JP2005229115A - Liquid film forming method and method of forming solid film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To suppress a discharge of liquid out of a substrate to be treated, and to uniformly form a liquid film in a technology which spirally feeds the liquid on the substrate to be treated to perform a film formation. <P>SOLUTION: A dripper is radially moved so that there may be changed a moving pitch of the dripper in a radial direction which is produced whenever the substrate to be treated makes a round while the liquid drips on the substrate to be treated from the dripper and at the same time the substrate to be treated is rotated. The rotational frequency of the substrate and the feed speed v of the liquid from the dripper are adjusted so that the dripped liquid film may not be moved by a centrifugal force applied on the dripped liquid film by accompanying a radial movement of the substrate to be treated of the dripper, and the liquid film is formed. Thereafter, the substrate to be treated is rotated by using a rotational frequency that is less than a maximum rotational frequency, by which the liquid film at a maximum periphery on the substrate to be treated does not move out of the substrate to be treated by the centrifugal force. The substrate to be treated is rotated by making the upper part of the substrate on which the liquid film is formed as almost closed space. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a liquid film forming method for forming a film by dropping a liquid spirally onto a substrate to be processed, and a solid film forming method using the liquid film forming method.

  The spin coating method that has been conventionally performed in the lithography process discharges most of the liquid dropped on the substrate to the outside of the substrate and forms the remaining several percent of the film. Many of them had an adverse effect on the environment. Further, in the case of a square substrate or a circular substrate having a large diameter of 12 inches or more, there is a problem that turbulence is generated in the outer peripheral portion of the substrate and the film thickness is nonuniform in that portion.

  JP-A-2-220428 discloses a technique for applying a chemical solution uniformly on the entire surface of a substrate without wasting it, by dropping a resist from a large number of nozzles arranged in a row, and spraying a gas or a liquid on the film formation surface from the back. A technique for obtaining a uniform film is described. Japanese Patent Application Laid-Open No. 6-151295 aims at obtaining a uniform film by providing a number of spray holes on a rod and dropping a resist on the substrate. Further, Japanese Patent Application Laid-Open No. 7-32001 describes a technique in which a spray head in which a large number of jet holes for spraying resist is formed is used to move relative to the substrate for coating. In any of these coating apparatuses, a plurality of dropping or spraying nozzles are arranged in a horizontal row and scanned along the substrate surface to obtain a uniform film.

  In addition to the coating method using an apparatus having a plurality of nozzles, there is a method of forming a liquid film by scanning a substrate to be processed using a single liquid discharge nozzle. In this method, depending on the operation method of the nozzle, there has been a problem that the processing time per one substrate becomes long and the amount of chemicals used becomes enormous.

  As a film forming method for solving these problems, Japanese Patent Application Laid-Open No. 2000-77326 discloses a method of applying a chemical solution in a spiral shape. Among these, “it is preferable to perform coating by moving the nozzle unit in the diameter direction (for example, X direction) of the wafer while rotating the wafer at a low speed (for example, 20 to 30 rpm) as a coating condition.” It is described. Further, it is described that “it is important to keep the relative speed of the wafer and the nozzle unit constant”. That is, it is described that the linear velocity of the nozzle is made constant.

  When the nozzle unit is moved at a constant speed, in order to make the linear velocity constant, the number of rotations inside the nozzle outer periphery must be increased. For example, in the case of a 200 mm wafer, even if the rotation speed at a radius of 100 mm is 30 rpm, the rotation speed is proportional to the reciprocal of the diameter, and it is necessary to rotate at 3000 rpm or more in a portion having a radius of 1 mm or less. When the wafer is rotated at 3000 rpm, even if the liquid application is started from the center of the substrate, the chemical solution is instantaneously released outside the substrate.

  In addition, when the wafer is rotated at a constant speed at a low speed, the nozzle movement speed at the center of the substrate is extremely fast, and even if the liquid is moved by applying vibration after coating, it cannot move completely and eventually in the center. There was a problem that a non-coated region was generated, and a uniform film could not be formed. As described above, when the chemical liquid is discharged at a constant linear velocity, there is a problem that a liquid film is not formed.

  As described above, in the technology of forming a liquid film by dropping a chemical solution while rotating the substrate to be processed and supplying the chemical solution spirally on the substrate to be processed, the linear velocity of the dropping nozzle with respect to the substrate to be processed is set. If it is fixed, there is a problem that the chemical solution is discharged out of the substrate or a liquid film is not formed uniformly.

  An object of the present invention is to provide a liquid film that can form a liquid film uniformly while suppressing the discharge of the liquid to the outside of the substrate to be processed in a technique for forming a film by supplying a liquid spirally onto the substrate to be processed. It is an object to provide a forming method, a solid film forming method, a liquid film forming apparatus, and a semiconductor device manufacturing method.

  The present invention is configured as follows to achieve the above object.

  (1) In the liquid film forming method according to the present invention, the liquid is dropped on the substrate to be processed from the dropping unit, and at the same time, the radial direction generated each time the substrate to be processed is rotated while rotating the substrate to be processed. The dropping portion is moved in the radial direction from the inner peripheral portion of the substrate to be processed toward the outer peripheral portion of the substrate so that the moving pitch of the dropping portion changes small, and the diameter of the substrate to be processed of the dropping portion is In order to prevent the dropped liquid film from moving due to the centrifugal force applied with the movement of the direction, the supply speed of the liquid from the dropping part is adjusted while gradually decreasing the number of rotations of the substrate. After forming a liquid film on the substrate and forming the liquid film, the liquid film at the outermost periphery on the substrate to be processed is used at a rotational speed equal to or lower than the maximum rotational speed at which the liquid film on the outer peripheral portion does not move out of the substrate to be processed by centrifugal force. The substrate to be processed is rotated, and the substrate is processed Rotation of the plate, and performs above the liquid film is formed substrate as substantially closed space.

  (2) In the method for forming a solid film according to the present invention, the liquid is dropped from the dropping unit onto the substrate to be processed, and at the same time, the radial direction generated each time the substrate to be processed is rotated while rotating the substrate to be processed. The dropping portion is moved in the radial direction from the inner peripheral portion of the substrate to be processed toward the outer peripheral portion of the substrate so that the moving pitch of the dropping portion of the substrate is small, and the dropping portion of the substrate to be processed is The supply speed of the liquid from the dropping unit while gradually decreasing the rotation speed of the substrate so that the dropped liquid film does not move due to the centrifugal force applied to the dropped liquid film along with the radial movement. Forming a liquid film on the substrate to be treated, and subjecting the substrate to be treated formed with the liquid film to a pressure lower than the vapor pressure at the processing temperature of the solvent in the liquid film. And a step of forming a solid layer by drying.

  (3) In the liquid film forming apparatus according to the present invention, a substrate to be processed is mounted, a substrate to be processed having a rotational drive system, and a columnar process configured to surround the substrate to be processed. A chamber, a dropping unit that continuously discharges liquid to the substrate to be processed, a dropping unit driving mechanism that moves the dropping unit in a radial direction of the substrate to be processed, and the dropping unit and the substrate to be processed A top plate provided with a slit through which the chemical solution discharged from the dropping unit passes, and a chemical blocking rate in the radial direction of the substrate to be processed, arranged between the top plate and the dropping unit And a plurality of chemical liquid partial blocking mechanisms arranged according to the above.

  As described above, according to the present invention, the dropping unit is moved in the radial direction so that the moving pitch of the dropping unit in the radial direction that occurs every time the substrate to be processed makes one round, and the dropping unit With the movement of the substrate to be processed in the radial direction, the number of rotations of the substrate and the liquid from the dropping unit are prevented from moving due to the centrifugal force applied to the dropped liquid film. By adjusting the supply speed, the liquid film does not move in the vicinity of the central portion and the outer peripheral portion, and a uniform liquid film can be formed without generating a region where the liquid film is not formed in the central portion of the substrate to be processed. .

  Embodiments of the present invention will be described below with reference to the drawings.

(First embodiment)
FIG. 1 is a configuration diagram showing a schematic configuration of a film forming apparatus used in the present invention.
As shown in FIG. 1, the target substrate holding unit 120 on which the target substrate 100 is installed is connected to a drive system 121 that rotates about the substrate 100. Further, a chemical supply nozzle (dropping unit) 122 that is movable in the radial direction by the nozzle drive system 123 while discharging the chemical is installed above the substrate 100 to be processed. A chemical liquid supply pump 125 that supplies the chemical liquid to the chemical liquid supply nozzle 122 is connected to the chemical liquid supply nozzle 122 via the chemical liquid supply pipe 124. The chemical solution discharge speed from the chemical solution supply nozzle 122 was controlled by controlling the chemical solution supply pressure from the chemical solution supply pump 125.

  The chemical solution supply nozzle 122 is configured as shown in FIG. 2, for example. As shown in FIG. 2, the chemical liquid supply nozzle 122 discharges the chemical liquid in the chemical liquid tank 201 and the chemical liquid tank 201 that temporarily stores the chemical liquid supplied from the chemical liquid supply pipe 124 connected to the chemical liquid supply pump (not shown). And a chemical solution discharge port 202.

  The chemical solution supply nozzle 122 starts to move from approximately the center of the substrate to be processed 100 by the nozzle drive system 123 and moves to a substantially edge portion of the substrate to be processed 100 while continuously supplying the chemical solution onto the substrate to be processed 100. The chemical solution supply ends when the chemical solution supply nozzle reaches the edge of the substrate 100 to be processed. Chemical solution blocking mechanisms 126a and 126b are provided at the movement start position and the movement end position of the chemical solution supply nozzle. The chemical solution blocking mechanism 126a at the movement start position supplies the chemical solution until the rotation speed of the substrate holding unit 120, the moving speed of the nozzle drive system 123, and the chemical solution discharge speed from the chemical solution supply nozzle 122 reach predetermined values required at the start of application. The chemical solution discharged from the nozzle 122 is blocked to prevent the chemical solution from reaching the substrate 100 to be processed. Further, the chemical blocking mechanism 126b at the movement end position stands by above the edge of the substrate to be processed 100 so that the chemical is not supplied to the edge of the substrate 100, and the chemical supply nozzle 122 is placed at the edge of the substrate 100 to be processed. When it comes, the chemical solution discharged from the nozzle 122 is blocked to prevent the chemical solution from reaching the substrate 100 to be processed.

  While the chemical solution is supplied onto the substrate 100, the rotation speed of the substrate holding unit 120, the moving speed of the nozzle drive system 123, and the discharge rate of the chemical solution from the chemical solution supply nozzle 122 are respectively rotation drive control unit 128 and nozzle drive control. Managed by the unit 127 and the chemical solution supply pump 125. A controller 129 that controls these three control units 125, 127, and 128 is disposed upstream thereof.

  The controller 129 determines the number of rotations, the nozzle drive speed, and the chemical liquid discharge speed of the rotation drive control unit 128 based on the position information of the chemical solution supply nozzle 122 on the target substrate 100, and the rotation drive control unit 128 and the nozzle drive control unit. 127, command each of the chemical supply pump 125. By operating each of them based on this command, the chemical solution is supplied spirally onto the substrate 100 to be processed. The chemical solution supplied onto the substrate to be processed 100 spreads and is combined with the adjacent liquid film to form one liquid film 101 on the substrate to be processed 100.

  After the liquid film 101 is formed, a process of drying and removing the solvent in the liquid film is performed on the substrate 100 to be processed. Examples of the drying method include heating, drying under reduced pressure below the saturated vapor pressure of the solvent, and a method of bringing the surface into contact with an air stream.

  After the liquid film is formed, the substrate to be processed is sent to a step of drying and removing the solvent in the liquid film. Examples of the drying method include heating, drying under reduced pressure below the saturated vapor pressure of the solvent, and a method of bringing the surface into contact with an air stream.

  Hereinafter, the case where this liquid film forming means is applied to the formation of an ArF photosensitive resin film having a film thickness of 400 nm will be described. A photosensitive resin solution having a solid content of 3% was used. In addition, the thing formed in the method similar to the following in the antireflection film which cancels the reflected light from a substrate surface at the time of ArF exposure on the to-be-processed substrate was used.

  For easy understanding, in the following, the translation drive direction of the substrate holding unit 120 including the diameter of the substrate 100 to be processed is defined as the X axis, and the trajectory of the discharge port when driving the chemical solution supply nozzle 122 orthogonal thereto is defined as the Y axis. To do. The intersection of the X axis and the Y axis will be referred to as an apparatus reference point, and the center of the circular substrate to be processed will be referred to as a substrate origin. The apparatus reference point is the origin (0, 0) of the XY coordinate system, and the unit of position is expressed in mm.

  Hereinafter, as shown in FIG. 3, the movement in the same direction as the nozzle movement direction at the time of supplying the chemical solution will be described as the + axis, and the opposite movement will be described as the − axis.

As a nozzle trajectory, the radial nozzle movement pitch change rate a for each rotation of the substrate was set to 0.99 (1% decrease). The number of spirals with respect to the origin is defined as a circumferential value n (n> 0 real number). Using this circumferential value n, and using the nozzle movement pitch d ₁ at n = 1, the radial nozzle movement pitch dn at the circumferential value _n is

It can be expressed as.
The nozzle radial direction position R _{n at} this time is

It can be expressed as.
In the following, conditions for enabling the formation of a liquid film with no uneven distribution of liquid film within the substrate surface without discharging the chemical solution outside the substrate will be described. First, it describes a radial nozzle movement pitch d _n does not change (a = 1) when condition is explained, and thereafter conditions for changing moving radially nozzle pitch d _n.

Meanwhile in the case of radial nozzle moving pitch d _n is a constant (a = 1), the chemical liquid supply per unit length of the helix from the area (S) rate of change in the diameter r is 2πr to the substrate in the radial direction r The quantity q is _calculated by using the chemical supply outermost diameter r _out and the chemical supply quantity q _nout per unit length of the spiral to the substrate at that time, q = q _nout · _r / r _out (5)
And it is sufficient. Further, the following equation (6) is established among the chemical solution supply speed v _n (cc / min), the substrate rotation number w _n (rpm), and the chemical solution supply amount q at the distance r from the substrate center. .

q = v _n / w _n (6)
Thus (5), (6) from the equation, may be determined the chemical feed rate v _n and substrate rotational frequency w _n at a distance r from the substrate center to satisfy the following equation (7).

In this case, the determination of chemical feed rate v _n and substrate rotational frequency w _n, there are the following three methods.

(I) The discharge amount of the chemical solution and the rotation speed of the substrate to be processed are determined according to the radial position (r / r _out ) of the chemical solution supply nozzle.

(II) The rotational speed of the substrate to be processed is determined according to the radial position (r / r _out ) of the chemical solution supply nozzle (the discharge amount is substantially constant).

(III) The discharge amount of the chemical solution is determined according to the radial direction position (r / r _out ) of the chemical solution supply nozzle (the rotation speed is substantially constant).

First, a description for the determination of chemical feed rate v _n and substrate rotational frequency w _n according to the method of (I).

The distance from the chemical feed rate v _n and substrate rotational frequency w _n in r, the following (8) respectively, using the coefficient b, can be expressed as equation (9).

On the other hand, the centrifugal force F applied to the liquid film in the minute unit area at the distance r from the substrate center uses the specific gravity c of the liquid,

It can be expressed.
Here placed and _{C = c (q nout / 2πr} out), when determining the relationship between r and the substrate rotational frequency w _n of the centrifugal force F is constant,

It becomes.
From equation (9) and equation (11), the substrate rotation speed w _nout at r _out is _calculated using the lower limit centrifugal force F, constant C, and coefficient b (usually 1) that cause fluidity in the spread liquid film. _nout ≦ (F / C) ^1/2 × b (12)
By defining as described above, it is possible to form a liquid film with no uneven distribution of the liquid film within the substrate surface without discharging the chemical solution outside the substrate. Incidentally, the chemical liquid feed rate v _n of the substrate rotational speed w _n and the substrate may be set to any value as long as the combination that satisfies the following equation (13) and (6).

Since the radial nozzle moving pitch d _n in the present embodiment is changing geometrically not constant (8), (9) is

And each can be replaced. The gist of the present invention can be achieved by using the formulas (8 ′) and (9 ′) and adjusting the centrifugal force F so that fluidity does not occur in the spread liquid film.

Next, a description for the determination of chemical feed rate v _n and substrate rotational frequency w _n according to the method of (II).
(Usually 1) the coefficient b is chemical feed rate v _n and substrate rotational frequency w _n at a distance r with

It can be expressed. (14) and (15) are values when the radial nozzle pitch generated every round of the substrate is constant, but in the present invention, dn is not constant but varies in a geometric series (14). , (15) is

And each can be replaced. The purpose of the present invention can be achieved by using the equations (16) and (17) and adjusting the centrifugal force F so that fluidity does not occur in the spread liquid film.

Next, a description for the determination of chemical feed rate v _n and substrate rotational frequency w _n according to the method of (III).

(Usually 1) the coefficient b is chemical feed rate v _n and substrate rotational frequency w _n at a distance r with

It can be expressed. (18), (19) but is a value when the radial direction nozzle pitch occurring every round substrate is constant, since in the present invention is changing geometrically rather than d _n is a constant ( 18) and (19) are

And each can be replaced. The purpose of the present invention can be achieved by using (20) and (21) and adjusting the centrifugal force F so that fluidity does not occur in the spread liquid film.

(Second Embodiment)
In the present embodiment, a method for applying a laser reactive film on a compact disc (CD) will be described. In consideration of processing with a blue semiconductor laser, a laser reaction film in which a dye having absorption at 400 to 550 nm was dissolved in an organic solvent was used. The solid content concentration in the solution was 3%. The application area of the compact disc is an area outside the diameter of 19 mm from the center (outer shape 55.4 mm). Application to this substrate was performed under the conditions of d ₁ = 1.5 and a = 0.955. That trajectory S _n of the chemical solution supply nozzle

And n was varied between 14.05282 and 41.72949. In actual application, it is necessary to express each of the nozzle radial direction position R _n , the chemical solution supply speed v _n , and the substrate rotation number w _n in relation to time. The procedure will be described with reference to the flowchart of FIG. 4, according to the first embodiment, is a flowchart illustrating a method of determining a nozzle radial position R _n, chemical feed rate v _n, the relation between the substrate rotational speed w _n with respect to time.

(Step S101)
First, the innermost circumference R _nin of the substrate to be processed is set as the calculation start position (first position) of the movement section of the chemical solution supply nozzle.

(Step S102)
_First, the substrate rotation speed w _nout = 107.6 rpm and the chemical solution discharge pressure (chemical solution supply speed) v _nout at R _nout = 55.4 are set. The rotational speed and the discharge pressure determined here are adjusted so that the chemical solution is not released outside the substrate during application.

  A method for calculating the number of revolutions at which the chemical solution does not scatter on the outer periphery of the substrate will be described. From the stopped state, the rotational speed was gradually increased at a rotational acceleration of 1 rpm / sec, and the rotational speed at which the chemical solution scattered outside the substrate was determined.

(Step S103)
The trajectory in the radial direction of the chemical solution supply nozzle, that is, the nozzle movement pitch at the nozzle position R _n is set. In this embodiment, the first term d _{1 of the} geometric series is 1.5, and the change rate a is 0.995.

(Step S104)
The nozzle position R _nin is set to the nozzle position R _i .
Note that the order of steps S101 to S104 is random, and is not limited to the order described here.

(Step S105)
A circumferential value i corresponding to the innermost circumference R _i (R _nin = 19 mm) of the compact disk is obtained using the set initial term d ₁ , change rate a, and equation (22). In the case of this embodiment, the circumferential value n corresponding to the innermost circumference R _nin = 19 mm of the compact disc was 14.005282.

(Step S106)
By _using the substrate rotational speed w _nout and the chemical solution discharge pressure v _{nout at} R _nout = 55.4, and the _equations (8 ′) and (9 ′), the chemical solution discharge pressure v _i at the peripheral value i (= 14.005282). (V _14.05282 ), the substrate rotation speed w _i (w _14.05282 ) is obtained.

On the other hand, the peripheral value n _out corresponding to the outermost periphery R _nout of the substrate is n _out = 41.772949. That is, the spiral trajectory of the chemical solution supply nozzle starting from a position 19 mm from the center of the substrate reaches the substrate edge after turning around 27.6767 on the substrate.

(Step S107)
It is determined whether the circumferential value i satisfies the condition of i ≧ 41.772949. If it is determined that i is not greater than 41.72949, step S108 is executed.

(Step S108)
A circumferential value Δi that changes in 0.05 seconds (unit time) is obtained, and a circumferential value i ′ = i + Δi after 0.05 seconds is obtained. Then, a chemical solution supply nozzle radial direction position R _{i ′} corresponding to the obtained circumferential value _{i ′} is calculated.

When the substrate board in the time t in seconds is rotating at a rotational speed w _n, the substrate during the time t s to time t + 0.05 seconds,
Δn = w _n /60×0.05 (rotation)
Only rotate.

Below, it demonstrates using a specific example. When the substrate rotation speed w _14.05282 = 180 rpm, the substrate rotates 0.15 times. Therefore, the peripheral value n after 0.05 second rotation at the substrate rotation speed w _14.05282 is n ′ = 14.005282 + 0.15 = 14.202082. R _14.20282 corresponding to n ′ = 14.020282 becomes R _14.20282 = 19.2112 [mm] from the equation (22).

(Step S109)
Then, the nozzle position Ri _′ (second position) after 0.05 seconds is newly set as Ri (first position).

(Step S106)
Then, the chemical solution discharge pressure at the nozzle position R _i (circumferential value i) is calculated by using the substrate rotation speed w _nout and the chemical solution discharge pressure v _{nout at} R _nout = 55.4 and the _equations (8 ′) and (9 ′). Find v _i and substrate rotation speed w _i .

(Step S107)
Steps S108, S109, and S106 are repeated until it is determined that i ≧ 41.772949.

According to the above-described procedure, it is possible to determine the relationship between the radial position of the dropping unit, the chemical solution discharge pressure (chemical solution supply speed), and the substrate rotation speed with respect to time. The period from an arbitrary time t s to t + 0.05 seconds regarded as R _n, v _n, the w _n are constant, respectively.

  Then, based on the obtained relationship, the position of the chemical solution supply nozzle in the radial direction, the chemical solution discharge pressure, and the rotation speed of the substrate to be processed are controlled to form a liquid film on the substrate to be processed.

The procedure shown above can be applied when there is no contradiction for the equipment in the innermost periphery. However, in the apparatus of the present embodiment, the chemical supply speed is controlled by controlling the discharge pressure. However, since the discharge pressure in the innermost circumference becomes smaller than ² kgF / cm ² which is the lower limit of the controllable pressure range, the control becomes impossible. In this case, the position of the chemical supply nozzle with respect to time, the chemical supply speed (chemical discharge pressure), and the number of rotations of the substrate may be determined from the outer periphery of the substrate.

Hereinafter, how to obtain the chemical supply nozzle position, the chemical supply speed (chemical discharge pressure), and the substrate rotation speed with respect to time from the outer periphery will be described with reference to FIGS. 5 and 6, according to the first embodiment, is a flowchart illustrating a method of determining a nozzle radial position R _n, chemical solution discharge pressure v _n, the relation between the substrate rotational speed w _n with respect to time.

(Step S201)
First, the outermost circumference R _nout of the substrate to be processed is set as the calculation start position (first position) of the movement section of the chemical solution supply nozzle.

(Steps S202 to S206)
Steps S202 to S206 are the same as steps S102 to S106 described above, and a description thereof will be omitted. However, in step S204, the nozzle position R _nout is set to the nozzle position R _i .

(Step S207)
It is determined whether the calculated substrate rotation speed w _i and chemical solution discharge pressure v _i are within the control range.

(Step S208)
If it is determined in step S207 that the substrate rotation speed w _i and the chemical solution discharge pressure v _i are not within the control range, b in equations (8 ′) and (9 ′) is appropriately adjusted to obtain the substrate rotation speed w _i. and calculate the chemical solution discharge pressure v _i, determines whether the substrate rotational speed w _i and chemical solution discharge pressure v _i is within the control range.

(Step S209)
As a result of the determination in step S208, if the substrate rotation speed wn _" and the chemical solution discharge pressure vn _" are not within the control range, the inside of the set chemical solution supply nozzle radial direction position is set as an unapplicable region, and the process ends.

(Step S210)
When it is determined in step S207 that the rotation speed w _i and the discharge amount v _i are within the control range, it is determined whether the circumferential value i satisfies the condition of i <14.05282. If it is determined that i <14.05282 is not satisfied, step S211 is executed.

(Step S211)
A circumferential value Δi that changes in 0.05 seconds (unit time) is obtained, and a circumferential value i ′ = i + Δi before 0.05 seconds is obtained. Then, a chemical solution supply nozzle radial direction position R _{i ′} corresponding to the obtained circumferential value _{i ′} is calculated.

(Step S212)
Then, the nozzle position Ri _′ (second position) after 0.05 seconds is newly set as Ri (first position).

(Step S206)
Then, the chemical solution discharge pressure at the nozzle position R _i (circumferential value i) is calculated by using the substrate rotation speed w _nout and the chemical solution discharge pressure v _{nout at} R _nout = 55.4 and the _equations (8 ′) and (9 ′). Find v _i and substrate rotation speed w _i .

  Steps S206, S207, S211, and S212 are repeated until it is determined that i <14.05282, or until it is determined that the region cannot be applied.

  FIG. 7 shows the relationship among the position of the chemical nozzle in the radial direction, the chemical discharge pressure, and the substrate rotation speed with respect to time, which is obtained by the procedure described above. 7A is a view showing the nozzle position from the center of the substrate with respect to the process time, FIG. 7B is a view showing the number of rotations of the substrate with respect to the process time, and FIG. 7C is a view showing the chemical discharge pressure with respect to the process time. It is.

  In addition, the method of determining the radial position of the chemical solution supply nozzle, the chemical solution discharge pressure, and the rotation speed of the substrate to be processed with respect to the above-described time is not only the case where the radial movement of the chemical solution supply nozzle is a geometrical series movement with respect to the circumferential value, The present invention can also be applied to a case where the radial movement of the chemical solution supply nozzle is constant.

The reason why the chemical discharge pressure is constant during the process time of 0 to 0.8 seconds is that the lower limit of the discharge pressure control is ² kgF / cm ² . In this region, the value of b is changed so that the value of the chemical solution discharge pressure v becomes constant in the equation (8 ′), and the substrate rotation speed is set according to (9 ′) accordingly. Similarly, the chemical discharge pressure is constant even after the process time of 12 seconds. This is because the upper limit value of the discharge pressure was 3.5 kgF / cm ² , and therefore the value of b was changed so as not to exceed the maximum chemical solution discharge pressure v _max corresponding to the maximum discharge pressure in the equation (8 ′). . In this way, the chemical solution supply speed and the substrate rotation speed are basically controlled by the equations (8 ′) and (9 ′), and the value b may be changed in a timely manner according to the restrictions of the apparatus.

  The position of the nozzle from the center of the substrate, the number of rotations of the substrate, and the supply speed of the chemical solution from the nozzle are adjusted using the apparatus shown in FIG. 1 according to each control pattern of FIG. 7, and a liquid having a thickness of 10 μm is formed on the circular substrate. A coating film was formed. After forming the coating film, the solvent was removed under reduced pressure, and baking was further performed to form a dye film having a film thickness of 0.3 μm and a film thickness uniformity of 1% or less on a circular substrate. In the present invention, the closer to the center, the wider the trajectory where the chemical solution is dropped by the chemical solution supply nozzle. However, when these trajectories widen after the application is completed but they are not connected to each other, they are filled with a closed space or a solvent atmosphere. It is desirable to hold the coated substrate in the formed space and move to a drying process such as decompression after waiting for the liquid film to sufficiently spread and level. In addition, when a solvent having a high drying rate is used, it is desirable that the coating itself be performed in a solvent atmosphere. The leveling is preferably performed at a rotation speed equal to or lower than the maximum rotation speed at which the outermost peripheral liquid film on the substrate to be processed does not move out of the substrate to be processed due to centrifugal force. The profile of the rotational speed is determined by the balance between the surface tension, interfacial tension, and centrifugal force of the liquid. At this time, minute irregularities may remain (particularly, on the outer peripheral portion of the substrate). In this case, in the process of increasing the viscosity of the liquid film, unevenness can be reduced as much as possible by applying vibration to the liquid film using sound waves, ultrasonic waves, or the like.

  Further, before the drying, the liquid may move inward due to surface tension, and the liquid film thickness at the edge portion of the substrate may become thin. In such a case, the substrate is opened at an upper system immediately before drying, and the substrate is rotated at about 150 to 200 rpm, thereby generating an air flow from the upper side toward the substrate surface at the center of the substrate and further toward the outer periphery of the substrate. By doing so, the liquid film moving inward may be pulled outward. By performing drying immediately, good film thickness uniformity with little film thickness fluctuation can be obtained even at the edge portion.

  Although this embodiment relates to the application of a compact disk, the present invention is not limited to this, and can also be applied to application to a donut-shaped substrate such as a DVD disk or a minidisk, and a circular semiconductor wafer. Further, the material is not limited to the laser light absorbing material, and can be applied to the application of a liquid containing a magnetic material or a liquid containing a metal material.

Also, the coating conditions are set as W _nout as in equation (12), the chemical solution supply speed and the corresponding chemical solution discharge pressure, the substrate rotation speed according to equations (8 ′) and (9 ′), and the substrate according to equation (3). Any control may be performed as long as the position of the chemical solution supply nozzle with respect to the center is determined and controlled. Further, the liquid discharge pressure and the number of rotations of the substrate may be controlled by adjusting the parameter d ₁ , a, n by dividing the chemical solution supply nozzle position into a plurality of regions by the parameter h.

(Third embodiment)
This embodiment relates to a technique for forming an interlayer insulating film of a semiconductor substrate by coating.

The substrate on which the wiring was formed was set in the coating apparatus shown in FIG. The application onto the substrate was determined as shown in the equation (15) so that d ₁ = 1.5 mm and a = 0.993 as the locus of the chemical solution supply nozzle.

However, since the film thickness abnormality occurred inside the diameter of 7.6 mm under this coating condition, d ₀ = 4.22 and a = 0.844 so as to eliminate the film thickness abnormality within the diameter of 7.6 mm (24 ).

That is, inside the diameter of 7.6 mm, the chemical solution supply nozzle position, the substrate rotation speed, and the chemical solution discharge pressure with respect to the processing time are calculated based on the control expression of the equation (24), and outside the diameter of 7.6 mm, the equation (23) is calculated. Based on the control equation, the chemical solution supply nozzle position, the substrate rotation speed, and the chemical solution discharge pressure with respect to the processing time were calculated.
The circumferential value n is 0.5 ≦ n ≦ 3.00 inside the diameter 7.6 mm, and the circumferential value n is 6.11 ≦ n ≦ 80.4 outside the diameter 7.6 mm.

  FIG. 8 shows the relationship between the chemical solution supply nozzle position, the substrate rotation speed, and the chemical solution discharge pressure with respect to the processing time calculated based on this. 8A is a view showing the nozzle position from the center of the substrate with respect to the process time, FIG. 8B is a view showing the number of rotations of the substrate with respect to the process time, and FIG. 8C is a view showing the chemical discharge pressure with respect to the process time. It is.

  Moreover, the locus | trajectory of the chemical | medical solution supply nozzle inside and outside the diameter of 7.6 mm dripped is shown in FIG. FIG. 9 is a diagram showing a locus of the chemical solution supply nozzle dropped based on the nozzle position from the center of the substrate, the substrate rotation speed, and the chemical solution discharge pressure with respect to the process time shown in FIG. In FIG. 9, reference numeral 601 denotes a trajectory inside the diameter 7.6 mm, 602 denotes a trajectory outside the diameter 7.6 mm, and 603 denotes a connection point between the inner trajectory of the diameter 7.6 m and the outer trajectory, and the substrate. A perfect circle whose diameter is the center is shown.

In the relationship between the process time and the chemical solution discharge pressure shown in FIG. 8C, the discharge pressure is constant between the process time 0 and 1.7 seconds because the discharge pressure control lower limit is ² kgF / cm ^2. Because it is. In this region, the value of b is changed so that the value of the chemical solution discharge pressure v becomes constant in the equation (8 ′), and the substrate rotation speed is set according to (9 ′) accordingly. Similarly, the discharge pressure is constant after the process time of 8.5 seconds. This is because the upper limit value of the discharge pressure was 3.5 kgF / cm ² , and therefore the value of b was changed so as not to exceed the maximum chemical solution discharge pressure v _max corresponding to the maximum discharge pressure in the equation (8 ′). . In this way, the chemical solution supply speed and the substrate rotation speed are basically controlled by the equations (8 ′) and (9 ′), and the value b may be changed in a timely manner according to the restrictions of the apparatus.

  According to each control pattern shown in FIG. 8, the position of the nozzle from the center of the substrate, the number of rotations of the substrate, and the supply speed of the chemical solution from the nozzle are adjusted using the apparatus shown in FIG. 1, and the thickness is 20 μm on the circular substrate. A liquid coating film was formed. After forming the coating film, the solvent was removed under reduced pressure, and baking was further performed to form an interlayer insulating film having a film thickness of 1 μm and a film thickness uniformity of 1% or less on a circular substrate. In the present invention, as the distance from the center is approached, the width of the trajectory where the chemical solution is dropped by the chemical solution supply nozzle is widened. It is desirable to hold the coated substrate in the remaining space and move to a drying step such as decompression after waiting for the liquid film to sufficiently spread and level. In addition, when a solvent having a high drying rate is used, it is desirable that the coating itself be performed in a solvent atmosphere. In the leveling, the profile is determined by the balance of the surface tension, interfacial tension, and centrifugal force of the liquid. At this time, minute unevenness may remain. In this case, in the process of increasing the viscosity of the liquid film, unevenness can be reduced as much as possible by applying vibration to the liquid film using sound waves, ultrasonic waves, or the like.

  Further, before the drying, the liquid may move inward due to surface tension, and the liquid film thickness at the edge portion of the substrate may become thin. In such a case, the upper part of the substrate is opened immediately before drying, and the liquid film at the outermost periphery on the substrate to be processed does not move out of the substrate to be processed by centrifugal force. When the liquid film that is moving inward is pulled outward by rotating at a rotational speed of, for example, about 70 to 200 rpm, generating an air flow from the upper side toward the substrate surface at the center of the substrate and further toward the outer periphery of the substrate. Good. By performing drying immediately, good film thickness uniformity with little film thickness fluctuation can be obtained even at the edge portion.

  In this embodiment, the central portion is applied while moving the chemical solution supply nozzle by another geometric series function. However, if the chemical solution has a sufficiently spreading property, a desired amount can be dropped on the center of the substrate. . In this case, after dripping at the center, the substrate is rotated to widen the liquid film to a position having a diameter of about 7.6 mm, and then the chemical liquid supply nozzle is moved according to the equation (23), and the chemical liquid supply corresponding to the position of the nozzle is performed. It is good to give speed (pressure) and substrate rotation speed.

  This embodiment relates to the application of an interlayer insulating film to a circular semiconductor substrate, but is not limited to this, and is not limited to this, but is applied to a circular semiconductor wafer such as an antireflection film, a photosensitive material film, a ferroelectric film, or a planarizing film. It can be applied to any coating film formation.

Also, the coating conditions are set as W _nout as in equation (12), the chemical solution supply speed and the corresponding chemical solution discharge pressure, the substrate rotation speed according to equations (8 ′) and (9 ′), and the substrate according to equation (3). Any control may be performed as long as the position of the chemical solution supply nozzle with respect to the center is determined and controlled. Further, the liquid discharge pressure and the number of rotations of the substrate may be controlled by adjusting the parameter d ₁ , a, n by dividing the chemical solution supply nozzle position into a plurality of regions by the parameter h.

  In this embodiment, the liquid line dropped on the spiral spreads due to the fluidity of the liquid on the substrate to be processed, and enables liquid film formation on the entire surface except the edge portion of the substrate to be processed. The liquid may remain linear at the center. In that case, reduce the radial movement pitch and rate of change of the chemical solution supply nozzle in the center, and irradiate the chemical solution that is excessive when dripping from the side of the continuously dripping chemical solution or aspirate the chemical solution itself It is preferable to adjust the chemical supply amount per unit area by inserting a shutter or the like to physically shut it off.

(Fourth embodiment)
Based on the method for determining the above parameters, a method for applying a laser reactive film to a compact disc (CD) will be described. In consideration of processing with a blue semiconductor laser, a laser reaction film in which a dye having absorption at 400 to 700 nm was dissolved in an organic solvent was used. The solid content concentration in the solution was 2%. The application area of the compact disc is an area outside the diameter of 19 mm from the center (outer shape 55.4 mm). Application to this substrate was performed under the conditions of d ₁ = 1.65 and a = 0.955. That trajectory S _n of the chemical solution supply nozzle

And n was varied between 14.202 and 41.729. When actually performing coating, the discharge position R _n, discharge rate v _n, it is necessary to represent the rotational speed w _n respectively in relation to time. The procedure will be described with reference to the flowchart of FIG. FIG. 10 is a flowchart showing a method for obtaining the relationship between the nozzle radial direction position R _n , the chemical solution supply speed v _n , and the substrate rotation number w _n with respect to the processing time according to the fourth embodiment of the present invention.

(Step S301)
First, the rotational speed w _nout = 61.26 rpm and the discharge pressure v _nout (= ² kgF / cm ² : discharge pressure increase / decrease of the chemical solution supply nozzle) at the outermost _peripheral discharge position R _nout = 55.4 mm are set. The rotation speed and the discharge amount determined here are adjusted so that the chemical solution is not released outside the substrate during application. Each control parameter was determined by the method (II) in which the number of rotations of the substrate to be processed was determined (constant discharge amount) according to the radial position (r / r _out ) of the chemical solution supply nozzle.

(Step S302)
The trajectory in the radial direction of the chemical solution supply nozzle, that is, the nozzle movement pitch at the nozzle position R _n is set. In this embodiment, the first term d _{1 of the} geometric series is 1.5, and the change rate a is 0.995.

(Step S303)
A circumferential value n _in corresponding to the innermost circumference R _in (R _nin = 19 mm) of the compact disk is obtained using the set initial term d ₁ , change rate a, and equation (25). In the case of this embodiment, the circumferential value n corresponding to the innermost circumference R _nin = 19 mm of the compact disc is 14.47596.

On the other hand, the peripheral value n _out corresponding to the outermost periphery R _nout of the substrate is n _out = 46.86691. That is, the spiral trajectory of the chemical solution supply nozzle starting from a position 19 mm from the center of the substrate reaches the substrate edge by making a round of 32.39094 (= n _out −n _in ) on the substrate.

(Step S304)
Substrate rotation number w _nout and chemical solution discharge pressure v _nout (= ² kgF / cm ² : discharge pressure increase / decrease of the chemical solution supply nozzle) at R _nin = 19 mm, and circumferential value i (= 14. The number of substrate rotations w _i (w _14.47596 ) at _14.47596 ) is obtained.

At this time, the coefficient b is adjusted so that the chemical discharge pressure does not change. That is, in the equation (16), v _n = ² kgF / cm ² is substituted to obtain a coefficient b that does not change the chemical discharge pressure. Then, the coefficients were determined b (17) is substituted into equation obtaining the substrate rotational frequency w _n.

(Step S305)
It is determined whether or not the circumferential value i satisfies the condition of i ≧ 46.86691. If it is determined that i is not greater than 46.86691, step S108 is executed.

(Step S306)
A circumferential value Δi that changes in 0.05 seconds (unit time) is obtained, and a circumferential value i ′ = i + Δi after 0.05 seconds is obtained. Then, a chemical solution supply nozzle radial direction position R _{i ′} corresponding to the obtained circumferential value _{i ′} is calculated. The period from an arbitrary time t s to t + 0.05 seconds regarded as R _n, v _n, the w _n are constant, respectively.

When the substrate board in the time t in seconds is rotating at a rotational speed w _n, the substrate during the time t s to time t + 0.05 seconds,

Only rotate.
For example, when w _14.47596 = 180 rpm, the rotation is 0.15. N after rotation 0.05 sec w _n therefore

become. R _14.62596 corresponding to n ′ = 14.662596 becomes R _14.62596 = 19.19733 from the formula (3).

(Step S307)
Then, the chemical solution supply nozzle position Ri _′ (second position) after 0.05 seconds is newly set as the nozzle position Ri (first position).

(Step S304)
Then, the nozzle position R _i (circumference) newly set in step 307 is calculated by using the substrate rotational speed w _nout and chemical solution discharge pressure v _{nout at} R _nout = 55.4, and _equations (8 ′) and (9 ′). The chemical solution discharge pressure v _i and the substrate rotation number w _i at the value i) are obtained.

(Step S305)
Steps S306, S307, and S304 are repeated until it is determined that i ≧ 46.86691.

By the above procedure, the discharge position R _n with respect to time, the discharge amount v _n, the rotational speed w _n is represented.

  FIG. 11 shows the relationship between the radial position of the chemical solution supply nozzle, the chemical solution supply pressure, and the rotation speed of the substrate to be processed with respect to the processing time obtained by these procedures. 11A shows the nozzle position in the radial direction from the substrate center with respect to the processing time, FIG. 11B shows the chemical discharge pressure with respect to the processing time, and FIG. 11C shows the substrate rotation speed with respect to the processing time. Yes.

  Using the apparatus shown in FIG. 1 according to each control pattern in FIG. 11, the position of the chemical solution supply nozzle from the center of the substrate and the substrate rotation speed are adjusted while keeping the chemical solution supply speed from the chemical solution supply nozzle constant. A liquid coating film having a thickness of 20 μm was formed on a circular substrate. After forming the coating film, the solvent was removed under reduced pressure, and baking was further performed to form a dye film having a film thickness of 0.4 μm and a film thickness uniformity of 1% or less on a circular substrate.

  If the liquid dropped on the substrate to be treated is slow to spread and difficult to connect to adjacent lines, place the substrate in a sealed container or solvent atmosphere to spread the liquid and connect the adjacent lines. Is desirable. In addition, when a solvent having a high drying rate is used, it is desirable that the coating itself be performed in a solvent atmosphere. During the leveling, the profile is determined by the balance of the surface tension, interfacial tension, and centrifugal force of the liquid. At this time, minute unevenness may remain. In this case, in the process of increasing the viscosity of the liquid film, the vibration including the wavelength in the range of about S / 2 to S with respect to the period S of the film thickness unevenness is applied to the liquid film using sound waves, ultrasonic waves, or the like. By giving, the unevenness can be made as small as possible.

  Further, before the drying, the liquid may move inward due to surface tension, and the liquid film thickness at the edge portion of the substrate may become thin. In such a case, by opening the upper part of the substrate immediately before drying and rotating the substrate at about 150 to 200 rpm, an air flow is generated from the upper part of the substrate toward the substrate surface and further toward the outer periphery of the substrate. And the liquid film moving inward can be pulled outward. Thereafter, by drying, good film thickness uniformity with small film thickness fluctuation can be obtained even at the edge portion.

  In the present embodiment, the application of the compact disc has been described. However, the present invention is not limited to this, and the present invention can also be applied to a donut-shaped substrate such as a DVD disk or a minidisk, and coating on a circular semiconductor wafer. Further, the material is not limited to the laser light absorbing material, and can be applied to the application of a liquid containing a magnetic material or a liquid containing a metal material.

Also, the application condition is set to W _nout as in the equation (12), the chemical solution supply speed and the corresponding chemical solution discharge pressure, the substrate rotation speed according to the equations (16) and (17), and the substrate center according to the equation (3). As long as the position of the chemical solution supply nozzle is determined and controlled, any control may be performed. Further, the liquid discharge pressure and the number of rotations of the substrate may be controlled by adjusting d ₁ , a, n in a plurality of regions with respect to the position of the chemical solution supply nozzle according to the parameter h.

(Fifth embodiment)
The coating film forming method described in the fourth embodiment was performed using the coating apparatus shown in FIG. FIG. 12 is a diagram showing a schematic configuration of a coating apparatus according to the fifth embodiment of the present invention. 12A is a plan view showing the configuration of the coating apparatus, and FIG. 12B is a cross-sectional view taken along the line AA ′ of FIG.

  The coating apparatus shown in FIG. 12 is provided with a substrate platform 702 having a rotation function in a lower unit 701. A top plate 703 is provided on the lower unit 701. The top plate 703 is provided with a slit 703a so that the chemical solution is dropped onto the substrate to be processed 700 from the chemical solution supply start position of the substrate to be processed 700 to the application end portion. When carrying in / out the substrate 700 to be processed, the top plate 703 is opened. The opening of the top plate 703 may be a mechanism in which the top plate 703 moves upward or a mechanism in which the lower unit 701 including the substrate mounting portion 702 on which the substrate 700 to be processed is moved moves downward.

  A chemical solution supply nozzle 122 that moves above the slit 703a of the top plate 703 is provided. A chemical solution supply pump (not shown) that supplies the chemical solution to the chemical solution supply nozzle 122 via the chemical solution supply pipe 124 is connected to the chemical solution supply nozzle 122. The chemical liquid discharge speed from the chemical liquid supply nozzle 122 was controlled by controlling the chemical liquid supply pressure from the chemical liquid supply pump.

On the top plate 703 at the chemical solution supply start position and the chemical solution supply end position, chemical solution blocking mechanisms 710 a and 710 b provided independently of the chemical solution supply nozzle 122 are provided.
While the chemical solution is supplied onto the substrate 700, the rotational speed of the substrate mounting portion 702, the moving speed of a drive system (not shown) for driving the nozzle, and the discharge rate of the chemical solution from the chemical supply nozzle 122 are each rotationally driven. It is managed by a control unit (not shown), a nozzle drive control unit (not shown), and a chemical solution supply pump (not shown). A controller (not shown) that supervises these three control units is arranged upstream thereof.

  The structure of the chemical solution blocking mechanism 710 (710a, 710b) will be described with reference to FIGS. 13 (a) and 13 (b). FIG. 13 is a diagram showing a schematic configuration of a chemical liquid blocking mechanism according to the fifth embodiment of the present invention. FIG. 13A shows an operating state in which the chemical solution is blocked, and FIG. 13B shows an operating state in which the chemical solution is not blocked. As shown in FIG. 13, the chemical liquid blocking mechanism includes a deformable pipe 721 and a gas injection nozzle 722 that are sequentially connected to a gas supply pipe 713 (not shown). The chemical liquid blocking mechanism is arranged so as to sandwich the chemical liquid 720 dropped from the chemical liquid supply nozzle 122 and the gas injection nozzle 722 so that the gas flow can be controlled by deforming and opening the deformable tube 721. And a chemical mist collection unit 724. The nozzle opening / closing control piezo 723 includes a piezo element that expands and contracts by controlling the applied voltage. The deformable tube 721 is deformed and opened by controlling the voltage applied to the piezo element. The deformation and opening of the deformable tube 721 may be performed directly by a piezo element or by a member connected to the piezo element.

A method for forming a film using this coating apparatus will be described below.
The operations of opening the top plate 703, transporting the substrate 700 to be processed into the lower unit 701, placing the substrate 700 to be placed on the substrate placement unit 702, and closing the top plate 703 are sequentially performed. Next, the chemical solution supply nozzle 122 is moved over the top plate 703 at the chemical solution supply start position in a state where supply of the chemical solution is stopped. After gas discharge is started from the gas injection nozzle 722 of the chemical solution blocking mechanism 710a, discharge of the chemical solution is started from the chemical solution supply nozzle 122. The discharged chemical liquid 720 is transported to the chemical liquid mist collection unit 724 by a gas flow formed in advance below the chemical liquid 720. At this time, the chemical mist collecting unit 724 performs suction sufficient to collect the mist generated when the chemical 720 collides with the gas. The sucked chemical solution is transported out of the coating apparatus through the waste pipe 714.

  When the discharge of the chemical liquid from the chemical liquid supply nozzle 122 is stable, the nozzle opening / closing control piezo 723 is pushed out, the deformable tube 721 is deformed, and the gas supply is shut off. Thereby, supply of the chemical solution 720 from the chemical solution supply nozzle 122 to the substrate 700 is started (the origin of the processing time). The radial position of the chemical solution supply nozzle, the chemical solution discharge pressure, and the substrate rotation speed are controlled based on the nozzle movement with respect to the processing time shown in FIG. 11, the discharge pressure of the chemical solution supply nozzle, and the control set value of the substrate rotation speed. I do.

  When the chemical solution supply nozzle 122 moves to the chemical solution supply end position on the outer periphery of the substrate to be processed, the chemical solution blocking mechanism 710b disposed on the outer peripheral portion is operated. The chemical liquid blocking mechanism 710b on the outer peripheral portion is disposed in advance above the chemical liquid supply end position, and the nozzle opening / closing control piezo 723 is provided when the chemical liquid 720 supplied from the chemical liquid supply nozzle 122 comes immediately before the gas injection nozzle 722. Returning, the deformation of the deformable tube 721 is released and gas injection is performed. The injected gas collides with the chemical solution 720 and changes the dropping trajectory of the chemical solution. The chemical solution whose dripping trajectory has been changed is guided to the chemical solution mist collection unit 724 and collected. The chemical solution supply nozzle 122 is stopped at this chemical solution supply end position, and the discharge of the chemical solution 720 is also stopped.

  When the discharge of the chemical liquid from the chemical liquid supply nozzle 122 is completely stopped, the nozzle opening / closing control piezo 723 of the chemical liquid blocking mechanism 710b is pushed out, the deformable tube 721 is deformed, and the gas supply is stopped.

  Further, the chemical solution supply nozzle 122 is retracted from above the top plate 703 and the top plate 703 is opened, and then the substrate to be processed 700 is unloaded from the lower unit 701. Note that the rotation of the substrate 700 is preferably continued until the top plate 703 is opened. This is because if the substrate to be processed 700 is stopped in a state where the top plate 703 is present, a difference in the environment above the substrate to be processed 700, for example, a change in film thickness occurs at the slit 703a portion.

  The substrate may be dried according to the fourth embodiment, and detailed description thereof is omitted.

(Sixth embodiment)
The present embodiment relates to a method of forming an interlayer insulating film on a semiconductor substrate by a coating method.

The semiconductor substrate having the wiring formed on the surface is set in the coating apparatus shown in FIG. The application to the semiconductor substrate was determined as shown in the equation (28) so that d ₁ = 1.65 mm and a = 0.0.99 as the locus of the chemical solution supply nozzle 122.

However, since the film thickness abnormality occurs inside the diameter of 9.8 mm under this application condition, a chemical solution partial blocking mechanism is provided within the diameter of 9.8 mm to partially block the chemical solution and adjust the supply amount of the chemical solution. In the region where the chemical solution was partially blocked, the condition at the radial position of 9.8 mm was used as it was in the sequence when the outside of the region was applied. That is, the rotation speed of the substrate to be processed is set to 180 rpm, the chemical solution discharge pressure is set to ² kgF / cm ^2, and the movement pitch / rotation of the chemical solution supply nozzle in the radial direction is set to a minimum pitch of 1. It was set to 609 mm. By making these parameters constant, the chemical liquid blocking rate C at the radial position r by the chemical liquid partial blocking mechanism increases monotonically from 0 to 1 between the radial positions 9.8 mm and 0 mm, as shown in Equation (29). It can be expressed by a linear expression.

Here, r is the radial position, r _c is the outermost diameter required chemical moiety blocked.

  The partial blocking of the chemical liquid is performed by injecting gas from a plurality of gas injection nozzles provided in the chemical liquid dropped from the chemical liquid supply nozzle 122. The cutoff rate is adjusted by optimizing the arrangement of the gas injection nozzle, the pipe diameter, and the gas pressure.

  An example of the arrangement of gas injection nozzles used for partial blocking is shown in FIG. FIG. 14 is a diagram illustrating an arrangement example of gas injection nozzles of the chemical liquid partial blocking mechanism according to the sixth embodiment of the present invention. As shown in FIG. 14, the gas injection nozzles 731a and b adjacent to one gas injection nozzle 731b are defined as one cutoff unit (two gas injection nozzles surrounded by a dotted line in the figure), and the width of these cutoff units. Optimized. If the interval between the adjacent gas injection nozzles 731 is narrow, a two-stage structure is used as shown in FIG.

  The outer diameter of one gas injection nozzle 731 is D, the inner diameter is a, and the chemical liquid blocking effective width at the blocking position is s. Here, the chemical blocking effective width s is a range (diameter) in which the gas discharged from one gas injection nozzle 731 has a chemical blocking capability.

Using these parameters, the chemical blocking rate C within one blocking unit is

It can be expressed as On the other hand, the distance between the centers of the first gas injection nozzle 731a, the third gas injection nozzle 731c, and one gas injection nozzle 731c is D + W. The positions of the gas injection nozzles 731b and 7c are determined from the equations (29) and (30) so that a desired cutoff rate C can be obtained at an intermediate position of this cutoff unit, that is, at a position of (D + W) / 2.

For example, the first gas injection nozzle 731a is set at the origin position (p = 0),

Consider the case where
Here, since it is composed of two nozzles per block unit, the equation (30 ′) is actually

Can be written. That is, when considering one nozzle as a reference, a value obtained by dividing the chemical effective blocking width s by the value obtained by subtracting the reference position p from the intermediate position r _i of the blocking unit width P by twice, and the blocking rate C. An intermediate position r _i is determined so as to be equal, and the blocking unit width P is determined based on the determined intermediate position r _i . Specifically:

When r _i is calculated assuming that the right sides of the expressions (29) and (30 ′) are equal, the expression (31) is obtained.

In the case of the present embodiment, specifically, the outer diameter D of the gas injection nozzle 731 is set to 0.5 mm, the chemical liquid blocking effective width s is set to 0.3 mm (gas injection nozzle inner diameter a = 0.25 mm), and the previous chemical liquid blocking is performed. with the outermost diameter r _c = 9.8 mm needed, the center position of the second gas injection nozzle _{731b 0.310mm (= r i),} 0.620mm the center position of the third gas injection nozzle 731c _{(= 2 (r i -p)} , p = 0) is defined as.

The center position of the fourth and fifth gas injection nozzles is substituted into the expression (32), which is a more general expression of (30), with the center position of the third gas injection nozzle as the reference position p (= 0.620 mm). Ask.

Then, the center position of the fourth gas injection nozzle _{p + r i (p = 0.620mm} ), the center position of the 5 th of the gas injection nozzle is determined to 2r-p (= p + 2 [r-p]).

Further, the center positions of the sixth, seventh, eighth, and ninth gas injection nozzles are obtained from the equation (31) with the center positions of the fifth, seventh,. More generally, the center position of the 2n, 2n + 1 (n = 2, 3,...) Th gas injection nozzle is obtained from the equation (32) with the center position of the 2n−1th gas injection nozzle as the reference position p. (32)

In this case, it means that it is impossible to perform the arrangement (overlay or flat) as shown in FIG. In this case, it is preferable to determine the position of the gas injection nozzle according to the equation (34) with the one partitioned by the center of the gas injection nozzles adjacent to each other as one block unit.

Also in the equation (34),

This means that it is difficult to arrange the last gas injection nozzle. In this case, fine adjustment may be made so that the gas injection nozzles having different outer diameters or different effective cutoff widths are used. When the effective blocking widths are different, in equations (29) to (33), the chemical liquid blocking effective widths s ₁ , s ₂ , and s ₃ of the left, center, and right gas injection nozzles are used, and s ₁ / _{2 + s 2 + s 3/} 2 can be substituted into. The (34) equation (35) may be substituted left, the _{s 1/2 + s 3/} 2 to s using chemical blocking effective width s _1, s ₃ of the right of the gas injection nozzle for.

Table 1 shows the result of determining the radial gas injection nozzle center position and the chemical liquid blocking effective width when the gas injection nozzle having an outer diameter of 0.5 mm is used. The gas injection nozzles Nos. 1 to 16 are determined by the equation (32), and the gas injection nozzle No. 17 is determined by the equation (34) while changing the chemical liquid blocking effective width s.

  The gas injection nozzles Nos. 1 to 16 had an inner diameter of 0.250 mm, and No. 17 with a different effective blocking width had an inner diameter of 0.300 mm. The gas pressure is adjusted so as to obtain a desired cutoff effective width for each gas injection nozzle.

  For example, the adjustment value of the gas pressure may be obtained by preparing a video camera 741 for observation as shown in FIG. 15 and acquiring the correlation between the gas pressure and the effective cutoff width. That is, the chemical liquid 720 is discharged from the chemical liquid supply nozzle 122 at the same discharge speed as that during application. The gas injection nozzle 731 is installed at a position separated by the same distance as when the chemical solution is shut off with an actual apparatus, and the chemical solution supply nozzle 122 is slowly moved in one direction while injecting gas at a specific gas pressure. The state of the chemical solution 720 is observed by an observation video camera 741 installed so as to sandwich the gas injection nozzle 731 and the chemical solution 720, and the blocking width is measured. The gas pressure is changed to obtain the discharge width value, and the optimum gas pressure is determined.

FIG. 16 shows the arrangement of the gas injection nozzles of the chemical liquid partial blocking mechanism created based on the center position and the blocking effective width of the gas injection nozzles in Table 1. As shown in FIG. 16, gas injection nozzles 731 _{1 to} 731 ₁₇ are arranged.

  Furthermore, the structure of the coating device provided with this chemical | medical solution interruption | blocking apparatus is shown in FIG. 17A is a plan view, and FIG. 17B is a cross-sectional view taken along the line A-A ′ of FIG. In FIG. 17, the same parts as those in FIG.

As shown in FIG. 17, when the substrate to be processed 700 is placed on the substrate platform 702, a chemical liquid partial blocking mechanism 750 is disposed on the top plate 703 above the center of the substrate 700 to be processed. ing. The chemical liquid partial blocking mechanism 750 includes a nozzle group 751 having ₁₇ gas injection nozzles 731 _{1 to} 731 17 whose arrangement positions are optimized, and a chemical mist collection at a position facing the nozzle group 751 across the slit 703a. Part 752. Also, a chemical blocking mechanism 710b using gas is disposed above the substrate edge portion.

  When carrying in / out the substrate 700 to be processed, the top plate 703 is opened. The opening of the top plate 703 may be a mechanism in which the top plate 703 moves upward or a mechanism in which the lower unit 701 including the substrate mounting portion 702 on which the substrate 700 to be processed is moved moves downward.

  While the chemical solution is supplied onto the substrate 700, the rotational speed of the substrate mounting portion 702, the moving speed of a drive system (not shown) for driving the nozzle, and the discharge rate of the chemical solution from the chemical supply nozzle 122 are each rotationally driven. It is managed by a control unit (not shown), a nozzle drive control unit (not shown), and a chemical solution supply pump (not shown). A controller (not shown) that supervises these three control units is arranged upstream thereof.

Next, a process of applying an interlayer insulating film on the substrate 700 will be described.
The substrate platform 702 and the lower unit 701 move downward to form a space between the top plate 703 and the substrate 700 to be processed is carried into the space by a transfer arm (not shown). Next, three pins (not shown) provided on the substrate platform 702 are raised to lift the substrate 700 to be processed from the transfer arm, and the transfer arm returns to the outside of the unit. As the three pins descend, the substrate platform 702 and the lower unit 701 move upward to connect to the top plate 703 to form a closed space. In the closed space, a thin slit 703a for supplying the chemical liquid from the chemical liquid supply nozzle 122 is provided.

  The chemical solution supply nozzle 122 moves to above the center of the substrate 700 to be processed, which is the chemical solution supply start position of the substrate 700 to be processed, with the supply of the chemical solution stopped. After the gas injection is started from the nozzle group 751 of the chemical liquid partial blocking mechanism 750, the discharge of the chemical liquid from the chemical liquid supply nozzle 122 is started. The discharged chemical liquid is transported to the chemical liquid mist collecting section by the gas flow formed below. At this time, the chemical mist collecting unit performs suction adjustment so that the mist generated when the chemical collides with the gas can also be collected. The sucked chemical solution is transported out of the coating apparatus through a waste pipe.

  When the discharge from the chemical solution supply nozzle 122 is stabilized, the movement of the chemical solution supply nozzle 122 is started based on the control shown in FIG. 18A shows the nozzle position in the radial direction from the substrate center with respect to the processing time, FIG. 18B shows the chemical discharge pressure with respect to the processing time, and FIG. 18C shows the substrate rotation speed with respect to the processing time. Yes.

From the center of the substrate 700 to the radial direction of 8.9 mm, the rotational speed of the substrate 700 to be processed is 180 rpm, the chemical solution discharge pressure is ² kgF / cm ^2, and the nozzle movement pitch / rotation in the radial direction is 1.609 mm. The chemical supply nozzle 122 starts to move from the center of the substrate 700 toward the outer periphery. Within the effective cut-off width of each gas injection nozzle, the chemical liquid dropped from the chemical liquid supply nozzle changes its dropping direction by gas injection and is transported to the chemical liquid mist collection unit. In a region other than the effective blocking width, the chemical solution is dropped on the substrate to be processed. By this operation, the chemical solution is shut off in a timely manner, and the dropped chemical solution spreads on the substrate to be processed within a region within a diameter of 8.9 mm of the substrate to be processed, and a liquid film having a uniform thickness is formed by connecting each of them. The The processing time from the center of the substrate to be processed to the diameter of 8.9 mm was about 5.89 seconds.

  After 5.89 seconds, the number of revolutions is controlled while moving the chemical solution supply nozzle 122 so that the radial movement pitch of the substrate 700 to be processed changes once in a geometric series. The gas irradiation from the nozzle group 751 was stopped when the droplets from the chemical solution supply nozzle passed through the effective cutoff width of the last gas injection nozzle.

  When the chemical solution supply nozzle 122 comes to the non-application area on the outer periphery of the substrate 700 to be processed, the chemical solution blocking mechanism 710b disposed on the outer peripheral portion is operated. The outer peripheral chemical liquid blocking mechanism 710b is arranged in advance above the non-application area, and immediately after the chemical liquid supplied from the chemical liquid supply nozzle enters the effective blocking width of the gas injection nozzle 711b, the nozzle opening / closing control piezo 723 is returned and deformed. The deformation of the universal tube 721 is released to perform gas injection. This gas collides with the chemical solution, and the trajectory of the chemical solution is changed and collected by the mist collecting unit 724. Further, at this position, the chemical solution supply nozzle 122 is stopped, and the discharge of the chemical solution is also stopped. When the discharge of the chemical liquid from the chemical liquid supply nozzle 122 was completely stopped, the nozzle opening / closing control piezo 723 was pushed out, the deformable tube 721 was deformed, and the gas injection was stopped. Note that an inert gas such as nitrogen, argon, or helium can be used as the gas.

  Further, the chemical solution supply nozzle 122 is retracted from above the top plate 703, the substrate mounting portion 702 and the lower unit 701 are moved downward, the substrate to be processed 700 is lifted with 3 pins, and a transfer arm is inserted into the generated gap. The substrate 700 was placed on the transfer arm by lowering the pins, and the substrate 700 was unloaded by moving the transfer arm out of the unit. Thereafter, the substrate platform 702 and the lower unit 701 were moved upward and stopped at a predetermined position, and the processing was completed.

  The liquid film formed on the substrate 700 may be dried according to the fourth embodiment, and detailed description thereof is omitted.

In the present embodiment, the gas injection nozzles are arranged at both ends and the center of the blocking unit, but the present invention is not limited to this. One may be arranged in the blocking unit. For example, as shown in FIG. 19, when the gas injection nozzle 761 is arranged in the middle of the shut-off unit, the gas injection is performed at a position r _i obtained by modifying the expression with the right side of the expression (30) as s / (D + W). A nozzle 761 may be disposed. Table 2 shows the nozzle arrangement position when the gas injection nozzle is arranged in the middle of the shut-off unit.

In this case, 14 gas injection nozzles having an outer diameter of 0.5 mm and an inner diameter of 0.3 mm can be used. FIG. 20 shows the arrangement of 14 gas injection nozzles. FIG. 20 is a diagram showing the configuration of the gas injection nozzles arranged at the arrangement positions shown in Table 2. As shown in FIG. 20, gas injection nozzles 761 _{1 to} 761 ₁₄ are arranged. It was necessary to widen the 14 th cutoff effective width of the gas injection nozzle 761 _14, from the other nozzle 14 th gas pressure of the gas injection nozzle 761 ₁₄ Based on blocking effective width determination method as shown in Table 2 Was also bigger. In Table 2, the center position of the gas injection nozzle is placed at the center of the shut-off unit, but this is not restrictive. An appropriate position can be selected as long as it is between the start point and end point of the blocking unit. Moreover, (the distance from the start point to the end point) the width of the blocking unit is dependent on the outermost diameter r _c required chemical blocking. The r _c is the physical property values of the desired liquid film thickness and chemical (e.g. solids, viscosity, density, surface presence of the active agent) to be dependent on the position of the gas injection nozzle it is desirable not fixed. The value of r _c based on the coating conditions determined calculated or experimentally, it is desirable to have a fine adjustment to mechanisms that can be placed based on the result. For fine adjustment, for example, a gas injection nozzle is arranged on a base of a shape memory alloy in which an elongation amount is recorded at a predetermined temperature, and a desired interval is reproduced by adjusting the temperature between the gas injection nozzles. Can be used.

Further, instead of using the gas injection nozzle for blocking the chemical solution, a chemical solution blocking rod disposed between the chemical solution supply nozzle and the substrate to be processed may be used. The position of the chemical liquid blocking rod at this time is, for example, if the blocking conditions in Tables 1 and 2 are used instead of the gas injection nozzle, the width of the chemical liquid blocking rod is made equal to the effective cutting width of the gas injection nozzle. The center of the ridge is preferably matched with the center position of the gas injection nozzle. In addition, when using a chemical | medical solution blocker, it is desirable that it is flatly placed. Even in the case of using the chemical blocking gutter (distance from the start point to the end point) blocking unit width is dependent on the outermost diameter r _c required chemical blocking. The r _c is the physical property values of the desired liquid film thickness and chemical (e.g. solids, viscosity, density, surface presence of the active agent) to be dependent on the position of the shut-off trough it is desirable not fixed.

Further, based on the coating conditions, the value of the outermost diameter r _c required chemical blocking calculations or experimentally obtained, it is desirable to have a fine adjustment to mechanisms that can be placed based on the result. For fine adjustment, for example, a chemical liquid barrier rod is arranged on the shape memory alloy base in which the elongation amount is recorded at a predetermined temperature, and a desired interval is reproduced by adjusting the temperature between the barrier rods. be able to. In addition, when a chemical solution barrier is used, there is a high possibility that the chemical solution blocked by the chemical barrier will solidify and become a dust generation source. Therefore, it is desirable to provide the coating apparatus with a mechanism that causes the solvent contained in the chemical solution to flow through the barrier and quickly transports the blocked chemical solution together with the solvent to the chemical recovery unit when the chemical solution is shut off. By flowing a solvent through the chemical liquid blocking rod, it is possible to suppress the precipitation of the solid content contained in the chemical liquid.

  Further, it is desirable that the soot has a two-layer structure as shown in FIG. FIG. 21 is a diagram showing a schematic configuration of a chemical liquid partial blocking mechanism constituted by scissors arranged in the upper layer and the lower layer. The first blocking rod 782 disposed in the upper layer causes the solvent contained in the chemical liquid to slightly overflow when the chemical liquid 781 is dropped. The solvent overflowing from the first blocking rod 782 becomes a droplet and falls on the second blocking rod 783 disposed in the lower layer. By collecting the dropped solvent and the chemical solution with the second blocking rod 783, the chemical solution 781 does not adhere to the side surface of the first blocking rod 782, and can be applied while maintaining cleanliness. In FIG. 21, the chemical liquid 786 dropped on the substrate 785 to be processed enters the first blocking width 782 due to fluidity. The blocking of the chemical solution referred to in the present embodiment is nothing but the adjustment of the dropping amount by blocking the chemical solution. Accordingly, the chemical solution 786 dropped on the substrate 785 to be processed enters the region blocked by the first and second blocking rods 782 and 783 due to the fluidity, and finally the chemical solutions are connected to each other. Become a liquid film. Furthermore, the main point of this embodiment is that a liquid film having a desired uniform thickness is formed by the surface tension of the chemical liquid.

The present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the scope of the invention at the stage of implementation. For example, in each of the above embodiments, the chemical droplet lower nozzle is moved from the inner peripheral portion of the substrate to be processed toward the outer peripheral portion, but the chemical droplet lower nozzle is moved from the outer peripheral portion of the substrate to be processed toward the inner peripheral portion. May be. In this case, the moving pitch of the dripping portion in the radial direction that occurs each time the substrate to be processed makes one round gradually increases. Further, the radial movement pitch d _R generated each time the substrate to be processed makes one round is determined as a value obtained by multiplying the movement pitch d _R0 immediately before by a change rate a ′ larger than 1.

  Further, the above embodiments include inventions at various stages, and various inventions can be extracted by appropriately combining a plurality of disclosed constituent elements. For example, even if some constituent requirements are deleted from all the constituent requirements shown in the embodiment, the problem described in the column of the problem to be solved by the invention can be solved, and the effect described in the column of the effect of the invention Can be obtained as an invention.

1 is a configuration diagram showing a schematic configuration of a film forming apparatus according to a first embodiment. The block diagram which shows schematic structure of the chemical | medical solution supply nozzle which comprises the film-forming apparatus shown in FIG. The top view which shows the nozzle moving direction at the time of chemical | medical solution supply. 9 is a flowchart illustrating a method for obtaining a relationship among a nozzle radial direction position R _n , a chemical solution supply speed v _n , and a substrate rotation number w _n with respect to time according to the second embodiment. 9 is a flowchart illustrating a method for obtaining a relationship among a nozzle radial direction position R _n , a chemical solution supply speed v _n , and a substrate rotation number w _n with respect to time according to the second embodiment. 9 is a flowchart illustrating a method for obtaining a relationship among a nozzle radial direction position R _n , a chemical solution supply speed v _n , and a substrate rotation number w _n with respect to time according to the second embodiment. The figure which shows the nozzle position from a substrate center with respect to process time, a board | substrate rotation speed, and a chemical | medical solution discharge pressure concerning 2nd Embodiment. The figure which shows the nozzle position from the substrate center with respect to process time, a board | substrate rotation speed, and a chemical | medical solution discharge pressure concerning 3rd Embodiment. The figure which shows the locus | trajectory of the chemical | medical solution supply nozzle dripped based on the nozzle position from the substrate center with respect to the process time shown in FIG. 8, a board | substrate rotation speed, and a chemical | medical solution discharge pressure. 9 is a flowchart showing a method for obtaining a relationship among a nozzle radial direction position R _n , a chemical solution supply speed v _n , and a substrate rotation number w _n with respect to a processing time according to the fourth embodiment. The figure which shows the nozzle position from a substrate center with respect to process time, a board | substrate rotation speed, and a chemical | medical solution discharge pressure concerning 4th Embodiment. The figure which shows schematic structure of the coating device concerning 5th Embodiment. The figure which shows schematic structure of the chemical | medical solution interruption | blocking mechanism concerning 5th Embodiment. The figure which shows the example of arrangement | positioning of the gas injection nozzle of the chemical | medical solution partial interruption | blocking mechanism concerning 6th Embodiment. The figure for demonstrating the determination method of the interruption | blocking width by the gas injection from a gas injection nozzle. The figure which shows arrangement | positioning of the gas injection nozzle of the chemical | medical solution partial interruption | blocking mechanism created based on the gas injection nozzle center position of Table 1, and an effective width | variety. The figure which shows schematic structure of the coating device which comprises a chemical | medical solution partial interruption | blocking mechanism. The figure which shows the nozzle position from a substrate center with respect to process time, a board | substrate rotation speed, and a chemical | medical solution discharge pressure concerning 6th Embodiment. The figure which shows the example which has arrange | positioned the gas injection nozzle in the middle of the interruption | blocking unit. The figure which shows the structure of the gas injection nozzle arrange | positioned by the arrangement position shown in Table 2. FIG. The figure which shows schematic structure of the chemical | medical solution partial interruption | blocking mechanism comprised with the scissors arrange | positioned at the upper layer and the lower layer.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 100 ... Substrate to be processed, 101 ... Liquid film, 120 ... Substrate holding part, 121 ... Drive system, 122 ... Chemical supply nozzle, 123 ... Nozzle drive system, 124 ... Chemical supply pipe, 125 ... Chemical supply pump, 126a, 126b ... Chemical solution blocking mechanism, 127... Nozzle drive control unit, 128... Rotation drive control unit, 129.

Claims (38)

While dropping the liquid on the substrate to be processed from the dropping unit, while rotating the substrate to be processed,
The dropping portion is radially directed from the inner peripheral portion of the substrate to be processed to the outer peripheral portion of the substrate so that the moving pitch of the dropping portion in the radial direction that occurs each time the substrate to be processed changes one time. Move
In addition, as the dripping portion moves in the radial direction of the substrate to be processed, the dripped liquid film is not moved by the centrifugal force applied to the dripping portion while gradually reducing the rotation speed of the substrate, A liquid film forming method, wherein a liquid film is formed on the substrate to be processed by adjusting a liquid supply speed. While dropping the liquid on the substrate to be processed from the dropping unit, while rotating the substrate to be processed,
The dropping portion is radially directed from the inner peripheral portion of the substrate to be processed to the outer peripheral portion of the substrate so that the moving pitch of the dropping portion in the radial direction that occurs each time the substrate to be processed changes one time. Move
In addition, as the dripping portion moves in the radial direction of the substrate to be processed, the dripped liquid film is not moved by the centrifugal force applied to the dripping portion while gradually reducing the rotation speed of the substrate, Adjusting the liquid supply rate to form a liquid film on the substrate to be processed;
A method of forming a liquid film, wherein a part of the liquid dropped from the dropping part is collected without being supplied onto the substrate to be processed. The liquid film forming method according to claim 2, wherein a part of the liquid dropped from the dropping part is collected in the vicinity of the center of the substrate to be processed. The vicinity of the center of the substrate to be processed is a region where at least one of the chemical solution discharge speed and the substrate rotation speed is outside the control limit, and when the control is performed in this state, the film thickness of the liquid film becomes thicker than the desired film thickness The method of forming a liquid film according to claim 3. The step of recovering a part of the liquid changes the dropping trajectory of the dropped liquid by injecting a gas onto a side surface of the liquid dropped from the dropping unit and causing the injected gas to collide with the liquid. The liquid film forming method according to claim 2, wherein the liquid film in which the dropping trajectory has been changed is recovered by a chemical recovery unit. 3. The liquid film according to claim 2, wherein when the liquid whose dropping trajectory has been changed is recovered by the liquid recovery unit, the liquid and the mist generated by the collision between the liquid and the gas are sucked. Forming method. While dropping the liquid on the substrate to be processed from the dropping unit and rotating the substrate to be processed, the moving pitch of the dropping unit in the radial direction that occurs each time the substrate to be processed makes one turn changes so as to be small. The dropping portion is moved in the radial direction from the inner peripheral portion of the substrate to be processed toward the outer peripheral portion of the substrate, and the dropped liquid film is moved along with the movement of the dropping portion in the radial direction of the substrate to be processed. Form the liquid film on the substrate to be processed by adjusting the supply speed of the liquid from the dropping part while gradually reducing the rotation speed of the substrate so that it does not move due to the centrifugal force applied to the dropped liquid film And a process of
Forming the solid film including a step of exposing the substrate on which the liquid film is formed to a pressure equal to or lower than a vapor pressure at a processing temperature of the solvent in the liquid film, and drying and removing the solvent to form a solid layer. Method. 8. The method for forming a solid film according to claim 7, wherein the solvent is dried and removed while vibrating the liquid film to form a solid layer having a substantially flat surface. The solid layer is any of an antireflection film used in an exposure process, a photosensitive film, a low dielectric film, an interlayer insulating film, a ferroelectric film, an electrode, a pattern transfer film, a laser light absorption film, and a magnetic film. The method for forming a solid film according to claim 7, wherein A step of setting one end of a moving section of a dropping unit for dropping a chemical solution while moving in a radial direction with respect to a rotating substrate to be processed as a first position;
The number of rotations of the substrate to be processed when the dripping portion is positioned at the outermost diameter of the chemical solution supply region of the substrate to be processed and the locus of the chemical liquid dropped onto the substrate to be processed from the dripping portion to the substrate Determining the chemical supply amount q ₀ per unit length in
Setting the movement pitch so that the movement pitch in the radial direction of the dropping section that occurs each time the substrate to be processed makes one round when the dropping section exists at an arbitrary position;
Determining a chemical supply speed and a substrate rotation speed from the dropping unit at the first position from the first position, the moving pitch of the dropping unit at the first position, and the chemical supply amount q ₀ ; ,
From the rotation angle when the substrate to be processed is rotated for a unit time after the dropping unit is positioned at the first position, and the moving pitch of the dropping unit at the first position, the dropping unit is unit time later. Determining a second position to be located;
Until the second position reaches the other end of the moving section, the second position is reset as a new first position, and the chemical supply speed from the dropping unit and the substrate rotation speed at the first position are reset. Determining the second position where the dropping unit is positioned after a unit time, and determining the relationship between the radial position of the dropping unit with respect to time, the chemical supply speed, and the substrate rotation speed And
Based on the determined relationship, the radial position of the dropping unit, the chemical solution supply speed and the rotation speed of the substrate to be processed are controlled, and a liquid film is formed on the substrate to be processed.
In the region where the chemical supply speed and the substrate rotation speed are out of control limits, the film thickness of the liquid film becomes thicker than desired.
Chemical feed rate at radial position r _c of the outermost immediately before the film thickness increases, performs control so as to be substantially equal to the substrate rotational frequency,
In the radial direction of the gas injection nozzle position r of the dropping unit, 1 / r _c the value obtained by multiplying r in with blocking ratio C represented by a value obtained by dividing 1, blocking the chemical discharged from the drip lower A method for forming a liquid film. The blocking of the chemical solution is performed by a gas injected from a gas injection nozzle disposed between the dropping unit and the substrate to be processed.
Determination of the arrangement position of the gas injection nozzle is
Setting an outer diameter D of the gas injection nozzle and a chemical liquid effective blocking width s in which the chemical liquid is blocked in a radial direction by a gas injected from one gas injection nozzle;
A value obtained by dividing the chemical liquid effective blocking width s by the value obtained by subtracting the reference position p from the intermediate position r _i of the blocking unit width P by dividing the chemical liquid supply starting position or the outermost peripheral position where chemical liquid blocking is performed as the reference position p. Determining an intermediate position r _i such that the cutoff rate C is equal, and determining a cutoff unit width P based on the determined intermediate position r _i ;
The position corresponding to the determined blocking unit width P is set as a new reference position from the chemical solution supply start position to the outermost peripheral position where the chemical solution is shut off, or between the outermost peripheral position where chemical solution is cut off and the chemical solution supply start position. While determining the intermediate position r _i and the blocking unit width P;
11. The liquid film forming method according to claim 10, further comprising a step of determining an arrangement position of the gas injection nozzle based on the determined cutoff unit width P and the intermediate position r _i . 12. The liquid film forming method according to claim 11, wherein the chemical liquid effective cutoff width is adjusted by changing at least one of an inner diameter of the gas injection nozzle and a gas pressure. The method of forming a liquid film according to claim 11, wherein the gas is an inert gas. 12. The liquid film forming apparatus according to claim 11, wherein the position of the gas injection nozzle is finely adjusted according to the application condition of the substrate to be processed. The blocking of the liquid is performed using a plurality of blocking rods arranged between the dropping unit and the substrate to be processed.
Determination of the arrangement position of the barrier rod is
Setting a radial width s of the barrier rod;
A value obtained by dividing the chemical liquid effective blocking width s by the value obtained by subtracting the reference position p from the intermediate position r _i of the blocking unit width P by dividing the chemical liquid supply starting position or the outermost peripheral position where chemical liquid blocking is performed as the reference position p. Determining an intermediate position r _i such that the cutoff rate C is equal, and determining the cutoff unit width P based on the determined intermediate position r _i .
The position corresponding to the determined blocking unit width P is set as a new reference position from the chemical solution supply start position to the outermost peripheral position where the chemical solution is shut off, or between the outermost peripheral position where chemical solution is cut off and the chemical solution supply start position. While determining the intermediate position r _i and the blocking unit width P;
The liquid film forming method according to claim 10, further comprising: determining an arrangement position of the barrier rod based on the determined barrier unit width P and the intermediate position r _i . 16. The liquid film forming method according to claim 15, wherein when the chemical liquid is shut off, a solvent contained in a liquid is caused to flow into the shutoff tank, and the liquid blocked by the shutoff pipe is transported to the liquid waste section together with the solvent. . The barrier rod is provided below the first barrier rod, the first barrier rod having a radial width substantially equal to the width s of the barrier rod, and the radial width is greater than the width of the first barrier rod. Comprising a short second barrier rod,
The chemical solution is blocked by the first blocking rod, the chemical solution overflowing from the first blocking rod is collected by the second blocking rod without overflowing the substrate to be processed, and the collected solution is discarded. The liquid film forming method according to claim 15, wherein the liquid film is transported to a part. 18. The liquid film forming method according to claim 17, wherein a solvent contained in the liquid dropped from the dripping portion is allowed to stand in the first barrier when the chemical is cut off. When the chemical liquid is shut off, the solvent contained in the liquid dripped from the dropping unit is caused to flow into a second soot, and the liquid collected by the second shutting soot together with the solvent is transported to a liquid waste part. The liquid film forming method according to claim 17 or 18. The liquid film forming method according to claim 15, wherein the position of the barrier is finely adjusted according to the application condition of the substrate to be processed. The chemical liquid effective blocking width s is set to a width sufficient for adjacent liquids supplied on the substrate to be processed that are not blocked by the chemical liquid blocking to be connected to each other due to the fluidity of the liquid on the substrate to be processed. 16. The liquid film forming method according to claim 11 or 15, wherein: A step of setting one end of a moving section of a dropping unit for dropping a chemical solution while moving in a radial direction with respect to a rotating substrate to be processed as a first position;
The number of rotations of the substrate to be processed when the dripping portion is positioned at the outermost diameter of the chemical solution supply region of the substrate to be processed and the locus of the chemical liquid dropped onto the substrate to be processed from the dripping portion to the substrate Determining the chemical supply amount q ₀ per unit length in
Setting the movement pitch so that the movement pitch in the radial direction of the dropping section that occurs each time the substrate to be processed makes one round when the dropping section exists at an arbitrary position;
Determining a chemical supply speed and a substrate rotation speed from the dropping unit at the first position from the first position, the moving pitch of the dropping unit at the first position, and the chemical supply amount q ₀ ; ,
From the rotation angle when the substrate to be processed is rotated for a unit time after the dropping unit is positioned at the first position, and the moving pitch of the dropping unit at the first position, the dropping unit is unit time later. Determining a second position to be located;
Until the second position reaches the other end of the moving section, the second position is reset as a new first position, and the chemical supply speed from the dropping unit and the substrate rotation speed at the first position are reset. Determining the second position where the dropping unit is positioned after a unit time, and determining the relationship between the radial position of the dropping unit with respect to time, the chemical supply speed, and the substrate rotation speed And
Based on the determined relationship, the radial position of the dropping part, the chemical solution supply speed and the substrate rotation speed are controlled to form a liquid film on the substrate to be processed,
In addition, the one end of the moving section is either the chemical supply start position or the end position, and the other end of the moving section of the dropping section correspondingly corresponds to the chemical supply end position and the start position. Determining the relationship between the radial position, the chemical solution supply speed and the substrate rotation speed, and controlling the radial position of the dropping unit, the chemical solution supply speed and the substrate rotation speed based on the relationship,
And in the region where the chemical solution supply speed and the substrate rotation speed are outside the control limit and the liquid film becomes thicker than the desired liquid film thickness,
At radial position r _c of the outermost the liquid thickness starts to become thicker, so that substantially equal to the movement pitch of the dropping portion in the radial direction that occurs each time the target substrate is rotated once, to perform the control of the dropping portion A method for forming a liquid film. A substrate to be processed on which a substrate to be processed is mounted and having a rotational drive system;
A columnar processing chamber configured to surround the substrate to be processed;
A dropping unit that continuously discharges liquid to the substrate to be processed;
A dropping unit driving mechanism for moving the dropping unit in the radial direction of the substrate to be processed;
A top plate provided between the dripping unit and the substrate to be processed and provided with a slit through which the chemical solution discharged from the dripping unit passes,
Liquid film formation characterized by comprising a plurality of chemical liquid partial blocking mechanisms disposed between the top plate and the dropping portion and arranged in accordance with the chemical liquid blocking rate in the radial direction of the substrate to be processed. apparatus. A plurality of the chemical liquid partial blocking mechanisms are arranged according to the chemical liquid blocking rate, and a gas injection nozzle that changes the discharge trajectory of the chemical liquid by injecting gas to the discharged liquid;
2. A liquid recovery mechanism that is disposed so as to sandwich the discharged liquid with each of the gas injection nozzles and that sucks and recovers the liquid whose trajectory has been changed by the gas injection nozzles. 24. The liquid film forming apparatus according to 23. Determination of the arrangement position of the gas injection nozzle is
Setting an outer diameter D of the gas injection nozzle and a chemical liquid effective blocking width s in which the chemical liquid is blocked in a radial direction by a gas injected from one gas injection nozzle;
A value obtained by dividing the chemical liquid effective blocking width s by the value obtained by subtracting the reference position p from the intermediate position r _i of the blocking unit width P by dividing the chemical liquid supply starting position or the outermost peripheral position where chemical liquid blocking is performed as the reference position p. Determining an intermediate position r _i such that the cutoff rate C is equal, and determining a cutoff unit width P based on the determined intermediate position r _i ;
The position corresponding to the determined blocking unit width P is set as a new reference position from the chemical solution supply start position to the outermost peripheral position where the chemical solution is shut off, or between the outermost peripheral position where chemical solution is cut off and the chemical solution supply start position. While determining the intermediate position r _i and the blocking unit width P;
Based on the determined cutoff unit width P and intermediate position r _i, liquid film forming apparatus according to claim 24, characterized in that it comprises the step of determining the position of the gas injection nozzle. 25. The liquid film forming apparatus according to claim 24, wherein an outer diameter of each of the gas injection nozzles is the same, and an inner diameter is selected according to a chemical liquid blocking width. The liquid film forming apparatus according to claim 24, wherein the gas injection nozzles are arranged in two stages. The liquid film forming apparatus according to claim 24, further comprising a position adjusting mechanism for finely adjusting a radial position of the gas injection nozzle. 25. The liquid film forming apparatus according to claim 24, wherein the gas injection nozzle includes a valve for intermittently injecting gas by opening and closing. A deformable tube is connected to the upstream side of the gas injection nozzle,
25. The liquid film forming apparatus according to claim 24, wherein the chemical liquid partial blocking mechanism further includes a pressurizing mechanism capable of crushing a part of the deformable tube. 31. The film forming apparatus according to claim 30, wherein the pressurizing mechanism uses a piezo element. 24. The liquid film forming apparatus according to claim 23, wherein the chemical liquid partial blocking mechanism includes a plurality of blocking rods arranged in accordance with a radial chemical blocking rate of the substrate to be processed. The arrangement of the blocking rod according to the radial chemical liquid blocking rate of the substrate to be processed,
Setting a radial width s of the barrier rod;
A value obtained by dividing the chemical liquid effective blocking width s by the value obtained by subtracting the reference position p from the intermediate position r _i of the blocking unit width P by dividing the chemical liquid supply starting position or the outermost peripheral position where chemical liquid blocking is performed as the reference position p. Determining an intermediate position r _i such that the cutoff rate C is equal, and determining a cutoff unit width P based on the determined intermediate position r _i ;
The position corresponding to the determined blocking unit width P is set as a new reference position from the chemical solution supply start position to the outermost peripheral position where the chemical solution is shut off, or between the outermost peripheral position where chemical solution is cut off and the chemical solution supply start position. While determining the intermediate position r _i and the blocking unit width P;
Based on the determined cutoff unit width P and intermediate position r _i, liquid film forming apparatus according to claim 32, wherein the comprising the step of determining the position of the cut-off trough. 33. The liquid film forming apparatus according to claim 32, wherein a chemical solution recovery unit is disposed downstream of the chemical solution flowing in the blocking cage. 33. The liquid film forming apparatus according to claim 32, further comprising a solvent supply mechanism that allows the solvent contained in the chemical liquid to flow into the blocking cage while the chemical solution is blocked in the blocking basket. The barrier rod is provided below the first barrier rod with a first barrier rod having a radial width substantially equal to the width s of the barrier rod, and the radial width is greater than the width of the first barrier rod. 33. The liquid film forming apparatus according to claim 32, comprising a short second barrier rod. 33. The liquid film forming apparatus according to claim 32, further comprising a position adjusting mechanism that adjusts a position of the blocking bar based on information on blocking the chemical liquid with respect to the substrate to be processed. A method for manufacturing a semiconductor device, comprising: forming a solid film on a semiconductor substrate using the method for forming a solid film according to claim 12.

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