WO2012008310A1

WO2012008310A1 - Developer liquid for photoresist and developing apparatus

Info

Publication number: WO2012008310A1
Application number: PCT/JP2011/065031
Authority: WO
Inventors: 真二小林; 信博高橋
Original assignee: 東京エレクトロン株式会社
Priority date: 2010-07-16
Filing date: 2011-06-30
Publication date: 2012-01-19
Also published as: JP2012022244A; TW201224682A

Abstract

Disclosed is a developing apparatus wherein a developer liquid supply block for supplying a developer liquid to a developer liquid nozzle is connected to the developer liquid nozzle. The developer liquid supply block comprises a developer liquid concentrate supply source that holds a developer liquid concentrate inside, an organic solvent supply source that holds an organic solvent inside, and a developer liquid supply source that produces a developer liquid by mixing the developer liquid concentrate and the organic solvent. As the organic solvent, one that is soluble in the developer liquid concentrate but is not neutralized with the developer liquid concentrate is used. The developer liquid is produced by mixing the developer liquid concentrate and the organic solvent so that the concentration of the organic solvent with respect to the developer liquid concentrate is 5% by mass or less.

Description

Photoresist developer and development processing apparatus

The present invention relates to a photoresist developer for developing a resist film on a substrate and a development processing apparatus using the photoresist developer.

For example, in a photolithography process in a semiconductor device manufacturing process, for example, a resist coating process is performed on a semiconductor wafer (hereinafter referred to as “wafer”) to form a resist film, and a predetermined pattern is exposed on the resist film. An exposure process, a development process for developing the exposed resist film, and the like are sequentially performed to form a predetermined resist pattern on the wafer.

When forming the above-described resist pattern, the resist pattern is required to be miniaturized in order to further increase the integration of the semiconductor device. Further, in order to form such a fine resist pattern with high dimensional accuracy, it is required to develop the resist film with higher accuracy in the development processing described above.

Therefore, for example, it has been proposed to develop a resist film using a developing solution and then perform a post-treatment with a quaternary ammonium hydroxide aqueous solution and a mixture of the aqueous solution and a compatible organic solvent (Patent Document 1). In such a case, in post-processing, the resist residue adhering to the boundary between the resist pattern end portion and the wafer after the development processing is removed to improve the dimensional accuracy of the resist pattern.

Japanese Patent Publication No. 6-38161

By the way, in the development process, the outside of the resist pattern is swollen by the developer, and a swollen layer is formed. When the swelling amount reaches a predetermined amount, the swelling layer dissolves and the resist film is developed.

However, since the dimensions of the desired resist pattern are fine, the developer may enter the resist film between the formation of the swelling layer and dissolution. In such a case, when the method of Patent Document 1 is used, post-processing is performed with the mixture in a state in which the developer enters the resist film in the development processing. Then, in the post-processing, the resist film may be further dissolved, and the shape of the resist pattern may not be a desired shape.

The present invention has been made in view of such a point, and an object thereof is to develop a resist film on a substrate with high accuracy and to improve the dimensional accuracy of a resist pattern formed on the resist film.

In order to achieve the above object, the present invention provides a photoresist developer for developing a resist film on a substrate, which is soluble in the developer stock solution of the resist film and does not neutralize with the developer stock solution. Has an organic solvent.

According to the present invention, when a photoresist developer (hereinafter sometimes simply referred to as “developer”) is supplied to the resist film on the substrate, the outside of the resist film where the resist pattern is formed is developed. The swelling layer is formed by swelling with the liquid. The outside of the swelling layer is dissolved by the organic solvent in the developer. Therefore, development of the resist film proceeds while maintaining the state where the swelling layer is thin. In other words, conventionally, the swelling layer could not be dissolved unless the swelling amount was a predetermined amount, but according to the present invention, this swelling layer that could not be dissolved conventionally can be dissolved. And since the thickness of a swelling layer can be made thinner than before, the resist film can be dissolved faster than before and the development speed of the resist film can be increased. That is, the sensitivity of the resist film can be improved. Then, the developer does not enter the resist film as in the conventional case. Therefore, the resist film can be developed with high accuracy, and the dimensional accuracy of the resist pattern formed on the resist film can be improved.

The resist film may be an EUV resist film. Note that the EUV resist refers to a resist used in so-called EUV lithography that performs an exposure process using EUV (Extreme Ultra Violet) that is extreme ultraviolet light having a wavelength of 13 nm to 14 nm, for example.

Here, in recent years, in response to demands for miniaturization of resist patterns, conventionally used exposure light sources for exposure processing include KrF laser (wavelength 248 nm), ArF laser (wavelength 193 nm), and F2 laser (wavelength 157 nm). The use of a light source that outputs the EUV having a shorter wavelength is being studied.

However, EUV resists have low sensitivity and a slow dissolution rate with a developer. Moreover, the line width of the resist pattern formed by performing EUV lithography is extremely fine, for example, 20 nm. For this reason, when developing an EUV resist film, the developer easily enters the EUV resist film between the formation of the swelling layer and dissolution, and it is difficult to form the resist pattern in a desired shape. .

Therefore, it is conceivable to add an acid generator (PAG; Photo Acid Generator) to the EUV resist to improve the sensitivity of the EUV resist. However, at present, the addition amount of the acid generator in the EUV resist is almost the limit, and no further improvement in sensitivity of the EUV resist can be expected.

It is also conceivable to increase the exposure amount of the EUV light source in the exposure process to increase the development speed. However, the exposure amount of the EUV light source used in EUV lithography is significantly lower than the exposure amount of the conventional exposure light source, and it is technically difficult to increase the exposure amount of the EUV light source at present.

In this respect, according to the present invention, as described above, the thickness of the swelling layer of the resist film for EUV can be reduced and the development speed of the resist film for EUV can be increased, so that the developer enters the resist film for EUV. There is nothing to do. Therefore, the EUV resist film can be developed with high accuracy, and the dimensional accuracy of the resist pattern formed on the EUV resist film can be improved.

The concentration of the organic solvent with respect to the developing stock solution may be set based on the developing speed of the resist film and the cross-sectional shape of the resist pattern formed on the resist film after development. In such a case, the concentration of the organic solvent with respect to the developing stock solution may be 5% by mass or less.

Another aspect of the present invention is a development processing apparatus for developing a resist film on a substrate using a photoresist developer, wherein the photoresist developer is soluble in a developing solution for the resist film. And a developing solution that has an organic solvent that does not neutralize with the developing solution, the developing processing apparatus supplying a developing solution for photoresist onto a substrate, and a developing solution that stores the developing solution therein. A mixture of a supply source, an organic solvent supply source storing the organic solvent therein, the developing solution supplied from the developing solution supply source, and the organic solvent supplied from the organic solvent supply source; A developer supply source for generating a resist developer and supplying the photoresist developer to the developer nozzle.

According to the present invention, the resist film on the substrate can be developed with high accuracy, and the dimensional accuracy of the resist pattern formed on the resist film can be improved.

It is a top view which shows the outline of a structure of the coating development processing system provided with the developing processing apparatus concerning this Embodiment. It is a front view of the coating and developing treatment system according to the present embodiment. It is a rear view of the coating and developing treatment system according to the present embodiment. It is a longitudinal cross-sectional view which shows the outline of a structure of a development processing apparatus. It is a cross-sectional view which shows the outline of a structure of a development processing apparatus. It is explanatory drawing which shows the outline of a structure of a developing solution supply block. It is explanatory drawing which shows a mode that a resist pattern is formed in the resist film for EUV with the developing solution of this Embodiment. It is explanatory drawing which shows a mode that a resist pattern is formed in the resist film for EUV with the conventional developing solution. It is a graph which shows the relationship between the line width of a resist pattern, and exposure amount.

Hereinafter, embodiments of the present invention will be described. FIG. 1 is a plan view showing an outline of a configuration of a coating and developing treatment system 1 including a developing treatment apparatus according to the present embodiment. FIG. 2 is a front view of the coating and developing treatment system 1, and FIG. 3 is a rear view of the coating and developing treatment system 1. In the present embodiment, the coating and developing processing system 1 performs so-called EUV lithography processing that performs exposure processing using EUV.

As shown in FIG. 1, the coating and developing treatment system 1 is a cassette that carries, for example, 25 wafers W from the outside to the coating and developing treatment system 1 in a cassette unit, and carries a wafer W into and out of the cassette C. A station 2, a processing station 3 in which a plurality of various processing apparatuses for performing predetermined processing in a single wafer type in a photolithography process are arranged in multiple stages, and an exposure apparatus provided adjacent to the processing station 3 4 and the interface station 5 that transfers the wafer W to and from the unit 4. The exposure apparatus 4 has a light source (not shown) that outputs EUV (wavelength 13 nm to 14 nm).

The cassette station 2 is provided with a cassette mounting table 6. The cassette mounting table 6 can mount a plurality of cassettes C in a row in the X direction (vertical direction in FIG. 1). The cassette station 2 is provided with a wafer transfer body 8 that can move in the X direction on the transfer path 7. The wafer carrier 8 is also movable in the wafer arrangement direction (Z direction; vertical direction) of the wafers W accommodated in the cassette C, and is selective to the wafers W in each cassette C arranged in the X direction. Can be accessed.

The wafer carrier 8 is rotatable in the θ direction around the Z axis, and a temperature control device 60 belonging to a third processing device group G3 on the processing station 3 side described later, and a transition device 61 for delivering the wafer W. Can also be accessed.

The processing station 3 adjacent to the cassette station 2 includes, for example, five processing device groups G1 to G5 in which a plurality of processing devices are arranged in multiple stages. A first processing device group G1 and a second processing device group G2 are sequentially arranged from the cassette station 2 side on the X direction negative direction (downward direction in FIG. 1) side of the processing station 3. A third processing device group G3, a fourth processing device group G4, and a fifth processing device group G5 are sequentially arranged from the cassette station 2 side on the X direction positive direction (upward direction in FIG. 1) side of the processing station 3. Has been placed. A first transfer device A1 is provided between the third processing device group G3 and the fourth processing device group G4, and the wafer W is supported and transferred inside the first transfer device A1. A first transfer arm 10 is provided. The first transfer arm 10 can selectively access each processing apparatus in the first processing apparatus group G1, the third processing apparatus group G3, and the fourth processing apparatus group G4 to transfer the wafer W. A second transfer device A2 is provided between the fourth processing device group G4 and the fifth processing device group G5, and the wafer W is supported and transferred inside the second transfer device A2. A second transfer arm 11 is provided. The second transfer arm 11 can selectively access each processing apparatus in the second processing apparatus group G2, the fourth processing apparatus group G4, and the fifth processing apparatus group G5 to transfer the wafer W.

As shown in FIG. 2, the first processing unit group G1 includes a liquid processing apparatus that supplies a predetermined liquid to the wafer W and performs processing, for example, a resist coating apparatus 20 that applies a resist solution for EUV to the wafer W, 21 and 22 and

bottom coating devices

23 and 24 for forming an antireflection film for preventing reflection of light during the exposure process are stacked in five stages in order from the bottom. In the second processing unit group G2, liquid processing units, for example, development processing units 30 to 34 for supplying a developing solution for photoresist to the wafer W and performing development processing are stacked in five stages in order from the bottom. In addition,

chemical chambers

40 and 41 for supplying various processing liquids to the liquid processing apparatuses in the processing apparatus groups G1 and G2 are provided at the bottom of the first processing apparatus group G1 and the second processing apparatus group G2. Each is provided.

As shown in FIG. 3, the third processing unit group G3 includes a temperature control unit 60, a transition unit 61, high-precision

temperature control units

62 and 63 that control the temperature of the wafer W under high-precision temperature control, and the wafer W. High temperature heat treatment apparatuses 64 to 67 for heat treatment at a high temperature are stacked in eight stages in order from the bottom.

In the fourth processing unit group G4, pre-baking devices 70 to 73 for heat-treating the wafer W after the resist coating treatment and post-baking devices 74 to 77 for heat-processing the wafer W after the development processing are arranged in eight stages in order from the bottom. It is superimposed on.

In the fifth processing apparatus group G5, a plurality of heat treatment apparatuses for heat-treating the wafer W, for example, high-precision temperature control apparatuses 80 to 82 and post-exposure baking apparatuses 83 to 87 are stacked in eight stages in order from the bottom.

As shown in FIG. 1, a plurality of processing apparatuses are arranged on the positive side in the X direction of the first transfer apparatus A1, and a hydrophobic processing apparatus for hydrophobizing the wafer W as shown in FIG. 90, 91 and

heating devices

92, 93 for heating the wafer W are stacked in four stages in order from the bottom. As shown in FIG. 1, a peripheral exposure device 94 that selectively exposes only the edge portion of the wafer W, for example, is disposed on the positive side in the X direction of the second transfer device A2.

The interface station 5 is provided with a wafer transfer body 101 that moves on a transfer path 100 extending in the X direction and a buffer cassette 102 as shown in FIG. The wafer transfer body 101 can move in the Z direction and can also rotate in the θ direction, and accesses the exposure apparatus 4 adjacent to the interface station 5, the buffer cassette 102, and the fifth processing apparatus group G5. The wafer W can be transferred.

Next, the configuration of the development processing apparatuses 30 to 34 described above will be described. As shown in FIG. 4, the development processing apparatus 30 has a processing container 110 in which a loading / unloading port (not shown) for the wafer W is formed on a side surface.

A spin chuck 120 that holds and rotates the wafer W is provided at the center in the processing container 110. The spin chuck 120 has a horizontal upper surface, and a suction port (not shown) for sucking the wafer W, for example, is provided on the upper surface. By suction from the suction port, the wafer W can be sucked and held on the spin chuck 120.

The spin chuck 120 includes a chuck driving unit 121 including, for example, a motor, and can be rotated at a predetermined speed by the chuck driving unit 121. Further, the chuck driving unit 121 is provided with an elevating drive source such as a cylinder, and the spin chuck 120 is movable up and down.

Around the spin chuck 120, there is provided a cup 122 that receives and collects the liquid scattered or dropped from the wafer W. The cup 122 has an opening larger than the wafer W so that the spin chuck 120 can be moved up and down on the upper surface. A lower surface of the cup 122 is connected to a discharge pipe 123 that discharges the collected liquid and an exhaust pipe 124 that exhausts the atmosphere in the cup 122.

As shown in FIG. 5, a rail 130 extending along the Y direction (left and right direction in FIG. 5) is formed on the negative side of the cup 122 in the X direction (downward direction in FIG. 5). The rail 130 is formed, for example, from the outer side of the cup 122 on the Y direction negative direction (left direction in FIG. 5) to the outer side on the Y direction positive direction (right direction in FIG. 5). For example, two

arms

131 and 132 are attached to the rail 130.

The first arm 131 supports a developer nozzle 133 for supplying a developer as shown in FIGS. The first arm 131 is movable on the rail 130 by a nozzle driving unit 134 shown in FIG. As a result, the developer nozzle 133 can move from the standby unit 135 installed outside the cup 122 on the positive side in the Y direction to above the center of the wafer W in the cup 122, and further on the surface of the wafer W. It can move in the radial direction of the wafer W. The first arm 131 can be moved up and down by a nozzle driving unit 134 and the height of the developer nozzle 133 can be adjusted.

As shown in FIG. 4, a developer supply pipe 137 communicating with the developer supply block 136 is connected to the developer nozzle 133. The detailed configuration of the developer supply block 136 will be described later.

The second arm 132 supports a cleaning liquid nozzle 140 for supplying a cleaning liquid, for example, pure water. The second arm 132 is movable on the rail 130 by the nozzle driving unit 141 shown in FIG. 5, and the cleaning liquid nozzle 140 is moved from the standby unit 142 provided on the outer side of the negative side of the cup 122 in the Y direction to the cup. It can be moved to above the center of the wafer W in 122. Further, the second arm 132 can be moved up and down by the nozzle driving unit 141, and the height of the cleaning liquid nozzle 140 can be adjusted. In the present embodiment, pure water is used as the cleaning liquid for performing the cleaning process on the wafer W, but other cleaning liquid may be used.

The cleaning liquid nozzle 140 is connected to a cleaning liquid supply pipe 144 communicating with the cleaning liquid supply source 143 as shown in FIG. A cleaning liquid is stored in the cleaning liquid supply source 143. The cleaning liquid supply pipe 144 is provided with a supply device group 145 including a valve for controlling the flow of the cleaning liquid, a flow rate adjusting unit, and the like. In the above configuration, the developer nozzle 133 that supplies the developer and the cleaning nozzle 140 that supplies the cleaning liquid are supported by separate arms, but are supported by the same arm, and development is controlled by controlling the movement of the arms. The movement and supply timing of the liquid nozzle 133 and the cleaning liquid nozzle 140 may be controlled.

Next, the configuration of the developer supply block 136 described above will be described. As shown in FIG. 6, the developer supply block 136 includes a developer supply source 150 that stores the developer solution therein. As the developing stock solution, for example, an alkaline TMAH developing stock solution (tetramethylammonium hydroxide developing stock solution) or a TBAH developing stock solution (tetrabutylammonium hydroxide developing stock solution) is used.

An air supply pipe 151 for supplying air, for example, an inert gas, to the developing solution supply source 150 is connected to the upper portion of the developing solution supply source 150. The air supply pipe 151 communicates with an air supply source 152 that stores air therein. Further, the air supply pipe 151 is provided with a supply device group 153 including a valve for controlling the flow of air, a flow rate adjusting unit, and the like. Then, air is supplied from the air supply source 152 into the developing stock solution supply source 150, the pressure in the developing stock solution supply source 150 is maintained at a predetermined pressure, and the developing stock solution in the developing stock solution supply source 150 is developed as described later. The undiluted solution supply pipe 154 is supplied.

Further, a developing solution supply pipe 154 for supplying a developing solution to a developing solution supply source 170 described later is connected to the upper portion of the developing solution supply source 150. The developing solution supply pipe 154 is provided with a supply device group 155 including a valve for controlling the flow of the developing solution, a flow rate adjusting unit, and the like.

The developer supply block 136 has an organic solvent supply source 160 for storing the organic solvent therein. As the organic solvent, for example, an organic solvent that is soluble in the developing stock solution and does not neutralize with the developing stock solution is used. Specifically, for example, isopropyl alcohol (IPA), acetone, γ-butyrolactone (GBL), N-methylpyrrolidinone (NMP), ethanol, tetrahydrofuran (THF), pyridine and the like are used. In addition, an ester compound such as ethyl lactate (EL) cannot be used for the organic solvent.

The upper part of the organic solvent supply source 160 is connected with an air supply pipe 161 for supplying air, for example, an inert gas, into the organic solvent supply source 160. The air supply pipe 161 communicates with an air supply source 162 that stores air therein. The air supply pipe 161 is provided with a supply device group 163 including a valve for controlling the flow of air, a flow rate adjusting unit, and the like. Then, air is supplied from the air supply source 162 into the organic solvent supply source 160, the pressure in the organic solvent supply source 160 is maintained at a predetermined pressure, and the organic solvent in the organic solvent supply source 160 is an organic material described later. The solvent is supplied to the solvent supply pipe 164.

Further, an organic solvent supply pipe 164 for supplying an organic solvent to a developer supply source 170 described later is connected to the upper part of the organic solvent supply source 160. The organic solvent supply pipe 164 is provided with a supply device group 165 including a valve for controlling the flow of the organic solvent, a flow rate adjusting unit, and the like.

Further, the developer supply block 136 has a developer supply source 170 that generates a developing stock solution therein. The developing solution supply source 170 is connected to the developing solution supply pipe 154 that communicates with the developing solution supply source 150 and the organic solvent supply pipe 164 that communicates with the organic solvent supply source 160. Then, a developing solution is supplied from the developing solution supply source 150 to the developing solution supply source 170 and an organic solvent is supplied from the organic solvent supply source 160. Thereafter, the developer stock solution and the organic solvent are mixed in the developer supply source 170 to generate a developer. That is, the developer supply source 170 functions as a mixer. The developer supply source 170 is connected to a developer supply pipe 137 communicating with the developer nozzle 133 described above. Then, the developer is supplied from the developer supply source 170 to the developer nozzle 133.

The configuration of the development processing apparatuses 31 to 34 is the same as the configuration of the development processing apparatus 30 described above, and a description thereof will be omitted.

In the coating and developing treatment system 1 described above, a control unit 200 is provided as shown in FIG. The control unit 200 is a computer, for example, and has a program storage unit (not shown). The program storage unit stores a program for executing development processing of the wafer W in the development processing apparatuses 30 to 34. In addition to this, the program storage unit controls the transfer of the wafer W between the cassette station 2, the processing station 3, the exposure apparatus 4, and the interface station 5, the operation of the drive system in the processing station 3, and the like. A program for executing wafer processing in the development processing system 1 is stored. This program is recorded on a computer-readable storage medium H such as a computer-readable hard disk (HD), flexible disk (FD), compact disk (CD), magnetic optical desk (MO), or memory card. May have been installed in the control unit 200 from the storage medium H.

The coating and developing treatment system 1 according to the present embodiment is configured as described above. Next, wafer processing performed in the coating and developing processing system 1 will be described.

First, when the cassette C containing a plurality of unprocessed wafers W is placed on the cassette mounting table 6, the wafers W in the cassette C are taken out one by one by the wafer carrier 8, and the third process is performed. It is conveyed to the temperature control device 60 of the device group G3. The wafer W transferred to the temperature adjusting device 60 is adjusted to a predetermined temperature. Thereafter, the wafer W is transferred to the bottom coating device 23 by the first transfer device A1, and an antireflection film is formed on the wafer W. The wafer W on which the antireflection film is formed is sequentially transferred by the first transfer device A1 to the heating device 92, the high-precision temperature adjusting device 62, and the hydrophobization processing device 90, and is subjected to predetermined processing in each device. Thereafter, the wafer W is transferred to the resist coating apparatus 20 by the first transfer apparatus A1. In the resist coating apparatus 20, a resist solution for EUV is applied on the wafer W, and an EUV resist film is formed on the wafer W.

The wafer W on which the EUV resist film is formed is transported to the pre-baking device 70 by the first transport device A1, and pre-baked. Subsequently, the wafer is sequentially transported to the peripheral exposure device 94 and the high-precision temperature control device 82 by the second transport device A2, and predetermined processing is performed in each device. Thereafter, the wafer W is transferred to the exposure apparatus 4 by the wafer transfer body 101 of the interface station 5. In the exposure apparatus 4, the EUV resist film on the wafer W is irradiated with EUV, and a predetermined pattern is selectively exposed to the EUV resist film.

The wafer W that has been subjected to the exposure processing is transferred to the post-exposure baking apparatus 83 by the wafer transfer body 101, and post-exposure baking is performed. Thereafter, the wafer W is transferred to the high-accuracy temperature adjusting device 81 by the second transfer device A2, and the temperature is adjusted.

Thereafter, the wafer W is transferred to the development processing apparatus 30 by the second transfer apparatus A2. In the development processing apparatus 30, a developer is supplied to the EUV resist film on the wafer W, and the EUV resist film is developed. The development processing of the wafer W in the development processing apparatus 30 will be described later.

When the EUV resist film on the wafer W is developed in the development processing apparatus 30, the wafer W is transferred to the post-baking apparatus 74 by the second transfer apparatus A2, and after the post-baking process is performed, the first W The temperature is adjusted by being conveyed to the high-precision temperature adjusting device 63 by the conveying device A1. Then, the wafer W is transferred to the transition device 61 by the first transfer device A1, and returned to the cassette C by the wafer transfer body 8 to complete a series of photolithography steps.

Next, a series of development processes for developing the EUV resist film on the wafer W in the above-described development processing apparatus 30 will be described.

The wafer W carried into the development processing apparatus 30 is first sucked and held by the spin chuck 120. Subsequently, the first arm 131 moves the developer nozzle 133 of the standby unit 135 to above the outer peripheral portion of the wafer W.

Next, the chuck driving unit 121 is controlled to rotate the wafer W at a predetermined rotational speed by the spin chuck 120. Subsequently, the developing solution is supplied from the developing solution supply block 136 to the developing solution nozzle 133, and the developing solution is applied from the developing solution nozzle 133 to the outer peripheral portion of the wafer W.

At this time, in the developer supply block 136, a predetermined amount of the developer stock adjusted by the supply device group 155 is supplied from the developer stock supply 150 to the developer supply 170. A predetermined amount of the organic solvent adjusted by the supply device group 165 is supplied from the organic solvent supply source 160 to the developer supply source 170. The organic solvent is supplied so that the concentration with respect to the developing stock solution is, for example, 5% by mass or less. Then, in the developer supply source 170, the developing stock solution and the organic solvent are mixed to generate a developer. The generated developer is supplied from the developer supply source 170 to the developer nozzle 133.

Thereafter, the developer nozzle 133 supplies the developer to the EUV resist film on the wafer W while moving to the center of the wafer W. Then, the belt-like developer supplied from the developer nozzle 133 is supplied onto the wafer W in a spiral shape. Then, the developer uniformly diffuses over the wafer W, and the entire surface of the wafer W is covered with the developer. As a result, the EUV resist film on the wafer W is developed, the exposed portion of the EUV resist film is dissolved, and a resist pattern is formed on the wafer W.

Here, development of the resist film for EUV will be described in detail with reference to FIG. In FIG. 7, the diagonally downward slanting line portion shows the resist layer R that is a region not swollen by the developer in the EUV resist film on the wafer W. Moreover, the upward slanting hatched portion indicates the swollen layer S that is a region swollen by the developer in the EUV resist film. A dotted line portion indicates a desired resist pattern P to be finally formed.

When the developing solution is supplied onto the EUV resist film, the outside of the EUV resist film is swollen by the developing solution as shown in FIG. At this time, the developing solution as in the prior art is composed of only the undiluted developer solution, when the organic solvent as in the present embodiment is not mixed, the thickness of the swollen layer S _P, as shown in FIG. 8 is thicker. That is, conventionally, when the swelling amount of the developing solution does not become a predetermined amount, it was not possible to dissolve the swollen layer S _P. For this reason, the developer may enter the resist layer R of the resist film for EUV after the swelling layer _SP is formed and dissolved, and the shape of the resist pattern may not be a desired shape. there were. In contrast, in the case of using the developer of this embodiment, the organic solvent in the developer because of dissolving the outside of the swelling layer S _P, the thickness of the swollen layer S as shown in FIG. 7 become thinner . That is, in the present embodiment, development of the resist film for EUV proceeds while the swelling layer S is kept thin. Therefore, it is possible to dissolve the EUV resist film faster than before, and to increase the development speed of the EUV resist film. That is, the sensitivity of the resist film for EUV can be improved. If it does so, a developing solution will not enter into the resist layer R like the past. Therefore, the EUV resist film can be developed with high accuracy, and a desired resist pattern P can be formed on the EUV resist film.

In order to form the desired resist pattern P on the EUV resist film in this way, the concentration of the organic solvent with respect to the developing stock solution was set to 5% by mass or less as described above. The concentration of the organic solvent is set based on the developing speed of the EUV resist film and the cross-sectional shape of the resist pattern formed on the EUV resist film after development. That is, the concentration of the organic solvent, the organic solvent dissolves the outer swelling layer S _P at an appropriate speed, to properly maintain the development rate of the EUV resist film, so that the developer does not enter into the resist layer R Set to In addition, the concentration of the organic solvent is set so that the resist pattern is not deformed by the organic solvent and an appropriate cross-sectional shape, for example, a rectangular cross-sectional shape is maintained. And when the inventors investigated, it turned out that 5 mass% or less is suitable for the density | concentration of the organic solvent which satisfy | fills such conditions.

Further, in order to form a desired resist pattern P on the EUV resist film in this way, as described above, an organic solvent that is soluble in the developing stock solution and does not neutralize with the developing stock solution is used. For example, when an organic solvent insoluble in the developing stock solution is used, the organic solvent directly dissolves the EUV resist, and the resist pattern itself cannot be formed. Therefore, it is necessary to use an organic solvent soluble in the developing stock solution. In addition, when an organic solvent that neutralizes with the developing stock solution, for example, an ester compound such as ethyl lactate (EL) described above that saponifies with the developing stock solution, the ethyl lactate is hydrolyzed by the alkali of the developing stock solution, and lactic acid And is broken down into ethanol. Since this lactic acid neutralizes the alkali, the developing ability of the alkaline developer is reduced, and the developing speed of the resist film for EUV is lowered. Thus, since the sensitivity of the resist film for EUV cannot be improved, the desired resist pattern P cannot be formed. Accordingly, it is necessary to use an organic solvent that does not neutralize with the developing solution.

Furthermore, as the developing stock solution, as described above, a TMAH developing stock solution, a TBAH developing stock solution, or the like is used, but a TBAH developing stock solution is more preferable. Since the molecular size of TBAH is larger than that of TMAH, the thickness of the swelling layer S can be reduced by using the TBAH developing stock solution. Further, since the TBAH molecular size is large, the TBAH developing stock solution is difficult to enter the resist layer R. Therefore, the dimensional accuracy of the resist pattern formed on the EUV resist film can be further improved.

When the EUV resist film on the wafer W is developed as described above, the first arm 131 moves the developer nozzle 133 from the upper center of the wafer W to the standby unit 135. At the same time, the cleaning liquid nozzle 140 of the standby unit 142 moves to above the center of the wafer W by the second arm 132. Thereafter, the wafer W is rotated, and the cleaning liquid is supplied from the cleaning liquid nozzle 140 to the center of the wafer W, whereby the wafer W is cleaned.

When performing a cleaning process of such wafer W, because the small thickness of the swollen layer S, developing solution remaining as compared to the conventional thick swelling layer S _P is a small amount. For this reason, the time required for the cleaning process can be reduced as compared with the conventional case. When the inventors examined, for example, when the thickness of the swollen layer S is 1/2 of the thickness of conventional swelling layer S _P, the time required for the cleaning process was found to be reduced to about 1/4 of the conventional.

After the cleaning process of the wafer W, the supply of the cleaning liquid from the cleaning liquid nozzle 140 is stopped, and the wafer W is rotated at an accelerated speed to dry and remove the cleaning liquid on the wafer W. Thus, a series of development processing of the wafer W is completed.

According to the above embodiment, the developer used for the development processing of the wafer W has the organic solvent that is soluble in the developing stock solution and does not neutralize with the developing stock solution. The organic solvent dissolves the outer swelling layer S _P, can reduce the thickness of the swollen layer S. That is, development of the resist film for EUV can be advanced while maintaining the state where the swelling layer S is thin. For this reason, the developing speed of the resist film for EUV can be made faster than before, and the sensitivity of the resist film for EUV can be improved. Then, the developer does not enter the resist layer R as in the conventional case. Therefore, the EUV resist film can be developed with high accuracy, and the dimensional accuracy of the resist pattern formed on the EUV resist film can be improved.

In the present embodiment, the concentration of the organic solvent with respect to the developing stock solution is set based on the developing speed of the resist film for EUV and the cross-sectional shape of the resist pattern formed on the resist film for EUV after development. It is as follows. In such a case, the organic solvent dissolves the outer swelling layer S _P at an appropriate speed, to properly maintain the development rate of the EUV resist film, it is possible to prevent the developer from entering the resist layer R . Further, the resist pattern is not deformed by the organic solvent, and an appropriate cross-sectional shape, for example, a rectangular cross-sectional shape can be maintained. Therefore, a desired resist pattern can be formed on the EUV resist film.

As described above, when developing the wafer W using the developer of the present embodiment, the sensitivity of the EUV resist film can be improved. As a result, the exposure amount of the EUV light source can be reduced in the exposure process performed before the development process. Therefore, it is possible to shorten the exposure time and improve the wafer processing throughput. For example, when the sensitivity of the resist film for EUV is improved by about 10%, the exposure amount can be reduced by about 10% and the exposure time can be shortened by about 10%. Then, the throughput of wafer processing can be improved by about 10%.

Here, the inventors verified the effect of reducing the exposure amount described above. In this verification, the resist film was exposed using an exposure light source that outputs a KrF laser, and the resist film was developed using three types of developers. As a specific developing solution, a conventional developing solution containing only 2.38% by mass of TMAH developing stock solution (hereinafter referred to as “conventional developing solution”) and 5% by mass with respect to 2.38% by mass of TMAH developing stock solution. % Isopropyl alcohol (IPA) mixed with the developer according to this embodiment (hereinafter referred to as “IPA-containing developer”) and 2.38% by mass of TMAH developing stock solution with 3% by mass of ethyl lactate A developer mixed with (EL) (hereinafter referred to as “EL-containing developer”) was used. And it verified by making target line width of the resist pattern after image development into 120 nm.

This verification result is shown in FIG. The vertical axis in FIG. 9 indicates the line width of the resist pattern, and the horizontal axis indicates the exposure amount. In FIG. 9, “Reference” is a graph when a conventional developer is used, “IPA 5%” is a graph when an IPA-containing developer is used, and “EL 3%” is an EL-containing developer. It is a graph at the time of using. In this verification, the target line width of the resist pattern was set to 120 nm by performing KrF exposure. However, even when the target line width of the resist pattern is reduced to, for example, 20 nm by performing EUV exposure, the tendency shown in FIG. This has been confirmed by the inventors.

Referring to FIG. 9, when a conventional developer is used, the exposure amount necessary for setting the resist pattern to the target line width of 120 nm is about 22 mJ / m ² . On the other hand, when the IPA-containing developer according to the present embodiment was used, the exposure amount necessary for setting the resist pattern to the target line width of 120 nm was about 19.5 mJ / m ² . Therefore, it has been found that the use of the developer of the present embodiment makes it possible to form a resist pattern having a desired dimension while reducing the exposure amount by about 11%.

In addition, when the IPA containing developer concerning this Embodiment is used in this way, it has also been confirmed that the LWR (Line Width Roughness) of a resist pattern does not deteriorate.

Further, when the EL-containing developer was used, the resist pattern could not be formed with a target line width of 120 nm. The reason for this is as described above, because the developing ability of the alkaline developer is reduced by lactic acid hydrolyzed from ethyl lactate.

According to the above embodiment, it is possible to reduce the thickness of the swollen layer S, as described above, the developing solution remaining after the development is a small amount compared with the conventional thick swelling layer S _P. For this reason, the time required for the cleaning process can be reduced as compared with the conventional case.

Further, according to the above embodiment, since the organic solvent is mixed in the developing stock solution, the surface tension of the developing solution is reduced. Here, when the surface tension acts on the resist pattern, the resist pattern tilts and falls, so-called pattern collapse may occur. In this embodiment, since the surface tension of the developer is reduced, the occurrence of such pattern collapse can be suppressed.

Further, according to the above embodiment, the developer supply block 136 includes a developer solution supply source 150 that stores the developer solution, an organic solvent supply source 160 that stores the organic solvent, and a mixture of the developer solution and the organic solvent. Since the developer supply sources 170 for generating the developer are provided, the concentration of the organic solvent relative to the developing solution can be freely set according to the target dimension of the resist pattern formed on the wafer W. Therefore, the dimensional accuracy of the resist pattern can be further improved. Further, immediately before the developer is supplied from the developer supply block 136 to the developer nozzle 133, the developer can be generated in the developer supply source 170, so that the developer mixed with the organic solvent is stored in advance. Compared to the case, the deterioration of the developer can be suppressed.

In the above embodiment, the resist film for EUV is developed, but the present invention can also be applied to the case of developing other resist films. For example, the present invention is useful when a fine resist pattern is formed on the wafer W by so-called double patterning.

Double patterning is a method of forming a fine resist pattern by performing two photolithography processes and synthesizing two resist patterns. Specifically, the first resist film is formed, exposed, and developed to form a first resist pattern on the first resist film, and then the second second resist film is formed, exposed, and A second resist pattern is formed on the second resist film by development. A fine resist pattern is realized by synthesizing the first resist pattern and the second resist pattern.

In the development process of the first resist film and the development process of the second resist film, the developer containing the organic solvent described in the above embodiment is used. Then, in each developing process, the thickness of the swelling layer S of the resist film can be reduced, and the developing speed of the resist film can be increased. Therefore, the dimensional accuracy of each of the first resist pattern and the second resist pattern can be improved, and a desired resist pattern P can be formed on the wafer W. Further, since the sensitivity of the resist film can be improved, the exposure amount of the exposure process can be reduced, the exposure time can be shortened, and the throughput of the wafer process can be improved.

In addition, if TMAH in the developer remains after the first development process, the second photolithography process cannot be performed properly, so that the first resist film is developed and cleaned properly after the first development. It is necessary to perform processing. In this respect, in the present embodiment, in the first development process, since the thickness of the swelling layer S of the first resist film is thin, the time required for cleaning can be shortened as compared with the prior art. For example, when the thickness of the swollen layer S becomes 1/2 of the thickness of conventional swelling layer S _P, the time required for the cleaning process can be shortened to the conventional 1/4. Specifically, for example, the cleaning process, which conventionally took 60 seconds, can be changed to 15 seconds in the present embodiment. Therefore, the throughput of wafer processing can be improved.

The preferred embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to such examples. It is obvious for those skilled in the art that various changes or modifications can be conceived within the scope of the idea described in the claims, and these naturally belong to the technical scope of the present invention. It is understood. The present invention is not limited to this example and can take various forms. The present invention can also be applied to a case where the substrate is another substrate such as an FPD (flat panel display) other than a wafer or a mask reticle for a photomask.

DESCRIPTION OF SYMBOLS 1 Coating development processing system 4 Exposure apparatus 30-34 Development processing apparatus 133 Developer liquid nozzle 136 Developer liquid supply block 140 Cleaning liquid nozzle 150 Developing stock solution supply source 160 Organic solvent supply source 170 Developer supply source 200 Control part R Resist layer S Swelling layer P (desired) resist pattern W wafer

Claims

A photoresist developer for developing a resist film on a substrate,
It has an organic solvent that is soluble in the developing solution of the resist film and does not neutralize with the developing solution.
The photoresist developer according to claim 1,
The resist film is a resist film for EUV.
The photoresist developer according to claim 1,
The concentration of the organic solvent with respect to the developing stock solution is set based on the developing speed of the resist film and the cross-sectional shape of the resist pattern formed on the resist film after development.
The photoresist developer according to claim 3,
The concentration of the organic solvent with respect to the developing stock solution is 5% by mass or less.
A development processing apparatus for developing a resist film on a substrate using a photoresist developer,
The photoresist developer has an organic solvent that is soluble in the developing solution of the resist film and does not neutralize with the developing solution.
The development processing apparatus includes:
A developer nozzle for supplying the photoresist developer on the substrate;
A developing solution supply source for storing the developing solution therein;
An organic solvent supply source for storing the organic solvent therein;
The developing solution supplied from the developing solution supply source and the organic solvent supplied from the organic solvent supply source are mixed to produce the photoresist developing solution, and the photoresist developing solution is used as the developing solution. A developer supply source for supplying to the nozzle.