JPH09330865A - Method and unit for heat treating x-ray mask, and method and unit for processing resist - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat treating method for producing an X-ray mask having high dimensional accuracy. SOLUTION: The heat treating unit for an X-ray mask substrate 1 comprises a substrate supported on a mask supporting frame, and an X-ray transmission membrane and an X-ray absorber formed sequentially on the substrate wherein a photosensitive resist film 13 is formed on the X-ray absorber. First and second temperature regulating members 3, 4 for heating or cooling the photosensitive resist film 13 and the X-ray mask substrate 1 are disposed closely above the X-ray absorber membrane provided with photosensitive resist film 13 and closely below the rear side of the X-ray mask substrate 1. Temperature of the photosensitive resist film 13 and the X-ray mask substrate 1 is set within a predetermined range by controlling the temperature of at least one of the first and second temperature regulating members 3, 4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat treatment method for an X-ray mask substrate and an apparatus therefor, and in particular, an X-ray mask substrate coated with a photosensitive resist is exposed by electron beam, X-ray, ion beam, ultraviolet ray or the like. The present invention relates to a heat treatment method and an apparatus therefor performed before or after. The present invention also relates to a processing apparatus and a processing method in pattern formation using a resist.

[0002]

2. Description of the Related Art In recent years, as design rules of semiconductor devices have become finer and more precise, demands for dimensional specifications and precision of exposure masks have become stricter with the innovation of exposure technology. In order to meet such demands, development of high-resolution and high-sensitivity resists has been rapidly developed. In particular, a chemically amplified resist having higher sensitivity and higher resolution than the conventional novolac-based resist is expected to be promising in the next semiconductor process, and is expected as an indispensable material in the future. The chemically amplified resist is a photosensitive composition containing an acid generator that generates an acid upon exposure to light and a compound having a substituent that is crosslinked or decomposed by the acid. When exposed, a polymer-based reaction occurs. Instead, the acid is generated from the acid generator. The acid generated here acts as a catalyst by heat treatment (PEB) after exposure, and in the case of a negative resist, a cross-linking reaction occurs in the polymer to selectively insolubilize the exposed portion in the developing solution. In the case of a positive type resist, a pattern is formed by changing the dissolution inhibiting group and selectively solubilizing the exposed part in a developing solution.

In such a chemically amplified resist, the reaction amount of the acid due to the heat treatment directly affects the resist size, so that the heat treatment temperature must be strictly controlled in order to form a pattern with a desired dimensional accuracy. There is. For example, in the case of a chemically amplified resist of a certain type, a line width of 0.
To form a pattern of 35 μm, the heat treatment temperature after exposure must be set within 0.3 ° C. With finer pattern dimensions, of course, the precision of the processing temperature becomes even more severe, and for example, the precision of about 0.2 ° C. is required for the dimensions of the 0.15 μm rule.

However, the conventional heat treatment of resist is
The resist pattern size was not changed substantially even if the heat treatment temperature was changed to some extent, only to reduce rattling of the resist side wall due to the standing wave of the exposure light. In order to use chemically amplified resists in the future, it is clear that it is a very important factor to reduce the environmental dependency, which is a process-related problem than in the past. In terms of control, improvement in temperature uniformity during heat treatment after exposure and accurate temperature control are required.

Usually, the heat treatment of the resist film after exposure is performed by placing a semiconductor substrate in contact with or in close proximity on a hot plate and applying heat from the back surface side of the substrate. Therefore, the temperature uniformity of the resist applied on the semiconductor substrate must be improved by refining the temperature control of the hot plate. In spite of this, due to insufficient performance of the hot plate itself and generation of temperature distribution due to convection of the heating atmosphere around the substrate, sufficient temperature control is not performed at present. Therefore, when the chemically amplified resist is used, there is a problem that it is difficult to improve the variation in the resist pattern size within the substrate surface. Also in the light exposure mask pattern, the dimensions of the resist pattern similarly vary. further,
As the diameter of silicon wafers and photolithography masks increases,
Achieving the temperature control of such a large semiconductor substrate with high accuracy is facing an increasingly difficult situation. The same problem is more serious for an X-ray mask used in X-ray lithography, which is expected as an exposure technique of 0.15 μm or less, and a conventional method is no longer used to perform highly accurate temperature control. Things have become difficult.

Incidentally, the conventional X-ray mask substrate is, for example,
The configuration is as shown in FIG. The X-ray mask substrate shown in FIG. 21 is an X-ray absorber film (0.
4 μm thick) 1a and X made of SiC provided thereunder
Line transparent thin film (2 μm thick) 1b, Si support substrate (600 μm thick, outer diameter 76 mm) supporting the X-ray transparent thin film 1
c, and a supporting frame SiO ₂ glass (4
mm thickness, outer diameter 100 mm, opening 60 mmφ) 1d. Further, a part of the Si substrate 1c is removed by back etching and a window (4
0 mm square) 1e is formed.

As described above, the X-ray mask substrate has a complicated structure as compared with a silicon wafer or a mask for light exposure, and is composed of a plurality of materials.
Especially, the heat transfer in the thickness direction of the substrate is different. Therefore, it is more difficult to uniformly heat-treat the resist applied on the substrate surface. Therefore, the temperature distribution inevitably tends to occur in the surface of the substrate, and as a result, the amount of heat supplied to the resist varies within the surface, and the desired dimensional accuracy cannot be achieved.

An example of a conventional heat treatment apparatus for an X-ray mask substrate is shown in FIG. Heat treatment apparatus 10 shown in FIG.
At 0, the temperature controller 101 sets the hot plate 102 to a desired temperature, and the X-ray mask substrate 103
Is heated from the back side of the. Using this heat treatment apparatus, after exposing a chemically amplified negative resist film coated on an X-ray mask substrate having a structure similar to that shown in FIG.
The resist pattern dimension obtained by heat treatment at 0 ° C. for 1 minute and further development treatment was measured by a dimension SEM in the range of 40 mm square in the center of the substrate.
It was found that the in-plane distribution of the 5 μm pattern was about 30%. From the value of the in-plane distribution of this dimension, when the temperature variation is converted based on the relationship between the resist dimension and the heat treatment temperature after exposure, it is estimated that the temperature distribution in the plane of the mask substrate was about ± 1 ° C. It

Regarding the in-plane distribution of the resist pattern size, the temperature distribution of the resist in the plane of the mask substrate occurs, and the temperature of the resist becomes higher as it is located in the center of the mask substrate.
This is because the temperature was low near the mask opening. The reason why such temperature distribution occurs is not only because the temperature uniformity of the hot plate of the conventional apparatus is insufficient, but also the X-ray transparent thin film region where the actual pattern is formed and the mask opening portion. This is also due to the difference in heat transfer coefficient between the mask support frame region supporting the X-ray transmissive thin film located at the position.

As described above, the chemically amplified resist has excellent characteristics such as high sensitivity and high resolution, so that it is an indispensable material in the next semiconductor process. At present, it is extremely difficult to perform a high heat treatment. Moreover, in the case of an X-ray mask substrate having a more complicated structure, it is not possible to perform temperature treatment with high uniformity in the upper surface, and as a result, the resist pattern dimension controllability is insufficient, and the X-ray with high dimensional accuracy is obtained. There is a problem that a mask substrate cannot be manufactured.

As described above, since the design rules of semiconductor devices are becoming finer and more precise, the circuit patterns of the LSI elements that make them up are becoming more and more miniaturized. In order to miniaturize the pattern, not only the line width is simply reduced, but also the dimensional accuracy and the positional accuracy of the pattern are required to be improved, and many technological developments have been made to meet these requirements. Incidentally, in forming a fine pattern, usually, on a resist film formed on a substrate, a method of scanning a charged particle beam such as an electron beam to directly draw a circuit pattern on a semiconductor substrate, or an ultraviolet ray or X
A method of irradiating a line to transfer a mask pattern onto a semiconductor substrate is used. In many cases, the mask pattern itself is also formed using a resist. Therefore, it is an important subject for forming a fine pattern to perform resist processing with high reproducibility, high accuracy, and uniformity.

On the other hand, the formation of a pattern using a resist requires several heat treatment steps, and the reproducibility and uniformity of those heat treatments are important. As described above, the chemically amplified resist is subjected to a heat treatment called PEB after the exposure and before the development, so that the pattern formation is performed by utilizing the diffusion of the acid generated by the exposure in the resist film. It has the advantage that it can be achieved. However, if this PEB process is performed non-uniformly, the uniformity of the obtained pattern will be seriously adversely affected, and therefore a highly accurate heat treatment apparatus of less than 0.2 ° C. is required. .

Here, FIG. 23 shows a schematic view of an example of a conventional heat treatment apparatus. In the heat treatment apparatus shown in FIG. 23, the entire furnace body 110 has a heater wire 112.
The substrate 111 is heated evenly by this, and the substrate 111 to be processed is inserted into the inside of the furnace body for heat treatment. In the heat treatment apparatus having such a configuration, it is necessary to use a part of the wall of the furnace body 110 as the entrance / exit of the workpiece 111, so that the uniformity of the internal temperature is degraded when the substrate is taken in and out. Moreover, since the furnace wall and the substrate to be processed are separated from each other, there is a problem that the temperature rising and cooling rates are slow. Further, as another example of the conventional heat treatment apparatus, one using a hot plate as shown in FIG. 24 is known. In this apparatus, a hot plate 114 uniformly heated by a heater 115 and a vertical drive mechanism 116 for vertically driving the substrate are provided, and the processed surface 111a coated with the resist is directed upward. Then, the substrate 111 is uniformly lowered to approach the hot plate 114 and heated from the lower surface of the substrate, that is, the side opposite to the surface 111a to be processed, to perform the heat treatment.

In an apparatus for performing resist processing, it is necessary to supply a liquid to the surface to be processed at the time of coating or developing the resist, so that the surface to be processed is required to face upward. For this reason, the apparatus having the configuration shown in FIGS. 23 and 24 has been used for the heat treatment.

However, recently, as the degree of integration of semiconductor devices has increased, the areas of semiconductor substrates and masks used for exposure have tended to increase, and as a result,
In order to suppress the deformation of these substrates and the like, they must be increased in the thickness direction. In the conventional method of heating the substrate from the surface opposite to the processed surface coated with resist, the temperature increase / decrease rate becomes slower as the substrate becomes thicker, and the temperature uniformity during processing is maintained. Things are getting harder. Such a problem becomes particularly remarkable in the processing of an X-ray mask substrate used for X-ray transfer, which is cited as a strong candidate for forming a fine pattern of 0.15 μm or less.

That is, since the X-ray mask substrate is three-dimensionally complicated and is formed of a plurality of members having different heat capacities and thermal conductivities, as shown in FIG. If the heating is done from the plane, the substrate will be heated through the thick gas layer. Therefore,
An effective method for increasing the size of the substrate to be processed and processing the X-ray mask because it is extremely difficult to uniformly heat-treat the entire surface to be processed due to the influence of the peripheral support frame, as the temperature rising and cooling rates are slow. Has not been found.

[0017]

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 perform heat treatment of an X-ray mask substrate coated with a photosensitive resist with high temperature uniformity. It is to provide a heat treatment method and an apparatus therefor that can be carried out.

Another object of the present invention is to provide a large substrate or X
An object of the present invention is to provide a resist processing apparatus and a resist processing method capable of forming a resist pattern having high dimensional uniformity even on a line mask substrate.

[0019]

In order to solve the above problems, the present invention provides a substrate supported by a mask support frame, and an X-ray transmission film and an X-ray absorber sequentially formed on the substrate. A method of heat-treating an X-ray mask substrate having a photosensitive resist film formed on the X-ray absorber, the photosensitive layer being above the X-ray absorber film formed with the photosensitive resist film. A first temperature adjusting member for heating or cooling the resist film and the X-ray mask substrate is arranged close to each other, and the photosensitive resist film and the X-ray mask substrate are provided below the back surface of the X-ray mask substrate. A second temperature adjusting member for heating or cooling is arranged in close proximity to the first temperature adjusting member.
The temperature of the at least one of the temperature adjusting member and the second temperature adjusting member is controlled to set the temperatures of the photosensitive resist film and the X-ray mask substrate within a predetermined range. A method for heat treating a substrate is provided.

Further, the present invention comprises a substrate supported by a mask support frame, an X-ray transmission film and an X-ray absorber formed on the substrate in sequence, and a photosensitive material is provided on the X-ray absorber. An apparatus for heat-treating an X-ray mask substrate on which a resist film is formed, with the photosensitive resist film facing upward,
A first mask for heating or cooling the photosensitive resist film and the X-ray mask substrate, the first mask being disposed close to and above the X-ray absorber film on which the photosensitive resist film of the X-ray mask substrate is formed;
Temperature adjusting member, a second temperature adjusting member which is disposed below and under the back surface of the X-ray mask substrate, and is for heating or cooling the photosensitive resist film and the X-ray mask substrate; A temperature control means for controlling the temperature of at least one of the first and second temperature adjusting members so as to set the temperatures of the resist film and the X-ray mask substrate within a predetermined range. A heat treatment apparatus for an X-ray mask substrate is provided.

Further, according to the present invention, a step of supplying a chemical solution onto the surface of the substrate to be processed from above the surface to be processed,
A step of heating or cooling the substrate to be processed with the chemical liquid supplied to the surface to be processed, wherein heating of the substrate to be processed is performed by setting a relative positional relationship between the surface to be processed to which the chemical liquid is applied and the surface of the heating means. Provided is a resist processing method, which is carried out by separating and facing the surface to be processed and the surface of the heating means.

The resist processing method of the present invention comprises a chemical liquid supply mechanism for supplying a chemical liquid onto a substrate to be processed, and rotation for rotating the substrate to be processed around an axis forming a significant angle with the normal to the principal surface of the substrate. The heating / cooling mechanism includes a mechanism, a removal prevention mechanism that prevents the substrate from falling off when the substrate to be processed is rotated, and a heating / cooling mechanism that heats or cools the substrate to be processed. Facing heating means, vertical driving means for vertically driving the substrate to be processed, positioning means for determining a positional relationship between the surface to be processed of the substrate to be processed and the surface of the heating means spaced apart from and facing the surface to be processed, and It can be performed using a resist processing apparatus characterized in that it has a movable means provided on the opposite side of the processed surface of the processed substrate.

Alternatively, the resist processing method of the present invention comprises
The heating / cooling mechanism is provided with a chemical liquid supply mechanism for supplying a chemical liquid onto the substrate to be processed and a heating / cooling mechanism for heating or cooling the substrate to be processed, wherein the heating / cooling mechanism is a heating means having a surface normal downward. Vertical drive means for driving the substrate up and down, positioning means for determining the positional relationship between the surface to be processed of the substrate to be processed and the surface of the heating means which is separated from and faces the surface to be processed, and the surface to be processed of the substrate to be processed. It is also possible to use a resist processing apparatus characterized by having a movable means provided on the opposite side.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in more detail with reference to the drawings. (Example I) In Example I, an X-ray mask substrate heat treatment method and apparatus of the present invention will be described.

(Example I-1) FIG. 1 is a schematic view showing an example of an X-ray mask substrate heat treatment apparatus of the present invention. Here, a case of using a chemically amplified negative resist and performing heat treatment after exposure will be described as an example. First, a chemically amplified resist was applied to an X-ray mask substrate 1 having the same structure as that shown in FIG. 21 to obtain a resist film, and this resist film was exposed. After that, the X-ray mask substrate was heat-treated as follows. That is, the inside of the heat treatment apparatus 2 is filled with an inert gas N ₂ which serves as a heat medium, and the above-mentioned substrate is conveyed into this apparatus and placed on the holding table 14, and the first temperature adjusting member 3 and It was arranged in the gap between the temperature adjusting member 2 and the temperature adjusting member 4.

FIG. 2 shows a side view and a plan view of the first temperature adjusting member 3 used here. As shown in FIG. 2A, the first temperature adjusting member is a circular shape having a planar shape thickness of 20 mm and an outer diameter of 76 mm. In addition, inside the first temperature adjusting member, as shown in FIG.
A heater wire 15 controlled by is formed, and further five temperature sensors 17 are embedded. A side view and a plan view of the second temperature adjusting member 4 are shown in FIG. As shown in FIG. 3A, the second temperature adjusting material has a circular shape with an outer diameter of 48 mm so that it can be inserted into the opening in a shape similar to the opening of the X-ray mask substrate 1. The upper surface is a 40 mm square regular square cone shape. FIG.
As shown in (b), a heater wire 16 controlled by the temperature control device 6 is formed inside the second temperature adjusting member 4 similarly to the first temperature adjusting member, and five heater wires 16 are formed. The temperature sensor 18 is embedded. The signals from the temperature sensors 17 and 18 are taken into the 5 and 6 temperature control devices and fed back when the temperature is controlled.

During the heat treatment of the X-ray mask substrate, the first temperature adjusting member 3 and the second temperature adjusting member 4 are respectively controlled by the temperature controllers 5 and 3 before the X-ray mask substrate 1 is transported. Is preset to a desired temperature by. In addition,
In the present embodiment, the set temperature is 110 ° C., and the temperature of each of the first temperature adjusting member and the second temperature adjusting member is adjusted so that the temperature of each of the first temperature adjusting member and the second temperature adjusting member is substantially evenly distributed in the plane.
And 6 have been adjusted.

Next, the first temperature adjusting member 3 is placed close to the X-ray mask substrate 1 under the control of the first drive controller 9 by the first drive mechanism 7, and the first temperature adjusting member 3 is placed at the first temperature. The gap between the adjusting member and the resist surface was set to about 100 μm.
Further, independently of this, the second temperature adjusting member 4 is
Under the control of the second drive control device 10 by the drive mechanism 8 of FIG. 3, the X-ray mask substrate 1 is arranged close to the back face of the X-ray mask substrate 1, and the gap between the second temperature adjusting member 4 and the back face of the mask substrate is about 100 μm.
m. At that time, the position of the outer peripheral portion of the X-ray mask substrate 1 is monitored by the distance sensor 11 provided on the first member and the distance sensor 12 provided on the second member to detect the first and second temperatures. The distance between the adjusting members 3 and 4 and the X-ray mask substrate 1 was set. The signals from the distance sensors 11 and 12 provide the drive control devices 5 and 6 with information on the amount of the gap between the members 3 and 4 and the X-ray mask substrate 1, and are fed back to the drive control.

In this state, the X-ray mask substrate 1 is heated for 1 minute to be heat-treated, and then each temperature adjusting member 3 is used.
And 4 are driven by drive mechanisms 7 and 8, and control devices 9 and 1
The X-ray mask substrate 1 was unloaded under the control of 0.

After the resist on the X-ray mask substrate 1 which has been subjected to the heat treatment as described above is developed to form a pattern, the pattern dimension is measured in a 40 mm square plane. It was found that the pattern dimension of was smaller by 10% than the design dimension of 0.15 μm.

It was confirmed that the in-plane uniformity of the resist pattern dimension was improved by the method of this example, as compared with the pattern dimension accuracy when heating after exposure with the conventional heat treatment apparatus shown in FIG. However, the resist pattern dimension becomes thicker toward the center of the X-ray mask substrate, and the dimension difference is 0.2 in terms of the heating temperature after exposure.
It was found to correspond to ° C. Therefore, in order to further improve the in-plane uniformity of the dimensional accuracy, the temperature setting of the first temperature adjusting member 3 is not changed and the second temperature adjusting member 4 is not changed.
In addition, the temperature control device 6 controls the temperature from the center toward the outer peripheral portion to 0.
The same heat treatment was performed by giving a temperature distribution having a temperature rising gradient of 2 ° C. An outline of the temperature distribution of the first temperature adjusting member 3 and the second temperature adjusting member 4 set under these heat treatment conditions is shown in the graph of FIG. In FIG. 4, curves a and b represent the temperature distributions of the first temperature adjusting member and the second temperature adjusting member, respectively. The temperature of the first temperature adjusting member (curve a) is
The temperature of the second temperature adjusting member (curve b) is set within a range of ± 0.1 ° C. over the Si substrate area of 76 mm.
The temperature is about 110.4 ° C. at the end of the window region and decreases toward the center of the substrate with the above temperature gradient.

Thus, the temperature is controlled and heat treatment is performed to form a resist pattern, and the obtained pattern dimensions are shown in the graph of FIG. As shown in FIG. 5, the in-plane variation of the resist pattern size after development has a center size of 0.15 μm.
It can be seen that ± 3% has been achieved.

FIG. 5 also shows the in-plane uniformity of resist pattern dimensions obtained after development when heat treatment was performed in the conventional apparatus, with the result of the central dimension of 0.15 μm. When the heat treatment is performed by the conventional apparatus, the in-plane variation of the pattern dimension reaches ± 20%, and it is understood that the variation of the pattern dimension can be greatly reduced by the present invention.

(Embodiment I-2) FIG. 6 shows a schematic view of a second example of the heat treatment apparatus for an X-ray mask substrate of the present invention. The structure of the heat treatment apparatus shown in FIG. 6 is basically the same as that of the heat treatment apparatus 2 shown in FIG.
The shapes of the first temperature adjusting member 24 and the second temperature adjusting member 25 differ depending on the shape of No. 2. The X-ray mask substrate 22 used here has a so-called mesa structure in which the pattern formation region is more convex than the peripheral portion as shown in FIG. 7, and this mask has a circular X-ray transparent thin film. Are formed.

As shown in FIG. 6, the first temperature adjusting member 2
No. 4 corresponds to the mesa structure of the X-ray mask substrate 22 and has a shape in which a part of the member adjacent to the surface of the X-ray mask substrate is recessed. The second temperature adjusting member 25 is used for the X-ray mask substrate 22.
A circular shape similar to the opening was formed. A heater wire and a temperature sensor (not shown) are formed on each member as in the case of (Example I-1).

Also in this embodiment, a chemically amplified negative resist coated X was prepared by the same recipe as in (Example I-1).
The line mask substrate 22 is conveyed to the heat treatment apparatus 21 and the holding table 1
After being placed on the substrate 4, the gap between the first temperature adjusting member 24 and the surface of the resist film 23 and the gap between the second temperature adjusting member 25 and the back surface of the mask substrate 22 were set to about 100 μm. The distance between each member and the X-ray mask substrate is monitored by the distance sensors 11 and 12, and the members 24 and 25 are also monitored.
Was driven by controlling the drive mechanisms 7 and 8 by the drive control devices 9 and 10, respectively. After the resist film 23 and the mask substrate 22 are heat-treated by heating for 1 minute by the temperature adjusting members 24 and 25 whose temperature is previously set to 110 ° C. by the temperature control devices 5 and 6, the members 24 and 25 are driven by a driving mechanism. Drive device 5,
The X-ray mask substrate 22 was carried out by controlling 6 and evacuating.
Next, the resist film 23 after the heat treatment was developed to obtain a resist pattern.

It was confirmed by dimension measurement that the in-plane uniformity of the obtained resist pattern dimension was within ± 3% with respect to the center dimension. Based on the value of the dimensional uniformity, the temperature uniformity within the mask substrate surface is within ± 0.1 ° C. when the temperature uniformity is converted from the relationship between the resist pattern dimension and the heat treatment temperature after exposure. It is expected that it was achieved with extremely high accuracy.

(Embodiment I-3) A schematic view of a third example of the heat treatment apparatus for an X-ray mask substrate of the present invention is shown in FIG. The structure of the heat treatment apparatus shown in FIG. 8 is basically (Example I-1).
1 is the same as that of the heat treatment apparatus 2 shown in FIG. 1, and the substrate having the same structure as that shown in (Example I-1) is used as the X-ray mask substrate 1 to be heat treated. The shapes of the first temperature adjusting member 3 and the second temperature adjusting member 4 were the same as in (Example I-1).

First, after transferring the X-ray mask substrate not coated with the resist into the apparatus by the same recipe as in Example (I-1), the first temperature adjusting member 3 and the surface of the X-ray mask substrate. And the gap between the second temperature adjusting member 4 and the back surface of the X-ray mask substrate were set to about 100 μm, respectively. At that time, the first temperature adjusting member 3 and the second temperature adjusting member 4 were placed close to the X-ray mask substrate under the control of the drive control devices 9 and 10 by the drive mechanisms 7 and 8 independently. Further, the position of the X-ray mask substrate was adjusted and set under the control of the drive controller 30 by the X-ray mask substrate drive mechanism 29.

First and second temperature adjusting members 3, 4 and X
The distance from the line mask substrate was monitored by distance sensors 11 and 12. Next, the X-ray mask substrate was heat-treated by the members 3 and 4 whose temperatures were set to 110 ° C. by the temperature controllers 5 and 6, respectively. When the in-plane temperature distribution of the X-ray mask substrate during this heat treatment was measured by a thermistor 31 previously formed on the mask substrate surface, it was found that the temperature around the mask opening was 0.5 ° C. lower than the set temperature. all right.

Therefore, in order to improve this temperature distribution,
By further changing the set temperature of the first temperature adjusting member 3 by the temperature control device 5 and giving a temperature distribution such that the peripheral portion becomes a high temperature, the temperature distribution in the substrate surface is monitored by the thermistor 31 step by step. Thus, the set temperature of the first temperature adjusting member 3 and the condition of distribution were determined so that the temperature distribution on the surface of the X-ray mask substrate was within a predetermined range. Here, the predetermined temperature distribution was within a range of ± 0.1 ° C.

Further, the gap amount between the front surface of the X-ray mask substrate and the first temperature adjusting member 3 and the gap amount between the rear surface of the X-ray mask substrate and the second temperature adjusting member 4 under this condition are stored.

Next, the temperature distribution X was measured here.
After carrying out the line mask substrate, another X-ray mask substrate coated with the chemically amplified resist was carried into this apparatus and subjected to heat treatment. At this time, the set temperature of each member and the temperature distribution of the first temperature adjusting member are the same as those obtained previously,
The respective drive control devices 9 and 10 and the mask drive control device 30 drive the respective members so that the gap amount between the X-ray mask substrate and the first and second temperature adjusting members also becomes the value stored previously. The mechanism was controlled to place the X-ray mask substrate 2 close to it. Under these conditions, the resist film was heat-treated for 1 minute, and then the X-ray mask substrate was carried out from the apparatus and developed to form a resist pattern.

When the dimensions of the obtained resist pattern were measured, the in-plane uniformity was within ± 3% with respect to the central dimension, and the dimensional accuracy was a permissible value of 1/2 of the specifications on the resist pattern dimension. there were.

As described above, according to the heat treatment method for the X-ray mask substrate of the present invention, the heat supplied to the photosensitive resist film formed on the substrate is controlled, so that the dimensional accuracy is remarkably improved. .

The heat treatment method and the apparatus therefor of the present invention are not limited to the examples described above, and various modifications can be made. For example, the X-ray mask substrate is not limited to the structure in which the window is formed on the back surface, and a substrate having any structure can be used. Further, the shapes and dimensions of the X-ray absorber film, the X-ray transparent thin film, the Si support substrate, and the support and reinforcement frame, which are the respective constituent elements of the X-ray mask substrate, are also limited to the materials shown in the prior art. The shape and size of the window can be determined as appropriate.

Further, the resist applied on the substrate may be a chemically amplified positive type resist. The heat treatment method and apparatus of the present invention exerts its effect particularly when the influence of the heat treatment temperature on the resist pattern size is very large like a chemically amplified resist, but a conventional resist other than the chemically amplified resist is used. Even if it is present, it is effective when precise control of heat treatment is required.

Further, the shape of the first temperature adjusting member arranged close to the front side of the X-ray mask substrate and the shape of the second temperature adjusting member arranged close to the rear side of the X-ray mask substrate are also dependent on the shape and size of the substrate to be heat treated. The shape can be changed as appropriate as long as it functions as a heat transfer means. From this meaning, fine holes or fine holes are formed in the first and second temperature adjusting members,
It is also possible to provide a through hole through which the atmospheric gas passes. The member used in the examples has a heater wire inside, but the temperature of the member can be controlled by other means. For example, a pipe that serves as a flow path for a liquid or gas that acts as a heat medium. The passage may be provided inside.

Further, in all of the above-mentioned embodiments, the temperature adjusting members are arranged so as to be parallel to the X-ray mask substrate and the gap dimension thereof is set to about 100 μm. However, the present invention is not limited to this, and it is appropriate. You can choose. Depending on the case, the surface of the member may be inclined with respect to the surface of the substrate to be heat-treated. It is also possible to perform heat treatment by controlling the amount of gap between each member and the surface of the substrate to be heat treated.

In the embodiments, the heat treatment of the resist film after exposure is described as an example, but the heat treatment of the resist film before exposure may be performed or the substrate cooling after the heat treatment may be performed. It is included in the heat treatment method of the invention. Further, in the embodiment, the temperature distribution of the first or second temperature adjusting member is adjusted in order to improve the in-plane uniformity of the resist temperature, but the temperature of both of these members is adjusted to make the resist temperature uniform. It doesn't matter.

The heat treatment method for the X-ray mask substrate of the present invention is
It is not limited to controlling the temperature and shape of each member in order to improve the in-plane uniformity of the resist temperature.
In order to give a desired in-plane distribution to the line mask substrate, the first
It is also possible to positively give the in-plane temperature distribution to the member and the second member. Alternatively, the present invention can be applied to a case where the temperature of each member is given a difference to achieve a desired temperature distribution in the thickness direction. (Example II) In Example II, a resist processing apparatus and a resist processing method of the present invention will be described.

(Embodiment II-1) FIG. 9 is a perspective view showing an example of a vertical reversing mechanism in the resist processing apparatus of the present invention, and FIG. 10 shows a resist processing apparatus using this vertical reversing mechanism. An explanatory diagram showing the configuration is shown. As shown in the configuration of FIG. 10, in the resist processing apparatus of the present embodiment, the configuration of a normal resist processing apparatus is provided with a vertical inversion mechanism 55 for vertically inverting the substrate to be processed.

The vertical reversing mechanism in the resist processing apparatus of Example (II-1) has a substrate holding mechanism 5 as shown in FIG.
The substrate holding mechanism 55a holds and releases the substrate by vertically moving the support block 55c up and down. The support block 55c is provided with an up-and-down movement mechanism 55 via an elastic body 55d so as not to apply an excessive force to the substrate to be processed.
connected to e. In addition, the vertical movement mechanism 55e supports only the portion of the substrate reinforcing frame of the X-ray mask substrate so as to reduce the influence of dust and prevent it from coming into contact with the pattern forming portion on the substrate surface and its vicinity. Is designed. A drop-out preventing portion 60 is formed in a portion that comes into contact with the upper and lower sides of the substrate so as not to fall off even when the substrate is turned upside down. In consideration of the actual operation, the drop-off prevention portion 60 is tapered to relieve the positioning error. On the other hand, the rotation mechanism 55b
Has a function of rotating the substrate about a rotation axis parallel to the principal plane of the substrate.

The upside down of the substrate is performed as follows. First, the substrate holding mechanism 55a is opened vertically, and the substrate (not shown) is placed on the arm 58 of the transfer mechanism in a state where the substrate support 61 is raised. The substrate is first moved by the transfer mechanism 57 onto the substrate support 61 while being placed on the arm 58 of the transfer mechanism, and the movement is detected by the sensor 5
After confirmation by 9, the transfer mechanism 57 moves the arm of the transfer mechanism downward so that the substrate is placed on the substrate support 61. After that, the arm 58 of the transfer mechanism is retracted, and this is confirmed by the sensor 59 of the transfer mechanism, and after confirming by the sensor 64 that the substrate is placed at the normal position on the substrate support portion 61, the substrate is held. The mechanism 55a sandwiches the substrate from above and below to support the substrate, and the substrate support portion 61 moves downward and retracts. That is, the substrate holding mechanism 55a
The lower support block 55c is designed to be located below the substrate support portion 61 before holding the substrate and above the substrate support portion 61 when holding the substrate.

After moving the substrate from the arm 58 to the substrate holding mechanism 55a as described above, the substrate holding mechanism 55a is moved.
It is confirmed that the substrate is normally supported by the sensor 62, the retracting of the substrate supporting portion 61 is confirmed by the sensor 63, and the rotating mechanism 55b is used to rotate the substrate 180 around the rotation axis parallel to the main plane. ° rotate. At this time, the rotation amount of the substrate can be monitored by monitoring the number of pulses supplied to the motor. Subsequently, after confirming by the sensor 65 that the substrate is normally directed to the main plane downward, the substrate support portion 61, which has been retracted downward, is raised, and this rise is confirmed by the sensor 63, and the substrate holding mechanism is held. 55
The substrate a is placed on the substrate support portion 61 by opening a up and down.
It is confirmed by the sensor 64 that the substrate is placed at the normal position on the substrate support, and the arm 58 of the transfer mechanism is inserted below the substrate. Then, by moving the substrate support portion 61 downward and retracting the substrate, the substrate is transferred to the arm 58 of the transfer mechanism.
The substrate can be placed on the transfer mechanism 57 and turned upside down and transferred to the transfer mechanism 57.

FIG. 11 shows details of the heating portion of the heating / cooling processing section 53 in the resist processing apparatus of this embodiment. As shown in FIG. 11, after receiving the X-ray mask substrate 49 from the arm of the transport mechanism 57, the substrate supporting unit 68 moves up and down above the hot plate 66 in which the heater 67 and the temperature sensor 71 are incorporated. By this, X
The heat treatment of the line mask substrate 49 is controlled. At this time, in order to maintain the uniformity of the heat treatment, it is important to accurately determine the distance between the surface of the hot plate 66 and the surface to be processed of the X-ray mask substrate 49. A positioning mechanism 69 is provided so that the distance between the hot plate surface and the X-ray mask substrate surface can be accurately determined. By the positioning mechanism 69, even if the processed surface on which the resist is applied faces the hot plate, consideration is given so that the processed surface does not come into contact with the hot plate surface to cause a defect in the pattern. .
Further, as a matter of course, since dust generation and temperature unevenness are expected in the vicinity of the contact portion between the positioning mechanism 69 and the X-ray mask substrate 49, it is desirable to be sufficiently separated from the pattern formation region.

Although not clearly shown in FIG. 11, the positioning mechanism 69 is arranged at three positions in the plane of the hot plate and can be adjusted independently of each other. Therefore, when the temperature distribution has a gradient, By adjusting the inclination of the X-ray mask substrate 49, the in-plane temperature uniformity can be improved. Further, in the heating / cooling processing section shown in FIG. 11, a back plate 70 is provided in order to improve the uniformity of the heating processing, and the back plate 70 is provided in synchronization with the vertical movement of the substrate supporting section 68. It is designed to approach and retract on the back side. A sensor 72 is attached to the back plate 70, and X from the transport mechanism 57 is attached.
When the line mask substrate 49 is delivered, it can be detected whether or not the substrate is placed at a normal position. In addition, the sensor 72 attached to the back plate 70
Also has a function of monitoring the distance between the X-ray mask substrate 49 and the back plate 70, and this sensor can be used to confirm that the relative positions of the two are proper.
The details of the cooling portion are essentially the same as those of FIG. 11 except that the function of the heater 67 is omitted from the heating portion.

Next, the manufacturing process of the X-ray mask substrate used in this embodiment will be described. 12 and 13 are sectional views showing the manufacturing process of the X-ray mask substrate. First, FIG.
As shown in (a), 4-inch Si (1
00) A wafer 41 is prepared, and the substrate temperature is 1025 ° C. and the pressure is 30 T on this Si wafer by using the low pressure CVD method.
Silane gas diluted with 10% hydrogen under the conditions of orr 15
0 sccm, 65% acetylene gas diluted with 10% hydrogen
cm, and 150 sccm of 100% hydrogen chloride gas,
A 10 μm-thick SiC film having a thickness of 1 μm as shown in FIG.
The film 42 was formed on the entire surface of the wafer 41.

Next, an Ar pressure of 1 mT is applied to the surface of the substrate on which the SiC film 42 is formed by using an RF sputtering device.
Under the condition of orr, the film thickness is 98n as shown in FIG.
m alumina film 43 is formed, and the alumina film 4
Similarly, using a RF sputtering device, a WR having a film thickness of 0.35 μm was formed under the conditions of Ar pressure of 3 mTorr.
An e-alloy film 44 was formed to obtain a structure as shown in FIG.

The stress of the obtained WRe film 44 is 17 MPa.
Since it was the tensile stress of 5 × 10 ¹⁵ atoms / cm ² at an accelerating voltage of 30 kV using an ion implanter,
After r ions were implanted to adjust the compressive stress to 3 MPa, a Cr film was vapor-deposited on the WRe film 44 with an electron beam vapor deposition apparatus to a thickness of 50 nm as shown in FIG.

Then, using an aluminum etching mask, a pressure of 10 mTorr and RT is applied by an RIE apparatus.
CF ₄ gas 25scc under the condition of power 200W
By supplying m and O ₂ gas of 40 sccm, as shown in FIG. 13A, the SiC film 42 in the central region of 30 mm square on the back surface of the Si wafer 41 was removed. Further, using a back etching device, a 1: 1 mixture of hydrofluoric acid and nitric acid was dropped onto the removed portion of the SiC film, and Si in this region was removed by etching, as shown in FIG.
A structure as shown in was obtained.

Then, using the RF sputtering apparatus again, the alumina film 46 having a film thickness of 98 nm is formed on the portion where the alignment mark at the time of transfer is formed on the X-ray mask through the aluminum stencil mask under the condition of Ar pressure of 1 mTorr. The film was formed from the back surface. Finally, using UV curable epoxy resin adhesive, outer diameter 125mm, inner diameter 72
A glass ring 47 having a thickness of 6 mm and a thickness of 6 mm was bonded as a reinforcing frame to prepare an X-ray mask substrate 49 as shown in FIG.

A resist process was performed on the X-ray mask substrate thus manufactured in accordance with the steps shown in FIG. Hereinafter, the resist processing method of the present invention will be described with reference to the explanatory view of FIG. 10 and the flowchart of FIG. The resist processing apparatus is kept in a state where amines are sufficiently removed from the surrounding atmosphere by a chemical filter.

First, as shown in the flow chart of FIG. 14, the X-ray mask substrate having the work surface set upward in the carry-in / out section (56 in FIG. 10) of the resist processing apparatus is moved by the transfer mechanism (57). After being transported to the pretreatment section (51), the hexamethyldisilazane vapor treatment is carried out for 10 seconds, and then the transport mechanism (57) is used to apply (5).
It was transported to 2). Here, 3 cm ³ of the chemically amplified positive resist was dropped on the X-ray substrate, and it was applied at 10 rpm for 5 seconds for 5 seconds.
The resist was spin-coated by performing processing in steps of 00 rpm for 30 seconds and 3000 rpm for 3 seconds. After that, as a so-called edge cut process, 2000
While rotating at rpm, the solvent propylene glycol monomethyl ether was sprayed on the wafer edge and the periphery of the back surface for 5 seconds to stop the solvent supply, and then the wafer was rotated at 2000 rpm for another 20 seconds to perform drying.

The substrate after being dried is conveyed to the upside-down mechanism (55) by the conveying mechanism (57) and turned upside down so that the surface to be processed faces downward, and then the heating / cooling processing section (53).
Transported to. Then, by performing a post-application baking treatment for 2 minutes on a hot plate heated to 110 ° C., unnecessary residual solvent was removed and further cooled on a cooling plate. Through the above steps, a resist film having a film thickness of 350 nm was formed. The state where the resist film 48 is formed on the X-ray mask substrate 49 is as shown in FIG.

The X-ray mask substrate on which the resist film has been formed is again moved up and down by the transport mechanism (57).
After being transported to 5) and turned upside down so that the surface to be processed faces upward, it is transported to the loading / unloading section (56) and then sent to the exposure step.

The exposure was carried out by using an electron beam drawing apparatus having an acceleration voltage of 50 kV and a standard irradiation amount of 9 μC / cm ^{2 with} the proximity effect corrected by the irradiation amount correction. The exposed X-ray mask substrate is again set with the surface to be processed facing upward in the carry-in / out section (56) of the resist processing apparatus, and transferred to the up / down reversing mechanism (55) by the transport mechanism (57).
After being turned upside down so that the surface to be processed faces downward, it is conveyed again to the heating / cooling processing section (53). Subsequently, heat treatment (PE for 150 seconds on a hot plate heated to 75 ° C.
B) was carried out, followed by cooling on a cooling plate.

The substrate after cooling is again transported by the transport mechanism (57).
Then, the sheet is conveyed to the upside-down reversing mechanism (the same 55), turned upside down so that the surface to be processed faces upward, and then conveyed to the developing section (the same 54). In this developing section, a dedicated developing solution (AD-10) having a concentration of 0.27 N was sprayed from above the substrate, and the development processing was performed by a paddle for 70 seconds. Then, rinse with deionized pure water at 2000 rpm for 15 seconds, and
Drying was performed by rotating at 00 rpm for 10 seconds. After that, it is again conveyed to the carry-in / out section (56) by the conveying mechanism (57), the resist pattern as shown in FIG. 13E is formed, and the resist process is completed.

The resist pattern obtained by the above method was evaluated using a dimension measuring SEM. Specifically, the pattern widths d ₁ and d ₂ in FIG. 15 are measured,
The in-plane distribution of the dimensional uniformity was evaluated. As a result of this measurement, the line width variation of the resist pattern when processed by the resist processing apparatus of the present embodiment is 27n at 3σ.
m. The line width variation when processed by the conventional resist processing apparatus is 3 in 3σ value.
It is 5 nm, which means that the present invention can improve the in-plane uniformity of the pattern dimension.

(Embodiment II-2) FIG. 17 is a perspective view showing another example of the vertical inversion mechanism in the resist processing apparatus of the present invention, and FIG. 18 is a resist processing apparatus using this vertical inversion mechanism. The explanatory view showing the structure of is shown. As shown in the configuration of FIG. 18, in the resist processing apparatus of the present embodiment, a vertically inverting mechanism for vertically inverting the substrate to be processed is incorporated in the transport mechanism itself.

In the resist processing apparatus of the embodiment (II-2), as shown in FIG.
It is composed of a pair of upper and lower parts, and holds and releases the substrate by vertically opening and closing. The arm 73 is connected to a vertical movement mechanism 77 via an elastic body 76 so as not to apply an excessive force to the substrate to be processed. Further, the arm 73 is designed to support only the substrate reinforcing frame portion of the X-ray mask substrate so as to reduce the influence of dust and not to contact the pattern forming portion and its vicinity. A drop-out preventing portion 74 is formed on the top and bottom of the substrate so that it does not fall off even when the substrate is turned upside down. In addition, the arm 73 is tapered in consideration of the actual operation so as to relieve the positioning error. On the other hand, the rotation mechanism 78
Has a function of rotating the substrate about a rotation axis parallel to the main plane.

The actual vertical inversion is performed as follows. First, the arm 73 is opened vertically, and the substrate support 6
1 is in a raised state, the substrate (not shown) is the substrate support 6
1. Then, after confirming by the sensor 64 that the substrate is placed at a normal position on the substrate support portion 61, the substrate is supported by the arm 73 sandwiching it from above and below, and the substrate support portion 61 moves downward. Save. That is, the support block on the lower side of the arm 73 is positioned below the substrate support portion 61 before holding the substrate, while
It is designed so as to be positioned above the substrate support portion 61 when holding the substrate.

After that, it is confirmed by the sensor 75 that the arm 73 normally supports the substrate, and the substrate supporting unit 6
After confirming the evacuation of 1 from the sensor 63, the rotation mechanism 7
180 about the rotation axis parallel to the main plane
° rotate. At this time, the rotation amount of the substrate can be monitored by monitoring the number of pulses supplied to the motor. Then, it is confirmed by the sensor 79 that the substrate is normally oriented with its principal plane downward, and the substrate is conveyed to the next resist processing section. Furthermore, another substrate support portion 6 that was retracted
1 '(not shown) is raised, and this rise is detected by the sensor 6
After confirmation by 3 '(not shown), the arm 73 is opened up and down and the substrate is placed on the substrate support 61'. By retracting the arm 73 rearward, the substrate can be turned upside down and handed over.

This embodiment (II-2) is shown in FIG. 11 except that the carrying mechanism 57 in FIG. 17 also has the function of the upside-down reversing mechanism, which is different from the embodiment (II-1). The details of the heating / cooling processing unit are the same. However, in the present embodiment, the surface to be processed of the substrate can be faced down in portions other than the coating section 52 and the developing section 54 in FIG. It is possible to significantly reduce the dust that is generated, and it has an advantage that the product yield can be improved.

Next, a resist processing method using the resist processing apparatus of this embodiment will be described with reference to the flowchart of FIG. 18 and the explanatory view of FIG. Note that the resist processing apparatus is kept in a state where amines are sufficiently removed from the surrounding atmosphere by a chemical filter.

First, as shown in the flow chart of FIG. 18, the X-ray mask substrate set with the surface to be processed facing downward in the loading / unloading section (56 in FIG. 17) of the resist processing apparatus is moved by the transfer mechanism (57). After being transported to the pretreatment section (51), the hexamethyldisilazane vapor treatment is carried out for 10 seconds, and then the transport mechanism (57) is used to apply (5).
2), the substrate is turned upside down and the coating unit 5
Delivered to 2. Here, chemically amplified positive resist 3c
m ³ was dropped, 10 rpm for 3 seconds, and 500 rpm for 3 seconds.
Then, the resist was spin-coated by performing the processing in a step of 3,000 rpm for 30 seconds. Then, as a so-called edge cut process, the solvent propylene glycol monomethyl ether was sprayed on the wafer edge and the back surface periphery for 5 seconds in a state of rotating at 2000 rpm, and after the solvent supply was stopped, 2000 rpm for another 20 seconds.
Drying was performed by rotating the wafer at.

The dried substrate is turned upside down by the transfer mechanism (57) so that the surface to be processed faces downward, and then transferred to the heating / cooling processing section (53). Then, a post-application baking treatment was performed for 2 minutes on a hot plate heated to 110 ° C. to remove unnecessary residual solvent, and then cooling was performed on a cooling plate. As a result, a resist film having a film thickness of 350 nm was formed. The X-ray mask substrate on which the resist film has been formed is again loaded and unloaded (56) by the transport mechanism (57).
To the exposure step.

The exposure was carried out by using an electron beam drawing apparatus having an acceleration voltage of 50 kV and a standard irradiation amount of 9 μC / cm ^{2 with} the proximity effect corrected by the irradiation amount correction. The exposed X-ray mask substrate is again set with the surface to be processed facing down in the carry-in / out section (56) of the resist processing apparatus, and is transported to the heating / cooling processing section (53) by the transport mechanism (57). Then, on a hot plate heated to 75 ° C, 1
A heat treatment (PEB) was carried out for 50 seconds, followed by cooling on a cooling plate.

The cooled substrate is conveyed to the developing section (54) by the conveying mechanism (57), turned upside down so that the surface to be processed faces up, and then handed over to the developing section (54).
In this developing section, a dedicated developer (AD-
10) was sprayed from above the substrate, and development processing was performed by a paddle for 70 seconds. Then, using deionized pure water, 2
Rinse for 15 seconds at 000 rpm, 4000r
Drying was done by spinning at pm for 10 seconds.
Then, the sheet is again turned upside down by the transport mechanism (same as 57), and then transported to the carry-in / out section (same as 56), and the resist processing ends.

The resist pattern obtained by the above method was evaluated using a dimension measuring SEM. Specifically, the pattern widths d ₁ and d ₂ in FIG. 15 are measured,
The in-plane distribution of the dimensional uniformity was evaluated. As a result, the variation of the line width when the treatment was performed by the conventional resist treatment apparatus was 35 nm in 3σ value, but could be 27 nm. Further, according to this embodiment, the amount of dust on the surface to be processed can be reduced to 60% of that in the conventional case.

The above-mentioned embodiments (II-1) and (II
In -2), the substrate was turned upside down by rotating it about an axis parallel to the main plane of the substrate, but the method of turning over the substrate is not limited to this, and other methods may be used. Is also possible. For example, as shown schematically in FIG. 19, the tip portion can be turned upside down by rotating each of them by 180 ° around two rotation axes (80a, 80b) forming an angle of 45 ° with the main plane of the substrate. You can Generally, if there are two independent rotation axes that are not parallel to the normal to the principal plane of the substrate, it is possible to turn the substrate upside down.

(Example II-3) FIG. 20 shows an example (II-
3 shows a heating / cooling processing unit in the resist processing apparatus of 3). In the heating / cooling processing unit of the resist processing apparatus of Example (II-3), as shown in FIG. 20, the processed substrate 49 on which the resist is applied is directed upward, and the processed substrate 49 is moved upward. The heat treatment is performed by bringing the hot plate 66 above it into proximity. The structure other than the heating / cooling processing unit 53 can be the same as that of the conventional resist processing apparatus.

In the heating section of the heating / cooling processing section shown in FIG. 20, the substrate supporting section 68 has the heater 67 and the temperature sensor 71 incorporated therein after receiving the X-ray mask substrate 49 from the arm k of the transfer mechanism. Hot plate 66
By moving up and down below the X-ray mask substrate 4
Control the heat treatment of 9. At this time, it is important to accurately determine the distance between the hot plate surface and the surface to be processed in order to maintain the uniformity of the heat treatment of the X-ray mask substrate. A positioning mechanism 69 is provided so that the distance between the surface and the X-ray mask substrate surface can be accurately determined. By the positioning mechanism 69, even if the processed surface on which the resist is applied faces the hot plate, consideration is given so that the processed surface does not come into contact with the hot plate surface to cause a defect in the pattern. . Also, of course,
Since dust generation and temperature unevenness are expected in the vicinity of the contact portion between the positioning mechanism 69 and the X-ray mask substrate 49, it is desirable to be sufficiently separated from the pattern formation region.

Although not clearly shown in FIG. 20, the positioning mechanisms 69 are arranged at three places and can be adjusted independently of each other. By adjusting the inclination of the mask substrate 49, the uniformity of the in-plane temperature can be improved. In addition, in the heating / cooling processing unit shown in FIG. 20, a back plate 70 is provided in order to improve the uniformity of the heating process, and X is synchronized with the vertical movement of the substrate supporting unit 68.
The back side of the line mask substrate 49 is made to approach and retract. Further, a sensor 72 is attached to the back plate 70, and when the sensor receives the X-ray mask substrate from the transport mechanism, it detects whether or not the substrate is placed at a normal position.

On the back plate 70, a positioning mechanism 8 for determining the relative position with respect to the X-ray mask substrate 49 is provided.
5 is attached to 3 places, back plate 70
The distance between the X-ray mask substrate 49 and the X-ray mask substrate 49 can be accurately determined. The substrate support portion 68 and the vertical drive mechanism 42 thereof, and the back plate 70 and the vertical drive mechanism 8 thereof.
4, elastic bodies 81 and 83 are respectively arranged, and a mechanism for transmitting the vertical drive without applying an excessive force to the X-ray mask substrate 49 by interposing these elastic bodies. The details of the cooling portion are the same as the heating portion except that the function of the heater 67 is omitted.

The present embodiment (II-3) does not require a complicated vertical inversion mechanism as in the above-mentioned embodiments (II-1) and (II-2), which leads to a reduction in manufacturing cost.
The resist treatment was carried out in the same manner as in the above-mentioned examples by using the apparatus and method, and the obtained results were evaluated in the same manner as described above. 28 nm, and the value obtained in the example (II-
Results similar to 1) and (II-2) were obtained.

As described above, according to the resist processing apparatus of the present invention, since the surface to be processed on which the resist is applied faces the surface of the hot plate, it is possible to use a thick substrate or a complicated structure. Even if there is, it is possible to suppress the disturbance of temperature uniformity without slowing down the rate of temperature rise and temperature decrease. As a result, the finish uniformity of the resist pattern size can be significantly improved.

The resist processing apparatus and processing method of the present invention, which has been described by taking the resist processing using the X-ray mask substrate as an example in the above-described embodiments, is not limited to the X-ray mask substrate, but may be a wafer or a glass. Obviously, it can be applied to the manufacture of a reticle mask and the like.

[0089]

As described in detail above, according to the first aspect of the present invention, there is provided a heat treatment method and apparatus capable of performing heat treatment of an X-ray mask substrate coated with a photosensitive resist with high temperature uniformity. It By using the method and apparatus of the first invention as described above, it becomes possible to manufacture an X-ray mask substrate with high dimensional accuracy.

According to the second invention, a large substrate or X
A resist processing apparatus and method capable of forming a resist pattern having high dimensional uniformity even when the substrate is thick like a line mask or has a complicated structure. INDUSTRIAL APPLICABILITY The method and apparatus of the present invention are effective for pattern formation using resist, and their industrial value is enormous.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing an example of a heat treatment apparatus for an X-ray mask substrate of the present invention.

FIG. 2 is a diagram showing a first temperature adjusting member.

FIG. 3 is a diagram showing a second temperature adjusting member.

FIG. 4 is a diagram showing a temperature distribution of a temperature adjusting member.

FIG. 5 is a diagram showing in-plane uniformity of resist pattern dimensions.

FIG. 6 is a schematic diagram showing another example of an X-ray mask substrate heat treatment apparatus of the present invention.

FIG. 7 is a cross-sectional view of an X-ray mask substrate having a mesa structure.

FIG. 8 is a schematic view showing another example of the heat treatment apparatus for an X-ray mask substrate of the present invention.

FIG. 9 is an explanatory diagram showing an example of a resist processing apparatus of the present invention.

FIG. 10 is a configuration diagram showing an embodiment of a resist processing method of the present invention.

FIG. 11 is an explanatory diagram showing an example of a heating / cooling processing unit of the resist processing apparatus of the present invention.

FIG. 12 is a cross-sectional view showing a manufacturing process of an X-ray mask substrate used in an embodiment of the present invention.

FIG. 13 is a cross-sectional view showing the manufacturing process of the X-ray mask substrate used in one embodiment of the present invention.

FIG. 14 is a flowchart showing an example of a resist processing method of the present invention.

FIG. 15 is a diagram showing an example of a pattern formed by using the present invention.

FIG. 16 is an explanatory diagram showing another example of the resist processing apparatus of the present invention.

FIG. 17 is a configuration diagram showing another example of the resist processing method of the present invention.

FIG. 18 is a flowchart showing another example of the resist processing method of the present invention.

FIG. 19 is a schematic diagram illustrating another example of the resist processing apparatus of the present invention.

FIG. 20 is an explanatory view showing another example of the resist processing apparatus of the present invention.

FIG. 21 is a sectional view showing an X-ray mask substrate.

FIG. 22 is a schematic view showing a conventional heat treatment apparatus for an X-ray mask substrate.

FIG. 23 is an explanatory diagram showing an example of a conventional resist processing apparatus.

FIG. 24 is an explanatory view showing another example of a conventional resist processing apparatus.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... X-ray mask substrate 1a ... X-ray absorber film 1b ... X-ray transmissive thin film 1c ... Support substrate 1d ... Reinforcement support frame 1e ... Window region 2, 21, 28, 100 ... Heat treatment apparatus 3 ... First temperature adjustment Member 4 ... Second temperature adjusting member 5, 6, 101 ... Temperature control device 7, 8 ... Drive mechanism 9, 10, 30 ... Drive control device 11, 12, 17, 18 ... Distance sensor 13 ... Resist film 14 ... Holding Stands 15, 16 ... Heater wire 22 ... X-ray mask substrate 23 ... Resist film 24 ... First temperature adjusting member 25 ... Second temperature adjusting member 29 ... X-ray mask substrate driving mechanism 31 ... Thermistor 41 ... Si substrate 42 ... SiC X-ray transparent thin film 43 ... Alumina antireflection film / etching stopper 44 ... WRe X-ray absorber 45 ... Cr etching mask 46 ... Alumina antireflection film 47 ... Gala Reinforcement frame 48 ... Electron beam resist 49 ... X-ray mask substrate 51 ... Pretreatment portion 52 ... Coating portion 53 ... Heating / cooling treatment portion 54 ... Development portion 55 ... Vertical inversion mechanism 55a ... Substrate holding mechanism 55b, 78 ... Rotation Mechanism 55c ... Support block 55d, 76, 81, 83 ... Elastic body 55e, 77 ... Vertical movement mechanism 56 ... Carry-in / out section 57 ... Transfer mechanism 58, 73 ... Transfer mechanism arm 59, 62, 63, 64, 65, 72, 75, 79 ... Sensors 60, 74 ... Fall-off prevention portions 61, 68 ... Substrate support portion 66 ... Hot plate 67 ... Heater 69, 85 ... Positioning mechanism 70 ... Back plate 71 ... Temperature sensors 80a, 80b ... Rotation shafts 82, 84 ... Vertical drive mechanism 102 ... Hot plate 103 ... X-ray mask substrate 104 ... Resist film 110 ... Furnace body 111 ... Processed substrate 112, 115 ... Heater wire 114 ... Hot plate 116 ... Vertical drive mechanism 117 ... Temperature sensor

Claims (16)

[Claims] 1. A substrate supported by a mask support frame, an X-ray transmission film and an X-ray absorber formed on the substrate in sequence, and a photosensitive resist film is formed on the X-ray absorber. And a first heat treatment method for heating or cooling the photosensitive resist film and the X-ray mask substrate above the X-ray absorber film having the photosensitive resist film formed thereon. The temperature adjusting members of (1) are arranged close to each other, and below the back surface of the X-ray mask substrate,
A second temperature adjusting member for heating or cooling the photosensitive resist film and the X-ray mask substrate is arranged in proximity to each other, and at least one of the first temperature adjusting member and the second temperature adjusting member is provided. A method for heat treating an X-ray mask substrate, wherein the temperature of the photosensitive resist film and the X-ray mask substrate is set within a predetermined range by controlling the temperature. 2. The X according to claim 1, wherein at least one of the first temperature adjusting member and the second temperature adjusting member has a shape corresponding to the shape of the X-ray mask substrate.
Method for heat treatment of line mask substrate. 3. The temperature distribution of at least one of the first temperature adjusting member and the second temperature adjusting member is controlled according to a desired in-plane temperature distribution of the photosensitive resist film and the X-ray mask substrate. The heat treatment method for an X-ray mask substrate according to claim 1, which is controlled by an apparatus. 4. The photosensitive resist formed on the X-ray absorber film of the X-ray mask substrate by the first drive mechanism controlled by a first drive control device. The second temperature adjusting member is moved and arranged at a predetermined distance from the film front surface, and the second temperature adjusting member is moved to a predetermined distance from the back surface of the X-ray mask substrate by a second drive mechanism controlled by a second drive control device. The X according to claim 1, which is moved / placed.
Method for heat treatment of line mask substrate. 5. The first temperature control member is driven by a first drive mechanism controlled by a first drive control device, and the second temperature control member is controlled by a second drive control device. Is driven by a second driving mechanism to form a gap with the first temperature adjusting member, and the X-ray mask substrate is controlled by a third driving mechanism controlled by a third driving control device. The X-ray mask substrate heat treatment method according to claim 1, wherein the X-ray mask substrate is moved and arranged at a predetermined position in a gap between the first temperature adjusting member and the second temperature adjusting member. 6. A substrate supported by a mask supporting frame, an X-ray transmission film and an X-ray absorber formed on the substrate in sequence, and a photosensitive resist film is formed on the X-ray absorber. An apparatus for heat-treating the formed X-ray mask substrate with the photosensitive resist film facing upward, wherein the photosensitive resist film of the X-ray mask substrate is formed on the X-ray mask substrate.
A first temperature adjusting member that is disposed above and above the radiation absorber film and that heats or cools the photosensitive resist film and the X-ray mask substrate; and below and below the back surface of the X-ray mask substrate. Placed
A second temperature adjusting member for heating or cooling the photosensitive resist film and the X-ray mask substrate; and the first temperature adjusting member for setting the temperatures of the photosensitive resist film and the X-ray mask substrate within a predetermined range. An X-ray mask substrate heat treatment apparatus comprising: a temperature control member for controlling the temperature of at least one of the temperature control member and the second temperature control member. 7. The heat treatment for an X-ray mask substrate according to claim 6, wherein at least one of the first temperature adjusting member and the second temperature adjusting member has a shape corresponding to the shape of the X mask substrate. apparatus. 8. A temperature distribution of at least one of the first temperature adjusting member and the second temperature adjusting member is controlled according to a desired in-plane temperature distribution of the photosensitive resist film and the X-ray mask substrate. The heat treatment apparatus for an X-ray mask substrate according to claim 6 or 7, further comprising a temperature controller for controlling the temperature. 9. A first driving mechanism for moving and arranging the first temperature adjusting member at a predetermined distance from a photosensitive resist film formed on the X-ray absorber film of the X-ray mask substrate. And a second drive mechanism for moving and arranging the first drive control device for controlling the drive mechanism and the second temperature control member at a predetermined distance from the back surface of the X-ray mask substrate, and this drive. The heat treatment device for an X-ray mask substrate according to claim 6, further comprising a second drive control device for controlling the mechanism. 10. A first drive mechanism for driving the first temperature adjusting member and a first drive mechanism for controlling the drive mechanism.
Second drive mechanism for driving the second temperature control member so as to form a predetermined gap between the drive control device and the first temperature adjustment member, and a second drive mechanism for controlling the drive mechanism. Drive controller, a third drive mechanism for moving and arranging the X-ray mask substrate to a predetermined position of the gap formed between the first and second temperature adjusting members, and this drive The heat treatment device for an X-ray mask substrate according to claim 6, further comprising a third drive control device for controlling the mechanism. 11. A chemical liquid supply mechanism for supplying a chemical liquid onto a substrate to be processed, a rotating mechanism for rotating the substrate to be processed around an axis forming a significant angle with a normal line of the main surface of the substrate, and the workpiece to be processed. A removal preventing mechanism that prevents the substrate from falling off during rotation of the substrate, and a heating / cooling mechanism that heats or cools the substrate to be processed, wherein the heating / cooling mechanism is a heating unit with a surface normal facing upward,
Vertical driving means for driving the substrate to be processed up and down, positioning means for determining a positional relationship between a surface to be processed of the substrate to be processed and a surface of the heating means which is separated from and faces the surface to be processed,
And a resist processing apparatus having movable means provided on the opposite side of the processed surface of the processed substrate. 12. The resist processing apparatus according to claim 11, wherein the significant angle is 90 °. 13. A chemical liquid supply mechanism for supplying a chemical liquid onto a substrate to be processed, and a heating / cooling mechanism for heating or cooling the substrate to be processed, wherein the heating / cooling mechanism is a heating device whose surface normal is directed downward. means,
Vertical driving means for driving the substrate to be processed up and down, positioning means for determining a positional relationship between a surface to be processed of the substrate to be processed and a surface of the heating means which is separated from and faces the surface to be processed,
And a resist processing apparatus having movable means provided on the opposite side of the processed surface of the processed substrate. 14. A step of supplying a chemical liquid onto the surface of the substrate to be processed from above the surface of the surface to be processed, and a step of heating or cooling the substrate to be processed having the liquid surface to be processed. The heating of the substrate to be processed is performed by determining the relative positional relationship between the surface to be processed coated with the chemical liquid and the surface of the heating means, and separating and facing the surface to be processed and the surface of the heating means. A resist processing method characterized by: 15. Prior to the step of heating the substrate to be processed, the step of rotating the substrate to be processed to invert the surface to be processed downward, and the substrate to be processed to a heating means whose surface normal is directed upward. A step of bringing them closer to each other, a step of determining a positional relationship between a surface to be processed of the substrate to be processed and a surface of the heating means spaced apart from and facing the surface to be processed, and provided on the opposite side of the surface to be processed of the substrate to be processed. A step of driving the movable means up and down, after the step of heating the substrate to be processed, a step of vertically moving a movable means provided on the opposite side of the surface to be processed of the substrate to be processed, the heating means 15. The resist processing method according to claim 14, further comprising: a step of waiting the substrate to be processed, and a step of rotating the substrate to be processed so that the surface to be processed is inverted upward. 16. Prior to the step of heating the substrate to be processed, a step of bringing the substrate to be processed closer to a heating means whose surface normal is directed downward, and a surface to be processed of the substrate to be processed and a distance to the surface to be processed. Heating the substrate to be processed, including a step of determining a positional relationship with the surface of the heating means facing each other, and a step of vertically moving a movable means provided on the opposite side of the surface to be processed of the substrate to be processed. 15. The method according to claim 14, further comprising a step of vertically moving a movable means provided on the opposite side of the processed surface of the substrate to be processed after the step, and a step of waiting the processed substrate from the heating means. Resist processing method.