JP7506985B2 - Liquid treatment apparatus and liquid treatment method - Google Patents

Description

This disclosure relates to a liquid processing device and a liquid processing method.

Patent Document 1 describes a liquid processing method in which a processing liquid is discharged from a nozzle for supplying a processing liquid onto a substrate, the method comprising the steps of: accommodating the nozzle in a cleaning chamber such that the inner peripheral surface around the tip of the nozzle is funnel-shaped and the lower end of the funnel is located above the tip of the nozzle; flowing a predetermined amount of the solvent from a first solvent supply means for supplying a solvent for the processing liquid into the cleaning chamber in a circumferential direction along the inner peripheral surface of the funnel through a first inlet provided in the funnel of the cleaning chamber, and performing cleaning by a vortex of the solvent swirling around the tip of the nozzle; and a second solvent supply means for supplying the solvent for the processing liquid. The method for cleaning a nozzle and preventing drying of a processing liquid in liquid processing is described, which includes the steps of: injecting a predetermined amount of the solvent from the cleaning means into the upper part of the funnel through a second inlet provided above the first inlet of the cleaning chamber to form a pool of the solvent in the cleaning chamber; and sucking the nozzle to move the liquid level of the processing liquid in the nozzle back toward the processing liquid supply line, and sucking the solvent in the pool into the tip of the nozzle to form a processing liquid layer, an air layer, and a processing liquid solvent layer in this order from the processing liquid supply line side inside the tip of the nozzle.

JP 2012-235132 A

The technology disclosed herein makes it possible to reduce defects caused by changes in the state of the processing liquid supplied to the substrate.

One aspect of the present disclosure is a liquid processing method for supplying a processing liquid to a substrate from a nozzle connected to a processing liquid supply path, the method comprising the steps of accommodating the nozzle in a storage chamber and forming a processing liquid layer, a gas layer and a solvent layer in a flow path inside the tip of the nozzle, in that order from the processing liquid supply path side, the formation of the gas layer comprising supplying an adjusted gas having an adjusted concentration of at least one of moisture, oxygen and solvent to the periphery of the tip of the nozzle in the storage chamber and introducing it into the flow path, the liquid processing comprising positioning the nozzle at a processing position for supplying the processing liquid to the substrate with the processing liquid layer, gas layer and solvent layer formed in the flow path of the nozzle, and supplying the solvent of the solvent layer and the processing liquid of the processing liquid layer to the substrate from the nozzle.

The technology disclosed herein makes it possible to suppress changes in the state of the processing liquid, such as drying or deterioration, and reduce defects resulting from these.

FIG. 1 is a schematic cross-sectional view showing one embodiment of a liquid treatment apparatus according to the present disclosure. FIG. 2 is a perspective view that shows a schematic configuration of the liquid processing apparatus. FIG. 3 is a perspective view showing a nozzle unit provided in the liquid processing apparatus. FIG. 4 is a schematic cross-sectional view showing a coating nozzle provided in the nozzle unit and a part of the standby unit. FIG. 5 is an explanatory diagram illustrating a method for forming a gas layer containing a high concentration of solvent between a treatment liquid layer and a solvent layer in a flow path on the tip side of a coating nozzle housed in a standby unit in a liquid treatment apparatus. FIG. 6 is an explanatory diagram illustrating a method for forming a low-humidity or low-oxygen gas layer between a treatment liquid layer and a solvent layer in a flow path on the tip side of a coating nozzle housed in a standby unit in a liquid treatment apparatus. Figure 7 is an explanatory diagram illustrating a method of forming a gas layer that is low in humidity or oxygen and contains a high concentration of solvent between a treatment liquid layer and a solvent layer in a flow path on the tip side of a coating nozzle housed in a standby unit in a liquid treatment device. FIG. 8 is a schematic cross-sectional view showing an example of a means for adjusting the atmospheric condition in the waiting unit.

In the semiconductor device manufacturing process, various processing liquids are applied to a substrate to form a concave-convex pattern on the substrate using photolithography technology. Examples of coating liquids include color filters (hereafter referred to as CF) and spin-on glass (hereafter referred to as SOG), and in recent years, it has been proposed to use metal-containing resists (hereafter referred to as metal-containing resists) that contain metal and form a film through hydrolysis and dehydration condensation reactions. These coatings are performed, for example, by ejecting the coating liquid from a nozzle onto approximately the center of a semiconductor wafer (hereafter referred to as "wafer") held by a spin chuck while the wafer is rotating.

In such a coating process, if the coating liquid becomes defective, for example, if it dries and hardens inside the nozzle, or if it is partially altered due to solute aggregation or chemical reaction, and if the stuck or altered part remains in the coating film that is supplied to the wafer and formed, it will cause defects in other processing steps and lead to defects in the uneven pattern. One factor that causes such defective coating liquid is the influence of the surrounding environment with which the coating liquid comes into contact when it is in the flow path inside the nozzle during non-coating processing.

The aforementioned Patent Document 1 describes a technology for isolating the resist liquid in the nozzle from the outside air around the nozzle tip in such a liquid processing device. To explain the mode of operation, first, a dummy discharge (dummy dispense) of the resist liquid in the nozzle is performed, and then the nozzle is sucked to form an air layer. Next, the tip of the nozzle is immersed in a solvent and the nozzle is sucked, forming an air layer and a solvent layer (solvent liquid layer) outside the resist liquid layer inside the nozzle tip.

The technology disclosed herein further reduces defects caused by changes in the state of the processing liquid supplied to the substrate.

The exemplary embodiment will be described in detail below with reference to the attached drawings. In the following description, the same elements or elements having the same functions are given the same reference numerals, and duplicated description will be omitted. The exemplary embodiment of the present disclosure relates to a liquid processing apparatus and a liquid processing method including a nozzle standby device that keeps a nozzle that ejects a processing liquid onto a substrate such as a semiconductor substrate, a glass substrate for liquid crystal display, a glass substrate for a photomask, or a substrate for an optical disk.

(Liquid Treatment Apparatus)
1 and 2 are schematic cross-sectional and perspective views of a liquid processing apparatus 1 according to an embodiment of the present disclosure. The liquid processing apparatus 1 includes a spin chuck 2, which is a substrate holding unit that horizontally holds a central portion of the back surface of a substrate, i.e., a wafer W, by suction. The spin chuck 2 is configured to be rotatable about a vertical axis and movable up and down by a drive mechanism 22 via a drive shaft 21 while holding the wafer W, and is set so that the center of the wafer W is located on the rotation axis. A cup 3 with an open upper side is provided around the spin chuck 2 so as to surround the wafer W on the spin chuck 2, and the upper end of the side peripheral surface of the cup 3 forms an inwardly inclined portion.

The bottom side of the cup 3 is provided with a liquid receiving portion 31, which is, for example, in the shape of a recess. The liquid receiving portion 31 is provided around the entire circumference below the periphery of the wafer W and is divided into an outer region 32 and an inner region 33. A drain port 34 is provided at the bottom of the outer region for discharging accumulated resist, and an exhaust port 35 is provided at the bottom of the inner region for exhausting the processing atmosphere.

A nozzle unit 4 that ejects a coating liquid toward the wafer W is provided above the surface of the wafer W held by the spin chuck 2. As shown in FIG. 3, this nozzle unit 4 is configured by integrally fixing a plurality of coating nozzles 41 (e.g., 10 nozzles) for ejecting the processing liquid and a single solvent nozzle 42 (e.g., one nozzle for ejecting the solvent of the processing liquid) to a common support part 48.

Examples of the processing liquid include the above-mentioned CF, SOG, and metal-containing resist, and the solvent is, for example, a thinner. Note that CF tends to solidify due to the volatilization of the solvent contained in the material or reaction with oxygen, while SOG tends to solidify due to reaction with moisture or oxygen. In addition, since the film of the metal-containing resist is formed through hydrolysis and dehydration condensation reactions, if there is an excess of moisture, many defects may occur as a result of heating and development after the coating process.
The coating nozzle 41 corresponds to the nozzle in the present disclosure, and hereinafter, the coating nozzle 41 and the solvent nozzle 42 may be referred to as the nozzles 41, 42. The nozzles 41, 42 are made of, for example, a fluororesin, and more specifically, are made of, for example, PFA (perfluoroalkoxyalkane).

The coating nozzle 41 and the solvent nozzle 42 are configured in the same manner, and as shown in FIG. 4 using the coating nozzle 41 as an example, the coating nozzle 41 has a base end 43 connected to a support 48, a cylindrical portion 44 extending vertically below the base end 43, and a generally conical tip portion 45 whose diameter decreases downward from the cylindrical portion 44. Inside the base end 43, the cylindrical portion 44, and the tip portion 45, a flow path 46 for the treatment liquid extending vertically (longitudinal direction) is formed, and the flow path 46 opens as a treatment liquid outlet 47 at the tip side below the nozzle. The upstream side of the flow path 46 is connected to a treatment liquid supply path (not shown). That is, the coating nozzle 41 is connected to this treatment liquid supply path. Although not shown, a suckback valve is provided upstream of the flow path 46 for the treatment liquid of each nozzle, and it is possible to control the discharge of the treatment liquid by opening and closing the flow path 46, and to change the height position of the liquid layer in the nozzle 41 by sucking the inside of the flow path 46. The formation of the liquid layer L and gas layer G in the nozzle tip side flow path described below is achieved by suction using a suck-back valve.

2 and 3, the coating nozzle 41 and the solvent nozzle 42 are supported by a common support 48 arranged in a straight line along the horizontal direction (Y-axis direction) of the liquid processing apparatus 1, and are configured to be freely moved by the moving mechanism 6 between a processing position where a processing liquid or the like is supplied to the wafer W on the spin chuck 2 and a waiting position where they are accommodated in a waiting unit 5 described later. For example, the moving mechanism 6 includes a horizontal moving part 61 guided along a guide extending in the horizontal direction (Y-axis direction) in FIG. 2, and an arm part 49 that extends horizontally from the horizontal moving part 61 and is raised and lowered by a lifting part 62 relative to the horizontal moving part 61, and a support part 48 is provided at the tip of the arm part 49.

A standby unit 5 is provided on the outside of the cup 3, as shown in Figures 1 and 2. In Figure 1, for convenience of illustration, the nozzle unit 4 and standby unit 5 are drawn larger and simplified than in reality. The standby unit 5 is provided with cylindrical nozzle housings 51 in which each application nozzle 41 and solvent nozzle 42 can be individually housed, for example as shown in Figure 4, for the number of nozzles, i.e., eleven in this embodiment, and these nozzle housings 51 are arranged in a straight line in the Y-axis direction, for example.

The nozzle storage section 51 will be described with reference to FIG. 4. The nozzle storage section 51 has a cylindrical shape, for example, in the portion that stores the cylindrical portion 44 and tip portion 45 of each nozzle 41, 42. Liquid that flows into the drain chamber 52 located at the lower end of the nozzle storage section 51 is discharged to the outside of the liquid processing device 1 via the discharge path 53. A valve V53 is provided in the discharge path 53. The nozzle storage section 51 forms a storage chamber.

The nozzle housing 51 is further provided with a gas supply path 54 for supplying dry air or _N2 (adjustment gas) into the nozzle housing 51, and a solvent supply path 57 for supplying a solvent into the nozzle housing 51. The gas supply path 54 is connected to a gas supply source 55 of dry air and _N2 , and a valve V54 for opening and closing the gas supply path 54 is provided therein. Although not shown, the gas supply source 55 of dry air and _N2 has a supply gas switching unit therein for switching whether to supply dry air or _N2 . The solvent supply path 57 is connected to a solvent supply source 58, and a valve V57 for opening and closing the solvent supply path 57 is provided therein.

The gas supply source 55, solvent supply source 58, valves V53, V54, V57, and suck-back valve (not shown) are controlled by the control unit 100. In other words, the timing of suck-back for all nozzles 41, 42, the control amount of the suck-back valve, the supply amount and supply timing of the gas supply source 55 and solvent supply source 58 in the standby unit 5, etc. are controlled based on a processing program previously stored in the control unit 100, and suck-back and other processing is performed. The control unit 100 also sets and controls the movement and discharge timing, discharge amount, etc. of the nozzles 41, 42, which are stored in the processing program, and each operation of the nozzles 41, 42 is performed based on the settings.

Next, the operation of the liquid processing apparatus 1 will be described with reference to FIG. 5. First, the nozzle unit 4 performs liquid processing on the wafer W, and then the nozzle unit 4 is moved above the waiting unit 5, and each of the nozzles 41 and 42 is accommodated in the corresponding nozzle accommodation portion 51. In this state, the resist liquid in the tip of the nozzle 41 is discharged (dummy dispense) and discharged into the nozzle accommodation portion 51 (FIG. 5(a)).

Next, the solvent is supplied into the nozzle accommodating part 51 through the solvent supply path 57 for a predetermined time to increase the solvent concentration of the atmosphere in the nozzle accommodating part 51 (FIG. 5(b)). At this time, for example, the solvent is supplied so as not to directly contact the tip 45 of the nozzle 41, and the valve V53 of the discharge path 53 is closed. Next, the suck-back valve sucks the inside of the flow path 46 of the nozzle 41 to raise the resist liquid level in the flow path 46, and the atmosphere in the nozzle accommodating part 51 with a high solvent concentration is taken into the flow path 46 at the tip 45 of the nozzle 41, and a gas layer G with a high solvent concentration is formed under the liquid layer L of the resist liquid in the flow path 46 (FIG. 5(c)). At this time, the solvent concentration of the gas layer G is higher than the atmosphere in the space (for example, the space in the cup 3) where the liquid processing is performed on the wafer W.
Thereafter, the valve V53 is opened to discharge the solvent from the nozzle housing portion 51, and the solvent is then supplied through the solvent supply path 57 toward the tip of the nozzle 41. In this state, the inside of the flow path 46 of the nozzle 41 is sucked by the suck-back valve to pull up the liquid layer L and gas layer G of the resist liquid in the flow path 46, and the solvent supplied toward the discharge port 47 of the nozzle 41 is taken into the flow path 46 at the tip of the nozzle 41, thereby forming a solvent layer S below the gas layer G in the flow path 46 ( FIG. 5( d) ).

By doing this, the solvent layer S seals the nozzle 41 outlet 47, preventing the resist liquid in the nozzle 41 from drying out due to the surrounding atmosphere, while the liquid layer L of the resist liquid comes into contact with the gas layer G, which has a high solvent concentration, so that drying and solidification near the resist liquid surface due to the solvent in the resist liquid evaporating into the gas layer can be more effectively prevented.

An example different from the above example will be described with reference to FIG. 6. After performing liquid processing in the same manner as in the above case, a dummy dispense is performed with the nozzle 41 in the nozzle storage section 51 (FIG. 6(a)). Next, dry air is supplied into the nozzle storage section 51 through the gas supply path 54 for a predetermined time to reduce the humidity of the atmosphere in the nozzle storage section 51 (FIG. 6(b)). At this time, the dry air is air with a lower humidity than the atmosphere outside the standby unit 5, and the valve V53 of the exhaust path 53 is closed. Also, dry air may be supplied into the nozzle storage section 51 before the nozzle 41 is stored in the nozzle storage section 51, that is, when the upper opening of the standby unit 5 is open. By doing so, the humidity of the atmosphere in the nozzle storage section 51 can be efficiently reduced.

Next, the suck-back valve is used to suck the inside of the flow path 46 of the nozzle 41, thereby raising the liquid level of the resist liquid in the flow path 46, and the low-humidity atmosphere in the nozzle housing 51 is taken into the flow path 46 at the tip of the nozzle 41, forming a low-humidity gas layer G below the liquid layer L of the resist liquid in the flow path 46 (FIG. 6(c)). After that, as in the above example, the solvent supplied toward the outlet 47 of the nozzle 41 is taken into the flow path 46 at the tip of the nozzle 41, forming a solvent layer S below the liquid layer L and gas layer G of the resist liquid in the flow path 46 at the tip of the nozzle 41 (FIG. 6(d)).

In this way, as in the above example, drying of the resist liquid in the nozzle 41 due to the surrounding atmosphere is suppressed, while the liquid layer L of the resist liquid comes into contact with the low humidity gas layer G, preventing a reaction between the resist liquid and moisture near the liquid surface of the resist liquid.

In the example shown in FIG. 6, if the gas supplied from the gas supply source 55 is _N2 instead of dry air, a gas layer G with a low oxygen concentration is formed between the liquid layer L of the resist liquid and the solvent layer S in the flow path 46 at the tip of the nozzle 41 through the same process. In addition, argon gas, for example, may be used instead of _N2 as a gas (inert gas) that is poorly reactive with the resist liquid. In this way, the liquid layer L of the resist liquid in the flow path 46 comes into contact with an inert gas with a low oxygen concentration, so that the risk of deterioration due to oxidation near the liquid surface of the resist liquid in the flow path 46 can be further reduced. In addition, if a low-humidity inert gas _N2 is used as the inert gas supplied from the gas supply source 55, the gas layer G can be made low in oxygen and humidity, which is useful when the resist liquid is a type that is affected by oxygen concentration and humidity and is prone to deterioration or drying.

An example different from the examples of Figs. 5 and 6 described above will be described with reference to Fig. 7. First, liquid processing is performed in the same manner as above, and then a dummy dispense is performed with the nozzle 41 in the nozzle storage section 51 (Fig. 7(a)). Next, the solvent is supplied to the nozzle storage section 51 through the solvent supply path 57 while the valve V53 of the discharge path 53 is closed, and a certain amount of solvent is stored. In this state, dry air is supplied to the nozzle storage section 51 through the gas supply path 54 from below the liquid surface of the stored solvent (Fig. 7(b)). Then, the supplied dry air comes into contact with the solvent, so that an atmosphere with a low moisture concentration and a high solvent concentration is formed in the nozzle storage section 51. At this time, the stored solvent is bubbled with the supplied gas (dry air), which promotes the evaporation of the solvent and efficiently forms an atmosphere with a high solvent concentration. Next, the suck-back valve is used to suck the inside of the flow path 46 of the nozzle 41, thereby raising the liquid level of the resist liquid in the flow path 46, and the atmosphere in the nozzle housing 51, which has a low moisture concentration and a high solvent concentration, is taken into the flow path 46 at the tip of the nozzle 41, and a gas layer G, which has a low moisture concentration and a high solvent concentration, is formed below the liquid layer L of the resist liquid in the flow path 46 (FIG. 7(c)). After that, as in each of the above-mentioned examples, the solvent supplied toward the discharge port 47 of the nozzle 41 is taken into the flow path 46 at the tip of the nozzle 41, and a solvent layer S is formed below the liquid layer L and gas layer G of the resist liquid in the flow path 46 at the tip of the nozzle 41 (FIG. 7(d)).

In the above example, if the gas supplied from the gas supply source 55 is _N2 instead of dry air, a gas layer G with a low oxygen concentration and a high solvent concentration is formed between the liquid layer L of the resist liquid and the solvent layer S in the flow path 46 at the tip of the nozzle 41 through the same process. If low humidity _N2 is used here, a gas layer G with an even lower moisture concentration is formed.

In addition, when a constant amount of solvent is always stored in the lower part of the nozzle housing 51, the liquid level of the solvent may be adjusted to be above or below the supply port of the gas supply path 54 by controlling the amount of solvent supplied or the amount of solvent discharged by opening and closing the valve V53, depending on the solvent concentration required when forming the gas layer G in the flow path 46 of the nozzles 41 and 42. In other words, when a high solvent concentration is required in the gas layer G, the liquid level of the solvent may be adjusted to a position higher than the supply port of the gas supply path 54, and when a low solvent concentration is required in the gas layer G, the liquid level of the solvent may be adjusted to a position lower than the supply port of the gas supply path 54.

By combining the conditions of solvent concentration, oxygen concentration, and humidity as desired as described above, it is possible to create an atmosphere that prevents drying and deterioration of various resist liquids.

When forming an atmosphere of a predetermined condition in the nozzle accommodating section 51 before forming a gas layer G in the flow path 46 in the nozzle 41, the following means may be used. For example, as shown in FIG. 8, a side inclined portion K having an inclination such that the outer shape becomes larger toward the base end 43 may be provided on the outer periphery of the side of the nozzle 41. In this way, the size of the gap between the side inclined portion K of the nozzle 41 and the side wall 51a forming the opening of the nozzle accommodating section 51 can be changed depending on the height position of the nozzle 41 when the nozzle 41 is accommodated in the nozzle accommodating section 51. In other words, the opening area between the nozzle accommodating section 51 and the nozzle 41 can be changed. By adjusting the opening area in this way, the area of the area where the atmosphere in the nozzle accommodating section 51 comes into contact with the atmosphere outside the waiting unit 5 can be changed, so that when adjusting the solvent concentration, oxygen concentration, and humidity of the atmosphere in the nozzle accommodating section 51 as in each of the above examples, the opening area between the nozzle accommodating section 51 and the nozzle 41 may also be adjusted.

This allows for more detailed adjustment of the atmospheric conditions within the nozzle storage section 51 by combining the conditions for supplying the solvent and gas into the nozzle storage section 51 with the above-mentioned opening area. In the example shown in FIG. 8, the side slope K provided on the outer periphery of the nozzle side is used as an example of a means for adjusting the opening area of the nozzle storage section 51. Alternatively, a lid body that can be driven independently of the nozzles 41 and 42 may be provided on the standby unit 5, and the opening area may be adjusted by adjusting the degree to which the gap between the nozzle storage section 51 and the nozzle 41 is blocked when the nozzles 41 and 42 are stored in the lid body.

An example of starting the coating process with the resist liquid layer L, gas layer G, and solvent layer S formed in the flow path 46 at the tip of the nozzle 41 described above will be described. After a new wafer W is held on the spin chuck 2, the nozzle 41 with the above three layers formed in the flow path 46 is positioned above the center of the wafer W. Next, when the resist liquid is ejected from the nozzle 41 while the wafer W is rotated by the spin chuck 2, the solvent of the solvent layer S located at the nozzle tip side is first supplied to the center of the wafer W. Then, since the gas layer G was formed on the solvent layer S in the flow path 46 of the nozzle 41, the resist liquid is supplied a short time after the supply of the solvent, so that the solvent supplied by the rotation of the wafer W spreads to some extent on the wafer W, and the resist liquid is supplied to the center of the wafer W.

The resist liquid spreads as the wafer W rotates, but since the solvent has already spread on the wafer W, the resist liquid spreads evenly on the wafer W. Since the amount of solvent in the solvent layer S formed in the flow path 46 at the tip of the nozzle 41 is limited, in order to ensure that the solvent is spread over the entire surface of the wafer, or to spread a larger amount of solvent on the wafer W in advance, the same type of solvent may be supplied from the nozzle 42 to the center of the wafer W prior to supply from the nozzle 41. In this case, the solvent of the solvent layer S and the resist liquid of the liquid layer L of the resist liquid are supplied from the nozzle 41 in order to the center of the wafer W where the solvent previously supplied from the nozzle 42 is present, so that the resist can be supplied evenly without causing any unnecessary bias in the solvent previously spread on the wafer W.

In addition, because the supply operation from the nozzle 41 ejects the solvent, gas, and resist liquid in that order from the nozzle 41, if the supply is continuous at a constant pressure, the flow rate and ejection state of the resist liquid at the start of ejection may become unstable. Therefore, in order to stably supply the resist liquid, it is advisable to temporarily weaken or set the ejection pressure to zero, for example, between the ejection of the solvent in the solvent layer S and the ejection of the resist liquid in the liquid layer L.

The embodiments disclosed herein should be considered in all respects as illustrative and not restrictive. The above-described embodiments may be omitted, substituted, or modified in various ways without departing from the scope and spirit of the appended claims.

W wafer 1 liquid processing device 2 spin chuck 3 cup 4 nozzle unit 5 waiting unit 6 moving mechanism

Claims (8)

In a liquid processing method, a processing liquid is supplied to a substrate from a nozzle connected to a processing liquid supply path,
accommodating the nozzle in a chamber;
forming a treatment liquid layer, a gas layer, and a solvent layer in this order from the treatment liquid supply path side in a flow path inside the tip of the nozzle,
forming the gas layer includes supplying an adjusted gas having an adjusted concentration of at least one of moisture, oxygen, and a solvent to a periphery of the tip of the nozzle in the containing chamber and taking the adjusted gas into the flow path;
The liquid processing method includes positioning the nozzle at a processing position for supplying the processing liquid to a substrate while the processing liquid layer, gas layer, and solvent layer are formed in a flow path of the nozzle, and supplying the solvent of the solvent layer and the processing liquid of the processing liquid layer from the nozzle to the substrate. The liquid treatment method according to claim 1, wherein the adjustment gas has a lower humidity than the atmosphere of the space in which the liquid treatment is performed. The liquid treatment method according to claim 1 or 2, wherein the adjustment gas is a gas having a higher solvent concentration than the atmosphere in the space in which the liquid treatment is performed. The liquid processing method according to claim 3, wherein the gas with a high solvent concentration is generated by supplying a predetermined gas from outside the storage chamber into the storage chamber so that the gas comes into contact with the stored solvent while the solvent is stored in a portion of the storage chamber. The liquid treatment method according to any one of claims 1 to 4, wherein the adjustment gas is a gas having an oxygen concentration lower than that of the atmosphere in the space in which the liquid treatment is performed. The liquid processing method according to claim 5, wherein the gas having a low oxygen concentration is generated by supplying an inert gas into the storage chamber. the liquid treatment further includes supplying a solvent that is the same as the solvent of the solvent layer to the substrate before supplying the solvent of the solvent layer and the treatment liquid of the treatment liquid layer to the substrate from the nozzle;
The liquid processing method according to any one of claims 1 to 6, wherein when the solvent of the solvent layer and the processing liquid of the processing liquid layer are supplied from the nozzle to the substrate, the solvent of the solvent layer ejected from the nozzle is supplied so as to hit the solvent already supplied to the substrate. A liquid processing apparatus for performing liquid processing by supplying a processing liquid to a substrate from a nozzle connected to a processing liquid supply path,
A housing portion that houses the nozzle therein;
A solvent supply unit that supplies a solvent into the container;
a gas supply unit that supplies a gas having an adjusted concentration of moisture or a solvent into the container;
A control unit;
Equipped with
the control unit controls the nozzle and at least one of the solvent supply unit and the gas supply unit to form an atmosphere of an adjusted gas having an adjusted concentration of at least one of moisture, oxygen, and a solvent in the container unit, and then forms a gas layer composed of the adjusted gas below a liquid layer of the treatment liquid in a flow path at the tip of the nozzle, and then forms a solvent layer below the gas layer;
The liquid processing is performed by positioning the nozzle at a processing position for supplying the processing liquid to the substrate while a liquid layer, a gas layer, and a solvent layer of the processing liquid are formed in the flow path of the nozzle, and supplying the solvent of the solvent layer and the processing liquid of the liquid layer of the processing liquid from the nozzle to the substrate.

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