JP6106394B2 - Resist solution supply device, resist coating device, resist solution temperature control method, resist solution storage device, and mask blank manufacturing method - Google Patents

Description

  The present invention relates to a resist solution supply device that supplies a resist solution used for photolithography pattern etching to a resist coating device, a resist coating device that receives supply of a resist solution from the resist solution supply device, a resist solution storage device that stores the resist solution, The present invention relates to a temperature management method for a resist solution and a mask blank manufacturing method in these apparatuses.

  Photolithographic techniques are indispensable in the manufacture of semiconductor devices typified by LSIs and flat panel displays (FPDs) and the formation and processing of fine structures such as magnetic disks and optical disks. In the mask process, a light shielding film pattern was already drawn by an electron beam or a short wavelength laser around 1975, and an organic solvent developing system was used as a resist. At present, a chemically amplified resist (CAR) is widely used mainly due to the demand for miniaturization of mask pattern dimensions and high-sensitivity exposure.

  For example, application of a resist to a mask blank in a photomask process is performed by a spin coating method. In the spin coating method, a target substrate is set on a spin coater, a predetermined amount of resist solution is dropped from a nozzle of a resist coating device onto the substrate surface, and then the spin coater is rotated at a high speed, whereby the resist solution is applied by diffusion. In order to apply the resist uniformly and to a desired thickness on the substrate surface, it is necessary to adjust the resist solution to a temperature (generally room temperature) most suitable for the viscosity condition.

  As a conventional technique for solving such a problem, a resist is provided in which a tube is provided around a supply pipe for supplying a resist solution to a dropping nozzle, and the temperature of the resist solution is adjusted by flowing a temperature adjusting liquid through the tube. A liquid supply apparatus is known (see, for example, Patent Document 1). In order to prevent the resist solution containing gelled insoluble matter from dripping from the nozzle, the supply pipe is provided with a heating means for actively aggregating the gelled component and a filter for removing the agglomerated foreign matter. A resist solution supply apparatus has been proposed (see, for example, Patent Document 2). Also, a photoresist coating liquid supply apparatus is disclosed that incorporates a circulating filtration device that circulates the resist liquid in a storage container and filters it with a filter in order to prevent increase in the particles of the resist liquid (see, for example, Patent Document 3). .

JP 2002-25887 A JP 2011-44521 A International Publication No. 2006/057345

  In a resist solution used for photolithography etching, there is usually a temperature difference between a temperature suitable for application by spin coating (approximately room temperature) and a temperature suitable for long-term storage (cold temperature). In particular, a chemically amplified resist widely used for photomask ground pattern etching has a characteristic that sensitivity changes remarkably when placed in a room temperature environment for a long time, and the necessity of temperature management is particularly high. In fact, there may be a difference in the exposure sensitivity between the resist solution at the initial stage of use and the resist solution after a certain period of time. This is considered to be due to a difference in accumulated time in which the resist solution is placed in a room temperature environment where the coating process is performed.

  In order to prevent the sensitivity of the resist solution from changing as much as possible, it may be possible to cool the resist solution to a temperature suitable for storage during periods of non-coating (for example, nights or holidays when the line is not in operation). It is done. However, in a chemically amplified resist that is easily affected by temperature, if there is a local temperature difference in the resist solution supply apparatus during cooling or storage, sensitivity may vary. For this reason, it is necessary to uniformly cool the entire resist solution during storage of the resist solution and to return it to a room temperature suitable for coating during the coating operation. In the conventional resist solution supply apparatus described above, for example, temperature control means or heating means is provided in the vicinity of the supply pipe of the nozzle, so there is a possibility that a local difference occurs in the temperature of the resist solution in the apparatus.

  The present invention has been made to solve such a problem, and by performing uniform temperature control of the resist solution applied to the substrate, the sensitivity change or quality degradation of the resist solution is caused as much as possible. It is an object of the present invention to provide a resist solution supply device, a resist solution storage device, a resist coating device, or a temperature management method for a resist solution, which is not allowed to occur. Another object of the present invention is to provide a method for manufacturing a mask blank.

  In order to solve the problems described above, the present invention provides a resist bottle for storing a resist solution used for photolithography, a liquid tank for immersing the resist bottle in a temperature adjustment liquid to be filled, and the liquid tank. A temperature adjusting liquid circulation means having an inlet for introducing the temperature adjusting liquid into the liquid tank and an outlet for discharging the temperature adjusting liquid from the liquid tank; and the inlet by the temperature adjusting liquid circulating means. And a supply means for supplying the resist solution in the resist bottle to a resist coating apparatus.

  According to this resist solution supply apparatus, a solution tank is provided that performs temperature management by immersing a resist bottle in a temperature adjusting solution. The liquid tank is a circulation type with inflow and outflow of the temperature adjustment liquid, and the temperature adjustment water is temperature-controlled outside the liquid tank, so that the temperature adjustment liquid in the liquid tank is not easily overheated and overcooled. The temperature adjustment liquid in the liquid tank is naturally stirred, and the temperature distribution of the liquid is less likely to occur in the liquid tank.

  It is preferable that the resist solution supply device includes a circulation unit configured so that the temperature adjustment liquid circulation unit rotates the flow of the temperature adjustment solution along the outer periphery of the resist bottle. As the temperature adjusting solution circulates around the resist bottle, the liquid temperature adjustment of the resist solution in the resist bottle is efficiently advanced.

  It is preferable that the inner wall of the liquid tank forms a circle in an arbitrary horizontal cross section. If the horizontal cross section of the liquid tank is circular, the temperature-controlled water easily circulates in the liquid tank. The shape of the liquid tank is particularly preferably a cylindrical shape having a flat bottom or a U-shaped bottom.

  Other tangential directions opposite to each other on the streamline in which the temperature adjusting liquid circulates in the one tangential direction and the outlet is provided in one tangential direction on the inner wall of the liquid tank. It is preferable that it is provided toward.

  According to this structure, since temperature control water flows along the wall surface of a liquid tank, temperature control water is circulated efficiently.

  In the resist solution supply apparatus, the inlet is provided on the upper side of the resist bottle and the outlet is provided on the lower side of the resist bottle, or the inlet is provided on the lower side of the resist bottle. The outlet is preferably provided on the upper side of the resist bottle.

  If the inlet and outlet are close to each other, the flow of temperature-controlled water is completed near the inlet and outlet, and the temperature-controlled water does not circulate throughout the tank. As a result, it becomes difficult to make the temperature in the liquid tank uniform. In addition, if the inlet and outlet are installed in a vertical relationship, the temperature adjustment liquid flows from top to bottom or from bottom to top. The temperature distribution is less likely to occur.

  The resist solution supply device continuously adjusts the temperature of the resist solution stored in the resist bottle by causing the temperature adjusting liquid whose temperature is controlled by the temperature control means to continuously flow into the liquid tank from the inlet. It is preferable to change and / or maintain the temperature of the temperature adjusting liquid.

  When the temperature of the temperature control water is intermittent control, overheating and overcooling of the temperature control water may occur. As a result, the resist solution is overheated when the temperature is raised, overcooled when the temperature is lowered, or the temperature fluctuates when the temperature is kept. According to this configuration, since the temperature of the temperature-controlled water is continuously managed, overheating when the resist solution is heated, overcooling when the temperature is lowered, and temperature fluctuations when keeping the temperature are suppressed.

  In the resist solution supply device, the temperature range of the temperature adjusting liquid controlled by the temperature control means is at least a first temperature suitable for application of the resist solution and a second temperature suitable for storage of the resist solution. It is preferable to include.

  In the resist solution supply device, it is preferable that a gap through which the temperature adjusting solution can flow in and out is provided between a bottom portion of the resist bottle and the liquid tank. According to this configuration, since the temperature adjustment liquid can be distributed between the bottom of the resist bottle and the bottom of the liquid tank, the temperature of the resist liquid can also be adjusted from the bottom of the resist bottle.

  Preferably, the resist solution supply device further includes a resist solution circulating means for circulating the resist solution in the resist bottle. By providing the resist solution circulating means, temperature distribution due to convection of the resist solution is less likely to occur. For this reason, the quality of the resist in the resist bottle can be kept constant.

  In the resist solution supply apparatus, it is preferable that a supply pump of the supply unit also serves as a circulation pump of the resist solution circulation unit. According to this configuration, the pump can be used for circulation until the temperature of the resist solution is stabilized, and can be switched to supply when the temperature of the resist solution is stabilized. By using the same pump for supply and circulation, piping can be simplified.

  Moreover, this invention is a resist coating apparatus provided with the dripping nozzle which dripped the resist liquid supplied by the said resist liquid supply apparatus on the substrate surface.

  The present invention also provides a resist bottle for storing a resist solution used for photolithography, a liquid tank for immersing the resist bottle in a temperature adjusting liquid to be filled, and the temperature adjusting liquid installed in the liquid tank. A temperature adjusting liquid circulating means having an inlet for flowing into the liquid tank, an outlet for discharging the temperature adjusting liquid from the liquid tank, and the temperature control for flowing into the liquid tank from the inlet by the temperature adjusting liquid circulating means. A resist solution temperature management method in a resist solution supply apparatus, comprising: temperature control means for controlling the temperature of the solution; and supply means for supplying the resist solution in the resist bottle to a resist coating apparatus, wherein the supply means Prior to the supply of the resist solution by the step, the temperature adjustment solution is allowed to flow into the solution tank while being controlled to a first temperature suitable for the application of the resist solution. A step of changing the temperature of the resist solution to the first temperature, and while the resist solution is supplied by the supply means, the flow of the temperature adjusting solution at the first temperature is continued, and the resist in the resist bottle is maintained. A step of maintaining the temperature of the solution at the first temperature, and after the supply of the resist solution by the supply means is finished, the temperature adjustment solution is changed from the first temperature to a second temperature suitable for storage of the resist solution. The temperature of the resist solution in the resist bottle is changed from the first temperature to the second temperature, and the temperature adjusting solution of the second temperature is Continuing the inflow, and storing the resist solution in the resist bottle at the second temperature.

  The present invention also provides a resist bottle for storing a resist solution used for photolithography, a liquid tank for immersing the resist bottle in a temperature adjustment liquid to be filled, and the temperature adjustment liquid installed in the liquid tank. A temperature adjusting liquid circulating means having an inlet for flowing the liquid into the liquid tank, an outlet for discharging the temperature adjusting liquid from the liquid tank, and the temperature adjusting liquid circulating means flowing into the liquid tank from the inlet. And a temperature control means for controlling the temperature of the temperature adjusting liquid.

  It is preferable that the resist solution storage device includes a circulation unit configured such that the temperature adjustment solution circulation unit circulates the flow of the temperature adjustment solution along the outer periphery of the resist bottle.

  In the resist solution storage device, the inner wall of the liquid tank forms a circle in an arbitrary horizontal cross section, the resist bottle is installed vertically in the liquid tank, and the inlet is one tangent in the inner periphery of the liquid tank It is preferable that the outlet is provided toward the other tangential direction opposite to each other on the streamline around which the temperature adjusting liquid circulates with respect to the one tangential direction.

  In the resist solution storage device, the inlet is provided on the upper side in the liquid tank, and the outlet is provided on the lower side in the liquid tank, or the inlet is a lower part in the liquid tank. It is preferable that the outlet is provided on the upper side in the liquid tank.

  The resist solution storage device continuously adjusts the temperature of the resist solution stored in the resist bottle by flowing the temperature-controlled solution, the temperature of which is controlled by the temperature control unit, from the inlet to the liquid tank. It is preferable to change and / or maintain the temperature of the temperature adjusting liquid.

  In the resist solution storage device, the temperature range of the temperature adjusting liquid controlled by the temperature control means is at least a first temperature suitable for application of the resist solution and a second temperature suitable for storage of the resist solution. It is preferable to include.

  In the resist solution storage device, it is preferable that a gap through which the temperature adjusting solution can flow in and out is provided between a bottom portion of the resist bottle and the liquid tank.

  Preferably, the resist solution storage device further includes a resist solution circulating means for circulating the resist solution in the resist bottle.

  Further, the present invention includes a step of forming a light shielding film on one surface of the glass substrate, a step of applying and fixing a resist solution for etching the light shielding film into a predetermined mask pattern on the surface of the light shielding film, A method for manufacturing a mask blank, comprising: a resist bottle that fills a resist bottle in which a resist solution is stored prior to a step of applying a resist solution to the surface of the light shielding film using a resist coating apparatus. The step of circulating in the liquid tank so that the temperature adjustment liquid circulates along the outer periphery of the resist bottle and the temperature of the temperature adjustment liquid flowing into the liquid tank are applied in a resist solution. The temperature of the resist solution stored in the resist bottle is adjusted to a temperature suitable for the application by continuously flowing the temperature adjusting liquid into the liquid tank. Comprising the steps of further and / or maintained, and a step of supplying the resist solution is changed and / or maintained at a temperature compatible with the coating on the resist coating apparatus, a method for producing a mask blank.

  According to the resist solution supply apparatus of the present invention, the entire resist solution in the resist bottle is uniformly changed to and / or maintained at the temperature of the controlled temperature adjusting solution. Thereby, it is possible to adjust and manage the resist solution at a desired temperature while preventing a local difference from occurring in the temperature of the resist solution. Therefore, it is possible to suppress the sensitivity change or quality deterioration of the resist solution.

  Further, according to the resist coating apparatus according to the present invention, a resist solution having a stable sensitivity quality can be received from the resist solution supply device. For this reason, the target board | substrate with which the resist solution of fixed quality was apply | coated can be provided.

  Further, according to the temperature control method for a resist solution according to the present invention, the resist solution temperature in the resist bottle is uniformly adjusted and managed over a first temperature suitable for application and a second temperature suitable for storage. can do. As a result, even when the resist solution is stored for a long period of time, it is possible to minimize the sensitivity change or quality deterioration with time.

  In addition, according to the resist solution storage device of the present invention, the resist solution can be stored by uniformly cooling without causing a local difference in the temperature of the resist solution. As a result, even when the resist solution is stored for a long period of time, a change in sensitivity or deterioration of quality over time can be minimized.

  Moreover, according to the manufacturing method of the mask blank which concerns on this invention, the mask blank by which the resist of the stable sensitivity quality was apply | coated can be provided. In addition, since the sensitivity of the resist to be applied is constant, it is not necessary to adjust the baking conditions after application every time batch processing is performed, which contributes to simplification of the mask blank manufacturing process.

FIG. 1 is a schematic view showing the configuration of a resist solution supply apparatus and a resist coating apparatus according to an embodiment of the present invention. FIG. 2 is a side view showing the inside of the resist solution supply apparatus according to the embodiment of FIG. 1, and is a view for explaining the flow of the temperature adjusting solution. FIG. 3 is a plan view of the liquid tank as viewed from above with the upper lid of the resist liquid supply apparatus according to one embodiment removed. FIG. 4 is a plan view of the liquid tank as viewed from above with the upper lid of the resist solution supply apparatus according to another embodiment removed. FIG. 5 is a diagram illustrating a temperature profile of the resist solution managed in the resist solution supply device or the resist solution storage device. FIG. 6 is a side view showing the inside of a resist solution supply device or a resist solution storage device according to another embodiment. FIG. 7 is a side view showing the inside of a resist solution supply device or a resist solution storage device according to still another embodiment. FIG. 8 is a side view showing the inside of a resist solution supply device or a resist solution storage device according to still another embodiment. FIG. 9 is a flow diagram illustrating a mask blank manufacturing process.

The main features of the embodiments described herein are first summarized.
(Feature 1) The temperature adjustment liquid is water (pure water).
(Feature 2) The resist bottle 11 is a container having a cylindrical shape in an arbitrary horizontal section.
If it is such a shape, it will become easy for temperature control water to circulate a resist bottle.
(Characteristic 3) The side wall of the liquid tank is formed with a window portion through which the state of the resist bottle in the liquid tank can be confirmed. As a result, the remaining amount of the resist solution can be visually confirmed.
(Feature 4) In order to suppress the thermal influence of the external environment, the liquid tank is provided with a heat insulating material. By providing the heat insulating material, heat transfer through the wall surface of the liquid tank is less likely to occur.
(Feature 5) An upper lid capable of fitting the neck portion of the resist bottle into the liquid tank is provided. Spattering of temperature-controlled water outside the liquid tank can be prevented. Also, by providing an upper lid,
It is more preferable if the resist bottle can be fixed to the upper lid. By fixing the resist bottle with the lid, even if buoyancy is applied to the resist bottle due to the difference in density between the resist solution and the temperature-controlled water or the increase in the bottle space due to consumption of the resist solution, the stability of the resist bottle is Maintained.

[Embodiments of resist solution supply apparatus and resist coating apparatus]
Embodiments of a resist solution supply apparatus and a resist coating apparatus according to the present invention will be described below with reference to the drawings. FIG. 1 is a schematic diagram showing the configuration of a resist solution supply device 1 and a resist coating device 2 according to one embodiment of the present invention. In FIG. 1, the main body of the resist solution supply apparatus 1 is shown by a partial cross-sectional view in which a part thereof is broken, and the configuration of the fluid control system is shown by a fluid circuit diagram. Further, the resist coating apparatus 2 includes a dropping nozzle 20 that drops a resist solution onto the surface of the target substrate S such as a photomask blank installed on the spin coater 3.

  The resist solution supply apparatus 1 includes a resist bottle 11 that can store a predetermined amount of a liquid resist solution, and a liquid tank 12 that can store the resist bottle 11 therein and immerse the resist bottle 11 in a temperature adjusting solution 14 that is filled. With. The resist bottle 11 is a cylindrical container in an arbitrary horizontal cross section. The outer surface of the resist bottle 11 is preferably flat with no irregularities such as protrusions, but does not have to be cylindrical with the same diameter uniformly from the top to the bottom. For example, as shown in FIG. 1, the resist bottle 11 may have a conical shoulder 11 a at the top.

  By making the resist bottle 11 a flat and cylindrical container, the circulation means 60 described later promotes the flow of the temperature adjusting liquid 14 that circulates around the resist bottle 11, and the flow is too fast to generate bubbles. It is possible to prevent the situation from occurring. Thereby, the temperature adjustment of the resist solution in the resist bottle 11 through the temperature adjusting solution 14 can be performed efficiently.

  The inner wall that defines the internal space of the liquid tank 12 has a cylindrical shape (an arbitrary horizontal cross section is a circle), and the resist bottle 11 is stored in the internal space. The diameter of the inner wall of the liquid tank 12 is slightly larger than the diameter of the resist bottle 11, and a gap with a predetermined width is formed between the inner wall of the liquid tank 12 and the resist bottle 11 for allowing the temperature adjusting liquid 14 to enter. A heat insulating material 15 is embedded in the wall of the liquid tank 12. In addition, the structure by which the heat insulating material 15 is affixed over the whole inner wall surface of the liquid tank 12 may be sufficient. By making the inner wall of the liquid tank 12 into a cylindrical shape, even when the resist bottle 11 to be installed is not cylindrical, the flow of the temperature adjusting liquid 14 can be formed or promoted. Although not shown, a window portion (for example, an ultraviolet non-transmissive transparent window) for visually measuring the amount of the resist solution in the resist bottle 11 may be provided in a part of the liquid tank 12.

  The liquid tank 12 is formed with liquid tightness so that the temperature adjustment liquid 14 can be filled to a certain height. Further, the liquid tank 12 is provided with an upper lid 18 capable of fitting the neck portion of the resist bottle 11 so that the temperature control water 14 is prevented from being scattered. Although pure water can be used as the temperature control liquid 14, for example, an aqueous liquid in which an evaporation inhibitor such as ethylene glycol is added to pure water for the purpose of stabilizing the liquid amount may be used.

  The temperature adjusting liquid 14 is supplied into the liquid tank 12 through the water supply line 16 in advance. Further, the temperature adjusting liquid 14 filled in the liquid tank 12 can be drained via the drain line 17. The liquid tank 12 is filled with the temperature adjustment liquid 14 at a level higher than the level of the resist liquid in the resist bottle 11 installed at a predetermined position on the gantry 13, whereby the resist bottle 11 is immersed in the temperature adjustment liquid 14. The Note that the heat insulating material 15 is interposed in the liquid tank 12, so that both the resist bottle 11 and the temperature adjusting liquid 14 are thermally blocked from the environment outside the liquid tank 12.

  As shown in FIG. 1, the resist bottle 11 is placed vertically on a gantry 13 provided at the bottom of the liquid tank 12. That is, the resist bottle 11 is detachably installed on the gantry 13 so that the resist bottle 11 that has become empty can be easily replaced. A holder guide portion 13 a that stably supports the bottom portion of the resist bottle 11 at a predetermined position may be formed around the gantry 13. A gap is formed between the bottom of the resist bottle 11 and the liquid tank 12 through which the temperature adjusting liquid 14 can flow in and out via the legs of the gantry 13.

  By forming a gap between the bottom of the resist bottle 11 and the liquid tank 12, the temperature adjustment liquid 14 comes into contact with the bottom of the resist bottle 11, and the temperature adjustment of the resist liquid becomes more uniform and efficient.

  The resist solution supply device 1 includes a resist solution supply means 30 for supplying the resist solution in the resist bottle 11 to the resist coating device 2. The resist solution supply means 30 is connected at least between the resist solution supply pump 31 and the resist bottle 11 and the suction side of the pump 31, and removes the resist solution in the resist bottle 11 by the negative pressure generated by the pump 31. It has a discharge pipe 32 to be sucked up, and a supply pipe 33 that is connected to the discharge side of the pump 31 and supplies the resist solution discharged from the pump 31 to the resist coating apparatus 2 (dropping nozzle 20).

  The pump 31 is preferably a rotary pump in which the resist solution discharge flow rate is constant and the occurrence of cavitation (bubbles) is extremely small. Further, a filter 34 for filtering and removing particles or gelled components that may be contained in the resist solution may be provided in the discharge side piping of the pump 31 as shown in FIG. Although not shown, such a filter may be provided in the suction side piping of the pump 31. Further, such a filter may be provided in the middle of a conduit through which the resist solution is circulated by the resist solution circulating means 70 described later.

  Further, the liquid tank 12 is provided with a temperature adjustment liquid circulation means 40 having an inlet 41 through which the temperature adjustment liquid 14 flows in and an outlet 42 through which the temperature adjustment liquid 14 flows out. In the example shown in FIG. 1, the inlet 41 of the temperature adjustment liquid 14 is provided on the upper side of the resist bottle 11, and the outlet 42 is provided on the lower side of the resist bottle 11. Alternatively, the inlet 41 may be provided on the lower side of the resist bottle 11 and the outlet 42 may be provided on the upper side of the resist bottle 11. Furthermore, you may make it switch the vertical position of the inflow port 41 and the outflow port 42 by providing the direction switching valve 43 and controlling the position of the valve. For example, when the temperature adjusting liquid 14 controlled to a cold temperature lower than the temperature of the resist solution in the resist bottle 11 is allowed to flow into the liquid tank 12 (at the time of cooling / storage), the upper side of the resist bottle 11 is moved to the lower side. On the other hand, when the temperature adjustment liquid 14 having a temperature higher than the temperature of the cooled resist solution, for example, about room temperature is caused to flow into the liquid tank 12 (at the time of temperature increase / application), the resist bottle 11 The positions of the inlet 41 and the outlet 42 may be switched so that a flow from the lower side to the upper side is formed.

  As described above, by providing the inlet 41 and the outlet 42 at positions spaced apart from each other in the vertical direction, the temperature adjustment liquid 14 can be efficiently moved in the vertical direction using the convection effect due to the temperature difference between the temperature adjustment liquid 14 and the resist liquid. A smooth flow can be formed.

  The temperature adjustment liquid circulation means 40 includes a circulation means 60 configured to circulate the temperature adjustment liquid 14 along the outer periphery of the resist bottle 11 along with the vertical flow of the temperature adjustment liquid 14 in the liquid tank 12. FIG. 2 is a side view showing the resist bottle 11 immersed in the temperature adjusting liquid 14 in the liquid tank 12, and a streamline F indicating the flow direction of the temperature adjusting liquid 14 by the circulating means 60 as an arrow is appended. Has been. In such a circulating means 60, the inlet 41 for allowing the temperature adjustment liquid 14 to flow into the liquid tank 12 is provided in one tangential direction on the outer periphery of the resist bottle 11, and the temperature adjustment liquid 14 is removed from the liquid tank 12. The outlet 42 to be discharged may be provided in the other tangential direction opposite to each other on the streamline around which the temperature adjusting liquid 14 circulates in the one tangential direction.

  FIG. 3 is a plan view of the liquid tank 12 as viewed from above with the upper lid 18 removed. In the circulation means 60 of the embodiment of FIG. 3, the inlet 41 and the outlet 42 form an angle of 180 degrees with respect to the resist bottle 11, and the inlet 41 and the outlet on the streamline along the outer periphery of the resist bottle 11. Each opening part of 42 has mutually opposed. FIG. 4 is a plan view of the liquid tank 12 as viewed from above according to another embodiment. In the circulation means 60 of the embodiment of FIG. 4, the inlet 41 and the outlet 42 are arranged in close proximity to each other, but the openings face each other on the streamline along the outer periphery of the resist bottle 11. . As shown in these examples, the inflow port 41 and the outflow port 42 have openings directed in a tangential direction along the outer periphery of the resist bottle 11, and the openings are mutually on the streamline that circulates the resist bottle 11. (Strictly speaking, since the vertical positions of the inlet 41 and the outlet 42 are different, each opening is projected onto one virtual horizontal plane as shown in the plan views of FIGS. 3 and 4.) In this case, the relative angle between the inlet 41 and the outlet 42 around the resist bottle 11 may be arbitrary.

  In this way, by arranging the inlet 41 and the outlet 42 of the temperature adjustment liquid 14 at positions facing each other on the streamline along the outer periphery of the resist bottle 11, the circulation of the temperature adjustment liquid 14 around the resist bottle 11 is performed. Can be created or promoted.

  Returning to FIG. 1, the temperature adjustment liquid circulation means 40 further includes the direction switching valve 43 and the variable flow pump 45 described above. The discharge port of the variable flow pump 45 is connected to the first primary port of the direction switching valve 43 through the positive pressure pipe 46, and the suction port of the variable flow pump 45 is connected to the first port of the direction switching valve 43 through the negative pressure pipe 47. Connected to the second primary port. An inflow pipe 44 connected to the inflow port 41 is connected to the first secondary port of the direction switching valve 43, and an outflow pipe 49 connected to the outflow port 42 is connected to the second secondary port of the direction switching valve 43. Is done. As shown in FIG. 1, a relief valve 91 is provided on the discharge side of the variable flow pump 45, and a protection circuit for allowing the high-pressure temperature adjusting liquid 14 to escape to the drain tank 92 when the variable flow pump 45 is overloaded. It may be provided.

  A temperature control means 50 including a heat exchanger 51 is provided in the middle of the positive pressure pipe 46. A temperature sensor 48 is provided in the negative pressure pipe 47. The temperature of the temperature adjustment liquid 14 flowing out from the liquid tank 12 is measured by the temperature sensor 48, and the result is input to the temperature control means 50. The temperature control means 50 controls the heat exchange rate by the heat exchanger 51 so that the temperature of the temperature adjusting liquid 14 from the liquid tank 12 becomes the target temperature. By such feedback temperature control, the temperature of the temperature adjusting liquid 14 flowing into the liquid tank 12 is controlled.

  In addition, a temperature sensor is provided in the positive pressure pipe 46, and the temperature adjustment liquid 14 is controlled by so-called feedforward control in which the heat exchanger 51 is controlled so that the temperature of the temperature adjustment liquid 14 flowing into the liquid tank 12 becomes a target temperature. The temperature may be controlled. Further, the flow rate of the variable flow pump 45 may be controlled according to the temperature difference of the temperature adjusting liquid 14 flowing through the positive pressure pipe 46 and the negative pressure pipe 47. For example, when the temperature difference between the return and return is large, the discharge flow rate of the variable flow pump 45 is maximized, and when the temperature difference is small, the discharge flow rate is limited, thereby improving the temperature control efficiency of the temperature adjusting liquid 14.

  The temperature control means 50 adjusts the resist in the resist bottle 11 from a first temperature suitable for application of the resist solution (for example, room temperature of 23 ° C.) to a second temperature suitable for storage of the resist solution (for example, cold temperature of 10 ° C.). When the temperature of the liquid is lowered (during cooling / storage), the target temperature is set to the second temperature to control the temperature of the temperature adjustment liquid 14. At this time, the valve position of the direction switching valve 43 may be switched so that the temperature adjustment liquid 14 flows from the upper side to the lower side of the resist bottle 11.

  The temperature adjusting liquid 14 controlled to the second temperature by the temperature control means 50 continuously flows into the liquid tank 12 from the inlet 41. Since the temperature-controlled liquid 14 whose temperature is controlled in advance flows in, a phenomenon that the temperature of the temperature-controlled liquid 14 in the resist bottle is excessively lowered does not occur. Accordingly, the temperature of the resist solution stored in the resist bottle 11 can be uniformly changed to, for example, 10 ° C. suitable for storage as a whole, and the resist solution can be stored while maintaining the temperature.

  Further, when the temperature of the resist solution is increased from the second temperature to the first temperature (application temperature) (temperature increase), the temperature control unit 50 sets the target temperature to the first temperature. Thus, the temperature of the temperature adjustment liquid 14 is controlled. At this time, the valve position of the direction switching valve 43 may be switched so that the temperature adjustment liquid 14 flows from the lower side to the upper side of the resist bottle 11.

  The temperature adjusting liquid 14 controlled to the first temperature by the temperature control means 50 continuously flows into the liquid tank 12 from the inlet 41. Since the temperature control liquid 14 whose temperature is controlled in advance flows in, the temperature of the temperature control liquid 14 in the resist bottle does not overheat. As a result, the temperature of the resist solution stored in the resist bottle 11 can be uniformly changed to, for example, 23 ° C. suitable for application as a whole, and the temperature can be maintained during the application operation.

  The resist solution supply apparatus 1 may further include a resist solution circulating means 70 for circulating the resist solution in the resist bottle 11. In FIG. 1, the resist solution circulation means 70 includes a pump 31, a discharge pipe 32 connected to the suction port of the pump 31 and having the suction port inserted into the resist bottle 11, and a supply pipe 33 connected to the discharge port of the pump 31. A return pipe 36 branched from the three-way valve 35 and having the inlet side inserted into the resist bottle 11 is provided. The pump 31 for circulating the resist solution is also used as the pump for supplying the dropping nozzle 20 described above.

  That is, the resist solution circulating means 70 functions by switching the communication of the three-way valve 35 to the return pipe 36 side. When supplying the resist solution to the resist coating apparatus 2, the communication of the three-way valve 35 is switched to the supply pipe 33 side. The three-way valve 35 may be constituted by an electromagnetic valve, and the switching of the resist solution supply / circulation operation mode may be automatically controlled by programming. Further, such switching may be manually performed as needed using a manually operated three-way valve 35.

  It is preferable that the resist solution is circulated by the resist solution circulation means 70 continuously when the temperature of the resist solution is changed or stored by the temperature control means 50 described above. Thereby, a local temperature difference can be hardly generated in the resist solution, and more uniform temperature management is possible.

  Further, a filter may be provided in either the discharge pipe 32 for discharging the resist solution and the return pipe 36 for injecting the resist solution, or either the discharge pipe 32 or the return pipe 36. In addition, it is preferable to circulate the resist solution while maintaining the cold temperature (second temperature) during a rest period in which application is not performed. By filtering the resist solution having a high viscosity with a filter by a cold temperature, it is possible to improve the trapping efficiency of the gelled component contained in the resist solution.

(Resist solution storage and temperature control operations)
The resist solution is stored and the temperature is controlled by the resist solution supply apparatus 1 having the above-described configuration, for example, as follows.

  First, a resist bottle 11 storing a resist solution is installed vertically on a gantry 13 in a liquid tank 12 in the resist solution supply apparatus 1. Then, the upper opening of the liquid tank 12 is closed by the upper lid 18, and for example, a temperature adjustment liquid 14 in which an evaporation inhibitor such as ethylene glycol is added to pure water is supplied into the liquid tank 12 through the water supply line 16. . The liquid tank 12 is filled with the temperature adjustment liquid 14 at a water level higher than the level of the resist liquid in the resist bottle 11, whereby the resist bottle 11 is immersed in the temperature adjustment liquid 14.

  The temperature adjustment liquid circulation means 40 of the resist liquid supply apparatus 1 drives the variable flow rate pump 45 to allow the temperature adjustment liquid 14 to flow into the liquid tank 12 at a predetermined flow rate via the inlet 41 and via the outlet 42. By flowing out the temperature control liquid 14 at the same flow rate, the temperature control liquid 14 is circulated while maintaining the water level in the liquid tank 12 constant. Thereby, in the liquid tank 12, the temperature adjusting liquid 14 flows continuously from the upper side to the lower side or from the lower side to the upper side while circling around the resist bottle 11.

  At the same time, the temperature control means 50 controls the exchange heat amount of the heat exchanger 51 so that the temperature of the temperature adjustment liquid 14 returned from the liquid tank 12 becomes the target temperature, and the temperature of the temperature adjustment liquid 14 that flows into the liquid tank 12. To the target temperature.

  Here, FIG. 5 is a diagram illustrating a temperature profile of the resist solution managed in the resist solution supply apparatus 1 or the resist solution storage apparatus. The temperature profile of the embodiment of FIG. 5 has at least four characteristic processes I to IV regarding the temperature adjustment management of the resist solution.

(First process I)
The first process I is a process until the temperature of the resist solution is raised to a first temperature suitable for the application of the resist solution (for example, room temperature of 23 ° C.) prior to the application of the resist solution. In the first process I shown in FIG. 5, the temperature control means 50 controls the temperature of the temperature adjustment liquid 14 to the first temperature, and the temperature adjustment liquid 14 at the first temperature is continuously supplied to the liquid tank 12. The resist solution in the resist bottle 11 is heated from the second temperature suitable for storage of the resist solution (for example, a cold temperature of 10 ° C.) to the first temperature.

(Second process II)
The second process II is a process of maintaining the temperature of the resist solution at the first temperature (room temperature) suitable for the application of the resist solution during the operation period in which the resist solution is supplied to the resist coating apparatus 2. In the second process II shown in FIG. 5, the temperature control means 50 continuously circulates the temperature adjusting liquid 14 in the liquid tank 12 while controlling the temperature of the temperature adjusting liquid 14 to the first temperature. As a result, the temperature of the resist solution in the resist bottle 11 is maintained at the first temperature. The period of the second process II substantially coincides with the operation period of the resist solution supply apparatus 1 and the resist coating apparatus 2, and it is assumed that the batch process of coating is intermittently performed a plurality of times during that period.

(Third process III)
The third step III is a step of cooling the temperature of the resist solution to the second temperature (cold temperature) suitable for storing the resist solution after the final coating batch processing is completed. In the third process III, the temperature control means 50 controls the temperature of the temperature adjustment liquid 14 to the second temperature, and continuously supplies the temperature adjustment liquid 14 of the second temperature to the liquid tank 12. By circulating, the resist solution in the resist bottle 11 is cooled from the first temperature to the second temperature.

(Fourth Process IV)
The fourth process IV is a process of maintaining the temperature of the resist solution at the second temperature (cold temperature) suitable for storing the resist solution during a rest period in which coating is not performed. In the fourth process IV, the temperature control means 50 continuously circulates the temperature adjusting liquid 14 in the liquid tank 12 while controlling the temperature of the temperature adjusting liquid 14 to the second temperature, thereby generating a resist. The temperature of the resist solution in the bottle 11 is maintained at the second temperature. This allows long-term storage in which resist solution sensitivity deterioration is suppressed.

  During at least a part of the first process I, the third process III, and the fourth process IV in which the resist solution is not supplied, the resist solution circulating means 70 is operated so that the inside of the resist bottle 11 The resist solution may be circulated.

  According to the resist solution supply apparatus 1 of the present embodiment, the resist solution is quickly and efficiently supplied to the first temperature (for example, 23 ° C.) without causing a local temperature difference in the resist solution in the resist bottle 11. Room temperature) to a second temperature (eg, a cold temperature of 10 ° C.). Further, similarly to the cooling, the resist solution in the resist bottle 11 can be uniformly and quickly recovered from the second temperature (cool temperature) to the first temperature (room temperature).

  In addition, the resist solution can be kept at the second temperature (cold temperature) and stored during a rest period in which application is not performed. As a result, for example, even when a chemically amplified resist having a large change in sensitivity at room temperature is used, the accumulated time that the resist solution is placed in the room temperature environment can be reduced, and the sensitivity deterioration of the resist solution can be minimized. it can.

  Further, by circulating the resist solution during a period in which application is not performed, it is possible to store the resist solution with little local temperature difference, and it is possible to positively supplement foreign matter with a filter.

[Embodiment of resist solution storage apparatus]
The resist solution supply device 1 having the above-described configuration also functions as a resist solution storage device that stores the resist solution. In this case, the resist solution storage device includes a resist bottle 11 that stores a certain amount of resist solution, a liquid tank 12 that immerses the resist bottle 11 with the temperature adjusting liquid 14 that is filled, and the temperature adjusting liquid 14 in the liquid tank 12. The temperature adjusting liquid circulating means 40 having an inlet 41 for flowing into the tank and an outlet 42 for discharging the temperature adjusting liquid 14 from the liquid tank 12, and the temperature of the temperature adjusting liquid 14 flowing into the liquid tank 12 from the inlet 41 are controlled. Temperature control means 50. As in the resist solution supply apparatus 1 shown in FIG. 1, it is preferable that the inner wall of the liquid tank 12 has a circular shape in an arbitrary horizontal cross section, and the substantially cylindrical resist bottle 11 is installed vertically in the liquid tank 12. As a result, a gap having a predetermined width is formed between the inner wall of the liquid tank 12 and the resist bottle 11 for allowing the temperature adjusting liquid 14 to enter.

  Further, the temperature adjustment liquid circulation means 40 of the resist solution storage device includes a circulation means 60 configured to circulate the flow of the temperature adjustment liquid 14 along the outer periphery of the resist bottle 11. For example, the circulation means 60 is provided on the streamline in which the inlet 41 is provided in one tangential direction in the inner circumference of the liquid tank 12 and the outlet 42 is circulated in the one tangential direction. It is configured by being provided toward other tangential directions facing each other.

  In this temperature control liquid circulation means 40, for example, an inlet 41 is provided on the upper side in the liquid tank 12, and an outlet 42 is provided on the lower side in the liquid tank 12. Further, the inlet 41 may be provided on the lower side in the liquid tank 12, and the outlet 42 may be provided on the upper side in the liquid tank 12. A configuration in which the upper and lower positions of the inlet 41 and the outlet 42 can be switched by controlling the position of the direction switching valve 43 as shown in FIG.

  According to this resist solution storage device, the temperature adjusting liquid 14 whose temperature is controlled by the temperature control means 50 is continuously introduced from the inlet 41 into the liquid tank 12, so that the resist solution stored in the resist bottle 11 can be stored. The temperature can be changed and / or maintained at a controlled temperature of the temperature adjustment liquid 14. The temperature range of the temperature adjustment liquid 14 controlled by the temperature control means 50 is at least a first temperature (for example, a room temperature of 23 ° C.) suitable for application of the resist liquid and a second temperature (for example, room temperature of 23 ° C.). For example, it is preferable to include a cold temperature of 10 ° C.

  The resist solution storage device may further include a resist solution circulating means 70 for circulating the resist solution in the resist bottle 11.

[Other Embodiments of Resist Solution Supply Device or Resist Solution Storage Device]
FIG. 6 is a resist solution supply device or a resist solution storage device according to another embodiment, and is a side view showing a configuration inside the device by breaking a portion of the solution tank 12. In the embodiment shown in FIG. 6, a flange 11 c is provided on the neck 11 b of the resist bottle 11. An opening 18a is formed in the upper lid 18 of the liquid tank 12, and the resist bottle 11 is suspended in the liquid tank 12 by detachably fixing the edge of the opening 18a and the outer peripheral portion of the flange 11c by fitting or the like. Supported in lowered form. Thereby, even when buoyancy occurs to a certain degree in the resist bottle 11 due to the density difference between the temperature adjusting liquid 14 and the resist liquid and the increase in the space in the bottle due to consumption of the resist liquid, the resist bottle 11 is stably provided in the liquid tank 12. Can be supported. Further, even if the gantry 13 shown in FIG. 1 is not provided, a gap through which the temperature adjusting liquid 14 can flow in and out is formed between the bottom of the resist bottle 11 and the liquid tank 12.

  FIG. 7 is a resist solution supply device or a resist solution storage device according to still another embodiment, and is a side view showing the internal configuration of the device by also breaking the portion of the solution tank 12. In the embodiment shown in FIG. 7, triangular ribs 12 a are spirally formed on the hollow cylindrical inner wall of the liquid tank 12. The triangular ribs 12a formed in a spiral shape along the direction in which the temperature adjusting liquid 14 circulates not only increases the strength of the liquid tank 12 body but also promotes the flow of the temperature adjusting liquid 14 in the rotating direction. The efficiency of heat exchange with the liquid can be improved. In addition, the triangular rib 12a does not need to be continuously connected spirally, and may be intermittent.

  FIG. 8 is a resist solution supply device or a resist solution storage device according to still another embodiment, and is a side view showing the internal structure of the device by similarly breaking the portion of the solution tank 12. In the embodiment of FIG. 8, the inlet 41 and the outlet 42 of the temperature adjusting liquid 14 are formed by through holes formed in the side wall portion of the liquid tank 12. Thereby, piping connected to the inflow port 41 and the outflow port 42 can be provided outside the liquid tank 12, and the flow path resistance of the temperature adjusting liquid 14 circulating around the resist bottle 11 can be reduced. Although not shown, either the inlet 41 or the outlet 42 may be provided at the bottom of the liquid tank 12.

[Embodiment in Manufacturing Mask Blank]
Photolithography technology is employed in the manufacture of semiconductor devices such as LSIs and flat panel displays (FPDs), and the formation and processing of fine structures such as magnetic disks, optical disks and micromachines. . A photomask used for such photolithography pattern etching is to draw a predetermined mask pattern on a photomask blank (herein simply referred to as “mask blank”) on which a light-shielding film is formed by a short wavelength laser or the like. It is manufactured by doing.

  The mask blank has a structure in which a light shielding film made of, for example, a Cr (chromium) metal thin film is formed on one surface of a transparent glass substrate, and a predetermined thickness of, for example, a chemically amplified resist (CAR: Chemically) is formed on the light shielding film side. Amplified Resist) is provided in a uniformly applied state. The sensitivity of the resist applied in advance to the mask blank is closely related to the exposure conditions for drawing the mask pattern. Therefore, variations in resist sensitivity affect the dimensional accuracy of the final mask pattern. End up. When the resist is a positive type, if the sensitivity of the resist increases due to deterioration over time, the width of the exposure pattern becomes wider than a specified value, and there is a possibility that a predetermined pattern dimensional accuracy cannot be ensured. Further, it is not desirable that a difference in resist sensitivity occurs in mask blanks manufactured by different batch processes.

  According to the present embodiment, the mask blank is manufactured, for example, according to the process flow shown in FIG.

  First, the surface of the glass substrate is polished to obtain high flatness with a surface roughness of 1 nm or less (step S1). A light shielding film made of a metal thin film such as Cr is formed on the polished surface of the glass substrate (step S2). As a method for forming the light shielding film, a vacuum deposition method, a sputtering method, or the like can be used.

  Prior to the resist coating process by the resist coating apparatus 2, the resist solution supply apparatus 1 is set up. For example, as shown in FIG. 1, the resist solution supply apparatus 1 is filled with a resist bottle 11 that stores a predetermined amount of resist solution, and a supply unit 30 that supplies the resist solution in the resist bottle 11 to the dropping nozzle 20. The temperature control includes a liquid tank 12 in which the resist bottle 11 is immersed with the temperature adjustment liquid 14, an inlet 41 for allowing the temperature adjustment liquid 14 to flow into the liquid tank 12, and an outlet 42 for allowing the temperature adjustment liquid 14 to flow out of the liquid tank 12. A liquid circulation means 40 and a temperature control means 50 for controlling the temperature of the temperature adjusting liquid 14 flowing into the liquid tank 12 from the inlet 41 are provided.

  In preparation of the resist solution supply apparatus 1, the resist bottle 11 in which the chemically amplified resist is stored is immersed in the liquid tank 12 filled with the temperature adjustment solution 14. Then, the temperature adjusting liquid circulating means 40 is operated to circulate in the liquid tank 12 so that the temperature adjusting liquid 14 circulates along the outer periphery of the resist bottle 11 (step S3).

  At the same time, the temperature control means 50 is operated to control the temperature of the temperature adjusting liquid 14 circulated in the liquid tank 12 to a temperature (for example, a room temperature of 23 ° C.) suitable for application of the resist liquid (step S4). Then, the flow of the temperature adjusting solution 14 is continued so that the temperature of the resist solution in the resist bottle 11 is maintained at the temperature (room temperature).

  After the temperature of the resist solution in the resist bottle 11 is returned to room temperature by circulation of the temperature adjusting solution 14, the resist solution is supplied from the resist solution supply device 1 to the resist supply device 2 by the supply means 30 (step S5). Then, a predetermined amount of resist solution is dropped from the dropping nozzle 20 onto the glass substrate placed on the spin coater 3. By rotating the spin coater 3 at a high speed, the resist solution is diffused on the surface of the glass substrate and uniformly applied (step S6).

  Then, the glass substrate coated with the resist solution is transferred to a hot plate apparatus and baked while maintaining the surface temperature of the substrate at about 100 ° C. (step S7). As a result, the organic solvent contained in the resist evaporates and the resist is fixed to the glass substrate.

  By storing the resist solution at a low temperature using the resist solution supply device 1, it is possible to suppress the deterioration of resist sensitivity (in the case of a positive chemically amplified resist) as much as possible. Therefore, according to the manufacturing method of the present embodiment, it is possible to provide a mask blank to which a resist having a stable sensitivity is applied. Further, since the sensitivity of the resist is stable, it is not necessary to set the conditions for the baking process every time the resist coating is batched, which contributes to the simplification of the mask blank manufacturing process.

  The embodiments described above are merely examples for explaining the invention, and these aspects are not to be construed as limiting the scope of the invention.

DESCRIPTION OF SYMBOLS 1 Resist liquid supply apparatus 2 Resist coating apparatus 3 Spin coater 11 Resist bottle 12 Liquid tank 13 Base 14 Temperature control liquid 15 Heat insulating material 16 Water supply line 17 Drain line 18 Top cover 20 Dripping nozzle 30 Resist liquid supply means 31 Pump 32 Discharge pipe 33 Supply pipe 34 Filter 35 Three-way valve 36 Return pipe 40 Temperature control liquid circulation means 41 Inlet 42 Outlet 43 Directional switching valve 45 Variable flow pump 48 Temperature sensor 50 Temperature control means 60 Circulation means 70 Resist liquid circulation means

Claims (22)

A resist bottle for storing a resist solution used for photolithography;
A liquid tank for immersing the resist bottle in a temperature adjusting liquid to be filled;
A temperature adjusting liquid circulation means having an inlet installed in the liquid tank and allowing the temperature adjusting liquid to flow into the liquid tank; and an outlet allowing the temperature adjusting liquid to flow out of the liquid tank;
Temperature control means for controlling the temperature of the temperature adjustment liquid flowing into the liquid tank from the inlet by the temperature adjustment liquid circulation means;
A supply means for supplying the resist solution in the resist bottle to a resist coating apparatus ,
The resist solution supply apparatus, wherein a temperature range of the temperature adjusting liquid controlled by the temperature control means includes at least a first temperature suitable for application of the resist solution and a second temperature suitable for storage of the resist solution.   2. The resist solution supply apparatus according to claim 1, wherein the temperature adjustment liquid circulation means includes a circulation means configured to circulate the flow of the temperature adjustment liquid along an outer periphery of the resist bottle.   3. The resist solution supply apparatus according to claim 1, wherein an inner wall of the liquid tank forms a circle in an arbitrary horizontal section. 4.   Other tangential directions opposite to each other on the streamline in which the temperature adjusting liquid circulates in the one tangential direction, and the outlet is provided in one tangential direction on the outer periphery of the resist bottle. The resist solution supply apparatus according to claim 1, which is provided toward   The resist solution supply apparatus according to claim 1, wherein the inflow port is provided on an upper side of the resist bottle, and the outflow port is provided on a lower side of the resist bottle.   The resist solution supply apparatus according to claim 1, wherein the inlet is provided on a lower side of the resist bottle, and the outlet is provided on an upper side of the resist bottle.   The temperature of the resist solution stored in the resist bottle is set to the temperature of the temperature adjustment liquid by continuously flowing the temperature adjustment liquid whose temperature is controlled by the temperature control means from the inlet into the liquid tank. The resist solution supply device according to claim 1, wherein the resist solution supply device is changed and / or maintained. Wherein the temperature control fluid outflow entrant gaps between the resist bottle bottom portion and the liquid tank is provided, the resist solution supply device according to any one of claims 1-7. Further comprising a resist solution A resist solution circulating means for circulating within the resist bottle, the resist solution supply device according to any one of claims 1-8. The resist solution supply apparatus according to claim 9 , wherein a supply pump of the supply unit also serves as a circulation pump of the resist solution circulation unit. Resist coating apparatus comprising a dropping nozzle for dropping a resist liquid supplied to the substrate surface by a resist solution supply device according to any one of claims 1-9. A resist bottle for storing a resist solution used for photolithography;
A liquid tank for immersing the resist bottle in a temperature adjusting liquid to be filled;
A temperature adjusting liquid circulation means having an inlet installed in the liquid tank and allowing the temperature adjusting liquid to flow into the liquid tank; and an outlet allowing the temperature adjusting liquid to flow out of the liquid tank;
Temperature control means for controlling the temperature of the temperature adjusting liquid that is caused to flow from the inlet to the liquid tank by the temperature adjusting liquid circulating means ,
A resist solution storage device in which the temperature range of the temperature adjusting liquid controlled by the temperature control means includes at least a first temperature suitable for application of the resist solution and a second temperature suitable for storage of the resist solution. The resist solution storage device according to claim 12 , wherein the temperature adjustment liquid circulation means includes a circulation means configured to circulate the flow of the temperature adjustment liquid along an outer periphery of the resist bottle. The resist solution storage device according to claim 12 or 13 , wherein an inner wall of the liquid tank forms a circle in an arbitrary horizontal cross section, and the resist bottle is installed vertically in the liquid tank. Other tangents facing each other on the streamline in which the temperature adjusting liquid circulates in the one tangential direction, and the outlet is provided in one tangential direction on the inner circumference of the liquid tank The resist solution storage device according to any one of claims 12 to 14 , provided in a direction. The inlet is provided at the upper portion of the liquid tank, wherein the outflow opening is arranged on the lower side of the liquid tank, the resist solution storage apparatus according to any one of claims 12-15. The inlet is provided in the lower side of the liquid tank, wherein the outflow opening is arranged on the upper side of the liquid tank, the resist solution storage apparatus according to any one of claims 12 to 16. The temperature of the resist solution stored in the resist bottle is set to the temperature of the temperature adjustment liquid by continuously flowing the temperature adjustment liquid whose temperature is controlled by the temperature control means from the inlet into the liquid tank. The resist solution storage device according to any one of claims 12 to 17 , which is changed and / or maintained. The resist solution storage device according to any one of claims 12 to 18 , wherein a gap through which the temperature adjusting liquid can flow in and out is provided between a bottom portion of the resist bottle and the liquid tank. Further comprising a resist solution A resist solution circulating means for circulating within the resist bottle, the resist solution storage apparatus according to any one of claims 12-19. A resist bottle for storing a resist solution used for photolithography;
A bath for immersing the resist bottle in a temperature adjusting solution to be filled;
A temperature adjusting liquid circulation means having an inlet installed in the liquid tank and allowing the temperature adjusting liquid to flow into the liquid tank; and an outlet allowing the temperature adjusting liquid to flow out of the liquid tank;
Temperature control means for controlling the temperature of the temperature adjustment liquid flowing into the liquid tank from the inlet by the temperature adjustment liquid circulation means;
A resist solution temperature control method in a resist solution supply device comprising: a supply means for supplying a resist solution in the resist bottle to a resist coating device;
Prior to the supply of the resist solution by the supply means, the temperature of the temperature of the resist solution in the resist bottle is adjusted by allowing the temperature adjusting solution to flow into the solution tank while controlling the temperature at a first temperature suitable for application of the resist solution. Changing to the first temperature;
Maintaining the temperature of the resist solution in the resist bottle at the first temperature by continuing the inflow of the temperature adjusting solution at the first temperature while supplying the resist solution by the supplying means;
After the supply of the resist solution by the supply means is finished, the temperature adjusting solution is allowed to flow into the solution tank while controlling the temperature from the first temperature to a second temperature suitable for storage of the resist solution. Changing the temperature of the resist solution in the bottle from the first temperature to the second temperature;
Continuing the inflow of the temperature adjustment liquid at the second temperature and storing the resist liquid in the resist bottle at the second temperature. The resist solution for etching on one surface of a glass substrate a film has been shielding light film with the mask pattern including more Engineering for fixing applied to the surface of the light shielding film, a method for producing a mask blank,
Prior to the step of applying a resist solution to the surface of the light shielding film using a resist coating apparatus,
Immersing the resist bottle in which the resist solution is stored in a liquid tank filled with the temperature adjustment liquid, and circulating the temperature adjustment liquid in the liquid tank so as to circulate along the outer periphery of the resist bottle;
Controlling the temperature of the temperature adjusting liquid flowing into the liquid tank to a first temperature suitable for application of a resist solution;
Changing and / or maintaining the temperature of the resist solution stored in the resist bottle to the first temperature by continuously flowing the temperature adjusting liquid into the liquid tank;
Supplying a resist solution changed and / or maintained at the first temperature to the resist coating apparatus;
After the supply of the resist solution is finished, the temperature adjustment solution is allowed to flow from the first temperature to the second bath while being controlled to a second temperature suitable for storage of the resist solution. Changing the temperature of the liquid from the first temperature to the second temperature;
Storing the resist solution in the resist bottle at the second temperature by continuing the inflow of the temperature adjusting solution at the second temperature .

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