KR20160052364A - A resist pattern forming apparatus, a resist pattern forming method - Google Patents

Abstract

Provided is a resist pattern forming apparatus which exhibits both light transmittancy and durability and enables acquisition of highly reliable patterns. Also provided is a resist pattern forming method. More specifically, the present invention relates to a resist pattern forming apparatus which includes: a spreading device spreading a resist film on a substrate; a developing device forming a pre-pattern by developing the resist film; a dehydration device dehydrating the pre-pattern after the development; a light irradiation device irradiating the pre-pattern with light after the dehydration; and a heating device curing the pre-pattern by heating the same after the light irradiation.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a resist pattern forming apparatus and a resist pattern forming method,

The present invention relates to a resist pattern forming apparatus and a resist pattern forming method.

Conventionally, there has been known a technique for applying a resist material to pre-bake, then subjecting the pre-pattern exposed and developed to bleaching exposure, thereby improving the light transmittance and durability of the pre-pattern (see, for example, Patent Document 1).

Japanese Laid-Open Patent Publication No. 2012-237854

However, in the above-mentioned prior art, the bleaching effect is not sufficiently obtained, the light transmittance and durability of the pattern after bleaching exposure can not be both satisfied, and the reliability of the organic EL panel or TFT panel manufactured using the pattern is lowered It was becoming a factor.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a resist pattern forming apparatus and a resist pattern forming method which can obtain a highly reliable pattern that combines light transmittance and durability.

According to a first aspect of the present invention, there is provided a developing apparatus comprising: a coating device for coating a resist film on a substrate; a developing device for forming a pre-pattern by performing development processing of the resist film; And a heating device for heating and curing the pre-pattern after the irradiation with light. The present invention also provides a resist pattern forming apparatus comprising:

According to the resist pattern forming apparatus according to the first aspect, the moisture of the free pattern is removed in advance by the dehydration treatment, whereby the naphthoquinone diazide after exposure is prevented from changing to indenecarboxylic acid. When the production of the carboxylic acid is suppressed, the pre-pattern is favorably polymerized. Therefore, after the light irradiation treatment, a pre-pattern having both light transmittance and durability is formed, so that the resist pattern obtained by curing the pre-pattern becomes highly reliable.

In the first aspect, the dewatering device may include a heating mechanism for heating the pre-pattern in a dewatering chamber supplied with an inert gas.

According to this configuration, moisture in the free pattern can be satisfactorily removed.

In the first aspect, the dewatering device may include a vacuum mechanism for making a space containing the free pattern in a vacuum atmosphere.

According to this constitution, since moisture is likely to evaporate in a vacuum atmosphere, water can be satisfactorily removed in the pre-pattern.

It is preferable that the dehydrating apparatus further includes a heating mechanism for heating the pre-pattern in the vacuum atmosphere.

In this way, moisture in the free pattern can be removed more efficiently.

In the first aspect, the dewatering device may include a heating mechanism for heating the pre-pattern.

According to this configuration, moisture in the free pattern can be satisfactorily removed.

In the first aspect, the light irradiation device may have a low dew point atmosphere in the processing chamber for performing the light irradiation process.

According to this structure, because the water content in the chamber is small, the diazonaphthoquinone contained in the free pattern causes photochemical reaction, and the resulting indene ketene bonds with the hydroxyl group of the resin, so that the whole film is polymerized well. Therefore, since the pre-pattern is favorably polymerized, a resist pattern excellent in light transmittance and durability can be formed.

In the first aspect, the light irradiation device may be configured to heat the pre-pattern at a treatment temperature of 20 ° C to 200 ° C when the light irradiation process is performed.

According to this configuration, the light irradiation process (bleaching process) of the pre-pattern can be satisfactorily performed.

In the first aspect, the light irradiation device may include a preheating part for holding the substrate under a low dew point atmosphere until the pre-pattern reaches the processing temperature before the light irradiation processing.

According to this configuration, the pre-pattern can be pre-heated to the processing temperature by the preheating portion while maintaining the dehydrated state of the pre-pattern. Therefore, since the pre-pattern is irradiated with light in a state of reaching a predetermined temperature not only to the surface but also to the interior thereof, the pre-pattern can be polymerized well.

According to a second aspect of the present invention, there is provided a method of manufacturing a resist pattern, comprising: a coating step of applying a resist film on a substrate; a developing step of forming a pre-pattern by performing a developing treatment of the resist film; There is provided a resist pattern forming method comprising a dewatering step, a light irradiation step of applying light irradiation treatment to the pre-pattern after the dewatering step, and a heating step of heating and curing the pre-pattern after the light irradiation step.

According to the resist pattern forming method according to the second aspect, the moisture of the pre-pattern is removed in advance by the dehydration treatment, whereby the naphthoquinone diazide after exposure is prevented from changing to indenecarboxylic acid. When the production of the carboxylic acid is suppressed, the pre-pattern is favorably polymerized. Therefore, since a pre-pattern having both light transmittance and durability is formed, the resist pattern obtained by curing the pre-pattern becomes highly reliable.

In the second aspect, the dewatering step may include a heating step of heating the pre-pattern in a dewatering chamber supplied with an inert gas.

According to this configuration, moisture in the free pattern can be satisfactorily removed.

In the second aspect, the dewatering step may include a vacuum step of setting a space containing the free pattern to a vacuum atmosphere.

According to this constitution, since moisture is likely to evaporate in a vacuum atmosphere, water can be satisfactorily removed in the pre-pattern.

It is preferable that the dehydration step is performed by heating the pre-pattern in the vacuum atmosphere.

In this way, moisture in the free pattern can be removed more efficiently.

In the second aspect, the dewatering process may be configured to perform dewatering process by heating the pre-pattern.

According to this configuration, moisture in the free pattern can be satisfactorily removed.

In the second aspect, the light irradiation step may be configured to perform the light irradiation processing in a processing chamber having a low dew point atmosphere.

According to this structure, because the water content in the chamber is small, the diazonaphthoquinone contained in the free pattern causes photochemical reaction, and the resulting indene ketene bonds with the hydroxyl group of the resin, so that the whole film is polymerized well. Therefore, since the pre-pattern is favorably polymerized, a resist pattern excellent in light transmittance and durability can be formed.

In the second aspect, when the light irradiation process is performed, the pre-pattern may be heated at a treatment temperature of 20 ° C to 200 ° C.

According to this configuration, the light irradiation process (bleaching process) of the pre-pattern can be satisfactorily performed.

In the second aspect, the light irradiation step may include a preheating step of holding the substrate under a low-dew point atmosphere until the pre-pattern reaches the processing temperature before the light irradiation processing .

According to this configuration, the preheating section can preheat the temperature of the pre-pattern to the processing temperature while maintaining the dehydration state of the pre-pattern. Therefore, since the pre-pattern is irradiated with light in a state of reaching a predetermined temperature not only to the surface but also to the interior thereof, the pre-pattern can be polymerized well.

According to the present invention, a highly reliable pattern that combines light transmittance and durability can be obtained.

1 is a plan view showing a pattern forming apparatus according to a first embodiment;
Fig. 2 is a view showing the structure when the dewatering unit according to the first embodiment is viewed from the -Y direction; Fig.
3 is a view showing a configuration when the light irradiation unit according to the first embodiment is viewed in the + Z direction;
4 is a view showing the operation of the light irradiation unit according to the first embodiment;
5 is a view showing the operation of the light irradiation unit according to the first embodiment;
6 is a process chart showing a pattern forming method according to the first embodiment;
7 is a view showing a configuration when the light irradiation unit according to the second embodiment is viewed in the -Y direction;
8 is a view showing the operation of the light irradiation unit according to the second embodiment;
9 is a view showing an operation of the light irradiation unit according to the second embodiment;
10 is a view showing the operation of the light irradiation unit according to the second embodiment;
11 is a view showing a configuration when the dehydrating unit related to the modified example is viewed in the -Y direction.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the following description, the XYZ orthogonal coordinate system is set, and the positional relationship of the respective members is described with reference to the XYZ orthogonal coordinate system. The direction orthogonal to the X axis direction is defined as the Y axis direction, and the direction orthogonal to the X axis direction and the Y axis direction (i.e., the vertical direction) is defined as the Z axis direction. The directions of rotation (inclination) around the X axis, the Y axis, and the Z axis are θX, θY, and θZ directions, respectively.

(First Embodiment)

1 is a plan view showing a pattern forming apparatus (SPA) according to the present embodiment.

The pattern forming apparatus SPA includes a loader / unloader (LU), a coating / developing processing unit (CD), an interface unit IF, and a control unit CONT arranged in a row in the X direction, for example. The pattern forming apparatus SPA has a configuration in which the coating and developing treatment section CD is sandwiched by the loader unloader LU and the interface section IF. The control section CONT processes each section of the pattern forming apparatus SPA in a general manner.

(Loader, unloader)

The loader unloader (LU) is a portion for carrying in and out cassettes (C) accommodating a plurality of substrates (G). The loader / unloader (LU) has a cassette standby portion (10) and a transport mechanism (11).

The cassette standby portion 10 is disposed, for example, on the -X side end of the pattern forming device SPA and accommodates a plurality of cassettes C. [ The cassettes C accommodated in the cassette standby portion 10 are arranged, for example, in the Y direction. The cassette standby portion 10 is provided with an opening (not shown) on the -X side, and the cassette C is transferred between the outside of the pattern forming apparatus SPA and the cassette holding portion 10 through the opening portion have.

The transport mechanism 11 is disposed on the + X side of the cassette standby portion 10 and carries the substrate G between the cassette C and the coating and development processing portion CD. The two transport mechanisms 11 are arranged, for example, along the Y direction, and the two transport mechanisms 11 have the same configuration, for example. The transport mechanism 11a disposed on the -Y side transports the substrate G from the loader / unloader (LU) to the coating and developing treatment section (CD). The transport mechanism 11b disposed on the + Y side transports the substrate G from the coating and development processing section CD to the loader unloader (LU).

The transport mechanism 11 has transport arms 12 (12a and 12b). The transfer arm 12 has a holding portion for holding the glass substrate, and is formed so as to be able to expand and contract in, for example, one direction. The carrying arm 12 is formed so as to be rotatable in the? Z direction. The transport arm 12 is capable of being directed in the respective directions of the cassette standby portion 10 and the coating and developing treatment portion CD, for example, by rotating in the? Z direction. The carrying arm 12 is made accessible to each of the cassette waiting portion 10 and the coating and developing portion CD by expanding and contracting the carrying arm 12.

(Coating and development processing unit)

The coating and developing treatment portion CD is a portion for performing a series of treatments including coating and developing on the substrate G. [ The coating and developing unit CD includes a scrubber unit SR, a dewatering unit DH, a coating unit CT, a prebake unit PR, an interface unit IF, a developing unit DV, a dewatering unit 58 ), A light irradiation unit (UV), and a post-baking unit (PB).

The coating and development processing section CD is configured to be divided in the Y direction so that the substrate G from the loader unloader LU is transported toward the interface section IF in the + . In the portion on the + Y side, the substrate G from the interface unit IF is transported in the -X direction toward the loader / unloader LU.

The scrubber unit SR is connected downstream of the loader / unloader (LU), and is a unit for cleaning the substrate (G). The scrubber unit SR has a dry cleaning device 41, a wet cleaning device 42 and an air knife device 43. Conveyor mechanisms CV1 and CV2 are formed on the -X side of the dry cleaning device 41 and the + X side of the air knife device 43, respectively. In the conveyor mechanisms CV1 and CV2, a belt mechanism (not shown) for conveying the substrate G is formed.

The dry cleaning apparatus 41 removes organic substances on the substrate G, for example, by irradiating the substrate G with ultraviolet rays such as an excimer laser. The wet cleaning device 42 has, for example, a scrubbing brush (not shown). The wet cleaning apparatus 42 cleans the substrate G using the cleaning liquid and the scrubbing brush. The air knife device 43 has, for example, an air knife injection mechanism (not shown). The air knife device 43 forms an air knife on the substrate G using an air knife injection mechanism to remove impurities on the substrate G. [

The dewatering bake unit DH is connected to the downstream of the scrubber unit SR and is a unit for dewatering the substrate G. The dewatering baking unit DH has a heating device 44, an HMDS device 46, and a cooling device 45. The heating device 44 and the HMDS device 46 are arranged so as to overlap in the Z direction. A conveyor mechanism CV3 is formed at a position overlapping the heating device 44 and the HMDS device 46 when viewed in the Z direction and a conveyor mechanism CV4 is provided at a position overlapping the cooling device 45 when viewed in the Z direction Respectively. A transport mechanism TR1 for transporting the substrate G is formed between the heating device 44 and the HMDS device 46 and the cooling device 45. [ The transport mechanism TR1 can be configured in the same manner as the transport mechanism 11 formed in, for example, the loader / unloader (LU).

The heating device 44 is configured to have a heater in a chamber capable of accommodating the substrate G, for example. The heating devices 44 are arranged in a plurality of stages in the Z direction, for example. The heating device 44 heats the substrate G at a predetermined temperature. The HMDS device 46 is a device for enhancing the adhesion between the resist film to be coated on the substrate G and the substrate G in the coating unit CT by hydrophilizing the HMDS gas on the substrate G, to be. The cooling device 45 has a temperature adjusting mechanism in a chamber capable of accommodating the substrate G to cool the substrate G to a predetermined temperature, for example.

The coating unit (coating apparatus) CT is connected downstream of the dewatering baking unit DH to form a resist film in a predetermined area on the substrate G. [ The coating unit CT has a coating unit 47, a reduced-pressure drying unit 48 and a peripheral edge removing unit 49. The application device 47 is a device for applying a resist film on the substrate G. As the application device 47, for example, a rotary application device, a non-spin application device, a slit nozzle application device or the like is used. And it is also possible to adopt a configuration in which these various coating devices can be exchanged. The reduced-pressure drying apparatus 48 dries the surface of the substrate G after applying the resist film. The peripheral edge removing device 49 is a device for removing the resist film applied on the periphery of the substrate G to trim the shape of the resist film.

The prebake unit PR is connected to the downstream side of the coating unit CT and is a unit for prebaking the substrate G. [ The pre-bak unit (PR) has a heating device (50) and a cooling device (51). A conveyor mechanism CV5 is formed at a position overlapping the heating device 50. [ A conveyor mechanism CV6 is formed at a position overlapping with the cooling device 51. [ The heating device 50 and the cooling device 51 are arranged along the Y direction so as to sandwich the transport mechanism TR2.

The interface unit IF is a part connected to the exposure apparatus EX. The interface unit IF has a buffer unit 52, a transport mechanism TR3, conveyor mechanisms CV7 and CV8, and an edge exposure apparatus EE. The buffer device 52 is disposed on the + X side of the transport mechanism TR2 of the pre-bake unit PR. On the + X side of the buffer device 52, a transport mechanism TR3 is formed.

The buffer device 52 is a device for temporarily holding the substrate G. The buffer device 52 is provided with a chamber (not shown) for accommodating the substrate G, a temperature control device for controlling the temperature in the chamber, a rotation control device for adjusting the position of the substrate G housed in the chamber in the? Respectively. In the chamber of the buffer device 52, the temperature of the substrate G can be maintained at a predetermined temperature. The conveyor mechanisms CV7 and CV8 are arranged so as to sandwich the cooling device 51 of the pre-baking unit PR in the X direction.

The developing unit (developing apparatus) DV is connected to the -X side of the cooling apparatus 51 of the pre-baking unit PR and performs developing processing of the exposed substrate G. On the developed substrate G, a resist film (pre-pattern) patterned in a predetermined shape is formed.

The developing unit DV has a developing device 55, a rinsing device 56 and an air knife device 57. [ The developing device 55 supplies a developer to the substrate G to perform development processing. The rinsing device 56 supplies the rinsing liquid to the developed substrate G and rinses the substrate G. [ The air knife device 57 forms an air knife on the substrate G and dries the pre-pattern on the substrate G. A conveyor mechanism CV9 is formed on the + X side of the developing device 55 and a conveyor mechanism CV10 is formed on the -X side of the air knife device 57. [ The conveyor mechanism CV10 conveys the substrate G from the air knife device 57 to the dewatering unit 58. [

(Dehydrating unit)

The dewatering unit 58 is connected to the -X side of the developing unit DV and performs dehydration processing of the developed substrate G.

2 is a view showing the structure when the dewatering unit 58 is viewed in the + Y direction.

2, the dewatering unit 58 has a chamber (dewatering chamber) 70, a gas supply unit 71, and a heating mechanism 72. As shown in Fig. The chamber 70 accommodates the substrate G on which the dehydration process is performed. The gas supply unit 71 supplies an inert gas into the chamber 70. The gas supply unit 71 supplies an inert gas such as nitrogen (N ₂ ), helium (He), or argon (Ar), for example. The heating mechanism 72 includes a heating unit such as a heater that heats the substrate G in the chamber 70. The heating temperature of the heating mechanism 72 is set to a value capable of evaporating moisture in the pre-pattern formed on the substrate (G).

On the -X side of the dewatering unit 58, a transport mechanism TR4 is formed. The transport mechanism TR4 transports the substrate G from the dewatering unit 58 to the post-baking unit PB. The transport mechanism TR4 has a robot arm capable of ascending and descending in the Z direction while holding the substrate G.

The light irradiation unit UV is connected to the + Y side of the transport mechanism TR4. The light irradiation unit (UV) performs a bleaching exposure which improves the visible light transmittance of the pre-pattern by irradiating the developed substrate G (pre-pattern) with light of a predetermined wavelength, for example.

The transport mechanism TR4 transports the substrate G from the dewatering unit 58 to the light irradiation unit UV and transfers the substrate G from the light irradiation unit UV to the post bake unit PB do. The transport mechanism TR4 has a robot arm capable of ascending and descending in the Z direction while holding the substrate G.

The post bake unit PB is connected to the downstream side of the transport mechanism TR4 to bake the substrate G after the optical processing. The post bake unit (PB) has a heating device (59) and a cooling device (60). Between the heating device 59 and the cooling device 60, a transport mechanism TR5 is formed. The transport mechanism TR5 transports the substrate G from the heating device 59 to the cooling device 60. [ The heating device 59 performs post-baking on the post-development substrate G. The cooling device 60 cools the substrate G after the post-baking.

(Light irradiation unit)

Fig. 3 is a view showing a configuration when the light irradiation unit UV is viewed in the + Z direction. Figs. 4 (a) and 4 (b) are diagrams showing the configuration when the light irradiation unit UV is viewed in the + Y direction. 5 (a) and 5 (b) are diagrams showing the configuration when the light irradiation unit UV is viewed in the + X direction. 3 to 5, a part of the configuration is omitted for easy identification of the drawings.

As shown in Figs. 3 and 4, the light irradiation unit UV has a standby unit 80 and a light irradiating unit 81. Fig.

The reserve apparatus 80 has a chamber 82, a pressure reducing mechanism 83, and a lifting mechanism 84. The preparatory apparatus 80 is formed as, for example, a preliminary chamber for temporarily accommodating the substrate G to be conveyed to the light irradiation apparatus 81. [ Of course, it may be used for other purposes. The standby device 80 has, for example, a substrate loading / unloading port 80a on the + Y side. In the preparatory apparatus 80, the substrate G can be received in a state in which the inside of the chamber 82 is depressurized by the decompression mechanism 83. As the pressure reducing mechanism 83, for example, a pump mechanism or the like is used.

The lifting mechanism 84 is formed so as to be movable in the Z direction. On the + Z side of the lifting mechanism 84, for example, a plurality of support pins 84a are formed. The end portions of the plurality of support pins 84a on the + Z side are formed, for example, in the same plane parallel to the XY plane. Therefore, the substrate G is supported parallel to the XY plane by the plurality of support pins 84a. The lifting mechanism 84 is adapted to transport the substrate G in the Z direction in the chamber 82 while supporting the substrate G accommodated in the chamber 82. [

The light irradiating device 81 is an apparatus which is connected to the spare device 80 and irradiates the substrate G with light. The light irradiation device 81 includes a chamber (processing chamber) 85, a light irradiation portion 86, a stage 87, a transfer mechanism 88, a transfer mechanism (substrate transfer portion) 89, And a gas supply unit 91. [ The light irradiation device 81 has, for example, a substrate loading / unloading port 81a on the + X side.

The substrate transfer port 81a is connected to the -X side of the spare device 80 and carries the substrate G in and out with respect to the spare device 80. [ A connecting portion 80b for connecting to the dewatering unit 58 is formed on the surface of the chamber 82 on the + X side. The connecting portion 80b physically connects the chamber 82 to the dewatering unit 58 side and connects the chamber 82 and the dewatering unit 58 electrically As shown in FIG.

The chamber 85 accommodates the substrate G on which the light irradiation process is performed. The chamber 85 is formed in a quadrangular shape in plan view, and is formed, for example, so that one direction is long. In the ceiling portion 85a of the chamber 85, an opening 85b for light manipulation is formed. The opening 85b is formed at a position corresponding to the light irradiating portion 86 in the chamber 85 when viewed in plan view. A lid portion 85c is formed on the ceiling portion 85a of the chamber 85. [ The lid portion 85c is formed at three points along the longitudinal direction of the chamber 85 when viewed from a plurality of points, for example, a plane. The lid portion 85c is formed at a position away from the opening portion 85b of the ceiling portion 85a of the chamber 85. [

In the chamber 85, a light shielding member 85d is formed at a position where the opening 85b is sandwiched. The light shielding member 85d is a plate-shaped member mounted on the ceiling portion 85a of the chamber 85 and shielding light from the light irradiation portion 86, for example. The light shielding member 85d is formed, for example, at a position dividing the inside of the chamber 85. [ The portions partitioned by the light shielding member 85d in the chamber 85 will hereinafter be referred to as a first substrate transfer section 85F, a processing section 85P and a second substrate transfer section 85S, respectively. The first substrate carrying portion 85F is a portion of the chamber 85 on the side of the reserve device 80 side. The processing unit 85P is a portion where the opening 85b is formed. The second substrate carrying section 85S is the portion farthest from the preparatory device 80. [

Light irradiated to the processing section 85P is shielded by the light shielding member 85d. Therefore, the light from the light irradiation unit 86 is irradiated only to the processing unit 85P without being irradiated onto the first substrate transfer unit 85F and the second substrate transfer unit 85S.

The light irradiating unit 86 is attached to the opening 85b of the chamber 85. [ The light irradiating unit 86 irradiates light including both ultraviolet rays (e.g., i-ray) and visible light rays (light having a wavelength of less than 300 nm, preferably more than 450 nm, And the like. The irradiation lamp is composed of, for example, a metal halide lamp or an LED lamp.

Here, in the present embodiment, the term " ultraviolet ray " means light having a lower limit of the wavelength range of about 1 nm and an upper limit of a short wavelength of the visible ray, and " visible light " means that the lower limit of the wavelength range is 360 to 400 nm , And the upper limit is about 760 to 830 nm.

The wavelength of light (irradiation light) irradiated by the light irradiation unit 86 is 300 nm or more, preferably 300 to 450 nm. By setting the wavelength of the irradiation light to 300 nm or more, the entire pattern tends to be hardened not only on the surface layer side but also inside of the pre-pattern. On the other hand, if it is not more than the preferable upper limit value, generation of radiant heat is suppressed, and an excessive increase in temperature at the time of curing can be suppressed.

The stage 87 is a plate-shaped member accommodated in the chamber 85 and formed along the longitudinal direction of the chamber 85. The stage 87 is disposed over the first substrate transfer section 85F, the processing section 85P, and the second substrate transfer section 85S. The stage 87 has a first opening 87a and a second opening 87b. The first opening 87a is formed in a portion disposed in the first substrate carrying portion 85F. The second opening 87b is formed over substantially the entire surface of the stage 87. [ The second opening 87b is connected to, for example, an air supply mechanism and a suction mechanism (not shown). Therefore, air is ejected from the second opening 87b, and an air layer is formed on the entire surface of the stage 87 by the air.

The receiving mechanism 88 has a substrate holding member 88a, a transmitting member 88b, a driving mechanism 88c, and a lifting mechanism 88d. The transfer mechanism 88 is formed so as to be movable between the apparatuses of both the preparatory apparatus 80 and the light irradiation apparatus 81.

The substrate holding member 88a has a comb-like portion 100 and a moving portion 101. The comb- The comb-like portion 100 is formed so that, for example, the comb portions are opposed to each other in the Y direction. And the substrate G is held on the comb-shaped portion 100. [ The base portion of the comb-shaped portion 100 is connected to the moving portion 101. [ The moving part 101 is formed so as to pass through the wall parts on the + Y side and the -Y side of the chamber 85. The moving part 101 has a fixing mechanism 102 on the + Y side and the -Y side of the chamber 85. The moving part 101 is fixed to the transmitting member 88b through a fixing mechanism 102. [

As the transmitting member 88b, for example, a linear member such as a wire is used. The transmitting member 88b is annularly formed so as to contact at least the side portions on the + Y side and the -Y side of the chamber 85. The transfer member 88b is formed along the X direction on the + Y side and -Y side of the chamber 85 in question.

As shown in Figs. 3 and 5 (b), the transmitting member 88b is pierced in the Y direction by the pulley portions 88f and 88g at the corners of the -X side of the chamber 85, respectively. As shown in Fig. 5 (b), a plurality of pulley portions 88h are formed on the -X side end face of the chamber 85. Fig. The transmitting member 88b is connected to the driving mechanism 88c through the pulley portion 88h on the -X side end face of the chamber 85. [ The + X side of the transmitting member 88b is engaged with the pulley portions 88i and 88j formed at the corner portion on the + X side of the chamber 85 as shown in Figs. 3 and 4 (b).

The drive mechanism 88c is formed on the -Z side of the chamber 85 as the outside of the chamber 85. [ The driving mechanism 88c has a motor (not shown), and drives the transmitting member 88b by rotating the motor. The elevating mechanism 88d shown in Fig. 4 is formed on the -Z side of the first substrate carrying section 85F, and is formed to be movable in the Z direction by an actuator (not shown). The lifting mechanism 88d has a plurality of support pins 88e. The support pin 88e is disposed at a position overlapping the first opening 87a formed in the stage 87 when viewed in the Z direction. As the lifting mechanism 88d moves in the Z direction, the support pin 88e is projected and retracted on the stage 87 with respect to the first opening 87a.

The transfer mechanism 88 drives the substrate holding member 88a in the X direction through the transfer member 88b by driving the transfer member 88b by the drive mechanism 88c formed outside the chamber 85 . The substrate holding member 88a inside the chamber 85 can be moved by driving the drive mechanism 88c formed outside the chamber 85. [ The transfer mechanism 88 is capable of receiving the substrate G held by the comb-shaped portion 100 by moving the lifting mechanism 88d in the Z direction.

The transport mechanism 89 has a substrate holding member 89a, a transmitting member 89b, and a drive mechanism 89c. For example, as shown in FIG. 5A, the transport mechanism 89 is formed on the -Z side of the transport mechanism 88.

The substrate holding member 89a is formed in an L shape when viewed in the Z direction, and four substrate holding members 89a are disposed one at a position corresponding to the edge portion of the substrate G in total. The substrate holding member 89a is capable of holding the edge portion of the substrate G. [ More specifically, the substrate holding member 89a is configured to hold the X side and the Y side surface (side surface) and the -Z side surface (bottom surface) of the edge portion of the substrate G. [ The four substrate holding members 89a are fixed to the supporting wire 105. The supporting wire 105 is constituted by two wires formed along the X direction and four wires formed along the Y direction, in total six wires. The supporting wire 105 is all tensioned.

The two wires 105X formed along the X direction connect the substrate holding members 89a arranged along the X direction among the four substrate holding members 89a. The four wires 105Y formed along the Y direction are formed so as to penetrate the chamber 85 in the Y direction. The wire 105Y on the most + X side among the four wires 105Y is connected to the two substrate holding members 89a on the + X side through the support member 106. [ The most-X side wire 105Y is connected to the two substrate holding members 89a on the -X side via the support member 107. [

On the + Y side of the chamber 85, two fixing mechanisms 108 fixed to the transmitting member 89b are formed. The + Y side end of the wire 105Y is connected to the two fixing mechanisms 108, respectively. Two fixing mechanisms 109 fixed to the transmitting member 89b are formed on the -Y side of the chamber 85 and the -Y side end of the wire 105Y is connected to the fixing mechanism 109, respectively.

As the transmitting member 89b, a linear member such as a wire is used. For example, two transfer members 89b are formed. The two fixing mechanisms 108 and the fixing mechanisms 109 are fixed to the respective transmitting members 89b one by one. One of the two transmitting members 89b is connected to the two substrate holding members 89a on the -X side and another one of the transmitting members 89b is connected to the two substrate holding members 89a on the + X side, Respectively.

Each of the transmitting members 89b is formed along the X direction on the side of the chamber 85, for example. Each of the transmitting members 89b is annularly formed so as to contact at least the side portions on the + Y side and the -Y side of the chamber 85. Each transmitting member 89b is formed along the X direction on the + Y side and -Y side of the chamber 85 in question.

As shown in Figs. 3 and 5 (b), each of the transmitting members 89b is pierced in the Y direction by the pulley portions 89f and 89g at the corner portions on the -X side of the chamber 85 . As shown in Fig. 5 (b), a plurality of pulley portions 89h are formed on the -X side end surface of the chamber 85. Fig. Each transmitting member 89b is connected to the driving mechanism 89c through the pulley portion 89h on the -X side end face of the chamber 85. [ The pulleys 89f, 89g, and 89h are independently movable so as not to entangle the two transmitting members 89b.

The arrangement of the pulley portions 88f, 89f, 88g, 89g, 88h, 89h may be such that the transfer member 88b and the two transmitting members 89b can independently move so as not to be entangled with each other. The present invention is not limited to the arrangement shown in the form, and it is of course not limited to this.

As the transmitting member 89b, for example, a linear member such as a wire is used as the transmitting member 88b. The transfer member 89b formed in the transfer mechanism 89 is disposed on the -Z side with respect to the transfer member 88b formed in the transfer mechanism 88, as shown in Fig. 4 (b).

3, each of the transmitting member 88b and the transmitting member 89b, for example, each portion formed along the chamber 85 is arranged so as to overlap when viewed in the Z direction. Therefore, like the transmitting member 88b, the transmitting member 89b is formed along the X direction on the side of the chamber 85, for example.

As shown in Figs. 3 and 5 (b), each of the transmitting members 89b is pierced in the Y direction by the pulley portions 89f and 89g at the corner portions on the -X side of the chamber 85 . As shown in Fig. 5 (b), a plurality of pulley portions 89h are formed on the -X side end surface of the chamber 85. Fig.

Each transmitting member 89b is connected to the driving mechanism 89c through the pulley portion 89h on the -X side end face of the chamber 85. [ On the + X side of each transmitting member 89b, as shown in Figs. 3 and 4 (b), the pulley portions 89i and 89j formed at the corners on the + X side of the chamber 85 are hooked .

The drive mechanism 89c is formed on the -Z side of the chamber 85 as the outside of the chamber 85. [ The drive mechanism 89c has a motor (not shown), and drives the respective transmitting members 89b by rotating the motor. One drive mechanism 89c is provided for each of the two transmitting members 89b. The four substrate holding members 89a can be moved at the same speed by synchronously controlling the drive mechanism 89c, for example.

The transport mechanism 89 is configured to move the substrate holding member 89a in the X direction through the transfer member 89b by driving the transfer member 89b by the drive mechanism 89c. As described above, the substrate holding member 89a inside the chamber 85 can be moved by driving the driving mechanism 89c formed outside the chamber 85.

The heating section 90 is formed at the bottom of the processing section 85P of the chamber 85, for example. The heating unit 90 has, for example, a heating device such as an electric heating wire and a temperature control device for adjusting the heating temperature of the heating device.

The gas supply unit 91 supplies an inert gas such as nitrogen (N ₂ ), helium (He), or argon (Ar) as a dry gas. Accordingly, the chamber 85 of the present embodiment can control the dew point of the internal atmosphere by the supply of the inert gas, and the moisture concentration in the atmosphere is controlled.

The gas supply part 91 is provided so that the internal atmosphere of the chamber 85 is maintained at a dew point of -80 캜 (moisture concentration of 0.54 ppm mass basis) to -5 캜 (moisture concentration of 4000 ppm mass basis) Adjust the supply. More specifically, it is preferable that the gas atmosphere in the chamber 85 be at least -80 占 폚 (at a moisture concentration of 0.54 ppm by mass) or higher and -14 占 폚 (at a moisture concentration of 1791 ppm by mass) , A dew point of -60 占 폚 (moisture concentration of 10.7 ppm mass basis) or more, and -20 占 폚 (moisture concentration of 1020 ppm mass basis) or less.

If the dew point (moisture concentration) of the atmosphere in which the pre-pattern is cured is set to a preferable upper limit value or less, the pattern hardly hardens. On the other hand, when it is more than the preferable lower limit value, the workability and the like are improved (for example, the apparatus is easy to operate and cost advantage is provided).

The oxygen concentration (on a mass basis) in the inner atmosphere of the chamber 85 is preferably as low as possible, and the specific oxygen concentration is preferably 1000 ppm or less, more preferably 500 ppm or less. When the oxygen concentration is set to a preferable upper limit value or less as described above, the curing of the pattern is more likely to proceed as described later.

The light irradiation unit (UV) heats the substrate (G) in the chamber (85) having a low dew point atmosphere by the heating unit (90). The heating section 90 heats the pre-pattern formed on the substrate G by exposure and development processing at a temperature higher than room temperature (for example, 20 占 폚) and at a temperature lower than 200 占 폚.

The light irradiation unit UV irradiates the substrate G with light of a predetermined wavelength in a low dew point atmosphere by driving the light irradiation unit 86 in a state in which the substrate G is heated by the heating unit 90 do.

(Pattern forming method)

The pattern forming method by the pattern forming apparatus (SPA) configured as described above will be described.

FIG. 6A is a process diagram showing a conventional pattern formation method as a comparison, and FIG. 6B is a process diagram showing a pattern formation method according to the present embodiment.

6 (a), the conventional pattern forming method includes a coating step S1, a prebaking step S2, an exposure step S3, a developing step S4, a light irradiation step A bleaching exposure step) S5, and a post-baking step S6 in this order.

On the contrary, the pattern forming method of the present embodiment is characterized in that the coating step (S1), the prebaking step (S2), the exposure step (S3), the developing step (S4) A dewatering step (SS1), a light irradiation step (S5), and a post-baking step (S6).

That is, in the pattern forming method of the present embodiment, the conventional pattern forming method differs greatly in that the dehydrating step (SS1) is provided between the developing step (S4) and the light irradiation step (S5).

Hereinafter, each step of the pattern forming method of the present embodiment will be described.

First, the cassette C containing the substrate G is loaded on the cassette-waiting portion 10 of the loader / unloader LU. The substrate G in the cassette C is transported to the scrubber unit SR through the transport mechanism 11. [

The substrate G conveyed to the scrubber unit SR is conveyed to the dry-cleaning apparatus 41 through the conveyor mechanism CV1. The substrate G is processed in the order of the dry cleaning device 41, the wet cleaning device 42 and the air knife device 43 in this order. The substrate G unloaded from the air knife device 43 is conveyed to the dewatering bake unit DH via the conveyor mechanism CV2.

In the dehydration bake unit DH, the substrate G is first subjected to the heat treatment by the heating device 44. The substrate G after the heating is transported in the Z direction, for example, and the HMDS device 46 performs the treatment with the HMDS gas. The substrate G after the HMDS processing is transported to the cooling device 45 by the transport mechanism TR1, and the cooling processing is performed. The substrate G after the cooling process is conveyed to the coating unit CT by the conveyor mechanism CV4.

(Coating step S1)

Thereafter, a coating process of applying a resist composition in the coating unit CT to form a resist film on the substrate G is carried out.

In the present embodiment, a positive resist composition for forming a pre-pattern is coated on a substrate G by exposure and development, in which the exposed portion is dissolved and removed. Examples of such a resist composition include the following resist compositions (r1) and (r2).

≪ Resist composition (r1) >

The resist composition (r1) is a positive resist composition obtained by dissolving an alkali-soluble resin, a specific phenol compound as a sensitivity improving agent, and a quinone diazide esterified compound as a photosensitive component in an organic solvent.

In the resist composition (r1), the alkali-soluble resin may be arbitrarily selected from those that can be commonly used as a film-forming material. Examples thereof include phenol resins, acrylic resins, copolymers of styrene and acrylic acid, polymers of hydroxystyrene, polyvinylphenol and poly-alpha-methylvinylphenol, which are known as resins for film formation of positive resist compositions . Of these, novolac resins which are particularly preferably used, and which are easily dissolved in an aqueous alkaline solution without being swollen and excellent in developability, are particularly suitable.

Examples of the phenol resin include a condensation reaction product of a phenol and an aldehyde, a condensation reaction product of a phenol and a ketone, a vinylphenol polymer, an isopropenylphenol polymer, and a hydrogenation reaction product of these phenol resins.

Examples of the phenols in the condensation reaction product include phenol, m-cresol, p-cresol, o-cresol, 2,3-xylenol, 2,5- Phenols such as m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4 butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol and 2-tert- Alkoxyphenols such as phenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol and m-propoxyphenol, o-isopropenylphenol, Isopropenylphenols such as 2-methyl-4-isopropenylphenol and 2-ethyl-4-isopropenylphenol, arylphenols such as phenylphenol, 4,4'-dihydroxybiphenyl, bisphenol A, And polyhydroxyphenols such as ricinole, hydroquinone and pyrogallol.

These may be used alone or in combination of two or more.

Among these phenols, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol and 2,3,5-trimethylphenol are particularly preferable.

Examples of the aldehydes in the condensation reaction product include aldehydes such as formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butylaldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanaldehyde, furfural, Methylbenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, o-hydroxybenzaldehyde, p-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, Benzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde and cinnamaldehyde.

These may be used alone or in combination of two or more.

Of these aldehydes, formaldehyde is preferable because of its availability, and in particular, hydroxybenzaldehyde and formaldehyde are preferably used in combination in order to improve heat resistance.

Examples of the ketones in the condensation reaction product include acetone, methyl ethyl ketone, diethyl ketone, and diphenyl ketone. These may be used alone or in combination of two or more.

In the combination of phenols and ketones, a combination of pyrogallol and acetone is particularly preferable.

Condensation reaction products of phenols and aldehydes or ketones can be prepared by a known method in the presence of an acidic catalyst. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, oxalic acid, paratoluenesulfonic acid and the like can be used.

The condensation reaction product thus obtained is preferably a product obtained by cutting the low-molecular region by treatment such as fractionation because of excellent heat resistance. The treatment such as fractionation is carried out by dissolving the resin obtained by the condensation reaction in a suitable solvent, for example, an alcohol such as methanol or ethanol, a ketone such as acetone or methyl ethyl ketone, ethylene glycol monoethyl ether acetate or tetrahydrofuran, And poured into water to effect precipitation.

Among them, in particular, it is preferable that the total phenolic repeating units contain 60 mol% or more of p-cresol repeating units and also contain 30 mol% or more of m-cresol repeating units and the polystyrene reduced weight average molecular weight (Mw) 2000 to 20000 is preferable.

When the proportion of the p-cresol-based repeating unit is less than 60 mol%, the sensitivity to temperature unevenness during the heat treatment tends to easily change. When the proportion of the m-cresol repeating unit is less than 30 mol%, the sensitivity tends to decrease.

The alkali-soluble resin may contain other phenol-based repeating units such as xylenol-based repeating units and trimethylphenol-based repeating units.

Particularly preferably, it is a two-component novolac resin comprising 60 to 70 mol% of a p-cresol-based repeating unit and 40 to 30 mol% of an m-cresol-based repeating unit, Norbornene resin having a low content of a low molecular weight compound of phenols and having a content of 10% or less in the GPC (Gel Permeation Chromatography) method is preferable. The bipolymer is sublimated in a prebake or postbake at a high temperature (for example, 130 DEG C) to contaminate the top plate of a furnace, and further contaminates the glass substrate coated with the resist composition, It is preferable to use a novolac resin having a low content.

Examples of the sensitivity enhancer in the resist composition (r1) include a phenol compound represented by the following general formula (I).

[Chemical Formula 1]

Wherein each of R ¹ to R ⁸ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms ; R ⁹ ~ R ¹¹ each independently represents a hydrogen atom or an alkyl group of carbon atoms from 1 to 6; Q is a hydrogen atom, a carbon atom number of 1 to 6 alkyl, in combination with R ⁹ carbon atoms chain 3-6 of A group forming a cycloalkyl group, or a group represented by the following formula (II).

(2)

(Wherein R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms A and b each represent an integer of 1 to 3; d represents an integer of 0 to 3; and n represents an integer of 0 to 3.]

Examples of the sensitivity enhancer in the resist composition (r1) include tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis , 3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) Phenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) Dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis 4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy -2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2- hydroxyphenylmethane, bis (5-cyclohexyl- Methylphenyl) -3,4-dihydroxyphenylmethane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [ - [1- (3-methyl-4-hydroxyphenyl) ethyl] benzene, 2- (2,3,4 Dihydroxyphenyl) -2- (2 ', 4'-dihydroxyphenyl) -2- (2', 3 ', 4'-trihydroxyphenyl) propane, Hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane and 2- (3-fluoro- -4'-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (4 Hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) Bis (2,4-dihydroxyphenyl) methane, bis (2, 4-dihydroxyphenyl) Di (4-hydroxyphenyl) cyclohexane, 2,4-bis [1- (4-hydroxyphenyl) isopropyl] -5-hydroxyphenol and the like.

Among these, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -2- 1- (4-hydroxyphenyl) isopropyl] -5-hydroxyphenol, 1,1-di (4-hydroxyphenyl) cyclohexane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene.

The sensitivity improving agents may be used alone or in combination of two or more.

The content of the sensitivity improving agent is preferably 5 to 25 parts by mass, more preferably 10 to 20 parts by mass, per 100 parts by mass of the alkali-soluble resin.

The quinone diazide esterified product (photosensitive component 1) represented by the following general formula (III), the quinone diazide esterified product represented by the following general formula (IV) (photosensitive component 2) , Esters of a phenol compound represented by the above general formula (I) with a 1,2-naphthoquinonediazide-5 (or 4) -sulfonyl compound, and the like.

(3)

[In the formula (III), R ¹⁴ independently represents an alkyl group having 1 to 5 carbon atoms, D independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, At least one of D represents a 1,2-naphthoquinonediazide-5-sulfonyl group, and l and m each independently represents 1 or 2. In formula (IV), a plurality of D's each independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one of D represents 1,2-naphthoquinonediazide -5-sulfonyl group.]

The average esterification rate of the photosensitive component 1 is preferably from 40 to 60%, more preferably from 45 to 55%. If the average esterification rate is less than 40%, the film thickness after development tends to easily occur, and the residual film ratio tends to be lowered. On the other hand, if it exceeds 60%, the sensitivity tends to remarkably decrease.

As the photosensitive component 1, a bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -3,4-di Quinonediazide esters of 1,2-naphthoquinonediazide-5-sulfonyl compounds of hydroxyphenylmethane are preferable, and among them, an esterification ratio of 50% is most preferable.

The average esterification ratio of the photosensitive component 2 is preferably 50 to 70%, more preferably 55 to 65%. If the average esterification rate is less than 50%, the film thickness after development tends to easily occur and the residual film ratio tends to be lowered. On the other hand, if it exceeds 70%, storage stability tends to be lowered.

As the photosensitive component 2, it is preferable to use a 1,2-naphthoquinone diazide-5-sulfonyl compound of 2,3,4,4'-tetrahydroxybenzophenone Is preferable. Of these, the esterification ratio of 59% is most preferable.

The photosensitive component may be used alone or in combination of two or more.

The content of the photosensitive component is preferably from 15 to 40 parts by mass, more preferably from 20 to 30 parts by mass, based on 100 parts by mass of the total amount of the alkali-soluble resin and the sensitivity improver.

Examples of the organic solvent in the resist composition (r1) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ketones such as ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol mono Polyhydric alcohols and derivatives thereof such as acetate, propylene glycol monoacetate, diethylene glycol monoacetate, or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether thereof; Ethers include esters such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate; benzene, toluene, xylene, methyl isobutyl ketone, methanol, ethanol , Propanol, butanol, hexanol, cyclohexanol, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate and the like The can.

The organic solvent may be used alone or in combination of two or more.

Of these, propylene glycol monomethyl ether acetate (PGMEA) is preferable because the resist composition imparts good applicability and the resist film on the substrate gives excellent film thickness uniformity.

PGMEA is preferably used as a sole solvent, but an organic solvent other than PGMEA may be used in combination with PGMEA. Examples of the organic solvent include ethyl lactate,? -Butyrolactone, propylene glycol monobutyl ether, and the like.

The total amount of the alkali-soluble resin, the sensitivity-enhancing agent and the photosensitive component in the resist composition (r1) is preferably not more than 30% by mass, more preferably not more than 20% by mass with respect to the total mass of the composition, To 28% by mass.

In this case, in consideration of the amount of the additive to be used, which will be described later, the content of the organic solvent is preferably 50 to 90% by mass, more preferably 65 to 85% by mass with respect to the total mass of the composition, Is 70 to 75% by mass.

In the resist composition (r1), an ultraviolet absorber for preventing halation such as 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dimethylamino-2', 4'- Dihydroxybenzophenone, 5-amino-3-methyl-1-phenyl-4- (4-hydroxyphenylazo) pyrazole, 4-dimethylamino-4'-hydroxyazobenzene, '-Ethoxyazobenzene, 4-diethylaminoazobenzene, curcumin and the like can be used.

To the resist composition (r1), a surfactant such as fluororad FC-430, FC431 (trade name, manufactured by Sumitomo 3M Co., Ltd.), FFA EF122A, EF122B, EF122C, EF126 (trade name, XR-104 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) and BYK-310 (trade name, manufactured by Vick Chemical Japan Co., Ltd.) can be used.

To the resist composition (r1), a preservative stabilizer such as benzoquinone, naphthoquinone, p-toluenesulfonic acid and the like, and optionally additives such as an additive resin, a plasticizer, a stabilizer and a contrast enhancer .

≪ Resist composition (r2) >

The resist composition (r2) is a positive resist composition containing a copolymer having a repeating unit represented by the following general formula (1) and a repeating unit represented by the general formula (2), and a photosensitive component.

When a resist film formed of the resist composition (r2) is applied to, for example, a microlens, a microlens having good heat resistance and chemical resistance can be formed.

[Chemical Formula 4]

[In the formulas (1) and (2), R ⁰ independently represents a hydrogen atom or a methyl group. R ²¹ represents a single bond or an alkylene group of 1 to 5 carbon atoms. R ²² represents an alkyl group having 1 to 5 carbon atoms. R ²³ represents a monovalent organic group having thermal crosslinkability. p represents an integer of 1 to 5, q represents an integer of 0 to 4, and p + q is 5 or less. Provided that a plurality of R ⁰ groups and R ²² groups in the repetition may be different from each other.

(A repeating unit represented by the general formula (1)

The repeating unit represented by the general formula (1) (hereinafter also referred to as " the repeating unit (1) ") shows alkali solubility.

In the above formula (1), R ⁰ is preferably a methyl group.

Examples of the alkylene group having 1 to 5 carbon atoms for R ²¹ include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a tert-butylene group, a pentylene group, Pentylene group, etc. Among them, a methylene group and an ethylene group are preferable.

At least one hydroxyl group is bonded to the benzene ring of the repeating unit (1). P representing the number of bonds of hydroxyl groups is an integer of 1 to 5, and is preferably 1 in view of production. In the benzene ring, at least one of the bonding positions of the hydroxyl groups is preferably at the 4-position when the bonding position of "-C (= O) -OR ²¹ -" is taken as 1 position.

In the benzene ring of the repeating unit (1), as R ²² , a linear or branched alkyl group having 1 to 5 carbon atoms may be bonded. Examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl and neopentyl. Is more preferably a methyl group or an ethyl group. q represents an integer of 0 to 4, more preferably 0.

The repeating unit (1) may be used singly or in combination of two or more.

The content of the repeating unit (1) in the copolymer having the repeating unit (1) and the repeating unit (2) is preferably 20 to 50 mol% based on the total of the repeating units constituting the copolymer. Within this range, it becomes easy to ensure alkali solubility during development.

(A repeating unit represented by the general formula (2)

The repeating unit represented by the general formula (2) (hereinafter also referred to as the "repeating unit (2)") includes a thermal crosslinking group (R ²³ ).

In the above formula (2), R ⁰ is preferably a methyl group.

Examples of the alkylene group having 1 to 5 carbon atoms for R ²¹ include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, a tert-butylene group, a pentylene group, Pentylene group, etc. Among them, a methylene group and an ethylene group are preferable.

In the formula (2), R ²³ represents a monovalent organic group having thermal crosslinking property (hereinafter, this organic group is referred to as a "heat crosslinking group"). The heat crosslinking group is a group which crosslinks by applying heat.

As R ²³ , an organic group containing any of an epoxy group and an oxetanyl group is preferable. Among them, it is more preferable that R ²³ is an organic group containing an epoxy group from the viewpoint of improving the crosslinking efficiency by heat treatment.

The repeating units (2) may be used alone or in combination of two or more.

The content of the repeating unit (2) in the copolymer having the repeating unit (1) and the repeating unit (2) is preferably from 50 to 80 mol% based on the total of the repeating units constituting the copolymer.

When the content of the repeating unit (2) in the copolymer is set to a preferable lower limit value or more, it is possible to reduce the decrease of the transmittance by the heat treatment and to secure the thermosetting property. On the other hand, The occurrence of residues during development can be further suppressed.

The copolymer having the repeating unit (1) and the repeating unit (2) may be either random polymerization or block polymerization.

As described above, by controlling the copolymer to have a different repeating unit of the repeating unit (1) and the repeating unit (2), control of the alkali dissolution rate and control of heat resistance are facilitated.

The mass average molecular weight (Mw: measured value by gel permeation chromatography (GPC) in terms of styrene conversion) of the copolymer is preferably 10,000 to 30,000. When the Mw of the copolymer is a preferable lower limit value or more, heat resistance is improved. For example, in the case of forming a microlens by using a copolymer, the lens shape can be easily maintained even during the firing treatment for hardening the microlens have. On the other hand, by setting it to be not more than the preferable upper limit value, the occurrence of residue at the time of development can be suppressed.

In addition, the resist composition (r2) preferably contains a copolymer having a repeating unit (1) and a repeating unit (2) and having a Mw of 10,000 to 30,000, whereby the glass transition temperature is high, A resist film having heat resistance capable of maintaining the shape can be formed. Since the resist composition (r2) contains a copolymer having a repeating unit containing a heat crosslinking group (R ²³ ), a resist film having high hardness and excellent chemical resistance can be formed.

The resist composition (r2) may be used in combination with a copolymer having the above-mentioned repeating unit (1) and repeating unit (2) together with a resin component other than the copolymer. Examples of such a resin component include an acrylic resin, a hydroxystyrene resin, and a novolak resin.

The photosensitive component used for the resist composition (r2) may be the same as the photosensitive component used for the above-mentioned resist composition (r1).

These photosensitive components may be used alone or in combination of two or more.

The content of the photosensitive component in the resist composition (r2) is preferably within a range of 10 to 40 mass% with respect to the solid content of the resist composition (r2). By setting the content of the photosensitive component to a preferable lower limit value or more, a good pattern can be formed. When the resist composition (r2) is used for microlens formation, a lens shape can be formed favorably at the time of development. On the other hand, by setting the content of the photosensitive component to a preferable upper limit value or less, the developing property can be improved and the occurrence of the residue at the time of development can be suppressed.

In the resist composition (r2), a copolymer having a repeating unit (1) and a repeating unit (2), and components other than the photosensitive component may be used if necessary.

The resist composition (r2) may be blended with a surfactant, for example, from the standpoint of coatability to a support, or may contain various additives such as a sensitizer and defoaming agent.

The resist composition (r2) can be prepared by dissolving the copolymer, the photosensitive component and, if necessary, other components in an organic solvent.

(Pre-baking step S2)

The substrate G after the coating process is transferred to the pre-baking unit PR, the pre-baking process is performed in the heating device 50, and the cooling process is performed in the cooling device 51. [ The substrate G that has been processed in the pre-bak unit PR is transported to the interface unit IF by the transport mechanism TR2.

(Exposure step (S3))

In the interface section IF, ambient temperature is adjusted in the buffer device 52, for example, and ambient exposure is performed in the peripheral exposure apparatus EE. After the peripheral exposure, the substrate G is transported to the exposure apparatus EX by the transport mechanism TR3, and subjected to exposure processing.

(Developing step S4)

The substrate G after the exposure process is subjected to the heating process and the cooling process, and then is returned to the developing unit DV. In the developing unit DV, development processing, rinsing processing and drying processing are successively performed on the substrate G, and a pre-pattern of a predetermined shape is formed on the substrate G. [ After the drying process, the substrate G is conveyed to the dewatering unit 58 by the conveyor mechanism CV10.

(Dehydration process (SS1))

In the dewatering unit 58, the substrate G is first transported into the chamber 70. The dewatering unit 58 encloses the chamber 70 by closing the substrate loading / unloading port after carrying the substrate G into the chamber 70 through a substrate loading / unloading port (not shown), and operates the gas supplying unit 71 And supplies an inert gas into the chamber 70. The dewatering unit 58 heats the substrate G by the heating mechanism 72 in the chamber 70 which has been supplied with the inert gas and is in the dewatering atmosphere. The heating mechanism 72 reduces the amount of water contained in the pre-pattern by heating the substrate G (a pre-pattern formed on the substrate G).

(Light irradiation step (S5))

The substrate G after the dewatering treatment is transported to the light irradiation unit UV by the transport mechanism TR4. In the light irradiation unit (UV), the substrate (G) is first conveyed into the chamber (82) of the standby device (80). The light irradiation unit UV transports the substrate G into the chamber 82 through the substrate transfer port 80a and closes the substrate transfer port 80a to seal the chamber 82, The decompression mechanism 83 is operated to perform decompression processing. After the pressure reduction processing, the lifting mechanism 84 is moved to the + Z side, and the substrate G is lifted by the support pin 84a. At this time, the substrate G is lifted up to a position (position on the + Z side) higher than the height of the substrate holding member 88a of the transfer mechanism 88.

After the substrate G is raised, the comb-like portion 100 of the substrate holding member 88a is inserted into the chamber 82 and the comb-like portion 100 is placed on the -Z side of the substrate G. Then, After the comb-shaped portion 100 is disposed, the lifting mechanism 84 is moved to the -Z side, and the lifted substrate G is moved to the -Z side. Since the comb-like portion 100 is disposed on the -Z side of the substrate G, the substrate G is transferred from the support pin 84a to the comb-shaped portion 100. [

After the substrate G is received, the substrate holding member 88a is moved to the -X side through the transfer member 88b by driving the drive mechanism 88c, and the substrate G is carried into the chamber 85 . After the substrate G is brought into the chamber 85, the inside of the chamber 85 is closed and the gas supply unit 91 is operated to set a low dew point atmosphere in the chamber 85. In the present embodiment, for example, the inside atmosphere of the chamber 85 is set to a dew point of -39.7 DEG C and an oxygen concentration of 812 ppm in the light irradiation unit UV.

The driving mechanism 88c is also driven while keeping the chamber 85 in a low dew point atmosphere so that the substrate G is overlapped with the first opening 87a of the first substrate carrying portion 85F when viewed in the Z direction, .

After the substrate G is disposed, the lifting mechanism 88d is moved to the + Z side, and the support pin 88e is projected from the first opening 87a. The substrate G is passed from the substrate holding member 88a to the support pin 88e because the substrate G is disposed on the + Z side of the support pin 88e. After the substrate G is transferred, the drive mechanism 89c is driven to move the substrate holding member 89a to the -Z side of the substrate G. [ At this time, the driving mechanism 89c is driven so that the four substrate holding members 89a overlap the four corners of the substrate G when viewed in the Z direction.

After positioning the substrate holding member 89a, the lifting mechanism 88d is moved to the -Z side, and the substrate G is moved to the -Z side. Since the substrate holding member 89a is disposed on the -Z side of the substrate G, the substrate G is transferred from the holding pin 88e to the substrate holding member 89a. When the substrate G is handled, for example, an air supply unit (not shown) is operated to blow out and suck air at a predetermined ejection amount and suction amount in the second opening 87b, A layer of air is formed. The substrate G is held between the air layer and the substrate holding member 89a because an air layer is formed between the substrate G and the stage 87 when the substrate G is handed over. Therefore, even if the substrate holding member 89a holds only the edge portion of the substrate G, the substrate G is stably held without being bent or cracked.

After the substrate G is held by the substrate holding member 89a, the driving mechanism 89c is driven to transport the substrate G to the processing unit 85P. Since the substrate G floats on the air layer and is transported, the substrate G can be transported with a small driving force. As a result, the burden on the transmitting member 89b is reduced.

After the substrate G is transferred to the processing portion 85P, the heating portion 90 is maintained in the heated state until the substrate G reaches the predetermined processing temperature in the chamber 85 having the low dew point atmosphere do. For example, the heating section 90 preheats the substrate G (the pre-pattern formed on the substrate G) until the temperature reaches 100 deg. C (predetermined processing temperature). That is, in the present embodiment, the heating section 90 also serves as a preheating section for preheating the pre-pattern. Further, a preheating mechanism capable of preheating (heating) the pre-pattern may be separately formed separately from the heating section 90. [

The light irradiation unit UV irradiates the processing unit 85P while heating the substrate G (pre-pattern) at a predetermined processing temperature by the heating unit 90 after the temperature of the substrate G reaches 100 占 폚, The substrate G is transported to the -X side within the substrate W, and the light irradiating unit 86 is driven.

With this operation, in the processing unit 85P, light of a predetermined wavelength is irradiated onto the free pattern on the substrate G from the light irradiation unit 86 in a state in which the substrate G is transported. Since the light shielding member 85d is formed on the + X side and the -X side of the processing unit 85P, the light is prevented from leaking from the processing unit 85P.

In the bleaching exposure treatment of the pre-pattern by the light irradiation unit (UV), the diazonaphthoquinone contained in the pre-pattern of the positive type resist is changed to indene ketene by photochemical reaction. The indenketen bonds with the hydroxyl group of the resin to polymerize the whole film, and the diazonaphthoquinone disappears. As a result, the diazonaphthoquinone dye (pale yellow to light brown) disappears, and the film constituting the free pattern has improved light transmittance.

However, for example, when the bleaching exposure is performed in the atmosphere, the indenketene is converted to carboxylic acid upon reaction with water (H ₂ O) in the atmosphere. Unlike indene ketene, the carboxylic acid does not bond with the resin and does not polymerize the entire film. For this reason, it is difficult to sufficiently improve the durability (resistance to dry etching and heat resistance) of the resist film.

That is, when the durability of the resist film is improved, it is important to inhibit the production of carboxylic acid by reaction of diazonaphthoquinone with water.

In the resist pattern forming method of the present embodiment, the dehydration step described above is provided before the bleaching exposure by the light irradiation unit (UV). By this dewatering step, the pre-pattern is heated in the dehydration atmosphere, so that moisture contained in the pre-pattern is evaporated and the moisture content (water content) in the pre-pattern is reduced. Therefore, the production of carboxylic acid by the reaction of diazonaphthoquinone with water at the time of bleaching exposure can be suppressed.

In the present embodiment, light irradiation is performed on the free pattern in the chamber 85 having a low dew point atmosphere. Therefore, when the diazonaphthoquinone is changed to indene ketene by the photochemical reaction, the periphery of the pre-pattern (in the chamber 85) is an environment with low water content (low-dew point atmosphere) There is no work.

In this embodiment, since the water content in the pre-pattern is reduced in advance by the dewatering step, generation of carboxylic acid during bleaching exposure can be further suppressed.

Therefore, the indene ketene bonds with the hydroxyl group of the resin without changing to the carboxylic acid, and the whole film is polymerized in an excellent manner, so that the hardness of the whole film is improved and the durability is excellent. In addition, since the diazonaphthoquinone dye disappears by making it into a polymer, it is excellent in light transmittance. Therefore, according to the present embodiment, it is possible to form a pre-pattern having both light transmittance and durability.

In the present embodiment, the light irradiating unit 86 irradiates, for example, light in a wavelength range of 350 to 450 nm to the free pattern. As a result, the above-described photochemical reaction is satisfactorily generated, so that the entire pattern can be cured not only on the surface layer side of the pre-pattern but also inside. By irradiating the light in the above-mentioned wavelength range, it is possible to suppress excessive temperature rise of the pre-pattern during curing while suppressing generation of radiant heat.

Since the processing portion 85P irradiates light while conveying the substrate G, the substrate G is gradually taken out to the second substrate conveyance portion 85S from the portion where light irradiation is completed. When light irradiation is completed on all of the substrates G, all of the substrates G are accommodated in the second substrate transfer section 85S. After the light irradiation is completed, the operations of the light irradiation unit 86 and the heating unit 90 are stopped, and the substrate G is transferred to the first substrate transfer unit 85F.

The substrate G transferred to the first substrate transfer section 85F is transferred from the transfer mechanism 89 to the substrate transfer mechanism 88 and transferred from the chamber 85 to the chamber 82 by the substrate transfer mechanism 88. [ . In the chamber 82, the substrate G is transferred from the substrate transfer mechanism 88 to the lifting mechanism 84, and then the substrate G is transferred from the chamber 82 through the substrate transfer port (80a) to the outside of the light irradiation unit (UV).

(Post-baking step S6)

Next, in the heating device 59, the post-baking process is performed on the substrate G. The heating device 59 heats (bakes) the substrate G at a predetermined processing temperature.

The processing temperature of the substrate G is set to, for example, 180 DEG C or higher. The processing time (baking time) by the heating device 59 is counted after the substrate G reaches the processing temperature.

The heating device 59 may heat the substrate G to a predetermined temperature in a short time, or the temperature may be gradually increased by providing a plurality of heating steps.

Since the pre-pattern formed in this embodiment has excellent durability (heat resistance), the pre-pattern is not deformed even when the post-baking treatment is performed at a high temperature, and the shape remains. Therefore, since the resist pattern obtained by curing the pre-pattern does not change its shape by the post-baking treatment, the resist pattern becomes highly reliable. In addition, since the pre-pattern is excellent in light transmittance, the resist pattern after the post-baking treatment is also excellent in light transmittance.

After the heating by the heating device 59, the substrate G is cooled by the cooling device 60. After the cooling process, the substrate G is accommodated in the cassette C through the transport mechanism 11. [ In this way, the substrate G is subjected to a series of processes after the coating process, the exposure process, and the developing process.

As described above, according to the present embodiment, a resist pattern with high reliability can be formed by hardening the pre-pattern by post bake processing in order to obtain a pre-pattern having both light transmittance and durability (heat resistance).

The resist pattern formed in this embodiment is excellent in durability (resistance to dry etching) and light transmittance, and therefore can be used as an interlayer insulating film of an active matrix substrate used for a liquid crystal display device, an organic EL display device, It can be suitably used as a permanent resist film such as a wafer coating material (a surface cover film, a bump protecting film, a multi-chip module (MCM) interlayer protective film, a junction coat), a package material (encapsulating material, die bonding material) have.

(Second Embodiment)

Next, a second embodiment of the present invention will be described.

The difference between the present embodiment and the above-described embodiment is the structure of the light irradiation unit. Therefore, in the following, the structure of the light irradiation unit will be mainly described, and the same or common components as those in the above embodiment will be denoted by the same reference numerals, and detailed description thereof will be omitted.

Fig. 7 is a view showing a configuration when the light irradiation unit UV1 of the present embodiment is viewed in the + Y direction. 7, the light irradiation unit UV1 includes a chamber 180, a light irradiation unit 86, a first stage 182, a first conveyance unit 183, a second stage 184, And a conveying unit 185. Fig. The chamber 180 is formed in the shape of a rectangular parallelepiped box, and an inert gas is supplied by a gas supply unit (not shown) so that the interior of the chamber 180 is in a low dew point atmosphere state. The chamber 180 is disposed on the side surface (the + Y side surface) of the developing unit DV. In this embodiment, in the light irradiation unit UV1, the chamber 180 is disposed on the upper surface (+ Z side surface) of the dewatering unit 58 (see Fig. 1).

A substrate carry-in / out port 180a is formed on a surface (predetermined surface) 180f of the chamber 180 on the -X side. The substrate carry-in / out port 180a carries out the carry-in and carry-out of the substrate G with respect to the chamber 180. [ A connecting portion 180b for connecting to the dewatering unit 58 is formed on the predetermined surface 180f of the chamber 180. [ The connecting portion 180b physically connects the chamber 180 to the dewatering unit 58 side and connects the chamber 180 and the dewatering unit 58 electrically As shown in FIG.

In this embodiment, the light irradiating unit 86 is mounted on the + Z side surface of the chamber 180, and the + Z side end is disposed so as to project outside the chamber 180.

The first stage 182 is formed inside the chamber 180. The first stage 182 supports the substrate G which is carried into the chamber 180. The first stage 182 is disposed on the + X side of the substrate carry-in / out port 180a and is capable of supporting the substrate G carried from the substrate carry-in / out port 180a. The first stage 182 has a transport mechanism (not shown) that transports the substrate G in the X direction. In addition, the first stage 182 can be elevated in the Z direction. The first stage 182 is movable between a height position (position in the Z direction) equivalent to the first carry section 183 and a height position equivalent to the second carry section 185. The first stage 182 can support the substrate G from the second transport section 185 at a position equivalent to the height of the second transport section 185. [ In addition, the first stage 182 can be raised and lowered while supporting the substrate G.

The first transport section 183 transports the substrate G transported from the first stage 182. The first transport section 183 has a transport mechanism 183a and a heating mechanism 183b. The transport mechanism 183a transports the substrate G in the + X direction while keeping the posture of the substrate G parallel to the horizontal plane (XY plane). The substrate G can be supported while maintaining the posture of the substrate G in a state in which the operation of the transport mechanism 183a is stopped. The heating mechanism 183b adjusts the temperature of the substrate G so that the temperature of the substrate G to be irradiated later is appropriately heated. For example, the heating mechanism 183b maintains the temperature of the substrate G at about 100 占 폚.

The second stage 184 is formed at the end on the + X side inside the chamber 180. The second stage 184 supports the substrate G transported from the first transport section 183. The second stage 184 has a transport mechanism (not shown) that transports the substrate G in the X direction. The second stage 184 is movable in the Z direction. The second stage 184 is movable between a height position (position in the Z direction) equivalent to the first carry section 183 and a height position equivalent to the second carry section 185. In addition, the second stage 184 can be raised and lowered while supporting the substrate G. When the second stage 184 is disposed at a position equivalent to the height of the second carry section 185, the second stage 184 can send the substrate G to the second carry section 185.

The second transport section 185 transports the substrate G transported from the second stage 184. The second carry section 185 is disposed on the + Z side of the first carry section 183. The second conveying section 185 is disposed opposite to the light irradiating section 86. The second transport section 185 has a transport mechanism 185a and a heating mechanism 185b. The transport mechanism 185a transports the substrate G in the -X direction while keeping the posture of the substrate G parallel to the horizontal plane (XY plane). The substrate G can be supported while maintaining the posture of the substrate G in a state in which the operation of the transport mechanism 185a is stopped. The heating mechanism 185b is disposed at a position where the substrate G is sandwiched between the heating mechanism 185b and the light irradiation portion 86 in the Z direction. The heating mechanism 185b heats the substrate G, which is irradiated with light by the light irradiation portion 86, from the -Z side. The heating mechanism 185b heats the substrate G supported by the transport mechanism 185a. The transport mechanism 185a is capable of transporting the substrate G to the first stage 182 when the first stage 182 is disposed on the -X side of the second transport section 185. [

The substrate G carried from the substrate loading / unloading port 180a is transported in the + X direction to the second stage 184 via the first stage 182 and the first transport section 183. In this manner, in the chamber 180, a first substrate transport path R1 for transporting the substrate G in one direction (+ X direction) is formed. The substrate G supported by the second stage 184 is transported in the -X direction to the first stage 182 via the second stage 184 and the second transport section 185. As described above, in the chamber 180, a second substrate transport path R2 for transporting the substrate G in one direction (-X direction) is formed. The second substrate transport path R2 is arranged in the + Z direction with respect to the first substrate transport path R1.

In the present embodiment, the light irradiating unit 86 may be movable along a transport path (second substrate transport path R2) of the substrate G to which light is irradiated. That is, the light irradiation unit 86 can be moved in the directions D1 and D2 parallel to the X-axis in Fig. For example, a horizontal movement mechanism for horizontally moving the light irradiating portion 86 can be formed in the chamber 180. With this structure, light can be irradiated to the substrate G while moving the light irradiation unit 86 in the direction D1 or the direction D2. Thus, the relative speed between the substrate G and the light irradiating unit 86, which are transported in the -X direction on the second transporting unit 185, can be freely changed. As a result, the light irradiation amount and tact time for the substrate G can be set freely.

Specifically, by irradiating light while moving the light irradiation part 86 in the same direction (direction D1) as the substrate G, the relative speed of the light irradiation part 86 with respect to the substrate G becomes The light irradiation amount on the substrate G can be increased without raising the output of the light irradiating unit 86. [ From another point of view, it is possible to maintain the light irradiation amount on the substrate G equally even if the conveying speed is increased, so that the conveying speed of the substrate G in the apparatus can be increased to improve the throughput.

On the other hand, when light irradiation is performed while moving the light irradiation part 86 in the direction opposite to the substrate G (direction D2), the relative speed between the substrate G and the light irradiation part 86 increases, (Tact time) required for light irradiation to the light source (e.g., G) is shortened. Accordingly, when the light irradiation step is a bottle neck, it is possible to improve the throughput. It is also possible to adjust the light irradiation amount on the substrate G without changing the conveying speed of the substrate G and the output of the light irradiating portion 86 by changing the moving speed of the light irradiating portion 86. [ When the light irradiating unit 86 is moved in the direction D2, it is easy to adjust the direction in which the light amount to the substrate G is reduced.

Further, the moving direction of the light irradiating unit 86 and the substrate conveying direction of the second conveying unit 185 may be substantially parallel. Specifically, the angle formed by the moving direction of the light irradiating unit 86 and the substrate transport direction of the second transport unit 185 may be 30 degrees or less.

Subsequently, the light irradiation process in the light irradiation unit UV1 of the present embodiment will be described.

8 to 10 are explanatory diagrams of the operation of the light irradiation unit UV1. Hereinafter, when a plurality of substrates G are carried in the light irradiation unit UV1, a plurality of substrates G1, G2, G3,. .

The control unit CONT moves the robot arm holding the substrate G in the + Z direction and moves the substrate G1 from the substrate loading / unloading port 180a to the inside of the chamber 180 . In the light irradiation unit UV1, the first stage 182 is disposed at a position equivalent to the height of the first transport section 183. Thus, the substrate G1 carried into the chamber 180 is placed on the first stage 182. [

Next, as shown in Fig. 8 (b), the control unit CONT conveys the substrate G1 placed on the first stage 182 in the + X direction and moves it to the first carrying unit 183. The control unit CONT temporarily holds the transport mechanism 183a after the substrate G1 is transported to the substantially central portion in the X direction of the first transport unit 183 and operates the heating mechanism 183b. With this operation, the substrate G1 supported by the transport mechanism 183a is adjusted to a desired temperature by the heating mechanism 183b.

After the substrate G1 is preliminarily heated for a predetermined time, the control unit CONT conveys the substrate G1 in the + X direction by the transport mechanism 183a as shown in Fig. 8 (c). The substrate G1 is transferred from the first carrying section 183 to the second stage 184.

The control unit CONT also loads another substrate G2 conveyed from the developing unit DV into the chamber 180. [ The control unit CONT moves the robot arm of the transport mechanism TR4 to the substrate loading and unloading port 180a and brings the substrate G2 into the chamber 180 from the substrate loading and unloading port 180a. The substrate G2 loaded into the interior of the chamber 180 is placed on the first stage 182.

9 (a), the control unit CONT moves the second stage 184 supporting the substrate G1 to the + Z side, and moves the second stage 184 in the height position of the second carry unit 185 . The control unit CONT also conveys the substrate G2 placed on the first stage 182 in the + X direction and moves it to the first carrying unit 183. The control unit CONT temporarily holds the transport mechanism 183a after the substrate G2 is transported to the substantially central portion in the X direction of the first transport unit 183 and operates the heating mechanism 183b. With this operation, the substrate G2 supported by the transport mechanism 183a is adjusted to a desired temperature by the heating mechanism 183b.

Next, the control unit CONT moves the first stage 182 in the + Z direction and aligns the first stage 182 with the height position of the second transport unit 185, as shown in Fig. 9 (b). The control unit CONT also transports the substrate G1 placed on the second stage 184 in the -X direction and moves it to the second transport unit 185. [ The control unit CONT irradiates the substrate G1 conveyed to the second conveyance unit 185 with light by the light irradiation unit 86. [ The control unit CONT activates the transport mechanism 185a to move the substrate G1 in the -X direction and operates the heating mechanism 185b to maintain the temperature of the substrate G1 at about 100 ° C.

In this state, the control unit CONT causes the light irradiation unit 86 to emit light. The light emitted from the light irradiation unit 86 is irradiated to the substrate G1. With this operation, light is irradiated onto the substrate G1 which is moved to the horizontal plane by the transport mechanism 185a. Irradiation of light is performed until the entire substrate G1 passes through the light irradiating section 86 in the -X direction. The substrate G1 transported in the -X direction by the second transport section 185 is placed on the first stage 182 previously placed as shown in Fig. 9 (c). After the substrate G1 is placed on the first stage 182, the control unit CONT moves the first stage 182 in the -Z direction and aligns the height position with the first transport unit 183.

10 (a), the controller CONT uses the robot arms of the first stage 182 and the transport mechanism TR4 to move the substrate G1 on the first stage 182 Out. The control unit CONT moves the substrate G2 that has been preliminarily heated by the first transfer unit 183 in the + X direction and places the substrate G2 on the second stage 184.

10 (b), the control unit CONT moves the second stage 184 supporting the substrate G2 to the + Z side, and moves the second stage 184 in the height position of the second transport unit 185 . The control unit CONT also conveys the substrate G3 placed on the first stage 182 in the + X direction and moves it to the first carrying unit 183. The control unit CONT temporarily holds the transport mechanism 183a after the substrate G3 is transported to the substantially central portion in the X direction of the first transport unit 183 and preliminarily heats the substrate G3.

Thereafter, the control unit CONT irradiates the substrate G2 and the substrate G3 in succession in the same manner as described above, and takes it out of the chamber 180 through the substrate loading / unloading port 180a. Further, a new substrate is brought into the chamber 180 through the substrate loading / unloading port 180a, and the light L is irradiated. The substrates G1 to G3 taken out of the chamber 180 are transported to the post-baking unit PB via the transport mechanism TR4. By repeating the above operation, the light irradiation process can be performed on the substrate G that has passed through the developing unit DV.

As described above, according to the present embodiment, the substrate loading / unloading port 180a capable of loading and unloading the substrate G is formed on the predetermined surface 180f, and the substrate loading / Since the substrate G moves inside the chamber 180 such that the substrate G carried into the chamber 180 moves to the outside of the chamber 180 through the substrate carry-in and discharge port 180a, Out is carried out on the same surface side (predetermined surface side) of the chamber 180. As a result, it is possible to save the space necessary for the transfer of the substrate G to / from the existing apparatus, so that it is possible to provide the light irradiating unit 86 with a small footprint.

10 (b), the control unit CONT controls the substrate G1 to irradiate the substrate G1 with light while moving the light irradiation unit 86 in the direction D1 or D2 It is possible. For example, when light irradiation is performed on the substrate G1 while moving the light irradiation unit 86 in the direction D1, the control unit CONT controls the light irradiation unit 86 to move the light irradiation unit 86 in the direction The substrate G1 is carried from the second stage 184 to the second transport section 185 and the light irradiation section 86 is moved in the direction D1) and starts irradiation of light to the substrate G1. The control unit CONT irradiates light while moving the light irradiation unit 86 at a slower speed than the substrate G1. The control unit CONT stops the movement of the light irradiating unit 86 at a position where the light irradiating unit 86 moving later on the substrate G1 reaches the rear end of the substrate G1. Thereafter, the control unit CONT moves the light irradiation unit 86 in the direction D2 and returns it to the movement start position.

Although the embodiment of the present invention has been described above, the present invention is not limited to the above-described embodiment, and can be appropriately changed without departing from the gist of the present invention.

(Modified example)

In the above embodiment, the light irradiation is performed in a state that the substrate G is heated in the low dew point atmosphere in the light irradiation unit (UV). However, the substrate G may be kept at a low temperature For example, at room temperature). In this case, the light irradiating apparatus 81 does not require the heating section 90. [ This eliminates the need for the heating unit 90, so that the apparatus configuration of the light irradiation device 81 is simplified and the cost is reduced.

Instead of the heating portion 90, a cooling device for cooling the substrate G may be formed. By doing so, the temperature of the substrate G can be lowered to room temperature in a short time by cooling the substrate G in a relatively high temperature state by heating the dewatering unit 58 in the cooling device. Therefore, the light irradiation unit UV substantially reduces the waiting time of the substrate G in the unit (the waiting time until the substrate G lowers to the low temperature), so that the tact time of the entire apparatus can be shortened have.

The configuration of the dewatering unit 58 for dehydrating treatment is not limited to the embodiment described above.

Fig. 11 is a view showing a configuration when the dewatering unit 158 according to the modification is viewed in the -Y direction. Fig.

As shown in Fig. 11, the dehydrating unit 158 has a chamber 170, a pressure reducing mechanism 171, and a heating mechanism 172, and can perform vacuum dehydration of the pre-pattern.

The chamber 170 accommodates the substrate G on which the dehydration process is performed. The decompression mechanism 171 is constituted by, for example, a vacuum pump or the like and artificially enlarges the steam partial pressure difference by decompressing the interior of the chamber 170 to evaporate moisture in the pre-pattern at a low temperature. In this configuration, since the chamber 170 is in a vacuum atmosphere, moisture in the free pattern evaporates at about room temperature. Therefore, the heating mechanism 17 of the present embodiment keeps the temperature of the substrate G constant so that the temperature of the pre-pattern is not lowered by the evaporation of moisture. Thus, it is possible to efficiently evaporate moisture in the free pattern.

In the dewatering unit 158 shown in Fig. 11, the configuration of the heating mechanism 17 is not essential, and the heating mechanism 17 may be omitted from the constituent elements. By doing so, the apparatus configuration of the dewatering unit 158 can be simplified, so that downsizing and cost reduction can be achieved.

Although the dewatering unit 58 of the above-described embodiment is provided with the gas supply unit 71 for supplying the inert gas in order to set the inside of the chamber 70 to a low moisture atmosphere, the present invention is not limited to this Do not. For example, the gas supply portion 71 may be omitted from the constituent elements of the dewatering unit 58. According to this configuration, since the dehydration process of the pre-pattern can be performed by the simple structure of heating the substrate G in the chamber 70, the apparatus configuration can be simplified and cost reduction can be achieved.

In the above embodiment, a dewatering device for dehydrating the free pattern in the light irradiation unit (UV) may be provided. For example, a dehydration process (substrate) of the substrate G may be performed in the chamber 82 of the standby unit 80 of the irradiation unit UV. In this case, a gas supply mechanism for supplying an inert gas into the chamber 82 may be provided instead of the decompression mechanism 83, and a heating device for heating the substrate G in the chamber 82 may be provided.

By doing so, the dewatering unit 58 formed between the developing unit DV and the transport mechanism TR4 shown in Fig. 1 can be omitted, so that the installation area of the pattern forming apparatus SPA can be suppressed.

In the above embodiment, the positive resist composition is applied on the substrate G to form a resist pattern. However, the present invention is not limited to the positive resist. For example, the present invention is also applicable to a negative resist composition in which the unexposed portion is dissolved and removed to form a free pattern. Examples of such a resist composition include resist compositions (r3) and (r4) exemplified below.

≪ Resist composition (r3) >

The resist composition (r3) is a chemically amplified negative resist composition containing an alkali-soluble resin and an acid generator.

In the resist composition (r3), the alkali-soluble resin may be selected from conventionally known resins in accordance with the light source used for exposure, in general, a resin used as a base resin of a negative-type chemically amplified resist composition It is possible to do. For example, novolak resins, polyhydroxystyrene resins, acrylic resins and the like.

As the alkali-soluble resin, a novolak resin, a polyhydroxystyrene resin, an acrylic resin and the like may be used individually or in combination of two or more.

When the resist composition (r3) contains the alkali-soluble resin, the acid generator, and the plasticizer to be described later, the content of the alkali-soluble resin is preferably in the range of about 100 parts by mass per 100 parts by mass of the total solid content of the alkali- More preferably 30 to 99 parts by mass, and still more preferably 65 to 95 parts by mass.

In the resist composition (r3), the acid generator is not particularly limited as long as it is a compound which generates an acid directly or indirectly by irradiation of light, and it can be arbitrarily selected and used from conventionally known ones.

The acid generators may be used alone or in combination of two or more.

The content of the acid generator in the resist composition (r3) is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, more preferably 0.05 to 2 parts by mass, relative to 100 parts by mass of the total solid content of the resist composition (r3) 0.1 to 1 part by mass.

In the resist composition (r3), components other than the alkali-soluble resin and the acid generator may be used as needed. For example, in addition to the alkali-soluble resin and the acid generator, a plasticizer may be added. By adding a plasticizer, generation of cracks can be suppressed. Examples of the plasticizer include an acrylic resin and a polyvinyl resin.

The resist composition (r3) may contain a crosslinking agent in addition to the alkali-soluble resin and the acid generator, or in addition to the alkali-soluble resin, the acid generator, and the plasticizer.

Examples of such a crosslinking agent include amino compounds such as melamine resin, urea resin, guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin and ethylene urea-formaldehyde resin, An alkoxymethylated amino resin such as methylated melamine resin or alkoxymethylated urea resin, and the like can be suitably used.

In the resist composition (r3), a fluorinated polymer compound having a constituent unit containing a base dissociable group (preferably a base dissociable group containing a fluorine atom) may be added in addition to each of the above components, if necessary.

The term " base dissociative group " is an organic group capable of dissociating by the action of a base. That is, the "base dissociable group" is dissociated by the action of an alkali developer (for example, a 2.38 mass% aqueous TMAH solution at 23 ° C.).

When the base dissociable group is dissociated by the action of an alkali developing solution, a hydrophilic group appears, so that the affinity to the alkaline developer is improved. That is, the fluorinated polymer compound is a "polymer compound having a fluorine atom", which has a high hydrophobicity, but also has a "base dissociable group", so that the affinity to an alkali developer is improved by the action of an alkali developer. Therefore, by using the negative resist composition, it is possible to form a resist film that is hydrophobic at the time of immersion exposure and is well dissolved in an alkali developing solution at the time of development.

To the resist composition (r3), in addition to the above-mentioned components, a quaternary agent such as a secondary or tertiary amine such as triethylamine, tributylamine, dibutylamine or triethanolamine, a surfactant, A functional silane coupling agent, a filler, a colorant, a viscosity adjusting agent, a defoaming agent, and the like may be added.

The resist composition (r3) can be prepared by dissolving an alkali-soluble resin, an acid generator and, if necessary, other components in an organic solvent.

≪ Resist composition (r4) >

The resist composition (r4) is a negative resist composition containing an alkali-soluble resin, a cationic polymerization initiator, and a sensitizer.

Examples of the alkali-soluble resin in the resist composition (r4) include a polyfunctional epoxy resin. The polyfunctional epoxy resin is not particularly limited as long as it is an epoxy resin having an epoxy group in one molecule sufficient for forming a resist pattern of a thick film. Examples of the polyfunctional epoxy resin include polyfunctional phenol novolak type epoxy resin, polyfunctional orthocresol novolak type epoxy Resins, polyfunctional triphenyl type novolak type epoxy resins, and polyfunctional bisphenol A novolac type epoxy resins.

As the alkali-soluble resin, an alkali-soluble substrate having photo-curability can also be used.

In the resist composition (r4), the cationic polymerization initiator generates a cationic moiety upon irradiation with an excimer laser such as ultraviolet ray, deep ultraviolet ray, KrF, ArF, X-ray or electron beam, ≪ / RTI > As the cationic polymerization initiator, any of conventionally known ones can be selected and used.

The cationic polymerization initiator may be used alone or in combination of two or more.

The content of the cationic polymerization initiator in the resist composition (r4) is preferably 0.5 to 20 parts by mass based on 100 parts by mass of the alkali-soluble resin. When the content of the cation polymerization initiator is 0.5 part by mass or more, sufficient optical sensitivity can be obtained. On the other hand, when the amount is 20 parts by mass or less, the resist film characteristics are improved.

In the resist composition (r4), the sensitizer is preferably composed of a naphthalene derivative or an anthracene or a derivative thereof capable of forming a bridge with the above-mentioned polyfunctional epoxy resin. By such a function of increasing and decreasing the sensitizer, the sensitivity of the resist composition can be further increased. Of these, dihydroxynaphthalene having two hydroxyl groups, or a sensitizer comprising anthracene is particularly preferable. Since these sensitizers have a plurality of directional rings, the resist pattern can be hardened.

The sensitizers may be used alone or in combination of two or more.

The content of the sensitizer in the resist composition (r4) is preferably 1 to 50 parts by mass based on 100 parts by mass of the alkali-soluble resin.

In the resist composition (r4), components other than the alkali-soluble resin, the cationic polymerization initiator and the sensitizer can be used if necessary.

For example, it is preferable to use an oxetane derivative in order to further enhance the curability of the resist pattern.

In addition, a photopolymerization initiating system for the photosensitive resin composition other than the above-described cation polymerization initiator may be used. In addition, a photopolymerizable compound may be blended because it is hard to cause hardening defects at the time of exposure and it is easy to obtain sufficient heat resistance.

The resist composition (r4) may contain miscible additives such as an additive resin for improving the performance of a resist pattern, a plasticizer, a stabilizer, a colorant, a coupling agent, a leveling agent, Can be appropriately blended.

The resist composition (r4) can be prepared by dissolving an alkali-soluble resin, a cationic polymerization initiator, a sensitizer, and, if necessary, other components in an organic solvent.

SPA: Pattern forming apparatus (resist pattern forming apparatus)
DV: developing unit (developing apparatus)
58, 158: Dewatering unit (dewatering device)
59: Heating device
70: chamber (dehydration chamber)
72, 172: Heating mechanism
81: Light irradiation device
85: chamber (processing chamber)
90: heating part (preheating part)

Claims (16)

A coating apparatus for coating a resist film on a substrate,
A developing device for forming the pre-pattern by performing the developing process of the resist film,
A dehydrating device for performing dehydration processing on the pre-pattern after development,
A light irradiating device for irradiating the pre-pattern after dewatering with light,
And a heating device for heating and curing the pre-pattern after the light irradiation. The method according to claim 1,
Wherein the dehydrating apparatus includes a heating mechanism for heating the pre-pattern in a dehydration chamber supplied with an inert gas. The method according to claim 1,
Wherein the dehydrating apparatus includes a vacuum mechanism for making a space containing the free pattern in a vacuum atmosphere. The method of claim 3,
Wherein the dehydrating apparatus further comprises a heating mechanism for heating the pre-pattern in the vacuum atmosphere. The method according to claim 1,
Wherein the dehydrating apparatus includes a heating mechanism for heating the pre-pattern. 6. The method according to any one of claims 1 to 5,
Wherein the light irradiation device has a low dew point atmosphere in the processing chamber for performing the light irradiation process. The method according to claim 6,
Wherein the light irradiation device comprises a heating portion for heating the pre-pattern at a treatment temperature of 20 占 폚 to 200 占 폚 when the light irradiation treatment is performed. 8. The method of claim 7,
Wherein the light irradiation device includes a preheating portion for holding the substrate under a low dew point atmosphere until the pre-pattern reaches the processing temperature before the light irradiation process. A coating step of applying a resist film on a substrate,
A developing step of developing the resist film to form a pre-pattern,
A dehydrating step of dehydrating the pre-pattern after the developing step,
A light irradiation step of irradiating the pre-pattern after the dewatering step with a light irradiation treatment,
And a heating step of heating and curing the pre-pattern after the light irradiation step. 10. The method of claim 9,
Wherein the dehydrating step includes a heating step of heating the pre-pattern in a dehydration chamber supplied with an inert gas. 10. The method of claim 9,
Wherein the dehydrating step includes a vacuum step of setting a space containing the free pattern to a vacuum atmosphere. 12. The method of claim 11,
Wherein the dehydrating step heats the pre-pattern in the vacuum atmosphere. 10. The method of claim 9,
Wherein the dewatering step is performed by heating the pre-pattern. 14. The method according to any one of claims 9 to 13,
Wherein the light irradiation step performs the light irradiation treatment in a processing chamber having a low dew point atmosphere. 15. The method of claim 14,
Wherein the light irradiation step heats the pre-pattern at a treatment temperature of 20 ° C to 200 ° C when the light irradiation treatment is performed. 16. The method of claim 15,
Wherein the light irradiation step includes a preheating step of holding the substrate under a low dew point atmosphere until the pre-pattern reaches the processing temperature before the light irradiation processing.

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