KR20220031481A - Substrate processing apparatus, semiconductor manufacturing equipment, and method of processing a substrate - Google Patents

Abstract

Provided is a substrate processing apparatus, which includes: a processing chamber capable of processing a substrate; a first supply device configured to supply a supercritical fluid of a first condition to the processing chamber; a second supply device configured to supply a supercritical fluid of a second condition to the processing chamber; a discharge device capable of discharging the supercritical fluid from the processing chamber; and a control device configured to control an operation of the first supply device, the second supply device, and the discharge device. The temperature of the supercritical fluid supplied by the second supply device is higher than the temperature of the supercritical fluid supplied by the first supply device.

Description

Substrate processing apparatus, semiconductor manufacturing equipment, and method of processing a substrate

The present invention relates to a substrate processing apparatus, semiconductor manufacturing equipment, and a substrate processing method, and more particularly, to a substrate processing apparatus having significantly less particle generation and low photoresist loss, semiconductor manufacturing equipment, and a substrate processing method.

There is a continuous demand for miniaturization of electronic devices. Accordingly, it is required to form a finer pattern, and a process using a supercritical fluid has been proposed due to pattern collapse due to surface tension or rotation. However, when the supercritical fluid is used, the surface tension can be remarkably reduced, but an economical manufacturing method with higher yield is required by further reducing the generation of particles.

The first technical problem to be achieved by the present invention is to provide a substrate processing apparatus with significantly less particle generation and less photoresist loss.

A second technical problem to be achieved by the present invention is to provide a semiconductor manufacturing equipment with significantly less particle generation and less photoresist loss.

A third technical problem to be achieved by the present invention is to provide a substrate processing method with significantly less particle generation and less photoresist loss.

In order to achieve the first technical problem, the present invention provides a processing space for processing a substrate, and a processing chamber capable of processing the substrate; a substrate support unit for supporting the substrate loaded in the processing space; a blocking plate positioned below the substrate support and blocking the supercritical fluid from being directly sprayed onto the substrate; a first supply device configured to supply a supercritical fluid of a first condition to the processing chamber; a second supply device configured to supply a supercritical fluid of a second condition having a temperature higher than that of the supercritical fluid of the first condition to the processing chamber; an exhaust device capable of draining the supercritical fluid from the processing chamber; and a control device configured to control operation of the first feeding device, the second feeding device, and the discharging device, wherein the control device is configured such that the first feeding device precedes the second feeding device and the second feeding device is the supercritical device. There is provided a substrate processing apparatus configured to supply a fluid.

Another aspect of the invention is a processing chamber configured to receive a semiconductor substrate comprising a layer of photoresist that has been exposed to extreme ultraviolet (EUV) and a developer for developing the layer of photoresist; a first supply device configured to supply a supercritical fluid having a temperature of about 35° C. to about 70° C. and a pressure of about 75 bar to about 90 bar to the processing chamber; a second supply device configured to supply a supercritical fluid having a temperature of about 70° C. to about 120° C. and a pressure of about 80 bar to about 150 bar to the processing chamber; an exhaust device capable of draining the supercritical fluid from the processing chamber; a control device configured to control operations of the first feeding device, the second feeding device, and the discharging device; and a pre-processing apparatus capable of pre-processing the interior of the processing chamber, wherein the control apparatus is configured to perform a cycle of pressurizing and depressurizing the interior of the processing chamber 2 to 15 times.

The present invention provides a transfer device configured to transfer a substrate between chamber modules performing a unit process in order to achieve the second technical problem; a first chamber module configured to coat a surface of the loaded substrate with photoresist; at least one second chamber module configured to bake the photoresist on the substrate; a third chamber module configured to irradiate extreme ultraviolet (EUV) to the photoresist on the substrate through an exposure mask; a fourth chamber module configured to provide a developer to the exposed surface of the photoresist; and a fifth chamber module configured to receive the substrate from the fourth chamber module and sequentially supply a supercritical fluid of a first temperature and a supercritical fluid of a second temperature different from the first temperature to the transferred substrate. It provides semiconductor manufacturing equipment comprising.

According to the present invention, a substrate including a photoresist layer for EUV exposed to extreme ultraviolet (EUV) and a developer for developing the photoresist layer for EUV is loaded into a processing chamber in order to achieve the third technical problem. to do; supplying a supercritical fluid of a first condition to the processing chamber; and supplying the supercritical fluid of a second condition to the processing chamber, wherein the step of supplying the supercritical fluid of the first condition is performed before the step of supplying the supercritical fluid of the second condition, Provided is a substrate processing method in which the temperature of the supercritical fluid under the first condition is lower than the temperature of the supercritical fluid under the second condition.

Another aspect of the present invention comprises the steps of forming an etched film and an anti-reflection film on a substrate; forming a photoresist layer for extreme ultra-violet (EUV) on the substrate; irradiating EUV to the EUV photoresist layer through an exposure mask; providing a developer on the exposed photoresist layer for EUV, and loading the substrate into a processing chamber; supplying a supercritical fluid of a first condition to the processing chamber; supplying a supercritical fluid of a second condition having a temperature higher than a temperature of the supercritical fluid of the first condition to the processing chamber; forming a photoresist pattern by drying the substrate with the supercritical fluid of the second condition; and forming a pattern on the layer to be etched by performing etching using the photoresist pattern as an etching mask, wherein the pattern of the layer to be etched has a width of about 5 nm to about 20 nm.

When the substrate processing apparatus, the semiconductor manufacturing equipment, and the substrate processing method of the present invention are used, the generation of particles is significantly reduced and the photoresist loss is reduced.

1 is a plan view showing an embodiment of a semiconductor manufacturing equipment.
2 is a block diagram conceptually illustrating the layout of exemplary chamber modules.
FIG. 3 is a schematic diagram for explaining EUV exposure performed on a photoresist layer on the substrate in the third chamber module of FIG. 2 .
4 is a schematic diagram showing a fifth chamber module according to an embodiment of the present invention.
5 is a phase diagram of carbon dioxide.
6 is a chart showing the first condition and the second condition on a temperature-pressure coordinate plane.
FIG. 7 is a schematic chart illustrating one embodiment of a method of supplying a supercritical fluid to rinse, remove, and dry a developer after the photoresist on the substrate of FIG. 5 exposed by EUV is developed.
8 and 9 are charts schematically showing a cycle configuration according to embodiments of the present invention, respectively.
10A is a flowchart illustrating an embodiment of a method of forming a patterned material film on a substrate.
10B is a flowchart illustrating an embodiment of a processing method for removing and drying a developer in a substrate processing apparatus.
11A to 11J are side cross-sectional views illustrating an embodiment of a method of forming a patterned material film on a substrate.
12 is a schematic diagram showing a fifth chamber module according to another embodiment of the present invention.
13 is a schematic diagram illustrating a pre-processing apparatus according to another embodiment of the present invention.
14A and 14B are charts showing changes in the number of particles when no pretreatment is applied and when a pretreatment is applied to a non-patterned wafer (NPW).
15 is a chart showing changes in the number of particles when no pretreatment is applied and when a pretreatment is applied to a patterned wafer (PW).
16 is a chart showing the relative removal amount of the developer according to the pretreatment temperature.

Hereinafter, preferred embodiments of the technical idea of the present invention will be described in detail with reference to the accompanying drawings. Like reference numerals are used throughout this specification to refer to like elements.

1 is a plan view showing an embodiment of the semiconductor manufacturing equipment (1).

Referring to FIG. 1 , the semiconductor manufacturing equipment 1 may include an index module 10 and a process processing module 20 . The index module 10 may include a load port 12 and a transport frame 14 . In some embodiments, the load port 12 , the transfer frame 14 , and the processing module 20 may be sequentially arranged in a line.

A carrier 18 in which the substrate is accommodated is seated on the load port 12 . As the carrier 18 , a Front Opening Unified Pod (FOUP) may be used. A plurality of load ports 12 may be provided. The number of load ports 12 may increase or decrease according to process efficiency and footprint conditions of the process processing module 20 . A plurality of slots are formed in the carrier 18 for receiving the substrates in a state in which they are arranged horizontally with respect to the ground.

The process processing module 20 may include a buffer unit 22 , a transfer chamber 24 , and a plurality of chamber modules 26 . A plurality of chamber modules 26 may be disposed on both sides of the transfer chamber 24 . In some embodiments, the chamber modules 26 on one side and the other side of the transfer chamber 24 may be provided to be symmetrical to each other with respect to the transfer chamber 24 .

In some embodiments, a plurality of chamber modules 26 are provided on one side of the transfer chamber 24 . Some of the chamber modules 26 may be disposed along the longitudinal direction of the transfer chamber 24 . In addition, some of the chamber modules 26 may be arranged to be stacked on each other. For example, at one side of the transfer chamber 24 , the chamber modules 26 may be arranged in an A×B arrangement. Here, A is the number of chamber modules 26 provided in a line along the x-direction 1, and B is the number of chamber modules 26 provided in a line along the z-direction. When four or six chamber modules 26 are provided on both sides of the transfer chamber 24 , the chamber modules 26 may be arranged in a 2×2 or 3×2 arrangement. The number of the chamber modules 26 may increase or decrease. In some embodiments, the chamber modules 26 may be provided on only one side of the transfer chamber 24 . Also, in some embodiments, the chamber modules 26 may be provided in a single layer on one or both sides of the transfer chamber 24 . In some embodiments, an additional chamber module facing the buffer unit 22 may be provided on one side of the transfer chamber 24 in the x direction. This will be described in more detail with reference to FIG. 2 .

The buffer unit 22 is arranged between the transfer frame 14 and the transfer chamber 24 . The buffer unit 22 provides a space for the substrate to stay before it is transferred between the chamber module 26 and the carrier 18 . The transfer frame 14 transfers the substrate between the carrier 18 seated on the load port 12 and the buffer unit 22 .

The transfer chamber 24 may include a transfer apparatus MTR, which transfers substrates between the buffer unit 22 and the chamber modules 26 and between the chamber modules 26 .

2 is a block diagram conceptually illustrating the layout of exemplary chamber modules 26 .

Referring to FIG. 2 , the chamber modules 26 may include a first chamber module CM1 configured to coat a surface of a loaded substrate with photoresist.

The substrate may be, for example, a semiconductor substrate. In some embodiments, the semiconductor substrate may be a semiconductor substrate such as Si or Ge, or a compound semiconductor substrate such as SiGe, SiC, GaAs, InAs, or InP.

The photoresist coated on the surface of the substrate may be a photosensitive polymer material whose chemical properties are changed by exposure to extreme ultraviolet (EUV) having a wavelength of 13.5 nm or less than 11 nm.

In some embodiments, the photoresist may include, for example, a (meth)acrylate-based polymer. The (meth)acrylate-based polymer may be an aliphatic (meth)acrylate-based polymer, for example, polymethylmethacrylate (PMMA), poly(t-butyl methacrylate) (poly(t- butylmethacrylate)), poly(methacrylic acid)), poly(norbornylmethacrylate), binary or terpolymer of repeating units of the (meth)acrylate-based polymers , or a combination thereof.

The photoresist may be a polymer in which a protecting group that can be deprotected by exposure to be described later is bonded to each repeating unit. The protecting group is a functional group that can be decomposed by acid, for example, tert-butoxycarbonyl (t-BOC), isonobonyl, 2-methyl-2-adamantyl, 2- Ethyl-2-adamantyl, 3-tetrahydrofuranyl (3-tetrahydrofuranyl), 3-oxodichlorohexyl (3-oxocyclohexyl), γ-butyllactone-3-yl (γ-butyllactone-3-yl), Mevaloniclactone, γ-butyrolactone-2-yl (γ-butyrolactone-2-yl), 3-methyl-γ butyrolactone-3-yl (3-methyl-γ-butyrolactone-3- yl), 2-tetrahydropyranyl (2-tetrahydropyranyl), 2-tetrahydrofuranyl (2-tetrahydrofuranyl), 2,3-propylenecarbonate-1-yl (2,3-propylenecarbonate-1-yl) , 1-methoxyethyl (1-methoxyethyl), 1-ethoxyethyl (1-ethoxyethyl), 1-(2-methoxyethoxy)ethyl (1-(2-methoxyethoxy)ethyl), 1-(2- Acetoxyethoxy)ethyl (1-(2-acetoxyethoxy)ethyl), t-butoxycarbonylmethyl (t-butoxycarbonylmethyl), methoxymethyl, ethoxymethyl, trimethoxysilyl ) and may be selected from the group consisting of triethoxysilyl, but is not limited thereto.

The photoresist may be formed, for example, to a thickness of about 30 to about 150 nm by a method such as spin coating, spray coating, or deep coating.

The chamber modules 26 may include at least one second chamber module CM2 configured to bake photoresist on the substrate. In the second chamber module CM2, the photoresist may be baked at a temperature of about 80° C. to about 130° C. for about 40 seconds to about 100 seconds.

The chamber modules 26 may include a third chamber module CM3 configured to irradiate extreme ultraviolet (EUV) to the photoresist on the substrate through an exposure mask.

3 is a schematic diagram for explaining EUV exposure performed on the photoresist layer on the substrate in the third chamber module CM3.

Referring to FIG. 3 , a light source CM310 providing extreme ultraviolet light (EUV) for exposure is provided in the third chamber module CM3. A slit CM340 for limiting the size of EUV light for exposure may be provided on the reflective mask R in which the circuit pattern to be transferred onto the substrate w is implemented as a mask pattern. The EUV light for exposure may be incident on the surface of the reflective mask R through the slit CM340. The incident EUV light is reflected with the image of the mask pattern on the surface of the reflective mask R.

An optical system in which a plurality of reflective lenses CM350 are combined may be configured to provide an optical path for the reflected EUV light to reach the substrate w. In some embodiments, an appropriate number of the reflective lenses CM350 may be combined to provide an optical path for transmitting the reflected exposure light having a pattern image on the substrate w.

In some embodiments, the reflective mask R may be mounted on the mask stage CM360. Also, the mask stage CM360 may include a cooling unit capable of cooling the mounted reflective mask R, for example, by a Peltier effect.

Also, a lens cooling unit CM370 capable of cooling the reflective lens CM350 by, for example, a Peltier effect may be provided behind at least one of the reflective lenses CM350.

Referring back to FIG. 2 , the chamber modules 26 may include a fourth chamber module CM4 configured to provide a developer to the exposed surface of the photoresist.

The developer may be provided on the surface of the photoresist by a method such as spin coating.

The developer may be, for example, a non-polar organic solvent. For example, the developer may be a developer capable of selectively removing soluble regions of the photoresist. In some embodiments, the developer is an aromatic hydrocarbon, cyclohexane, cyclohexanone, acyclic or cyclic ethers, acetates, propionates, butyrates. , lactates, or a combination thereof. For example, n-butyl acetate (nBA), propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), γ-butyrolactone (GBL), isopropanol (IPA), etc. may be used as the developer.

The chamber modules 26 receive the substrate from the fourth chamber module CM4, and apply a supercritical fluid of a first temperature and a supercritical fluid of a second temperature different from the first temperature to the transferred substrate. It may include a fifth chamber module CM5 configured to sequentially supply.

4 is a schematic diagram illustrating a fifth chamber module CM5 according to an embodiment of the present invention.

Referring to FIG. 4 , the fifth chamber module CM5 includes a processing chamber 530 capable of processing a substrate W, and a first configured to supply a supercritical fluid of a first condition to the processing chamber 530 . a supply device 510 , a second supply device 520 configured to supply a supercritical fluid of a second condition to the processing chamber 530 , and a discharge device capable of discharging the supercritical fluid from the processing chamber 530 . 560 , and a control device 540 configured to control the operation of the first feeding device 510 , the second feeding device 520 , and the discharging device 560 .

The processing chamber 530 may include a vessel 531 , a support 533 capable of supporting the substrate W, and a blocking plate 536 .

The vessel 531 may provide a processing space PS capable of processing the substrate W. For example, a drying process of drying the substrate W using a supercritical fluid may be performed in the processing space PS. The vessel 531 may be made of a material capable of withstanding a high pressure greater than or equal to the critical pressure of the supercritical fluid.

The vessel 531 may include an upper vessel 531U, a lower vessel 531L, a first supply port 538 , a second supply port 535 , and an exhaust port 539 .

The upper vessel 531U and the lower vessel 531L may be coupled to each other so as to be switchable between a closed position for sealing the processing space PS and an open position for opening the processing space PS to the atmosphere. In some embodiments, the lower vessel 531L forms a space with an open top, and the upper vessel 531U may be coupled to the upper vessel 531U to cover the space of the lower vessel 531L. . In this case, the upper vessel 531U may generally constitute an upper wall of the vessel 531 , and the lower vessel 531L may generally constitute a bottom wall and sidewalls of the vessel 531 . However, in other embodiments, the upper vessel 531U may generally constitute an upper wall and sidewalls of the vessel 531 , and the lower vessel 531L may constitute a bottom wall of the vessel 531 . Alternatively, the upper vessel 531U and the lower vessel 531L may together form a sidewall of the vessel 531 .

In some embodiments, the transition between the closed position and the open position of the vessel 531 is a lifting member that causes the upper vessel 531U and/or the lower vessel 531L to rise or lower, and movement thereof It may be performed by a driving member that drives the , and a controller that controls their movement.

The blocking plate 536 may block the supercritical fluid supplied through the first supply device 510 and the second supply device 520 from being directly sprayed onto the substrate W. For example, the blocking plate 536 is disposed between the first supply port 538 and the substrate support 533 so that the supercritical fluid injected from the first supply port 538 is supported on the substrate support 533 ( W) can block direct spraying. For example, the supercritical fluid injected from the first supply port 538 and reaching the blocking plate 536 moves along the surface of the blocking plate 536 and then to the substrate W supported by the substrate support 533 . can be reached

The blocking plate 536 may have a shape corresponding to the substrate W, for example, may have a disk shape. The blocking plate 536 may be configured to have a radius equal to or greater than the radius of the substrate W in order to effectively block the supercritical fluid from being directly injected onto the substrate W. Alternatively, the blocking plate 536 may be configured to have a smaller radius than the substrate W so that the supercritical fluid reaches the substrate W relatively easily.

In some embodiments, the blocking plate 536 may be disposed on the lower vessel 531L, and may be spaced apart from the surface of the lower vessel 531L by a predetermined distance by the support 537 . The first supply port 538 and/or the exhaust port 539 formed in the lower vessel 531L may vertically overlap the blocking plate 536 . In this case, the blocking plate 536 is a substrate supported on the substrate support 533 while the supercritical fluid injected from the first supply port 538 has a predetermined stream along the surface of the blocking plate 536 . (W) can be reached. The barrier plate 536 may also allow the fluid inside the vessel 530 to exit through the exhaust port 539 while having a predetermined stream leading to the exhaust port 539 along the surface of the barrier plate 536 . .

In some embodiments, the first supply device 510 includes a first storage tank 512 capable of maintaining the supercritical fluid in a first condition, the first storage tank 512 and the processing chamber 530 . ) may include a first supply conduit 514 connecting them, and a first control valve 516 capable of regulating the flow of the supercritical fluid flowing through the first supply conduit 514 .

In some embodiments, the second supply device 520 includes a second storage tank 522 capable of maintaining the supercritical fluid in a second condition, the second storage tank 522 and the processing chamber 530 . ) connecting a second supply conduit 524, and a second control valve 526 and a third control valve 525 capable of regulating the flow of the supercritical fluid flowing through the second supply conduit 524. may include

The supercritical fluid may be carbon dioxide in a supercritical state. 5 is a phase diagram of carbon dioxide.

Referring to FIG. 5 , the temperature of the triple point of carbon dioxide is -56.6° C. and the pressure is 5.1 bar. In addition, the critical temperature of carbon dioxide is 31.0° C. and the critical pressure is 73.8 bar. Since carbon dioxide has a relatively low critical temperature and critical pressure, it is easy to make it into a supercritical state and is inexpensive. In addition, carbon dioxide is non-toxic and harmless to the human body, and has the characteristics of non-combustibility and chemical inertness. Since carbon dioxide in a supercritical state has a diffusion coefficient that is about 10 to about 100 times greater than that of water or other organic solvents, it can quickly penetrate and replace the organic solvent, and the substrate having a fine circuit pattern due to little surface tension It can be advantageously used for drying of In addition, carbon dioxide can be recycled as a by-product of various chemical reactions, and it is eco-friendly in that the organic solvent can be easily recycled if it is converted into a gas after being used in the supercritical drying process and separated from the organic solvent.

As shown in FIG. 5, a state having a temperature and pressure greater than the critical temperature and pressure is called a supercritical state, which has properties similar to gas, such as very low surface tension as described above, and properties similar to liquids, such as excellent It has cleaning power and substitution power.

The first condition and the second condition are each a supercritical state, and there is a difference between the first condition and the second condition in at least one of temperature and pressure. The second temperature is higher than the temperature of the first condition, which will be described in more detail below.

6 is a chart showing the first condition and the second condition on a temperature-pressure coordinate plane. The horizontal and vertical axes of FIG. 6 are not scaled in proportion to numbers.

Referring to FIG. 6 , the temperature of the first condition may be from about 35° C. to about 70° C., and the pressure of the first condition may be from about 75 bar to about 90 bar, in an arbitrary state in the first region Z1. can be defined. In addition, the temperature of the second condition may be about 70° C. to about 120° C., and the pressure of the second condition may be about 80 bar to about 150 bar, and may be defined as an arbitrary state in the second region Z2. .

Referring back to FIG. 4 , the first supply conduit 514 may be connected to the bottom of the processing chamber 530 , and the second supply conduit 524 may be connected to the top of the processing chamber 530 . .

In some embodiments, the first supply conduit 514 may be connected to the top of the processing chamber 530 , and the second supply conduit 524 may be connected to the bottom of the processing chamber 530 . . In some embodiments, the first supply conduit 514 and the second supply conduit 524 may be connected to the bottom of the processing chamber 530 . In some embodiments, the first supply conduit 514 and the second supply conduit 524 may be connected to an upper portion of the processing chamber 530 .

The exhaust device 560 may include an exhaust pump 564 capable of forcibly discharging the fluid in the internal space of the processing chamber 530 and a first exhaust conduit 562 connected to the exhaust pump 564 . there is. Also, the discharge device 560 may include a second discharge conduit 563 through which the fluid in the internal space of the processing chamber 530 may be discharged spontaneously.

The first discharge conduit 562 and the second discharge conduit 563 may be provided with a fourth control valve 565 and a fifth control valve 567 capable of regulating the flow of a fluid flowing therethrough, respectively. .

The discharging device 560 may further include a concentration measuring device 550 capable of measuring the concentration of the developer at the outlet of the processing chamber 530 .

The fifth chamber module CM5 may further include a purge gas supply device 570 capable of supplying a purge gas into the processing chamber 530 .

The purge gas supply device 570 may be configured to supply a purge gas from an external purge gas source to the processing chamber 530 through a purge gas supply conduit 574 . 4 shows that the purge gas and the supercritical fluid supplied through the second supply conduit 524 are supplied to the same manifold and then introduced into the processing chamber 530, but the present invention is not limited thereto. not. In some embodiments, the purge gas supply conduit 574 may be connected directly to the processing chamber 530 so that the purge gas may be directly supplied to the processing chamber 530 .

The purge gas may be any gas having inert or significantly low chemical activity, such as helium (He), neon (Ne), argon (Ar), or nitrogen (N ₂ ). A sixth control valve 576 capable of controlling the flow of the purge gas flowing through the purge gas supply conduit 574 may be provided.

The first, second, third, fourth, fifth, and sixth control valves 516 , 526 , 525 , 565 , 567 , and 576 may be connected to a control device 540 to control opening and closing. . The control device 540 may include processing circuitry such as hardware including logic circuitry, a hardware/software combination such as processor-executed software, or a combination thereof. For example, more specifically, the processing circuit may include a central processing unit (CPU), an arithmetic logic unit (ALU), a digital signal processing unit, a microcomputer, a System-on-Chip (System-on-Chip). , SoC), field programmable gate array (FPGA), programmable logic unit, microprocessor, application-specific integrated circuit (ASIC), etc. .

In some embodiments, the control device 540 may be a control device for controlling the semiconductor manufacturing equipment 1 of FIG. 1 . In some embodiments, the control device 540 may use a control device for controlling the semiconductor manufacturing equipment 1 of FIG. 1 as a master control device, and may be a slave control device connected to the master control device. In some embodiments, the control device 540 may be a control device connected to the control device for controlling the semiconductor manufacturing equipment 1 of FIG. 1 in a cascade manner.

Hereinafter, the supply of the supercritical fluid and the purge gas to the processing chamber 530 and the discharge of the fluid inside the processing chamber 530 are all controlled by the control device 540 unless otherwise specified. .

FIG. 7 is a schematic chart illustrating an embodiment of a method of supplying a supercritical fluid to rinse, remove, and dry a developer after the photoresist on the substrate W of FIG. 5 exposed by EUV is developed. .

4 and 7 together, the supercritical fluid of a first condition is supplied from the first supply device 510 to the processing chamber 530 . At this time, the temperature of the supercritical fluid may decrease somewhat due to adiabatic expansion. In order to supply the supercritical fluid of a first condition from the first supply device 510 to the processing chamber 530 , the control device 540 may open the first control valve 516 .

At this time, a part of the developer is removed, and the removed developer may be transferred to the supercritical fluid. Also, a portion of the supercritical fluid may diffuse into the developer. Since the developers described above with reference to FIG. 2 have excellent compatibility with carbon dioxide, carbon dioxide in a supercritical state may be relatively easily diffused into the developer.

By the above process, the concentration of the developer in the layer of the developer provided on the photoresist surface can be lowered. If a relatively high temperature (ie, second condition) supercritical fluid is directly supplied without supplying the relatively low temperature (ie, first condition) supercritical fluid, the concentration of the developer is high (and thus the developer In a state where the activity is still high), the photoresist may be removed unnecessarily, thereby increasing the frequency of generation of organic particles.

Thereafter, the supercritical fluid of the second condition is supplied from the second supply device 520 to the processing chamber 530 . Since the temperature and pressure of the second condition are higher than the temperature and pressure of the first condition, the pressure and temperature inside the processing chamber 530 may steadily increase. In order to supply the supercritical fluid of the second condition from the second supply device 520 to the processing chamber 530 , the control device 540 shuts off the first control valve 516 and the third control valve 525 . can be opened In this case, the supercritical fluid of the second condition may be supplied to the processing space PS through the first supply port 538 positioned below the processing chamber 530 .

In some embodiments, the control device 540 shuts off the first control valve 516 to supply a supercritical fluid of a second condition from the second supply device 520 to the processing chamber 530 , and The second control valve 526 may be opened.

When the temperature and pressure inside the processing chamber 530 reach the state A, the fifth control valve 567 may be opened to decrease the pressure inside the processing chamber 530 . When the fifth control valve 567 is opened, the fluid inside the processing chamber 530 may be spontaneously discharged through the second discharge conduit 563 because the pressure inside the processing chamber 530 is high. As the fluid inside the processing chamber 530 is discharged, the pressure inside the processing chamber 530 may decrease, and the temperature may also decrease due to adiabatic expansion to reach state B.

In other words, the temperature T ₂ of the state B is lower than the temperature T ₁ of the state A, and the pressure P ₂ of the state B is lower than the pressure P ₁ of the state A.

Thereafter, when the temperature and pressure inside the processing chamber 530 reach state B, the fifth control valve 567 is closed, and the second condition is passed from the second supply device 520 to the processing chamber 530 . Critical fluid is supplied. The supercritical fluid may be supplied until the state A (or near it) is reached, thereby increasing the temperature and pressure inside the processing chamber 530 . At this time, in order to supply the supercritical fluid of the second condition from the second supply device 520 to the processing chamber 530 , the control device 540 shuts off the fifth control valve 567 and closes the second control valve ( 526) can be opened.

As shown in FIG. 7 , transition from state A to state B and then to state A again may be defined as one cycle. As the cycle is repeated two or more times, the developer may be cleanly removed by the high-temperature supercritical fluid. Since the concentration of the developer is lowered by the supercritical fluid of low temperature (that is, under the first condition), the activity of the developer is limited even when the supercritical fluid of high temperature is supplied. Thereby, the degree to which the photoresist is additionally removed is insignificant, and as a result, the generation of organic particles can be significantly reduced.

In addition, the developer vaporizes and discharges the mixed supercritical fluid (state A → state B), and by additionally supplying pure supercritical fluid (state B → state A), the developer can be continuously vaporized and removed toward the supercritical fluid. there is.

The cycle may be performed 2 to 15 times to remove all of the developer on the substrate. If the cycle is performed only once, the developer may remain without being completely removed. Since 15 cycles are sufficient to remove all the developer on the substrate, if the cycle is performed more than 15 times, the manufacturing cost may increase and economically disadvantageous.

The time taken to perform one cycle may be from about 3 seconds to about 20 seconds. If the time taken to perform the above one cycle is too short, the time required for removing the developer may not be secured, and the number of cycles required for removing the developer may further increase. If the time taken to perform one cycle is too long, it may take too long to manufacture, which may be economically disadvantageous.

8 and 9 are charts schematically showing a cycle configuration according to embodiments of the present invention, respectively.

Referring first to FIG. 8 , the cycle is between a state A having a first temperature T ₁ and a first pressure P ₁ and a state B having a second temperature T ₂ and a second pressure P ₂ . It can be configured to go back and forth. At this time, the state A and the state B may be determined to belong to the second region Z2 (refer to FIG. 6 ), respectively.

Referring to FIG. 9 , the cycle includes a state A' having a third temperature (T ₃ ) and a third pressure (P ₃ ) and a state B' having a fourth temperature (T ₄ ) and a fourth pressure (P ₄ ). It can be configured to go back and forth between them. In this case, it may be determined that the state A' belongs to the second region Z2 (refer to FIG. 6) and the state B' belongs to the first region Z1 (refer to FIG. 6).

Referring back to FIGS. 4 and 7 , the fluid in the processing chamber 530 may then be removed. The fifth control valve 567 may be opened to remove the fluid from the internal space of the processing chamber 530 . Then, when the pressure in the internal space of the processing chamber 530 is lowered to a certain extent, the fourth control valve 565 is opened and the exhaust pump 564 is operated to remove the fluid from the internal space of the processing chamber 530 . there is. In some embodiments, the fourth control valve 565 and the fifth control valve 567 are simultaneously opened and the exhaust pump 564 is directly operated to rapidly drain the fluid from the interior space of the processing chamber 530 . can be removed

In order to check whether the developer has been sufficiently removed, the concentration of the developer may be measured using the concentration measuring device 550 . That is, when the concentration of the developer detected by the concentration measuring device 550 is higher than the allowable value, the sixth control valve 576 may be opened to supply the purge gas into the processing chamber 530 . The supply of the purge gas may be performed until the concentration of the developer measured by the concentration measuring device 550 becomes lower than an allowable value.

10A is a flowchart illustrating an embodiment of a method of forming a patterned material film on a substrate, and FIG. 10B is a flowchart illustrating an embodiment of a processing method for removing and drying a developer in a substrate processing apparatus. 11A to 11J are side cross-sectional views illustrating an embodiment of a method of forming a patterned material film on a substrate.

Referring to FIGS. 10A and 11A , a layer to be etched 110 may be formed on the substrate 101 ( S100 ).

The substrate 101 may include silicon (Si), for example, crystalline Si, polycrystalline Si, or amorphous Si. In some other embodiments, the substrate 101 is a semiconductor such as Ge (germanium), or SiGe (silicon germanium), SiC (silicon carbide), GaAs (gallium arsenide), InAs (indium arsenide), or InP (indium phosphide) ) may include a compound semiconductor such as In some embodiments, the substrate 101 may have a silicon on insulator (SOI) structure. For example, the substrate 101 may include a buried oxide layer (BOX). In some embodiments, the substrate 101 may include a conductive region, for example, a well doped with an impurity or a structure doped with an impurity.

In addition, semiconductor devices such as transistors and diodes may be formed on the substrate 101 . In addition, a plurality of wirings may be arranged in multiple layers on the substrate 101 and may be electrically separated by an interlayer insulating layer.

The layer to be etched 110 may be formed of a conductive layer, a dielectric layer, an insulating layer, or a combination thereof. For example, the etched layer 110 may be made of metal, alloy, metal carbide, metal nitride, metal oxynitride, metal oxycarbide, semiconductor, polysilicon, oxide, nitride, oxynitride, or a combination thereof, The present invention is not limited thereto.

Referring to FIGS. 10A and 11B , an anti-reflection film 120 may be formed on the etched film 110 .

The anti-reflection layer 120 may prevent total reflection of light in a subsequent exposure process. The anti-reflection layer 120 may include an organic component having a light absorption structure and a solvent for dispersing the same. The light absorption structure may be, for example, a hydrocarbon compound having one or more benzene rings or a structure in which benzene rings are fused.

The anti-reflection film 120 may be formed by, for example, spin coating. However, the present invention is not limited thereto.

Referring to FIGS. 10A and 11C , a photoresist layer 130 for EUV may be formed on the anti-reflection layer 120 ( S200 ).

The EUV photoresist layer 130 may be formed by a method such as spin coating, spray coating, or deep coating. The EUV photoresist layer 130 may be formed to a thickness of, for example, about 30 to about 150 nm. After the EUV photoresist layer 130 is formed, a soft bake process may be performed at a temperature of about 80° C. to about 130° C. for about 40 seconds to about 100 seconds.

Since the material of the EUV photoresist layer 130 has been described in detail with reference to FIG. 2 , an additional description thereof will be omitted.

Referring to FIGS. 10A and 11D , the EUV photoresist layer 130 may be exposed using an EUV optical system as shown in FIG. 3 ( S300 ).

Depending on the type of photoresist used, an exposed portion may be removed by development or an unexposed portion may be removed by development. Hereinafter, a case in which an unexposed portion is removed by a negative tone developer (NTD) will be described. A person skilled in the art will understand that the same method is applicable to the case where the exposed portion is later removed by a positive tone developer (PTD).

The exposed EUV photoresist layer 130 ′ may be divided into an exposed portion 130b and a non-exposed portion 130a . The exposed portion 130b generates an acid from the photo-acid generator in which EUV is contained in the EUV photoresist layer 130 ′, thereby deprotecting the photosensitive polymer. On the other hand, since the non-exposed portion 130a is not irradiated with EUV, such a chemical reaction does not occur.

By deprotection of the photosensitive polymer, for example, an ester group (-COOR) before exposure may be converted into a carboxyl group (-COOH). R bonded to the ester group may be the protecting group described above.

Referring to FIGS. 10A and 11E , the EUV photoresist layer 130 ′ may be developed ( S400 ).

The EUV photoresist layer 130 ′ may be developed using a developer such as a non-polar organic solvent. Since the developer and its application method have been described in detail with reference to FIG. 2 , a detailed description thereof will be omitted.

In order to develop the EUV photoresist layer 130 ′, a developer layer 140 may be formed on the EUV photoresist layer 130 ′. Since the developer of the developer layer 140 has good compatibility with polymers that are not exposed to EUV and maintain a protecting group, the unexposed portion is dissolved in the developer layer 140 . In addition, since the portion exposed to EUV is deprotected, compatibility with the developer is relatively poor.

10A and 11F , the unexposed portion 130a is dissolved to obtain a mixed developer layer 145 . The concentration of the developer in the developer layer 145 may have a first concentration.

Since the exposed portion 130b is not dissolved in the developer of the developer layer 145, it remains in its original state.

Hereinafter, the step of drying the photoresist pattern by removing the developer will be described with reference to FIG. 10B ( S500 ).

Referring to FIGS. 10A, 10B, and 11G , the supercritical fluid 150 having the first condition of relatively low temperature is supplied to the substrate ( S110 ).

Since the supercritical fluid 150 of the first condition has a relatively low temperature while in the supercritical state, the chemical activity of the developer is limited. Accordingly, a portion of the deprotected exposed portion 130b is suppressed from reacting with the developer as compared to when the supercritical fluid having a relatively high temperature is supplied.

Meanwhile, since the supercritical fluid 150 has high compatibility with the developer, it dissolves and diffuses into the developer layer 145a. In addition, the developer inside the developer layer 145a may also be vaporized and diffused toward the supercritical fluid 150 . The vaporized developer 154 may diffuse toward the bulk of the supercritical fluid 150 according to a concentration gradient.

As a result, the concentration of the developer in the developer layer 145a may decrease with time and may have a second concentration lower than the first concentration.

Referring to FIGS. 10A, 10B, and 11H , a supercritical fluid having a relatively high temperature second condition is supplied to the substrate ( S120 ).

Although the supercritical fluid 150 under the first condition has a relatively high temperature, since the concentration of the developer in the developer layer 145b is low, a portion of the deprotected exposed portion 130b reacts with the developer. can be suppressed.

Since the temperature of the supercritical fluid 150 is high, compatibility with the developer may be further increased, and mass transfer between the supercritical fluid 150 and the developer layer 145b may be more active.

As described with reference to FIG. 7 , the developer layer 145b may be gradually removed by repeating the decompression and pressurization of the supercritical fluid ( S130 ). Since the cycle of decompression and pressurization of the supercritical fluid has been described in detail with reference to FIGS. 7 to 9 , an additional description thereof will be omitted herein.

10B and 11I , after the developer layer 145b is sufficiently removed, the supercritical fluid 150 may be discharged from the processing chamber 530 to be removed ( S140 ). Removal of supercritical fluid 150 may be removed via discharge device 560 .

Thereafter, the concentration of the developer is measured using the concentration measuring device 550 (refer to FIG. 4 ), and if the concentration of the developer is determined to be higher than an allowable value, the processing chamber 530 may be purged with a purge gas. (S150).

Since steps S140 and S150 have been described in detail with reference to FIGS. 4 and 7, detailed descriptions are omitted here.

When the concentration of the developer in the processing chamber 530 is sufficiently low, the substrate may be removed from the processing chamber 530 and pre-clean may be performed on the processing chamber 530 ( S160 ). The pretreatment will be described in more detail later.

Referring to FIGS. 10A and 11J , the layer to be etched 110 may be patterned by anisotropic etching using the exposed portion 130b as an etch mask to form a fine pattern 110p ( S600 ). In this case, the exposed anti-reflection layer 120 may be removed. The layer to be etched 110 may be patterned by a method such as plasma etching, reactive ion etching (RIE), or ion beam etching, but is not particularly limited.

Thereafter, the exposed portion 130b and the anti-reflection film 120 on the micro-pattern 110p may be removed to obtain a final micro-pattern 110p. The fine pattern 110p may have a width of about 5 nm to about 20 nm. In some embodiments, the fine pattern 110p may have a width of about 3 nm to about 20 nm.

The micropattern 110p obtained after etching the layer 110 to be etched may constitute various elements necessary for implementing an integrated circuit device. For example, the micropattern 110p may be an active region defined on a substrate of a semiconductor device. In another example, the fine pattern 110p may include a plurality of contact hole patterns or a line and space pattern. In another example, the fine pattern 110p may be formed of a conductive pattern or an insulating pattern. For example, the conductive pattern may include a pattern for forming a plurality of bit lines, a pattern for forming a plurality of direct contacts, and a plurality of buried contacts disposed in a cell array region of the integrated circuit device. A pattern for forming a contact), a pattern for forming a plurality of capacitor lower electrodes, or a plurality of conductive patterns disposed in a core region of an integrated circuit device may be configured.

12 is a schematic diagram illustrating a fifth chamber module CM5 according to another embodiment of the present invention. The fifth chamber module CM5 of FIG. 12 is different from the fifth chamber module CM5 of FIG. 4 in that it further includes a pretreatment device 580 . Therefore, the following description will focus on these differences, and overlapping descriptions will be omitted.

Referring to FIG. 12 , the pretreatment device 580 includes a third storage tank 582 capable of maintaining the supercritical fluid as a third condition, and a third storage tank 582 connecting the third storage tank 582 and the processing chamber 530 . a pretreatment conduit 584 , and a pretreatment control valve 586 capable of regulating the flow of the supercritical fluid flowing through the pretreatment conduit 584 .

The supercritical fluid may be carbon dioxide in a supercritical state, the temperature of the third condition may be about 70° C. to about 120° C., and the pressure of the third condition may be about 80 bar to about 150 bar. In some embodiments, the temperature and/or pressure of the third condition may be higher than the temperature and/or pressure of the first condition. In some embodiments, the temperature and/or pressure of the third condition may be substantially the same as the temperature and/or pressure of the second condition.

The pretreatment control valve 586 may also be controlled by the control device 540 . The control device 540 may control the pretreatment of the treatment chamber 530 by opening and closing the pretreatment control valve 586 .

Since the pretreatment device 580 of FIG. 12 uses a supercritical fluid, the processing chamber 530 may be sealed except for a conduit for the supercritical fluid to enter and exit.

13 is a schematic diagram illustrating a pre-processing apparatus 600 according to another embodiment of the present invention.

Referring to FIG. 13 , the preprocessing apparatus 600 may be inserted into the inner space of the processing chamber 530 through an inlet through which a substrate may be loaded and unloaded.

The pretreatment device 600 may include a pretreatment arm 610 and a heater or light irradiation device 620 provided at an end thereof. The heater or light irradiation device 620 emits heat or light so that organic particles in the processing chamber 530 can be decomposed. Since the pretreatment device 600 is used in a state in which the pretreatment arm 610 extends from the outside to the inside of the treatment chamber 530 , the inlet of the treatment chamber 530 may be open during the pretreatment.

14A and 14B are charts showing changes in the number of particles when no pretreatment is applied and when a pretreatment is applied to a non-patterned wafer (NPW).

Referring to FIG. 14A , when the substrate was repeatedly treated without performing pretreatment, the number of particles on the substrate increased to an unmeasurable extent.

On the other hand, referring to FIG. 14B , as shown in FIG. 12 , when the pretreatment was performed using a high temperature supercritical fluid and the substrate was repeatedly treated, there was no significant change in the number of particles compared to before the pretreatment as well as the measurement It was confirmed that the value obtained was also well maintained within 20.

15 is a chart showing changes in the number of particles when no pretreatment is applied and when a pretreatment is applied to a patterned wafer (PW).

As shown in FIG. 15 , it was confirmed that when the pre-treatment was not applied, the number of particles was significantly higher than when the pre-treatment was applied.

16 is a chart showing the relative removal amount of the developer according to the pretreatment temperature.

Referring to FIG. 16 , the ratio of the developer removed by the supercritical fluid while changing the temperature of the supercritical fluid used for pretreatment to 50° C., 60° C., 70° C., and 80° C., respectively, is shown. Here, a higher percentage of developer extraction means that more developer has been extracted, and therefore less amount of developer remaining inside the processing chamber.

When the temperature of the supercritical fluid used in the pretreatment is set to 50° C. to 70° C., it is confirmed that the extraction percentage is 70% or less, but when the temperature of the supercritical fluid is 80° C., it is confirmed that the extraction percentage is higher than 90%.

Although the embodiments of the present invention have been described in detail as described above, those of ordinary skill in the art to which the present invention pertains, without departing from the spirit and scope of the present invention as defined in the appended claims The present invention may be practiced with various modifications. Accordingly, modifications of future embodiments of the present invention will not depart from the teachings of the present invention.

510: first supply device 512: first storage tank
514: first supply conduit 516: first control valve
520: second supply device 522: second storage tank
524 second supply conduit 526 second control valve
530 processing chamber 540 control device
550: concentration measuring device 560: discharging device
562: first exhaust conduit 563: second exhaust conduit
565: fourth control valve 567: fifth control valve
576: sixth control valve 570: purge gas supply device
574: purge gas supply conduit

Claims (20)

a processing chamber providing a processing space for processing a substrate and capable of processing the substrate;
a substrate support unit for supporting the substrate loaded in the processing space;
a blocking plate positioned below the substrate support and blocking the supercritical fluid from being directly sprayed onto the substrate;
a first supply device configured to supply a supercritical fluid of a first condition to the processing chamber;
a second supply device configured to supply a supercritical fluid of a second condition having a temperature higher than that of the supercritical fluid of the first condition to the processing chamber;
an exhaust device capable of draining the supercritical fluid from the processing chamber; and
a control device configured to control operations of the first feeding device, the second feeding device, and the discharging device;
including,
and the control device is configured such that the first supply device supplies the supercritical fluid prior to the second supply device. The method of claim 1,
The first condition is a temperature of about 35° C. to about 70° C. and a pressure of about 75 bar to about 90 bar, and the second condition is a temperature of about 70° C. to about 120° C. and a pressure of about 80 bar to about 150 bar. A substrate processing apparatus, characterized in that. The method of claim 1,
The discharge device is:
an exhaust pump capable of forcibly discharging the fluid in the inner space of the processing chamber and a first exhaust conduit connected to the exhaust pump; and
a second exhaust conduit through which the fluid in the interior space of the processing chamber can be discharged spontaneously;
A substrate processing apparatus comprising a. The method of claim 1,
the first supply device comprises a first storage tank capable of maintaining the supercritical fluid in the first condition and a first supply conduit connecting the first storage tank and the processing chamber;
wherein the second supply device includes a second storage tank capable of maintaining the supercritical fluid in the second condition, and a second supply conduit connecting the second storage tank and the processing chamber. . The method of claim 1,
The substrate processing apparatus of claim 1, further comprising a pre-processing device capable of pre-processing the interior of the processing chamber. 6. The method of claim 5,
the processing chamber includes an inlet capable of receiving a substrate;
The pretreatment device is:
a pretreatment arm extending into the interior of the processing chamber through the inlet; and
a heater or light irradiation device provided at an end of the pretreatment arm;
A substrate processing apparatus comprising a. 6. The method of claim 5,
the pretreatment device is configured to supply a supercritical fluid of a third condition to the treatment chamber through a pretreatment conduit;
The temperature and pressure of the third condition are higher than the temperature and pressure of the first condition. The method of claim 1,
and the control device is configured to perform a cycle of pressurizing and depressurizing the inside of the processing chamber 2 to 15 times. 9. The method of claim 8,
The substrate processing apparatus of claim 1 , wherein the pressurization and depressurization are performed within a temperature range of about 70° C. to about 120° C. and a pressure of about 80 bar to about 150 bar. a transfer device configured to transfer a substrate between chamber modules performing a unit process;
a first chamber module configured to coat a surface of the loaded substrate with photoresist;
at least one second chamber module configured to bake the photoresist on the substrate;
a third chamber module configured to irradiate extreme ultraviolet (EUV) to the photoresist on the substrate through an exposure mask;
a fourth chamber module configured to provide a developer to the exposed surface of the photoresist; and
a fifth chamber module configured to receive the substrate from the fourth chamber module and sequentially supply a supercritical fluid having a first temperature and a supercritical fluid having a second temperature different from the first temperature to the transferred substrate;
Semiconductor manufacturing equipment comprising a. 11. The method of claim 10,
The developer is an acetate-based solvent, and the supercritical fluid is a semiconductor manufacturing equipment, characterized in that carbon dioxide. 11. The method of claim 10,
The fifth chamber module comprises:
processing chamber;
a first supply device configured to supply a supercritical fluid of a first condition to the processing chamber;
a second supply device configured to supply a supercritical fluid of a second condition to the processing chamber; and
a control device configured to control operations of the first and second feeding devices;
further comprising,
The first condition includes the first temperature,
The second condition includes the second temperature,
wherein the second temperature is higher than the first temperature. 13. The method of claim 12,
and the control device is configured to perform a cycle of pressurizing and depressurizing the inside of the processing chamber 2 to 15 times. a processing chamber configured to receive a semiconductor substrate comprising a photoresist layer exposed to extreme ultraviolet (EUV) and a developer for developing the photoresist layer;
a first supply device configured to supply a supercritical fluid having a temperature of about 35° C. to about 70° C. and a pressure of about 75 bar to about 90 bar to the processing chamber;
a second supply device configured to supply a supercritical fluid having a temperature of about 70° C. to about 120° C. and a pressure of about 80 bar to about 150 bar to the processing chamber;
an exhaust device capable of draining the supercritical fluid from the processing chamber;
a control device configured to control operations of the first feeding device, the second feeding device, and the discharging device; and
a pretreatment device capable of pretreatment of the interior of the treatment chamber;
including,
and the control device is configured to perform a cycle of pressurizing and depressurizing the inside of the processing chamber 2 to 15 times. 15. The method of claim 14,
wherein the control device is configured to supply a supercritical fluid from the second supply device to the processing chamber for the pressurization and exhaust the supercritical fluid in the processing chamber through the discharge device for the pressure reduction. substrate processing equipment. 16. The method of claim 15,
The discharge device is:
an exhaust pump capable of forcibly discharging gas in the internal space of the processing chamber and a first exhaust conduit connected to the exhaust pump; and
a second exhaust conduit through which gas in the interior space of the processing chamber can be discharged spontaneously;
wherein the control device is configured to discharge the supercritical fluid inside the processing chamber through the first exhaust conduit and the second exhaust conduit after completion of the cycle. loading a substrate including a photoresist layer for EUV exposed to extreme ultraviolet (EUV) and a developer for developing the photoresist layer for EUV into a processing chamber;
supplying a supercritical fluid of a first condition to the processing chamber; and
supplying a supercritical fluid of a second condition to the processing chamber;
including,
The step of supplying the supercritical fluid of the first condition is performed before the step of supplying the supercritical fluid of the second condition,
The temperature of the supercritical fluid of the first condition is lower than the temperature of the supercritical fluid of the second condition. 18. The method of claim 17,
The method of claim 1, wherein the temperature of the first condition is about 35°C to about 70°C, and the temperature of the second condition is about 70°C to about 120°C. 18. The method of claim 17,
The method of claim 1, further comprising repeatedly performing a cycle of pressurizing and depressurizing the inside of the processing chamber after supplying the supercritical fluid of the second condition. forming an etched film and an anti-reflection film on the substrate;
forming a photoresist layer for extreme ultra-violet (EUV) on the substrate;
irradiating EUV to the EUV photoresist layer through an exposure mask;
providing a developer on the exposed photoresist layer for EUV, and loading the substrate into a processing chamber;
supplying a supercritical fluid of a first condition to the processing chamber;
supplying a supercritical fluid of a second condition having a temperature higher than a temperature of the supercritical fluid of the first condition to the processing chamber;
forming a photoresist pattern by drying the substrate with the supercritical fluid of the second condition; and
forming a pattern on the layer to be etched by performing etching using the photoresist pattern as an etching mask;
Including, the width of the pattern of the etched layer is about 5 nm to about 20 nm substrate processing method.

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