mixture is controlled using the gas mixture control and flushing line control valves. Providing a continuous supply of the HH / VS / CG mixture helps to minimize variations in the supply that could affect the consistency of the process.

[0084] Preferably, according to the "dual containment" strategy discussed above, the HH / VS / CG mixture supply line is a gas delivery tube that remains within a conduit, where the conduit is connected to a purge gas supply line to purge any HH that escapes through the walls of the conduit in use, and the purge gas supply line is used to pass purge gas over the outer surface of the gas delivery tube through the conduit. Advantageously, as described above, even though the plastic tube may be porous to HH, the dual containment scheme enables the HH / VS / CG mixture to be supplied through the plastic tube because any HH that leaks through the tube can be safely removed by the purge gas. In view of this, the gas delivery tube can be plastic, such as a perfluoroalkoxy alkane polymer.

[0085] In such an embodiment, the system can include a housing that at least houses a portion (optionally all) of the HH supply line and optionally at least a portion of one or more of the VS supply line, CG supply line, VS / CG mixture supply line, and HH / VS / CG mixture supply line, where the conduit is open within the housing. The housing is commonly referred to as a "gas mixing box". Advantageously, this scheme means that any HH that escapes from the HH supply line or the HH / VS / CG mixture supply line will be transported to the housing where the HH can be safely removed. This limits the number of discharge ports where leaked HH must be removed, thus providing a safety advantage. Additionally, configuring the system such that leaked HH flows to a common housing (regardless of whether the leak originated from the HH supply line or the HH / VS / CG mixture supply line) can facilitate and simplify the detection of HH leaks. Accordingly, the system can include an HH detector for detecting HH in the housing. The detector can be located within the housing itself or can be configured to detect HH from a discharge port of the housing.

[0086] Optionally, one end of the conduit is covered or sealed. In such an embodiment, the purge gas supply line may have an outlet near the covered / sealed end of the conduit so that the purge gas leaving the purge gas supply line impinges on the covered / sealed end and back blows the conduit during use. Advantageously, this scheme implements the "double confinement" strategy in a particularly simple manner. In particular, the purge gas can be introduced (using the purge gas supply line) and removed through the same end of the conduit. When the system includes a housing (at least partially) containing the HH supply line, the conduit may have a first end open towards the housing, an intermediate section extending along and around the gas delivery tube, and a second end that is covered or sealed (e.g., an end sealed near the outer periphery of the gas delivery tube). Advantageously, this configuration causes hydrogen halide leaking from the conduit to be delivered into the housing and discharged from the housing. In such an embodiment, the purge gas supply line may extend from the housing through the conduit to the covered or sealed end. This implements the "double confinement" scheme in a particularly simple and effective manner, achieving both purge gas delivery and purge gas removal through the housing. In particular, this scheme does not require the conduit to include a separate port for introducing the purge gas supply line, which provides greater flexibility with respect to the type of material used for the conduit (e.g., relatively thin, flexible materials can be used).

[0087] Preferably, in the "double confinement" embodiment, the heater for heating the HH / VS / CG mixture supply line is fixed within the conduit. This brings the HH / VS / CG mixture supply line into close proximity to the heater, thus facilitating efficient heat transfer. In addition, the ability to flow gas through the conduit helps to minimize damage to the heater, which might otherwise be damaged due to HH leakage through the gas delivery tube.

[0088] Preferably, in the "dual restriction" embodiment, the dispensing outlet includes the housing, which includes a nozzle tube (a continuous portion of the gas delivery tube, or a separate component of the tube) extending to the nozzle outlet (and preferably extending to the gas mixture control valve and the flush line controlled by the flush line valve), wherein the conduit opens into the housing to allow purge gas to enter the housing. In other words, the interior of the housing of the dispensing outlet is in fluid communication with the conduit such that purge gas can enter the housing. Advantageously, this configuration can be used to heat the nozzle tube and the nozzle outlet, since the purge gas heated by the HH / VS / CG mixture supply line heater can enter the housing and heat the nozzle tube and the nozzle outlet. Heating the dispensing outlet with the heated gas can, in a relatively straightforward manner, heat each of the components in the dispensing outlet to the same temperature without the need to provide electrical heating components for each dispensing outlet component (which would have small dimensions). Suitably, in such an embodiment, the housing is sealed so that the purge gas entering the housing through the conduit also exits through the same conduit. In such a case, the housing effectively "covers" the conduit such that the purge gas must backflush the conduit.

[0089] In these embodiments, the outlet of the purge gas supply line preferably opens into or near the housing of the dispensing outlet (e.g., less than 5 cm, less than 4 cm, less than 3 cm, less than 2 cm, or less than 1 cm from the housing). In this way, the purge gas is delivered into the housing and can flow back through the conduit without encountering significant backflow. In contrast, if the outlet of the purge gas supply line opens at a remote distance from the housing, the airflow into and out of the housing will be more complex (less laminar) due to the interference of the gas returning from the housing and the gas delivered from the purge gas supply line. In such an embodiment, the purge gas supply line preferably extends along the gas delivery tube within the conduit, and the same heater is used to heat both the gas delivery tube and the purge gas supply line in use. This not only simplifies the construction of the equipment but also allows the purge gas to maintain the housing at or near the same temperature as the gas delivery tube while being transported through the conduit.

[0090] Preferably, the dispensing outlet is mounted on a movable arm such that the dispensing outlet can move / scan the entire surface of the substrate in use. For example, the gas delivery system can have a dispensing outlet that includes the housing, which includes a nozzle tube extending to the nozzle outlet (and preferably to the flush line controlled by the gas mixture control valve and the flush line valve), wherein the dispensing outlet and its above-described components are mounted on the movable arm. In this way, the nozzle outlet can scan the entire substrate surface without affecting the relative configuration of the nozzle outlet with respect to the other components of the dispensing outlet.

[0091] Optionally, the HH / VS / CG mixture supply line and the heater for heating the HH / VS / CG mixture supply line are surrounded by thermal insulation material. This helps to ensure efficient heating of the gas mixture supply line.

[0092] In a particularly preferred embodiment, the gas delivery system comprises:

[0093] - a hydrogen halide (HH) supply line connected to an HH source;

[0094] - a vaporized solvent (VS) supply line connected to a solvent source; and

[0095] - a carrier gas (CG) supply line connected to a carrier gas source;

[0096] wherein:

[0097] - the VS supply line and the CG supply line are combined to form a VS / CG mixture supply line;

[0098] - the VS / CG mixture supply line and the HH supply line are combined to form an HH / VS / CG mixture supply line;

[0099] - the HH / VS / CG mixture supply line includes a dispensing outlet for dispensing the HH / VS / CG mixture onto a substrate, the dispensing outlet including a housing that includes: a nozzle tube that extends to a nozzle outlet (and preferably a gas mixture control valve; and a flush line controlled by a flush line control valve);

[0100] - at least a portion (optionally all) of the HH supply line (and optionally at least a portion of one or more of the VS supply line, the CG supply line, the VS / CG mixture supply line, and the HH / VS / CG mixture supply line) is housed within a shroud;

[0101] - the HH / VS / CG mixture supply line is a gas delivery tube held within a conduit, where the conduit is connected to a purge gas supply line to purge any HH that escapes through the wall of the gas delivery tube in use, the purge gas supply line for causing a purge gas to flow over the outer surface of the gas delivery tube via the conduit, where the conduit is open in the shroud and the housing of the dispensing outlet; and

[0102] - the system includes a heater for heating the HH / VS / CG mixture supply line in use (preferably, where the heater for heating the HH / VS / CG mixture supply line is held within the conduit).

[0103] In view of the advantages of the above-mentioned "dual restriction strategy", another aspect of the present invention provides a heatable gas dispenser, which comprises: a gas delivery pipe extending to a dispensing outlet including a housing, the housing comprising: a nozzle pipe extending to a nozzle outlet (and preferably a gas mixture control valve; and a flushing line controlled by the above-mentioned flushing line control valve), wherein the gas delivery pipe is held within an open conduit within the housing, and the conduit further comprises: a heater for heating the gas delivery pipe and a purge gas supply line for allowing a purge gas to flow through the outer surface of the gas delivery pipe via the conduit. As described above, the dispenser can heat the gas transmitted through the gas delivery pipe and the dispensing outlet itself.

[0104] In another aspect, the present invention provides a processing apparatus for processing a substrate according to the method of the present invention. The apparatus preferably comprises:

[0105] - a processing chamber;

[0106] - a substrate support within the processing chamber;

[0107] - means for rotating the substrate support; and

[0108] - a gas delivery system comprising the dispensing outlet as described above.

[0109] Optionally, the processing apparatus may further comprise a liquid delivery system adapted to dispense a liquid onto a substrate supported on the substrate support. Such an apparatus can perform liquid processing steps, such as etching and rinsing, on the substrate before and / or after (optionally before) drying or otherwise processing the substrate using the gas delivery system. When the processing apparatus comprises a liquid delivery system, the apparatus preferably has a liquid disposal system as described in the applicant's patent EP 1609172.

[0110] Preferably, the dispensing outlet of the gas delivery system is positioned such that the orifice is 2 to 20 mm, such as 2 to 15 mm, 2 to 10 mm, or 2 to 5 mm, from the substrate surface during use, and the HH / VS / CG mixture is supplied through the orifice.

[0111] The orifice of the dispensing outlet may be, for example, 4 to 22 mm, such as 4 to 17 mm, 4 to 12 mm, or 4 to 7 mm from the upper surface of the substrate support. The upper surface of the substrate support is defined as the uppermost part of the substrate support, below which is the area provided for the substrate.

[0112] The substrate support may be a rotatable platform having suitable substrate gripping means. The rotatable platform may support the substrate by, for example, a vacuum chuck (or gripping means), an edge gripping chuck, or a Bernoulli chuck (or gripping means). The processing chamber of the processing apparatus of the present invention may include an annular liquid collector that surrounds the rotating platform and the substrate to collect liquid from the substrate surface. BRIEF DESCRIPTION OF THE DRAWINGS

[0113] Embodiments of the present invention will now be described, by way of example only, with reference to the accompanying drawings, in which:

[0114] Figure 1A-1C A cross-sectional view of a substrate having HAR features is shown, which shows the development of friction between the HAR features after a rinsing step, and subsequent repair of the friction using the method of the present invention;

[0115] Figure 2A and 2B A processing apparatus for performing a rinsing process and then dispensing a gas mixture according to the method of the present invention is shown;

[0116] Figure 3 shows Figure 2A and 2B the various gas delivery lines used in, which includes a heater for heating the HH / VS / CG mixture supply line;

[0117] Figure 4 and Figure 3 is the same as, but includes additional heaters for heating the VS / CG mixture supply line and the HH supply line;

[0118] Figure 5 and Figure 4 is the same as, but supplies the HH / VS / CG mixture via a tube fixed within the conduit itself according to the "dual restriction" scheme described above;

[0119] Figure 6 is Figure 5 a longitudinal cross-sectional view of the HH / VS / CG mixture supply line of, which shows the dual restriction scheme in more detail;

[0120] Figure 7 is Figure 5 a cross-sectional view of the HH / VS / CG mixture supply line of, which again shows the dual restriction scheme in more detail;

[0121] Figure 8 An alternative embodiment of the "dual restriction" scheme is shown. DETAILED DESCRIPTION

[0122] In Figure 1AIn [description], it shows substrate 1 before wet processing and drying. Substrate 1 includes high aspect ratio (HAR) pillars 2a, 2b, 2c, and 2d formed on underlying layer 3. The feature has an aspect ratio of approximately 5:1 (height to width). Figure 1B It shows substrate 1 after wet processing and drying. During the drying process, the capillary action of the liquid between pillars 2b and 2c causes the structure to collapse, forcing the pillars to contact each other. Once in contact, in this case, the pillars adhere together via a combination of van der Waals forces and bridging oxide bonds between the structures. The type of bridging oxide bond depends on the type of material forming the pillars, but can include, for example, silicon oxide (SiO x ), silicon oxynitride (SiO x N y ), and titanium oxide (TiO x ). In Figure 1C , the structure has been treated with a gas mixture of HF, IPA, and nitrogen according to the method of the present invention to break the bonding interaction between pillars 2b and 2c.

[0123] Figure 2A And 2B It shows an example of device 10 for implementing the method of the present invention. The device includes a chamber 51 that houses a rotating chuck 12. Substrate 1 is attached to the surface of rotating chuck 12 via a suitable mechanism (in this case, via the use of gripping pins 13). Suitable examples of gripping pins are shown and described in the applicant's previous application US 2018 / 0047593. The surface 14 of rotating chuck 12 is transparent, and a heater 15 is provided below surface 14. In this example, heater 15 includes a plurality of light-emitting diodes (LEDs) arranged in one or more radial regions to radially heat substrate 1. The heater can be operated to provide a moving heat wave that moves from the central position of the substrate outward to the radial outer edge of the substrate while the rotating chuck 12 rotates. Suitable examples of rotating chucks for radially heating the substrate are shown and illustrated in US2018 / 0047593.

[0124] As shown, the chuck rotation motor 16 rotates chuck 12 by rotating shaft 17. In other examples, motor 16 includes a rotor and a stator, and the rotor is magnetically driven without the need for physical contact. Suitable examples are shown in the applicant's previous patent US6,485,531.

[0125] In a first step, a first rinse liquid is delivered to the rotating substrate 1 via a liquid delivery arm 21 and a nozzle 22. A valve 24 selectively supplies the rinse liquid from a liquid supply source 20 to the arm 21. The arm 21 and the nozzle 22 scan the entire substrate 1 via an arm motor 23 to ensure that all areas of the substrate are treated. The liquid rotating away from the substrate 1 is collected by a first liquid collector 54 that surrounds the chuck 12 at the circumference and is then removed there via a drainage device 57. The gas (especially the mist generated when the rotating liquid impacts the liquid collector) inside the first liquid collector 54 is removed by an exhaust device 56. Suitable examples of liquid collection devices are shown in the applicant's previous patent EP 1 609 172 B.

[0126] Next, the chuck 12 is lifted within the housing 51 along the rotation axis of the chuck 12 to a second position by a chuck lift motor 18. Then a rinsing procedure is carried out with a second liquid, where the liquid rotates away and falls into the liquid collector 55 and is removed by a separate liquid drainage device and gas exhaust device.

[0127] After the rinsing is completed, the arm motor 23 rotates the liquid delivery arm 21 from the surface of the substrate 1 to an idle position, and the arm motor 33 rotates the gas delivery arm 31 to a position above the substrate. This is shown in more detail in Figure 2B wherein, in Figure 2B the liquid delivery arm 21 has been rotated to an idle position and the gas delivery arm 31 has been rotated to a position above the substrate.

[0128] Then the substrate 1 is treated with a gas mixture according to the method of the present invention. A gas delivery system (shown in more detail in Figures 3-5 ) delivers a gas mixture of HF, IPA, and nitrogen from a gas supply source 30 to the nozzle 34 via a control valve 32 and a heated supply line. In this embodiment, the horizontal position of the nozzle 34 is adjusted by an arm motor 33 so that the nozzle scans the surface of the entire rotating substrate 1 generally from the center outwards. The operation of the motors and various valves is coordinated by a controller 40.

[0129] During the treatment, a fan 52 continuously supplies air to the chamber 51. To avoid pressure buildup in the chamber 51, the air entering via the fan filter unit is discharged to a lesser extent via the exhaust device 56 and via the exhaust device 53.

[0130] Figures 3 to 5 A gas delivery system according to the present invention is shown, which can be used as the gas delivery system in Figures 2A-2B In Figure 3In this process, isopropyl alcohol (IPA) and molecular nitrogen are supplied to the evaporator 102 to generate a vaporized solvent. Subsequently, the vaporized solvent is combined with HF and also diluted with molecular nitrogen (preferably pre-heated nitrogen), and then advances along the gas delivery pipe heated by the heater 103. Valves 104 and 105 are used to control the flow of the mixed streams of HF, IPA, and nitrogen gas to the nozzle 106 and the discharge device, respectively. The nozzle has a downward orientation to supply the gas to the substrate below (not shown). In this way, the gas mixed stream can be continuously prepared and supplied, and can be alternately delivered to the substrate or returned to the discharge device as needed. This continuous flow ensures the consistency of the supplied gas and is more conducive to minimizing the possibility of droplet formation.

[0131] Valves 104 and 105 are air-operated valves, thus eliminating the need to set moving parts near the nozzle, where the presence of moving parts may generate debris that can contaminate and / or damage the equipment and the substrate. Separate gas lines are provided to actuate the valves (not shown). These valves are linked such that when valve 104 is open, valve 105 is closed, and vice versa. In the resting state (when no air is supplied to the valves), valve 105 is open and valve 104 is closed, thus minimizing the possibility of unintentional gas supply from the nozzle 106. In other words, the default position is for the gas to leave through the purge line.

[0132] Valve 105 is located approximately 2 - 20 cm near the opening of nozzle 104 to reduce the time delay between the opening of valve 105 and the delivery of gas from nozzle 106 and to minimize the possibility of contamination caused by the gas occupying the nozzle before gas delivery.

[0133] Valves 104 and 105 and nozzle 106 are provided as Figure 2A part of the 2B gas delivery arm shown in. This enables nozzle 106 to scan the entire surface of the substrate in use without affecting the positions of the valves relative to each other and their positions relative to nozzle 106.

[0134] Figure 4 The gas delivery system 110 of Figure 3 is the same as that shown, but includes additional heaters 107 and 108. Heater 107 heats the IPA and nitrogen gas streams from the evaporator until the point where HF is introduced into the mixture. Heater 108 heats HF until the point where it combines with the mixture of IPA and nitrogen.

[0135] In Figure 5 this process, Figure 4 the system of Figure 6 is further modified to include a dual-restriction system 200 for delivering the HF / IPA / nitrogen mixture. In this system ( 7In the more detailed display, the HA / IPA / nitrogen mixture is supplied via the perfluoroalkoxy alkane polymer (PFA) gas delivery tube 201 heated by the heater 203. The gas delivery tube 201 and the heater 203 are enclosed within the outer tube 202, and the open end of the outer tube 202 is sealed to and interconnected with the gas mixing chamber 208 and the nozzle housing 205. The outer tube 202 also houses the purge gas tube 204, which is located beside the gas delivery tube 201 and the heater 203 (as shown in Figure 7 ), and extends into the nozzle housing 205. It is shown that the purge gas tube 204 enters through the side of the outer tube 202, but it is equally possible (and indeed advantageous) for the tube 204 to be introduced through the gas mixing chamber 208. In this case, the outer tube 202 is wavy to maintain elasticity and facilitate the insertion of various components. The elasticity of the tube is advantageous when the housing 205 and the valves 213 and 214 and the nozzle 212 move with the gas delivery arm 31.

[0136] In use, the gas mixture of HF, IPA, and nitrogen flows along the gas delivery tube 201. At the same time, the nitrogen purge gas tube 204 is heated by the heater 203 while the nitrogen purge gas flows through the tube 204 before being ejected into the nozzle housing 205. When the nitrogen purge gas is ejected into the nozzle housing 205, the heated nitrogen purge gas circulates within the housing (as shown in Figure 6 ) and transfers heat to the nozzle assembly (such as the nozzle tube, valves 213 and 214, and the nozzle 212), thereby minimizing the formation of droplets in the HF / IPA / nitrogen mixture ejected from the nozzle 212. The nozzle housing 205 is sealed, which means that then the nitrogen purge gas must return to the gas mixing chamber 208 via the tube 202 (as shown by the arrow 209 in Figure 5 ), and the nitrogen purge gas is removed from the gas mixing chamber 208 by the discharge device 210. In this way, a nitrogen gas flow back to the gas mixing chamber 208 is established above the outer surface of the gas delivery tube 201 to carry away any HF leaking through the wall of the gas delivery tube 201 and / or the nozzle assembly. In this case, the system includes an HF sensor 206 to detect the level of HF in the gas mixing chamber 208. In this way, the sensor can detect HF leakage via the gas delivery tube for supplying the gas mixture and any leakage in the HF supply line.

[0137] Although not shown in Figures 5-7 , the heater 203 can also extend into the nozzle housing 205 to provide additional heating.

[0138] Figure 8Shows an alternative embodiment of the dual restriction system 300, where the outer tube 302 has a closed end 303 sealed near the gas delivery tube 301. In this embodiment, the nitrogen purge gas does not enter the nozzle device but is directed back into the outer tube 302 by the closed end 303.

[0139] Example

[0140] The repair process disclosed in WO2019 / 083735 was carried out on a substrate having nanocolumns (corresponding to cylinders with a diameter of 30 nm, a pitch of 90 nm, and a height of 600 nm). It was found that the process of the present invention could repair 90% of the collapsed structures, resulting in a collapse percentage of less than 10%.

[0141] Any features disclosed in the foregoing description, or in the following claims, or in the drawings in a particular form, or for performing the said function, or for obtaining the disclosed result, may, where appropriate, be used separately or in any combination to achieve various forms of the present invention.

[0142] Although the present invention has been illustrated above with reference to exemplary embodiments, many equivalent modifications and variations will be apparent to those skilled in the art. Therefore, the above-described exemplary embodiments of the present invention should be considered illustrative rather than restrictive. Various changes may be made to the above embodiments without departing from the spirit and scope of the present invention.

[0143] For the avoidance of any doubt, any theoretical explanations provided herein are provided for the purpose of improving the reader's understanding. The present invention is not intended to be limited by any of these theoretical explanations.

[0144] The title of any paragraph used herein is for organizational purposes only and should not be construed as limiting the subject matter described.

[0145] In this specification, which includes the following claims, unless otherwise specifically required,

[0146] otherwise the words "comprising" and "including" and variations such as "comprises", "includes", and "contains" shall be understood to imply the inclusion of the stated integers or steps or groups of integers or steps, but not the exclusion of any other integers or steps or groups of integers or steps.

[0147] It should be noted that the singular forms "a", "an", and "the" used in the specification and the appended claims include plural referents unless the context clearly dictates otherwise. Ranges may be expressed herein as from "about" one particular value and / or to "about" another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values are expressed as approximations by use of the antecedent "about", it will be understood that the particular value forms another embodiment. The term "about" associated with a numerical value is optional and means, for example, + / - 10%.

Claims

1. A gas delivery system for dispensing a gas mixture onto a substrate, comprising: A hydrogen halide supply line connected to a hydrogen halide source; A vaporized solvent supply line connected to a solvent source; and A carrier gas supply line connected to a carrier gas source; Wherein: The vaporized solvent supply line and the carrier gas supply line are combined to form a VS / CG mixture supply line; The VS / CG mixture supply line and the hydrogen halide supply line are combined to form a HH / VS / CG mixture supply line; The HH / VS / CG mixture supply line includes a dispensing outlet for dispensing the HH / VS / CG mixture onto the substrate; and The system includes a heater for heating the HH / VS / CG mixture supply line in use; Wherein the HH / VS / CG mixture supply line is a gas delivery tube held in a conduit, and wherein the conduit includes a purge gas supply line configured to allow the purge gas to flow over the outer surface of the gas delivery tube via the conduit to purge any hydrogen halide that escapes through the wall of the gas delivery tube in use.

2. The gas delivery system according to claim 1, wherein the dispensing outlet includes a housing that houses a nozzle tube extending to a nozzle outlet, wherein the nozzle tube and the nozzle outlet are for dispensing the HH / VS / CG mixture onto the substrate, and wherein the conduit opens into the housing in use to allow the purge gas to enter the housing in use.

3. The gas delivery system according to claim 1 or 2, wherein the purge gas supply line extends along the heater of the HH / VS / CG supply line to heat the purge gas in use before the purge gas exits the purge gas supply line.

4. The gas delivery system according to claim 1 or 2, wherein the dispensing outlet includes a dispensing outlet housing that houses a nozzle tube extending to a nozzle outlet, and wherein the heater for heating the HH / VS / CG mixture supply line extends into the housing.

5. The gas delivery system according to claim 4, wherein the dispensing outlet is mounted on a movable arm for scanning the entire substrate with the nozzle outlet in use.

6. The gas delivery system according to claim 1 or 2, wherein the system includes an outer cover that houses at least a portion of the hydrogen halide supply line and selectively houses at least a portion of one or more of the vaporized solvent supply line, the carrier gas supply line, the VS / CG mixture supply line, and the HH / VS / CG mixture supply line, and wherein the conduit opens into the outer cover in use to allow the purge gas to enter the outer cover in use after flowing over the outer surface of the gas delivery tube.

7. The gas delivery system according to claim 6, wherein the purge gas supply line is inserted from the outer cover into the conduit.

8. The gas delivery system according to claim 6, further comprising a hydrogen halide detector for detecting hydrogen halide in the outer cover.

9. The gas delivery system according to claim 1 or 2, wherein the gas delivery pipe is made of plastic.

10. The gas delivery system according to claim 9, wherein the gas delivery pipe is made of perfluoroalkoxy alkane polymer.

11. The gas delivery system according to claim 1 or 2, wherein the heater for heating the HH / VS / CG mixture supply line is an electric heater held within the conduit.

12. The gas delivery system according to claim 1 or 2, wherein the dispensing outlet includes a gas mixture control valve to control the flow of the HH / VS / CG mixture flowing to the nozzle outlet having a nozzle orifice, and wherein the distance between the gas mixture control valve and the nozzle orifice is 2 to 20 cm.

13. The gas delivery system according to claim 12, wherein the dispensing outlet and the gas mixture control valve are mounted on a movable arm for scanning the nozzle outlet across the entire substrate during use.

14. The gas delivery system according to claim 1 or 2, wherein the dispensing outlet further includes a flushing line controlled by a flushing line control valve.

15. The gas delivery system according to claim 1 or 2, wherein the dispensing outlet includes both a gas mixture control valve and a flushing line controlled by a flushing line control valve.

16. The gas delivery system according to claim 1 or 2, further comprising one or more heaters to heat the hydrogen halide supply line and / or the VS / CG mixture supply line during use.

17. The gas delivery system according to claim 1, wherein: the HH / VS / CG mixture supply line includes a dispensing outlet for dispensing the HH / VS / CG mixture onto the substrate, the dispensing outlet including a housing that houses a nozzle tube extending to the nozzle outlet; at least a portion of the hydrogen halide supply line is housed within a shroud; and the HH / VS / CG mixture supply line is a gas delivery pipe held within a conduit, wherein the conduit is connected to a purge gas supply line configured to enable purge gas to flow over the outer surface of the gas delivery pipe via the conduit to purge any hydrogen halide escaping through the wall of the pipe during use, wherein the conduit opens towards the shroud and the housing of the dispensing outlet.

18. A processing apparatus for processing a substrate with a mixture of hydrogen halide, vaporized solvent, and carrier gas, comprising: a processing chamber; a substrate support within the processing chamber for supporting the substrate; means for rotating the substrate support; and the gas delivery system according to any one of claims 1 to 16, adapted to dispense a mixture of hydrogen halide, vaporized solvent, and carrier gas onto a substrate supported on the substrate support.

19. The processing apparatus according to claim 18, further comprising a liquid delivery system adapted to dispense liquid onto a substrate supported on the substrate support.

20. A substrate processing method, comprising: combining a vaporized solvent with hydrogen halide to form a gas mixture; Flowing the gas mixture through a gas mixture supply line; and Distributing the gas mixture onto the surface of the substrate; Wherein the gas mixture supply line is heated to limit condensation of the gas mixture during transportation; Wherein the gas mixture supply line includes a gas delivery pipe and a distribution outlet, the distribution outlet having a housing that houses a nozzle pipe extending to a nozzle outlet; Wherein the gas delivery pipe is held within a conduit that is connected to and open to the housing of the distribution outlet, the conduit including a purge gas supply line; The method includes flowing heated purge gas from the purge gas supply line into the housing of the distribution outlet to heat the distribution outlet, and then flowing the heated purge gas back via the conduit above the outer surface of the gas delivery pipe to purge any hydrogen halide escaping through the wall of the gas delivery pipe.

21. The method according to claim 20, wherein the conduit is connected at one end to the housing of the distribution outlet and at the other end to an outer shroud, wherein the outlet of the purge gas supply line is open to or near the housing of the distribution outlet, and the purge gas is then discharged from the outer shroud.

22. The method according to claim 20, wherein the gas delivery pipe extends in parallel with the purge gas supply line, and the same heater is used to heat both the gas delivery pipe and the purge gas supply line.

23. The method according to any one of claims 20-22, wherein the gas mixture supply line is heated to at least 40 °C.

24. The method according to any one of claims 20-22, wherein the gas mixture supply line is heated to 50 °C to 100 °C.

25. The method according to any one of claims 20-22, wherein: (i) the vaporized solvent is an alcohol; and / or (ii) the hydrogen halide is hydrogen fluoride; and / or (iii) the gas mixture includes a carrier gas.

26. The method according to claim 25, wherein the vaporized solvent is isopropyl alcohol.

27. The method according to any one of claims 20-22, wherein: (i) the vaporized solvent is an alcohol; and / or (ii) the hydrogen halide is hydrogen fluoride; and / or (iii) the gas mixture includes an inert gas.

28. The method according to claim 27, wherein the vaporized solvent is isopropyl alcohol.

29. The method according to any one of claims 20-22, wherein: (i) the vaporized solvent is an alcohol; and / or (ii) the hydrogen halide is hydrogen fluoride; and / or (iii) the gas mixture includes nitrogen.

30. The method according to claim 29, wherein the vaporized solvent is isopropyl alcohol.

31. The method according to any one of claims 20-22, wherein the substrate is a patterned substrate having one or more surface structures, the surface structures: Having an aspect ratio of at least 5:1; and / or Having a width of 50 nm or less: and / or -arranged in an array, wherein the pitch between the structures is less than 400% of the width of the structures.

32. The method according to any one of claims 20-22, wherein the method is for detaching one or more surface structures of adjacent components adhered to the substrate.

33. The method according to any one of claims 20-22, wherein the method is for drying the patterned substrate.

34. The method according to any one of claims 20-22, wherein the method is performed using the gas delivery system according to any one of claims 1-17.

35. A heatable gas distributor comprising a gas delivery tube extending to a distribution outlet, the distribution outlet comprising a housing that houses: a nozzle tube extending to a nozzle outlet, wherein the gas delivery tube is held within a conduit that is open towards the housing, the conduit further housing: a heater for heating the gas delivery tube; and a purge gas supply line configured such that purge gas can flow through the conduit over the outer surface of the gas delivery tube in use.

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