Substrate processing method and substrate processing apparatus
阅读说明:本技术 衬底处理方法及衬底处理装置 (Substrate processing method and substrate processing apparatus ) 是由 尾辻正幸 高桥弘明 加藤雅彦 藤原直澄 山口佑 佐佐木悠太 于 2019-06-28 设计创作,主要内容包括:本发明涉及衬底处理方法及衬底处理装置。该衬底处理方法包括:干燥前处理液供给工序,向衬底的表面供给干燥前处理液,所述干燥前处理液包含形成凝固体的凝固体形成物质、和与上述凝固体形成物质互溶的溶解物质,并且所述干燥前处理液具有比上述凝固体形成物质的凝固点低的凝固点;凝固体形成工序,通过使上述衬底的表面上的上述干燥前处理液的一部分固化,从而在上述干燥前处理液中形成包含上述凝固体形成物质的上述凝固体;液体除去工序,在将上述凝固体保留于上述衬底的表面上的同时,将上述衬底的表面上的上述干燥前处理液除去;和固体除去工序,通过使保留于上述衬底的表面上的上述凝固体变化为气体,从而将所述凝固体从上述衬底的表面除去。(The present invention relates to a substrate processing method and a substrate processing apparatus. The substrate processing method includes: a drying pretreatment liquid supply step of supplying a drying pretreatment liquid to the surface of the substrate, the drying pretreatment liquid containing a solidification product-forming substance that forms a solidification product and a dissolving substance that is compatible with the solidification product-forming substance, and the drying pretreatment liquid having a solidification point lower than the solidification point of the solidification product-forming substance; a solidified body forming step of forming the solidified body containing the solidified body forming substance in the drying pretreatment liquid by solidifying a part of the drying pretreatment liquid on the surface of the substrate; a liquid removing step of removing the drying pretreatment liquid on the surface of the substrate while leaving the solidified material on the surface of the substrate; and a solid removal step of removing the solidified material remaining on the surface of the substrate from the surface of the substrate by changing the solidified material to a gas.)
1. A substrate processing method comprising the steps of:
a drying pretreatment liquid supply step of supplying a drying pretreatment liquid to a surface of a substrate, the drying pretreatment liquid including a solidification product forming substance that forms a solidification product and a dissolving substance that is compatible with the solidification product forming substance, the drying pretreatment liquid having a solidification point lower than a solidification point of the solidification product forming substance;
a solidified body forming step of forming the solidified body containing the solidified body forming substance in the pre-drying treatment liquid by solidifying a part of the pre-drying treatment liquid on the surface of the substrate;
a liquid removing step of removing the drying pretreatment liquid on the surface of the substrate while leaving the solidified material on the surface of the substrate; and
and a solid removal step of removing the solidified body remaining on the surface of the substrate from the surface of the substrate by changing the solidified body to a gas.
2. The substrate processing method according to claim 1, wherein the solidified material forming step comprises a cooling step of cooling the pre-drying treatment liquid on the surface of the substrate.
3. The substrate processing method according to claim 2, wherein the cooling step comprises a deposition step of cooling the pre-drying treatment liquid on the surface of the substrate so that a saturated concentration of the solidified-body forming substance in the pre-drying treatment liquid on the surface of the substrate is reduced to a value lower than a concentration of the solidified-body forming substance in the pre-drying treatment liquid on the surface of the substrate.
4. The substrate processing method according to claim 3, further comprising a preliminary heating step of heating to evaporate a part of the pretreatment liquid before cooling the pretreatment liquid on the surface of the substrate.
5. The substrate processing method according to claim 4, wherein a vapor pressure of the dissolved substance is higher than a vapor pressure of the solidification body forming substance.
6. The substrate processing method according to claim 2, wherein a concentration of the solidified material forming substance in the pre-drying treatment liquid is equal to or higher than a eutectic point concentration of the solidified material forming substance and a dissolved substance in the pre-drying treatment liquid,
the cooling step includes a solidifying step of cooling the drying pretreatment liquid on the surface of the substrate to a temperature not higher than the solidifying point of the drying pretreatment liquid.
7. The substrate processing method according to any one of claims 2 to 6, wherein the cooling step comprises an indirect cooling step of cooling the pre-drying treatment liquid on the surface of the substrate through the substrate to form the solidified body in a bottom layer in contact with the surface of the substrate in the pre-drying treatment liquid,
the liquid removing step includes a step of removing the drying pretreatment liquid located on the solidified body while leaving the solidified body on the surface of the substrate.
8. The substrate processing method according to claim 7, wherein the indirect cooling step comprises a cooling fluid supply step of supplying a cooling fluid, which is a fluid having a temperature lower than a temperature of the drying pretreatment liquid on the surface of the substrate, to the back surface of the substrate in a state where the drying pretreatment liquid is on the surface of the substrate.
9. The substrate processing method according to claim 7, wherein the indirect cooling step comprises a cooling member disposing step of disposing a cooling member having a temperature lower than the temperature of the drying pretreatment liquid on the front surface of the substrate on the back surface side of the substrate.
10. The substrate processing method according to any one of claims 1 to 5, wherein the liquid removing step comprises a substrate rotation holding step of holding the substrate horizontally and rotating the substrate around a vertical rotation axis to remove the pre-drying treatment liquid on the surface of the substrate while holding the solidified body on the surface of the substrate.
11. The substrate processing method according to any one of claims 1 to 7, wherein the liquid removing step includes a gas supplying step of removing the drying pretreatment liquid on the surface of the substrate while leaving the solidified body on the surface of the substrate by ejecting a gas toward the surface of the substrate.
12. The substrate processing method according to any one of claims 1 to 7, wherein the liquid removing step comprises an evaporation step of evaporating the pre-drying treatment liquid on the surface of the substrate by heating, thereby removing the pre-drying treatment liquid on the surface of the substrate while leaving the solidified body on the surface of the substrate.
13. The substrate processing method according to any one of claims 1 to 7, wherein a solidification point of the solidification-forming substance is room temperature or higher,
the freezing point of the drying pretreatment liquid is lower than room temperature,
the drying pretreatment liquid supply step includes a step of supplying the drying pretreatment liquid at room temperature to the surface of the substrate.
14. The substrate processing method according to any one of claims 1 to 7, further comprising a film thickness reducing step of reducing a film thickness of the pre-drying treatment liquid by removing a part of the pre-drying treatment liquid on the surface of the substrate by centrifugal force by rotating the substrate around a vertical rotation axis while keeping the substrate horizontal before the solidified body is formed.
15. The substrate processing method according to any one of claims 1 to 7, wherein the solid removal process comprises at least one of: a sublimation step of sublimating the solidified material from a solid to a gas; a decomposition step of changing the solidified material into a gas without passing through a liquid by decomposing the solidified material; and a reaction step of changing the solidified material into a gas without passing through a liquid by a reaction of the solidified material.
16. The substrate processing method according to any one of claims 1 to 7, further comprising a substrate transfer step of transferring the substrate having the solidified material remaining on the surface of the substrate from a1 st chamber in which the liquid removal step is performed to a 2 nd chamber in which the solid removal step is performed.
17. A substrate processing apparatus includes:
a pre-drying treatment liquid supply means for supplying a pre-drying treatment liquid to a surface of a substrate, the pre-drying treatment liquid containing a solidification product forming substance that forms a solidification product and a dissolving substance that is compatible with the solidification product forming substance, and the pre-drying treatment liquid having a solidification point lower than a solidification point of the solidification product forming substance;
a solidified body forming means for forming the solidified body containing the solidified body forming substance in the pre-drying treatment liquid by solidifying a part of the pre-drying treatment liquid on the surface of the substrate;
a liquid removing mechanism that removes the drying pretreatment liquid on the surface of the substrate while leaving the solidified body on the surface of the substrate; and
a solid removal mechanism that removes the solidified body remaining on the surface of the substrate from the surface of the substrate by changing the solidified body to a gas.
Technical Field
The present invention relates to a substrate processing method and a substrate processing apparatus for processing a substrate. Examples of the substrate to be processed include a semiconductor wafer, a substrate for a liquid crystal Display device, a substrate for an optical disk, a substrate for a magnetic disk, a substrate for a magneto-optical disk, a substrate for a photomask, a ceramic substrate, a substrate for a solar cell, and a substrate for a Flat Panel Display (FPD) such as an organic EL (electroluminescence) Display device.
Background
In a manufacturing process of a semiconductor device, a liquid crystal display device, or the like, a substrate such as a semiconductor wafer or a glass substrate for a liquid crystal display device is subjected to a treatment as needed. Such a process includes supplying a process liquid such as a chemical liquid or a rinse liquid to the substrate. After the treatment liquid is supplied, the treatment liquid is removed from the substrate, and the substrate is dried.
When drying a substrate in a state where a pattern is formed on the surface of the substrate, there are cases where: a force caused by the surface tension of the processing liquid attached to the substrate is applied to the pattern, and the pattern collapses. As a countermeasure, the following method is adopted: a liquid having a low surface tension such as IPA (isopropyl alcohol) or a hydrophobizing agent having a pattern contact angle close to 90 degrees is supplied to the substrate. However, even if IPA or a hydrophobizing agent is used, the pattern collapse force cannot be zero, and therefore, depending on the strength of the pattern, the pattern collapse cannot be sufficiently prevented even if these measures are taken.
In recent years, sublimation drying has been attracting attention as a technique for preventing pattern collapse. For example, japanese patent laid-open publication No. 2015-142069 discloses a substrate processing method and a substrate processing apparatus for performing sublimation drying. In the sublimation drying described in jp 2015-142069 a, a melt of a sublimable substance is supplied to the surface of the substrate, and the DIW on the substrate is replaced with the melt of the sublimable substance. Then, the sublimable substance on the substrate is solidified. Then, the solidified body of the sublimable substance on the substrate is sublimated. Thereby, the melt of the sublimable substance is removed from the substrate, and the substrate is dried. Japanese patent laid-open publication No. 2015-142069 discloses tert-butanol as a specific example of the sublimable substance. According to the disclosure of Japanese patent laid-open publication No. 2015-142069, the freezing point of t-butanol is 25 ℃.
Disclosure of Invention
As described above, in japanese patent laid-open publication No. 2015-142069, a melt of a sublimable substance is supplied to a substrate. When the room temperature is 23 ℃, for example, the freezing point of t-butanol, which is one of specific examples of the sublimable substance, is higher than the room temperature. Therefore, when the substrate processing apparatus is disposed in a room temperature space, the sublimable substance must be heated in order to maintain the sublimable substance as a liquid.
Japanese patent laid-open publication No. 2015-142069 describes that the inside of a storage tank for storing a tert-butanol liquid is maintained at a temperature higher than the freezing point of tert-butanol. Therefore, the substrate processing apparatus described in japanese patent application laid-open No. 2015-142069 is assumed to be disposed in a room temperature space, and the interior of the storage tank is heated by a heater. Therefore, energy is required to heat the heater.
Accordingly, an object of the present invention is to provide a substrate processing method and a substrate processing apparatus, which can reduce the amount of energy consumption required for substrate processing and reduce the pattern collapse rate generated when drying a substrate.
The invention provides a substrate processing method, which comprises the following steps: a drying pretreatment liquid supply step of supplying a drying pretreatment liquid to the surface of the substrate, the drying pretreatment liquid containing a solidification product-forming substance that forms a solidification product and a dissolving substance that is compatible with the solidification product-forming substance, and the drying pretreatment liquid having a solidification point lower than the solidification point of the solidification product-forming substance; a solidified body forming step of forming the solidified body containing the solidified body forming substance in the drying pretreatment liquid by solidifying a part of the drying pretreatment liquid on the surface of the substrate; a liquid removing step of removing the drying pretreatment liquid on the surface of the substrate while leaving the solidified material on the surface of the substrate; and a solid removal step of removing the solidified material remaining on the surface of the substrate from the surface of the substrate by changing the solidified material to a gas.
According to this method, a solution before drying containing the solidification product forming substance is supplied to the surface of the substrate, instead of supplying the melt of the solidification product forming substance to the surface of the substrate. The pre-drying treatment solution contains a solidification product forming substance for forming a solidification product and a dissolving substance compatible with the solidification product forming substance. That is, the solidification point of the pretreatment liquid to be dried is lowered by mutual dissolution of the solidification product forming substance and the dissolving substance. The solidifying point of the drying pretreatment liquid is lower than that of a solidified body forming substance.
If the freezing point of the pretreatment liquid is lower than room temperature (for example, 23 ℃ C. or a value in the vicinity thereof) (for example, the pressure in the substrate processing apparatus, for example, a value of 1 atm or a value in the vicinity thereof), it is not necessary to heat the pretreatment liquid to maintain the pretreatment liquid as a liquid. Therefore, a heater for heating the pretreatment liquid for drying may not be provided. Even if the freezing point of the pretreatment liquid for drying is not lower than room temperature at normal pressure and the pretreatment liquid for drying needs to be heated in order to maintain the pretreatment liquid for drying as a liquid, the amount of heat to be applied can be reduced as compared with the case of using a melt of a solidification product-forming substance. This can reduce the amount of energy consumed.
After the drying pretreatment liquid is supplied to the surface of the substrate, a part of the drying pretreatment liquid on the surface of the substrate is solidified. Thereby, a solidified material containing a solidified material-forming substance is formed in the drying pretreatment liquid. Then, the residual pre-drying treatment liquid is removed from the surface of the substrate. Thereby, the solidified body remains on the surface of the substrate. Then, the solidified body is changed into a gas. In this way, the solidified body disappears from the surface of the substrate. Therefore, even if a fragile pattern is formed on the surface of the substrate, the substrate is dried so that no liquid level is formed between the adjacent 2 patterns, and therefore, the substrate can be dried while suppressing pattern collapse.
In the case where the solution before drying is a solution in which the solute and the solvent are uniformly dissolved in each other, one of the solid-forming substance and the dissolved substance may be the solute and the other of the solid-forming substance and the dissolved substance may be the solvent. Both the solidification product and the dissolved substance may be solutes. That is, the pretreatment liquid for drying may contain a solvent that is compatible with the solidification product-forming substance and the dissolving substance. In this case, the vapor pressure of the solvent may be the same as or different from the vapor pressure of the solidification product-forming substance. Similarly, the vapor pressure of the solvent may be the same as or different from the vapor pressure of the dissolved substance.
The solidified material-forming substance may be a sublimable substance that changes from a solid to a gas without passing through a liquid at normal temperature or normal pressure, or may be a substance other than a sublimable substance. Similarly, the dissolved substance may be a sublimable substance or a substance other than a sublimable substance. For example, the solidified material may be a sublimable material, and the dissolved material may be a sublimable material different from the solidified material.
The sublimable substance may be a substance that sublimes when the pressure is reduced to a value lower than the normal pressure at room temperature (for example, 22 to 25 ℃). In this case, the solidified material can be sublimated by a relatively simple method of reducing the pressure of the atmosphere in contact with the solidified material. Alternatively, the sublimable substance may be a substance that sublimes when heated to a temperature higher than room temperature under normal pressure. In this case, the solidified material can be sublimated by a relatively simple method such as heating the solidified material.
In one embodiment of the present invention, the solidified material forming step includes a cooling step of cooling the liquid before drying on the surface of the substrate.
According to this method, the drying pretreatment liquid on the surface of the substrate is cooled. When the saturated concentration of the coagulation forming substance in the pre-drying treatment liquid is lower than the concentration of the coagulation forming substance in the pre-drying treatment liquid, crystals containing the coagulation forming substance precipitate. Thereby, a solidified material containing a solidified material-forming substance can be formed in the drying pretreatment liquid. If the cooling temperature of the pre-drying treatment liquid is lower than the freezing point of the pre-drying treatment liquid, a solidified body is formed in the pre-drying treatment liquid by solidification of the pre-drying treatment liquid. Thereby, a solidified material containing a solidified material-forming substance can be formed in the drying pretreatment liquid.
The cooling temperature of the pretreatment liquid for drying may be a temperature lower than room temperature and equal to or lower than the freezing point of the pretreatment liquid for drying, or a temperature lower than room temperature and higher than the freezing point of the pretreatment liquid for drying.
In one embodiment of the present invention, the cooling step includes a precipitation step of cooling the drying pretreatment liquid on the surface of the substrate so that a saturated concentration of the solidification material in the drying pretreatment liquid on the surface of the substrate is reduced to a value lower than a concentration of the solidification material in the drying pretreatment liquid on the surface of the substrate.
In the above method, the pre-drying treatment liquid on the surface of the substrate is cooled, and the saturation concentration of the solidification product-forming substance in the pre-drying treatment liquid is reduced. When the saturated concentration of the solidification product-forming substance is lower than the concentration of the solidification product-forming substance, crystals of the solidification product-forming substance or crystals mainly composed of the solidification product-forming substance precipitate. Thus, a solidified body of high purity of the solidified body-forming substance can be formed in the drying pretreatment liquid, and a solidified body of high purity of the solidified body-forming substance can be left on the surface of the substrate.
In one embodiment of the present invention, the method further includes a preliminary heating step of heating to evaporate a part of the liquid before drying on the surface of the substrate before cooling the liquid before drying on the surface of the substrate.
By the above method, the drying pretreatment liquid on the surface of the substrate is heated. This causes a part of the pre-drying treatment liquid to evaporate, thereby reducing the amount of the pre-drying treatment liquid on the substrate. Then, the drying pretreatment liquid on the surface of the substrate is cooled to reduce the saturation concentration of the solidification product-forming substance. Since the amount of the drying pretreatment liquid on the substrate is reduced by heating the drying pretreatment liquid in advance, a solidified body can be formed in a shorter time than in the case where the drying pretreatment liquid is not heated.
The preliminary heating step may include at least one of the following steps: a heating gas supply step of ejecting a heating gas having a temperature higher than the temperature of the pre-drying treatment liquid on the front surface of the substrate toward at least one of the front surface and the back surface of the substrate; a heating liquid supply step of ejecting a heating liquid higher in temperature than the drying pretreatment liquid on the front surface of the substrate toward the back surface of the substrate; a proximity heating step of disposing a heating member having a temperature higher than the temperature of the pre-drying treatment liquid on the surface of the substrate on the front surface side or the back surface side of the substrate in a state of being separated from the substrate; a contact heating step of bringing a heating member having a temperature higher than the temperature of the pre-drying treatment liquid on the front surface of the substrate into contact with the back surface of the substrate; and a light irradiation step of irradiating the drying pretreatment liquid on the surface of the substrate with light. The light irradiation step may include a whole irradiation step of simultaneously irradiating light to the entire surface of the substrate, or a partial irradiation step of moving the irradiation region within the surface of the substrate while irradiating light to an irradiation region representing only a partial region within the surface of the substrate, or may include both of the whole irradiation step and the partial irradiation step.
In one embodiment of the present invention, the vapor pressure of the dissolved substance is higher than the vapor pressure of the solidified material-forming substance.
By the above method, the vapor pressure of the dissolved substance contained in the pre-drying treatment liquid is higher than the vapor pressure of the solidification product-forming substance contained in the pre-drying treatment liquid. Therefore, when heating is performed before cooling the pretreatment liquid for drying, the dissolved substance evaporates at an evaporation rate greater than the evaporation rate of the solidification product-forming substance (evaporation amount per unit time). This can increase the concentration of the solidification product-forming substance in the pretreatment liquid for drying. Therefore, a solidified body can be formed in a shorter time than in the case where the pretreatment liquid is not heated for drying.
In one embodiment of the present invention, the concentration of the solidification material in the pre-drying treatment liquid is equal to or higher than the eutectic point concentration of the solidification material and the dissolved material in the pre-drying treatment liquid, and the cooling step includes a solidification step of cooling the pre-drying treatment liquid on the surface of the substrate to a temperature lower than the solidification point of the pre-drying treatment liquid.
By the above method, the drying pretreatment liquid on the surface of the substrate is cooled to the freezing point or less of the drying pretreatment liquid. Thereby, a part of the drying pretreatment liquid is solidified, and the solidified material gradually becomes larger. Since the concentration of the solidification product-forming substance is equal to or higher than the eutectic point concentration of the solidification product-forming substance and the dissolved substance, a solidification product of the solidification product-forming substance or a solidification product containing the solidification product-forming substance as a main component is formed in the drying pretreatment liquid at the start of solidification of the drying pretreatment liquid. Thus, a solidified product having a high purity of a solidified product-forming substance can be formed in the drying pretreatment liquid.
On the other hand, when the solidification of the solidification product-forming substance proceeds by cooling the pretreatment liquid for drying, the concentration of the solidification product-forming substance in the pretreatment liquid for drying gradually decreases. In other words, the concentration of the dissolved substance in the pretreatment liquid for drying gradually increases. Then, the drying pretreatment liquid in which the concentration of the dissolved substance has increased is removed from the substrate, and a solidified body having a high purity of the solidified body-forming substance remains on the substrate. Therefore, the solidified material contained in the pretreatment liquid for drying can be effectively utilized.
The eutectic point concentration of the solidification product-forming substance and the dissolved substance in the pretreatment liquid for drying is a concentration at which crystals of both the solidification product-forming substance and the dissolved substance precipitate from the pretreatment liquid for drying when the pretreatment liquid for drying is cooled to a temperature not higher than the solidification point of the pretreatment liquid for drying.
In one embodiment of the present invention, the cooling step includes an indirect cooling step of cooling the liquid before drying on the surface of the substrate through the substrate, thereby forming the solidified body in a bottom layer in contact with the surface of the substrate in the liquid before drying. The liquid removing step includes a step of removing the drying pretreatment liquid present on the solidified material while leaving the solidified material on the surface of the substrate.
According to this method, the drying pretreatment liquid on the surface of the substrate is indirectly cooled by cooling the substrate, instead of directly cooling the drying pretreatment liquid on the surface of the substrate. Therefore, the primer layer in contact with the surface of the substrate (including the surface of the pattern in the case where the pattern is formed) in the drying pretreatment liquid on the surface of the substrate is efficiently cooled, and a solidified body is formed at the interface between the drying pretreatment liquid and the substrate. The remaining pre-drying treatment solution remained on the solidified body. Therefore, when the drying pretreatment liquid is removed from the solidified body, the drying pretreatment liquid can be removed from the surface of the substrate while the solidified body remains on the surface of the substrate.
In one embodiment of the present invention, the indirect cooling step includes a cooling fluid supply step of supplying a cooling fluid, which has a lower temperature than the temperature of the drying pretreatment liquid on the surface of the substrate, to the back surface of the substrate in a state where the drying pretreatment liquid is on the surface of the substrate.
According to this method, a cooling fluid, which is at least one of a gas and a liquid having a temperature lower than a temperature of a pretreatment for drying on the surface of the substrate, is brought into contact with the back surface of the substrate. This allows the pretreatment liquid for drying on the surface of the substrate to be indirectly cooled.
In one embodiment of the present invention, the indirect cooling step includes a cooling member disposing step of disposing a cooling member having a temperature lower than the temperature of the drying pretreatment liquid on the front surface of the substrate on the back surface side of the substrate.
According to this method, a cooling member having a temperature lower than the temperature of the drying pretreatment liquid on the front surface of the substrate is disposed on the back surface side of the substrate (which is a plane opposite to the front surface of the substrate). In the case where the cooling member is brought into contact with the back surface of the substrate, the substrate is directly cooled by the cooling member. In the case where the cooling member is not brought into contact with the back surface of the substrate but is brought close to the back surface of the substrate, the substrate is indirectly cooled by the cooling member. Therefore, in either case, the pretreatment liquid for drying on the surface of the substrate can be indirectly cooled without bringing the fluid into contact with the substrate.
In addition to or instead of the indirect cooling process, the cooling process may include at least one of the following processes: a cooling gas supply step of ejecting a cooling gas having a temperature lower than the temperature of the drying pretreatment liquid on the surface of the substrate toward the drying pretreatment liquid on the surface of the substrate; a preliminary cooling step of cooling the substrate before supplying the drying pretreatment liquid to the surface of the substrate; a vaporization cooling step of ejecting a low-humidity gas having a humidity lower than that of an atmosphere in contact with the pre-drying treatment liquid on the surface of the substrate toward the pre-drying treatment liquid on the surface of the substrate, thereby evaporating the pre-drying treatment liquid and extracting vaporization heat from the pre-drying treatment liquid; and a melting and cooling step of melting the solidification product in the pre-drying treatment liquid to extract heat of fusion from the pre-drying treatment liquid on the surface of the substrate.
When the cooling step includes the gasification cooling step, the low-humidity gas may be an inert gas, clean air (air filtered by a filter), or dry air (dehumidified clean air), or a gas other than these gases. An example of the inert gas is a gas having a humidity of, for example, 10% or less, and the clean air is a gas having a humidity of, for example, 40% or less. The humidity of the dry air is lower than that of the clean air.
In one embodiment of the present invention, the liquid removing step includes a substrate rotation holding step of holding the substrate horizontally and rotating the substrate around a vertical rotation axis to remove the drying pretreatment liquid on the surface of the substrate while holding the solidified body on the surface of the substrate.
According to this method, after a solidified body is formed in the pretreatment liquid for drying, the substrate is rotated about a vertical rotation axis while being kept horizontal. The drying pretreatment liquid on the substrate is discharged from the substrate by a centrifugal force. This allows the excess drying pretreatment liquid to be removed from the surface of the substrate while the solidified material remains on the surface of the substrate.
In one embodiment of the present invention, the liquid removing step includes a gas supplying step of ejecting a gas toward the surface of the substrate to remove the drying pretreatment liquid on the surface of the substrate while leaving the solidified body on the surface of the substrate.
According to this method, after a solidified body is formed in the drying pretreatment liquid, a gas is blown onto the surface of the substrate. The drying pretreatment liquid on the substrate is discharged from the substrate by the pressure of the gas. This allows the excess drying pretreatment liquid to be removed from the surface of the substrate while the solidified material remains on the surface of the substrate.
In one embodiment of the present invention, the liquid removing step includes an evaporation step of evaporating the drying pretreatment liquid on the surface of the substrate by heating, thereby removing the drying pretreatment liquid on the surface of the substrate while leaving the solidified body on the surface of the substrate.
According to this method, after a solidified body is formed in the pre-drying treatment liquid, the pre-drying treatment liquid on the surface of the substrate is heated. Thereby, the pretreatment liquid for drying is evaporated and discharged from the substrate. Therefore, the excess drying pretreatment liquid can be removed from the surface of the substrate while the solidified body remains on the surface of the substrate.
In addition to or instead of at least one of the substrate rotation holding step, the gas supply step, and the evaporation step, the liquid removal step may include at least one of the following steps: a pressure reduction step of reducing a pressure of an atmosphere in contact with the drying pretreatment liquid on the surface of the substrate; a light irradiation step of irradiating the drying pretreatment liquid on the surface of the substrate with light; and an ultrasonic vibration applying step of applying ultrasonic vibration to the drying pretreatment liquid on the surface of the substrate.
In one embodiment of the present invention, the solidification point of the solidification product-forming substance is at least room temperature, and the solidification point of the pretreatment liquid for drying is lower than room temperature. The drying pretreatment liquid supply step includes a step of supplying the drying pretreatment liquid at room temperature to the surface of the substrate.
According to this method, a drying pretreatment liquid at room temperature is supplied to a substrate. The solidification point of the solidification body forming substance is above room temperature, on the other hand, the solidification point of the drying pretreatment liquid is lower than room temperature. In the case of supplying a melt of a solidification product-forming substance to a substrate, the solidification product-forming substance must be heated in order to maintain the solidification product-forming substance as a liquid. In contrast, when the drying pretreatment liquid is supplied to the substrate, the drying pretreatment liquid can be maintained in a liquid state without heating the drying pretreatment liquid. This can reduce the amount of energy consumed for substrate processing.
In one embodiment of the present invention, the method further includes a film thickness reducing step of reducing a film thickness of the drying pretreatment liquid by removing a part of the drying pretreatment liquid on the surface of the substrate by centrifugal force by rotating the substrate around a vertical rotation axis while keeping the substrate horizontal before the solidified body is formed.
According to this method, the substrate is rotated around the vertical rotation axis while being kept horizontal before the solidified body is formed in the drying pretreatment liquid. A part of the drying pretreatment liquid on the surface of the substrate is removed from the substrate by a centrifugal force. This reduces the film thickness of the pretreatment liquid before drying. Then, a solidified body is formed. Since the film thickness of the liquid before drying is reduced, a solidified body can be formed in a short time, and the solidified body can be made thin. Therefore, the time required for forming the solidified material and the time required for vaporizing the solidified material can be shortened. This can reduce the amount of energy consumed for substrate processing.
The solid removal step may include at least one of the following steps: a sublimation step of sublimating the solidified material from a solid to a gas; a decomposition step of changing the solidified material into a gas without passing through a liquid by decomposition (e.g., thermal decomposition) of the solidified material; and a reaction step of changing the solidified material into a gas without passing through a liquid by a reaction (for example, an oxidation reaction) of the solidified material.
The sublimation process may include at least one of the following processes: a substrate rotation holding step of rotating the substrate around a vertical rotation axis while holding the substrate horizontally; a gas supply step of blowing a gas to the solidified material; a heating step of heating the solidified material; a pressure reduction step of reducing the pressure of the atmosphere in contact with the solidified material; a light irradiation step of irradiating the solidified body with light; and an ultrasonic vibration applying step of applying ultrasonic vibration to the solidified material.
In one embodiment of the present invention, the method further includes a substrate transfer step of transferring the substrate having the solidified material remaining on the surface of the substrate from a1 st chamber in which the liquid removal step is performed to a 2 nd chamber in which the solid removal step is performed.
According to this method, when the substrate is disposed in the 1 st chamber, the drying pretreatment liquid on the surface of the substrate is removed while the solidified body remains on the surface of the substrate. Then, the substrate is transferred from the 1 st chamber to the 2 nd chamber. When the substrate is disposed in the 2 nd chamber, the solidified material remaining on the surface of the substrate is vaporized. In this way, since the removal of the pretreatment solution for drying and the removal of the solidified material are performed in different chambers, the structures in the 1 st chamber and the 2 nd chamber can be simplified, and the respective chambers can be downsized.
The present invention is a substrate processing apparatus, comprising the following mechanisms: a drying pretreatment liquid supply means for supplying a drying pretreatment liquid to a surface of a substrate, the drying pretreatment liquid containing a solidification product-forming substance that forms a solidification product and a dissolving substance that is compatible with the solidification product-forming substance, and the drying pretreatment liquid having a solidification point lower than a solidification point of the solidification product-forming substance; a solidified material forming means for forming the solidified material containing the solidified material forming substance in the drying pretreatment liquid by solidifying a part of the drying pretreatment liquid on the surface of the substrate; a liquid removing mechanism that removes the drying pretreatment liquid on the surface of the substrate while leaving the solidified material on the surface of the substrate; and a solid removal mechanism that removes the solidified material remaining on the surface of the substrate from the surface of the substrate by changing the solidified material to a gas.
With the above configuration, the liquid before drying containing the solidified material is supplied to the surface of the substrate, instead of supplying the molten liquid of the solidified material to the surface of the substrate. The pre-drying treatment solution contains a solidification product forming substance for forming a solidification product and a dissolving substance compatible with the solidification product forming substance. That is, the solidification point of the pretreatment liquid to be dried is lowered by mutual dissolution of the solidification product forming substance and the dissolving substance. The solidifying point of the drying pretreatment liquid is lower than that of a solidified body forming substance.
If the freezing point of the pretreatment liquid is lower than room temperature (for example, 23 ℃ C. or a value in the vicinity thereof) (for example, the pressure in the substrate processing apparatus, for example, a value of 1 atm or a value in the vicinity thereof), it is not necessary to heat the pretreatment liquid to maintain the pretreatment liquid as a liquid. Therefore, a heater for heating the pretreatment liquid for drying may not be provided. Even if the freezing point of the pretreatment liquid for drying is not lower than room temperature at normal pressure and the pretreatment liquid for drying needs to be heated in order to maintain the pretreatment liquid for drying as a liquid, the amount of heat to be applied can be reduced as compared with the case of using a melt of a solidification product-forming substance. This can reduce the amount of energy consumed.
After supplying the drying pretreatment liquid to the surface of the substrate, a part of the drying pretreatment liquid on the surface of the substrate is solidified. Thereby, a solidified material containing a solidified material-forming substance is formed in the drying pretreatment liquid. Then, the residual pre-drying treatment liquid is removed from the surface of the substrate. Thereby, the solidified body remains on the surface of the substrate. Then, the solidified body is changed into a gas. In this way, the solidified body disappears from the surface of the substrate. Therefore, even if a fragile pattern is formed on the surface of the substrate, the substrate is dried so that no liquid level is formed between the adjacent 2 patterns, and therefore, the substrate can be dried while suppressing pattern collapse.
In the case where the solution before drying is a solution in which the solute and the solvent are uniformly dissolved in each other, one of the solid-forming substance and the dissolved substance may be the solute and the other of the solid-forming substance and the dissolved substance may be the solvent. Both the solidification product and the dissolved substance may be solutes. That is, the pretreatment liquid for drying may contain a solvent that is compatible with the solidification product-forming substance and the dissolving substance. In this case, the vapor pressure of the solvent may be the same as or different from the vapor pressure of the solidification product-forming substance. Similarly, the vapor pressure of the solvent may be the same as or different from the vapor pressure of the dissolved substance.
The solidified material-forming substance may be a sublimable substance that changes from a solid to a gas without passing through a liquid at normal temperature or normal pressure, or may be a substance other than a sublimable substance. Similarly, the dissolved substance may be a sublimable substance or a substance other than a sublimable substance. For example, the solidified material may be a sublimable material, and the dissolved material may be a sublimable material different from the solidified material.
The sublimable substance may be a substance that sublimes when the pressure is reduced to a value lower than the normal pressure at room temperature (for example, 22 to 25 ℃). In this case, the solidified material can be sublimated by a relatively simple method of reducing the pressure of the atmosphere in contact with the solidified material. Alternatively, the sublimable substance may be a substance that sublimes when heated to a temperature higher than room temperature under normal pressure. In this case, the solidified material can be sublimated by a relatively simple method such as heating the solidified material.
The above and still other objects, features and effects of the present invention will be apparent from the following description of the embodiments with reference to the accompanying drawings.
Drawings
Fig. 1A is a schematic view of a substrate processing apparatus according to
Fig. 1B is a schematic view of the substrate processing apparatus viewed from the side.
Fig. 2 is a schematic view of a substrate processing apparatus with the inside of a processing unit viewed horizontally.
Fig. 3 is a block diagram showing hardware of the control apparatus.
Fig. 4 is a process diagram for explaining an example of substrate processing (process example 1) performed by using the substrate processing apparatus.
Fig. 5A is a schematic view showing a state of the substrate when the substrate processing shown in fig. 4 is performed.
Fig. 5B is a schematic view showing a state of the substrate when the substrate processing shown in fig. 4 is performed.
Fig. 5C is a schematic view showing a state of the substrate when the substrate processing shown in fig. 4 is performed.
Fig. 5D is a schematic view showing a state of the substrate when the substrate processing shown in fig. 4 is performed.
Fig. 6 is a graph of an image (image) showing the manner of change in the concentration and saturation concentration of a solidification product-forming substance in the pretreatment liquid for drying.
Fig. 7 is a process diagram for explaining another example (process example 2) of substrate processing performed by the substrate processing apparatus.
Fig. 8A is a schematic view showing a state of the substrate when the substrate processing shown in fig. 7 is performed.
Fig. 8B is a schematic view showing a state of the substrate when the substrate processing shown in fig. 7 is performed.
Fig. 8C is a schematic view showing a state of the substrate when the substrate processing shown in fig. 7 is performed.
Fig. 9 is a graph of an image showing the change pattern of the freezing point and temperature of the pretreatment liquid before drying on the substrate.
Fig. 10 is a schematic view of the spin chuck and the blocking member according to
Fig. 11A is a schematic view showing a state of a substrate when a drying pretreatment liquid on the substrate is heated by a built-in heater.
Fig. 11B is a schematic view showing a state of the substrate when the pre-drying treatment liquid on the substrate is cooled by the cooling plate.
Fig. 12 is a schematic view for explaining the conveyance of the substrate from the wet processing unit for removing the surplus drying pretreatment liquid to the dry processing unit for changing the solidified material into a gas without passing through the liquid.
Detailed Description
In the following description, the gas pressure in the
Fig. 1A is a schematic view of a
As shown in fig. 1A, the
The carrying manipulator comprises: an indexer robot (indexerrobot) IR for carrying the substrate W in and out of the carrier C on the load port LP; and a Central Robot (CR) for carrying in and out the substrate W to and from the plurality of
The plurality of
Fig. 2 is a schematic view of the inside of the
The
The
The
The
The
The
When the processing liquid is supplied to the rotating substrate W, at least one of the
The
The
The
Although not shown, the
The
The rinse
The rinse
The pretreatment-for-drying
The pre-drying treatment liquid contains a solidified material forming substance forming the solidified material 101 (see fig. 5B) and a dissolved substance compatible with the solidified material forming substance. The drying pretreatment liquid is a solution formed by uniformly and mutually dissolving a solute and a solvent. Either one of the solidification product forming substance and the dissolution product may be a solute. When the pre-drying treatment liquid contains a solvent that is compatible with the solid-forming substance and the dissolving substance, both the solid-forming substance and the dissolving substance may be solutes.
The solidified material-forming substance may be a sublimable substance that changes from a solid to a gas without passing through a liquid at normal temperature or normal pressure, or may be a substance other than a sublimable substance. Similarly, the dissolved substance may be a sublimable substance or a substance other than a sublimable substance. The sublimable substance contained in the pretreatment liquid for drying may be two or more. That is, both the solidified material forming substance and the dissolved material may be sublimable substances, and the liquid before drying may contain sublimable substances different from the solidified material forming substance and the dissolved material.
The sublimable substance may be any of alcohols such as 2-methyl-2-propanol (alternatively referred to as t-butanol and t-butyl alcohol) and cyclohexanol, fluorocarbon compounds, 1, 3, 5-trioxane (alternatively referred to as trioxymethylene), camphor (alternatively referred to as camphor-2-one (camphre) and camphor (campher)), naphthalene, and iodine, or may be any other substance.
The solvent may be at least one selected from the group consisting of, for example, pure water, IPA, HFE (hydrofluoroether), acetone, PGMEA (propylene glycol monomethyl ether acetate), PGEE (propylene glycol monoethyl ether, 1-ethoxy-2-propanol), and ethylene glycol. Alternatively, the sublimable substance may be a solvent.
Hereinafter, an example in which the solidified material forming substance is a sublimable substance will be described. When both the solidified material-forming substance and the dissolved material are sublimable substances, the drying pretreatment liquid may be a solution containing only cyclohexanol and tert-butanol. Alternatively, they may contain a solvent such as IPA. The vapor pressure of IPA is higher than that of t-butanol and higher than that of cyclohexanol. The vapor pressure of tert-butanol is higher than that of cyclohexanol. Therefore, t-butanol evaporates at a greater evaporation rate than cyclohexanol.
The freezing point of cyclohexanol (the freezing point at 1 atm. hereinafter) is 24 ℃ or a value in the vicinity thereof. The freezing point of t-butanol is 25 ℃ or a value in the vicinity thereof. In the case where the pre-drying treatment liquid is a solution containing only cyclohexanol and tert-butyl alcohol, the freezing point of the pre-drying treatment liquid is lower than the freezing point of cyclohexanol and lower than the freezing point of tert-butyl alcohol. That is, the freezing point of the drying pretreatment liquid is lower than the freezing points of the respective components contained in the drying pretreatment liquid. The freezing point of the pretreatment liquid for drying is lower than room temperature (a value at or near 23 ℃). The
As described later, the replacement liquid is supplied to the upper surface of the substrate W covered with the liquid film of the rinsing liquid, and the drying pretreatment liquid is supplied to the upper surface of the substrate W covered with the liquid film of the replacement liquid. The replacement liquid is a liquid which is miscible with both the rinsing liquid and the pretreatment liquid for drying. The replacement liquid is, for example, IPA or HFE. The replacement liquid may be a mixed liquid of IPA and HFE, or may contain at least one of IPA and HFE and components other than these. IPA and HFE are miscible liquids with both water and hydrofluorocarbons. HFE is insoluble, and HFE can be supplied to the substrate W after the rinsing liquid on the substrate W is replaced with IPA to be mixed with IPA.
When the replacement liquid is supplied to the upper surface of the substrate W covered with the liquid film of the rinse liquid, most of the rinse liquid on the substrate W is washed away by the replacement liquid and discharged from the substrate W. The remaining trace amount of the rinsing solution dissolves in the replacement solution and diffuses in the replacement solution. The rinse liquid after the diffusion is discharged from the substrate W together with the replacement liquid. Therefore, the rinsing liquid on the substrate W can be efficiently replaced with the replacement liquid. For the same reason, the replacement liquid on the substrate W can be efficiently replaced with the drying pretreatment liquid. This can reduce the amount of the rinsing liquid contained in the drying pretreatment liquid on the substrate W.
The pre-drying
Similarly, the replacement
The
The blocking
The plurality of nozzles include a
The
The inner peripheral surface of the blocking
The plurality of nozzles include a lower surface nozzle 71 that discharges the processing liquid toward the center of the lower surface of the substrate W. The lower surface nozzle 71 includes: a nozzle disc portion disposed between the
The lower surface nozzle 71 is connected to a
The lower surface nozzle 71 is also connected to a cooling
The outer peripheral surface of the lower nozzle 71 and the inner peripheral surface of the
The inert gas ejected from the lower central opening 81 of the
Fig. 3 is a block diagram showing hardware of the
The
The
The CPU91 executes the program P stored in the
The
The
Next, 2 examples of processing the substrate W will be described.
The substrate W to be processed is a semiconductor wafer such as a silicon wafer. The surface of the substrate W corresponds to a device formation surface on which devices such as transistors and capacitors are formed. The substrate W may be one having a pattern P1 (see fig. 5B) formed on the front surface of the substrate W as a pattern formation surface, or one having no pattern P1 formed on the front surface of the substrate W. In the latter case, the pattern P1 may be formed in the chemical liquid supply step described later.
Example of
First, an example in which the
Fig. 4 is a process diagram for explaining an example of the processing of the substrate W (the first processing example 1) performed by the
When the
Specifically, in a state where the blocking
Next, the
Next, a chemical liquid supplying step (step S3 in fig. 4) of supplying a chemical liquid onto the upper surface of the substrate W to form a liquid film of the chemical liquid covering the entire upper surface of the substrate W is performed.
Specifically, the
The chemical solution discharged from the
Next, a rinsing liquid supply step (step S4 in fig. 4) of supplying pure water, which is an example of a rinsing liquid, to the upper surface of the substrate W to wash away the chemical liquid on the substrate W is performed.
Specifically, the
The pure water discharged from the rinse
Next, a replacement liquid supplying step (step S5 in fig. 4) of supplying a replacement liquid, which is compatible with both the rinsing liquid and the drying pretreatment liquid, to the upper surface of the substrate W to replace the pure water on the substrate W with the replacement liquid is performed.
Specifically, the
The replacement liquid discharged from the replacement
Next, a drying pretreatment liquid supply step (step S6 in fig. 4) of supplying the drying pretreatment liquid to the upper surface of the substrate W to form a liquid film of the drying pretreatment liquid on the substrate W is performed.
Specifically, the
The pretreatment liquid for drying discharged from the pretreatment liquid for drying
Next, a film thickness reducing step (step S7 in fig. 4) is performed in which a part of the drying pretreatment liquid on the substrate W is removed, and the film thickness of the drying pretreatment liquid (the thickness of the liquid film) on the substrate W is reduced while maintaining a state in which the entire upper surface of the substrate W is covered with the liquid film of the drying pretreatment liquid.
Specifically, before or after the ejection of the drying pretreatment liquid is stopped, the
Next, a preheating step (step S8 in fig. 4) of supplying hot water having a temperature higher than the temperature of the pretreatment solution for drying on the substrate W to the lower surface of the substrate W to heat the pretreatment solution for drying on the substrate W to a preheating temperature is performed.
Specifically, the blocking member lifting and lowering
The hot water jetted upward from the lower surface nozzle 71 is applied to the center of the lower surface of the substrate W and then flows outward along the lower surface of the rotating substrate W. Thereby, hot water is supplied to the entire lower surface area of the substrate W. The temperature of the hot water is above room temperature and below the boiling point of water. The temperature of the substrate W and the temperature of the pre-drying treatment liquid on the substrate W are lower than the temperature of the hot water. Therefore, the pretreatment solution for drying on the substrate W is uniformly heated through the substrate W. Thereby, the drying pretreatment liquid on the substrate W is heated to the preheating temperature. When a predetermined time has elapsed after the
As shown in fig. 5A, when the drying pretreatment liquid on the substrate W is heated, the solidified material and the dissolved material contained in the drying pretreatment liquid are evaporated. This causes a part of the drying pretreatment liquid on the substrate W to evaporate, thereby reducing the thickness of the drying pretreatment liquid. Since the vapor pressure of the dissolved substance is higher than that of the solidification product-forming substance, the evaporation rate of the dissolved substance is higher than that of the solidification product-forming substance. Therefore, when the drying pretreatment liquid is continuously heated, the concentration of the solidification product-forming substance in the drying pretreatment liquid increases, and the solidification point of the drying pretreatment liquid increases. The heating of the pre-drying treatment liquid may be stopped before the crystals containing the solidification product-forming substance are precipitated, or may be stopped after the crystals containing the solidification product-forming substance are precipitated in the pre-drying treatment liquid.
Next, in order to reduce the saturated concentration of the solidification material in the pre-drying treatment liquid on the substrate W to a value lower than the concentration of the solidification material in the pre-drying treatment liquid on the substrate W, a deposition step (step S9 in fig. 4) is performed in which cold water having a temperature lower than the temperature of the pre-drying treatment liquid on the substrate W is supplied to the lower surface of the substrate W, thereby cooling the pre-drying treatment liquid on the substrate W.
Specifically, after the
As shown in fig. 6, when the pre-drying treatment liquid is heated, the saturation concentration of the solidification product-forming substance in the pre-drying treatment liquid increases; when the pre-drying treatment liquid is cooled, the saturated concentration of the solidification product-forming substance in the pre-drying treatment liquid is decreased. Fig. 6 shows an example in which the saturated concentration of the coagulation forming substance in the pre-drying treatment liquid is equal to the concentration of the coagulation forming substance in the pre-drying treatment liquid at time T1. After time T1, the saturated concentration of the coagulation substance in the pretreatment liquid for drying was lower than the concentration of the coagulation substance in the pretreatment liquid for drying, and crystals containing the coagulation substance precipitated. Thereby, a solidified
The pretreatment liquid for drying on the substrate W is not directly cooled, but is indirectly cooled through the substrate W. The solidified
The thickness of the solidified
After the solidified
The removal of the pretreatment solution for drying may be performed by ejecting nitrogen gas toward the upper surface of the rotating substrate W, or may be performed by accelerating the substrate W in the rotation direction. Alternatively, both the ejection of the nitrogen gas and the acceleration of the substrate W may be performed. When the remaining drying pretreatment liquid is removed from the substrate W after the solidified
When the remaining pretreatment solution for drying is discharged by the nitrogen gas discharge, the
When the substrate W is accelerated to discharge the excess pre-drying treatment liquid, the
Next, a sublimation step (step S11 in fig. 4) of sublimating the solidified
Specifically, in a state where the
When the substrate W starts to rotate at the sublimation rate, the solidified
Next, a carrying-out step of carrying out the substrate W from the
Specifically, the blocking member lifting and lowering
Example of
Next, an example in which the drying pretreatment liquid on the substrate W is cooled to a temperature equal to or lower than the freezing point thereof in order to solidify a part of the drying pretreatment liquid will be described.
Fig. 7 is a process diagram for explaining an example of the processing of the substrate W (process example 2) performed by the
Hereinafter, a flow from the solidification step to the sublimation step will be described. The steps other than these are the same as those in the processing example 1, and therefore, the description thereof is omitted.
After the film thickness reducing step (step S7 in fig. 7) is performed, a solidifying step (step S14 in fig. 7) is performed in which cold water having a temperature lower than the temperature of the drying pretreatment liquid on the substrate W is supplied to the lower surface of the substrate W to cool the drying pretreatment liquid on the substrate W to the freezing point or lower of the drying pretreatment liquid.
Specifically, after the
Since the cooling temperature of the pre-drying treatment liquid is lower than the freezing point of the pre-drying treatment liquid on the substrate W, if the cooling of the pre-drying treatment liquid is continued, the actual temperature of the pre-drying treatment liquid is lowered to the freezing point of the pre-drying treatment liquid. Fig. 9 shows an example in which the actual temperature of the pretreatment liquid for drying is equal to the freezing point of the pretreatment liquid for drying at time T2. After time T2, a part of the drying pretreatment liquid on the substrate W solidifies, and the solidified
The pretreatment liquid for drying on the substrate W is not directly cooled, but is indirectly cooled through the substrate W. The solidified
The thickness of the solidified
After the solidified
The removal of the pretreatment solution for drying may be performed by ejecting nitrogen gas toward the upper surface of the rotating substrate W, or may be performed by accelerating the substrate W in the rotation direction. Alternatively, both the ejection of the nitrogen gas and the acceleration of the substrate W may be performed. When the remaining drying pretreatment liquid is removed from the substrate W after the solidified
When the remaining pretreatment solution for drying is discharged by the nitrogen gas discharge, the
When the substrate W is accelerated to discharge the excess pre-drying treatment liquid, the
Next, a sublimation step (step S11 in fig. 7) of sublimating the solidified
Specifically, in a state where the
When the substrate W starts to rotate at the sublimation rate, the solidified
As described above, in
If the freezing point of the pretreatment liquid is lower than room temperature (for example, 23 ℃ or a value near it) (for example, the pressure in the
After supplying the drying pretreatment liquid to the surface of the substrate W, a part of the drying pretreatment liquid on the surface of the substrate W is solidified. Thereby, the solidified
In the treatment example 1, the drying pretreatment liquid on the surface of the substrate W is cooled to lower the saturation concentration of the solidification product-forming substance in the drying pretreatment liquid. When the saturated concentration of the solidification product-forming substance is lower than the concentration of the solidification product-forming substance, crystals of the solidification product-forming substance or crystals mainly composed of the solidification product-forming substance precipitate. Thus, the solidified
In the 1 st processing example, the drying pretreatment liquid on the surface of the substrate W is heated. This causes a part of the pre-drying treatment liquid to evaporate, thereby reducing the amount of the pre-drying treatment liquid on the substrate W. Then, the drying pretreatment liquid on the surface of the substrate W is cooled to reduce the saturation concentration of the solidification product-forming substance. Since the amount of the drying pretreatment liquid on the substrate W is reduced by heating the drying pretreatment liquid in advance, the solidified
In the treatment example 1, the vapor pressure of the dissolved substance contained in the pretreatment liquid for drying is higher than the vapor pressure of the solidification product-forming substance contained in the pretreatment liquid for drying. Therefore, when heating is performed before cooling the pretreatment liquid for drying, the dissolved substance evaporates at an evaporation rate greater than the evaporation rate of the solidification product-forming substance (evaporation amount per unit time). This can increase the concentration of the solidification product-forming substance in the pretreatment liquid for drying. Therefore, the solidified
In the process example 2, the drying pretreatment liquid on the surface of the substrate W is cooled to a temperature lower than the freezing point of the drying pretreatment liquid. Thereby, a part of the drying pretreatment liquid is solidified, and the solidified
On the other hand, when the solidification of the solidification product-forming substance proceeds by cooling the pretreatment liquid for drying, the concentration of the solidification product-forming substance in the pretreatment liquid for drying gradually decreases. In other words, the concentration of the dissolved substance in the pretreatment liquid for drying gradually increases. Then, the drying pretreatment liquid in which the concentration of the dissolved substance has increased is removed from the substrate W, and the solidified
In the processing examples 1 and 2, the drying pretreatment liquid on the surface of the substrate W is indirectly cooled by cooling the substrate W without directly cooling the drying pretreatment liquid on the surface of the substrate W. Therefore, the
In the processing examples 1 and 2, a drying pretreatment liquid at room temperature was supplied to the substrate W. The solidification point of the solidification body forming substance is above room temperature, and on the other hand, the solidification point of the drying pretreatment liquid is lower than room temperature. When supplying a melt of a solidification product-forming substance to the substrate W, the solidification product-forming substance must be heated in order to maintain the solidification product-forming substance in a liquid state. On the other hand, when the drying pretreatment liquid is supplied to the substrate W, the drying pretreatment liquid can be maintained in a liquid state without heating the drying pretreatment liquid. This reduces the amount of energy consumed for processing the substrate W.
In the processing examples 1 and 2, the substrate W is rotated about the vertical rotation axis a1 while being kept horizontal until the solidified
Next,
The main differences between
Fig. 10 is a schematic view of the
As shown in fig. 10, the built-in
The
The
The
The
Fig. 11A is a schematic view showing a state of the substrate W when the drying pretreatment liquid on the substrate W is heated by the built-in
As shown in fig. 11A, in the preliminary heating step (step S8 in fig. 4), the temperature of the built-in
In the case of using the built-in
Fig. 11B is a schematic view showing a state of the substrate W when the pretreatment liquid for drying on the substrate W is cooled by the
As shown in fig. 11B, in at least one of the deposition step (step S9 in fig. 4) and the solidification step (step S14 in fig. 7), the temperature of the
In
Next,
The main differences between
Fig. 12 is a schematic view for explaining the conveyance of the substrate W from the wet processing unit 2W from which the surplus drying pretreatment liquid is removed to the
The plurality of
The steps from the carrying-in step (step S1 in fig. 4) to the liquid removing step (step S10 in fig. 4) shown in fig. 4, or the steps from the carrying-in step (step S1 in fig. 7) to the liquid removing step (step S10 in fig. 7) shown in fig. 7 are performed in the
In
Other embodiments
The present invention is not limited to the above-described embodiments, and various modifications can be made.
For example, in at least one of the processing examples 1 and 2, in order to maintain the drying pretreatment liquid on the substrate W as a liquid, a temperature maintaining step may be performed in which the drying pretreatment liquid on the substrate W is maintained at a liquid maintaining temperature higher than the freezing point of the drying pretreatment liquid and lower than the boiling point of the drying pretreatment liquid.
When the difference between the solidification point of the pre-drying treatment liquid and the room temperature is small, the solidified
In the case where the rinse liquid on the substrate W such as pure water can be replaced with the drying pretreatment liquid, the drying pretreatment liquid supply step may be performed without performing a replacement liquid supply step of replacing the rinse liquid on the substrate W with the replacement liquid.
In the preliminary heating step, a heated gas having a temperature higher than the temperature of the pretreatment solution for drying on the substrate W may be ejected toward the upper surface or the lower surface of the substrate W without bringing hot water, which is an example of the heated liquid, into contact with the lower surface of the substrate W. For example, the heated nitrogen gas may be ejected toward the upper surface or the lower surface of the substrate W. Both the ejection of the heating liquid and the ejection of the heating gas may be performed.
In
The
The heating lamps may be a whole-body lamp that irradiates light toward the entire upper surface of the substrate W at the same time, or may be a partial lamp that irradiates light toward only an irradiation region indicating a partial region within the upper surface of the substrate W. In the latter case, the
At least one of the deposition step (step S9 in fig. 4) and the solidification step (step S14 in fig. 7) may be such that, instead of bringing cold water (which is an example of a cooling liquid) into contact with the lower surface of the substrate W, a cooling gas having a temperature lower than the temperature of the drying pretreatment liquid on the substrate W is ejected toward the upper surface or the lower surface of the substrate W. For example, the cooled nitrogen gas may be ejected toward the upper surface or the lower surface of the substrate W. Both of the ejection of the coolant and the ejection of the cooling gas may be performed.
The liquid removing step (step S10 in fig. 4 and step S10 in fig. 7) may be an evaporation step of heating the drying pretreatment liquid on the substrate W at a temperature at which the solidified
For example, heated nitrogen gas may be ejected toward the upper surface of the substrate W. In this case, the surplus drying pretreatment liquid is removed from the substrate W not only by the pressure of the nitrogen gas flowing radially along the upper surface of the substrate W but also by evaporation by heating. Therefore, the excess pretreatment liquid for drying can be removed in a shorter time. In order to further promote the removal of the surplus drying pretreatment liquid, the substrate W may be accelerated in the rotation direction in addition to the ejection of the heated nitrogen gas.
Instead of the film thickness reducing step (step S7 in fig. 4 and 7) of reducing the film thickness of the drying pretreatment liquid on the substrate W, the preheating step (step S8 in fig. 4) or the solidifying step (step S14 in fig. 7) may be performed after the drying pretreatment liquid supplying step (step S6 in fig. 4).
The blocking
The blocking
The blocking
The
The
The
Two or more of the foregoing all configurations may be combined. Two or more of the above-described entire steps may be combined.
The drying
Although the embodiments of the present invention have been described in detail, they are merely specific examples used for explaining the technical contents of the present invention, and the present invention should not be construed as being limited to these specific examples, and the scope of the present invention is not limited to the appended claims.
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