JP4611961B2 - Application method - Google Patents

Description

  The present invention relates to a coating method for coating a coating material such as a resist on a substrate to be processed such as a silicon substrate in a manufacturing process of a semiconductor device.

A general application method so far will be described with reference to FIG. In FIG. 7, the vertical axis represents the number of rotations (rotation speed) per unit time of the wafer 10, and the horizontal axis represents the elapsed time of the coating process.
Between time t0 and time t1 shown in FIG. 7, after the wafer 10 is stably rotated at 1000 rpm to 3000 rpm, a predetermined amount of resist is dropped. Next, once the dropping of the resist is stopped, the wafer 10 is accelerated to a rotational speed at which a desired film thickness is obtained, and is rotated at the rotational speed for several seconds between times t1 and t2. Thereafter, the back surface of the wafer 10 is cleaned at time t2 to t3, dried after time t4, and the process ends.

  In such a coating method, since the rotation speed of the wafer 10 is relatively low, the resist spreads relatively slowly. Therefore, the organic solvent contained in the resist may be dried before the resist spreads, resulting in uneven coating. As a preventive measure, an excessive amount of resist is supplied. As a result, drying due to volatilization of the organic solvent contained in the resist is prevented, but 96% or more of the dropping liquid is discharged to the outside of the wafer 10. As a result, the liquid was wasted.

In contrast to general coating methods, several methods have been proposed as liquid-saving coating methods that consume as little waste as possible (see, for example, Patent Documents 1 and 2).
In Patent Document 1, as shown in FIG. 8, between time t0 and time t1, a predetermined amount of resist is dropped onto the non-rotating wafer 11, and once the resist dropping is stopped, the rotation speed is 4000 rpm or higher. Then, the dropped resist is spread all at once. For this reason, there is little volatilization of the volatile organic solvent contained in the resist, and there is little volatilization of the volatile organic solvent even without supplying an excessive amount of liquid. Absent. The effect can be confirmed not only in the static coating in which the resist is dropped in such a stationary state and then accelerated and started to rotate, but also in the dynamic coating which is a method of dropping the resist when the rotation is stabilized after the acceleration. It is disclosed.

In addition, between the times t1 and t2 in FIG. 8, the high-speed rotation speed is reduced to a predetermined rotation speed, and after rotating at this rotation speed for several seconds, the back surface of the wafer 11 is cleaned at the time t2 to t3. After drying at time t4 and thereafter, the process ends.
In Patent Document 2, liquid saving is achieved by once wetting the wafer by dropping only the organic solvent before dropping the resist and lowering the critical surface tension.
Japanese Patent Laid-Open No. 10-022210 JP 2003-136010 A

However, the above conventional example has the following problems.
In Patent Document 1, in the case of static coating, after a certain amount of resist is dropped on a stationary wafer, the stationary state continues for a certain period until acceleration, and the resist is dropped on a silicon substrate having a high critical surface tension and rotated. Therefore, it takes time to spread and the organic solvent evaporates. For this reason, a certain amount of resist is required. Even in the case of dynamic coating, since a certain amount of resist is dropped on a wafer rotating at a constant speed and then the state of a constant speed continues until acceleration, the resist is released to the outside of the silicon substrate to a small extent. In addition, since the resist is dropped onto the substrate to be processed having a high critical surface tension and spread by rotation, it takes time to spread, and the evaporation of the organic solvent proceeds, so that an extra resist is required. Therefore, in the method of Patent Document 1, the amount of resist to be dropped increases and there is a limit to liquid saving.

In order to realize further liquid saving, it is necessary to change the temperature of the resist itself, the environmental temperature around the resist, and the like, which leads to a decrease in throughput.
Further, in Patent Document 1, when the wafer is rotated at a high speed rotation of 4000 rpm or more, the wafer has a linear portion (orientation flat) for clarifying the crystal direction, and the center of weight of the wafer and the center of the spin chuck. Is about 0.4 mm, and this deviation may cause the rotational axis to be shaken and adversely affect the in-plane film thickness uniformity. In order to solve this problem, Patent Document 1 solves this problem by modifying the counterweight and the infrared sensor or the reflection sensor as means for adjusting the total center. However, the modification of the apparatus or another dedicated apparatus is required. End up.

On the other hand, in Patent Document 2, the wafer is once wetted with an organic solvent before dropping the resist to reduce the critical surface tension, thereby achieving liquid saving. In the prewetting method, the organic solvent and the resist are discharged. In addition, it is necessary to individually have nozzles to be operated, and it is necessary to control nozzle driving with high accuracy, so that a dedicated device is required, which increases the cost. In addition, since only the organic solvent is dropped first, the amount of waste liquid is increased and the cost of raw materials is increased.
The present invention has been made in view of such problems, and can improve the uniformity of the film thickness while further improving the liquid saving without using dedicated equipment, and the cost of equipment and raw materials. It aims at providing the coating method which can aim at reduction.

In order to achieve the above object, in the coating method according to claim 1 of the present invention, the substrate is rotated after the coating liquid is dropped from above the substrate while the rotation of the substrate is stopped. In the coating method in which the coating liquid is applied to the upper surface of the substrate by the accompanying centrifugal force, the rotation of the substrate starts at the same time as the coating liquid comes into contact with the upper surface of the substrate, and the rotation speed of the substrate is 4000 rpm or more and 8000 rpm or less. characterized in that it comprises a first acceleration application step until the rotation speed to accelerate the rotational speed of the substrate at 20000 rpm / sec or more 40000 rpm / sec following acceleration.

The coating method according to claim 2 of the present invention is the coating method according to claim 1 , wherein the substrate is rotated at a constant speed at the first rotation speed after the rotation speed of the substrate is accelerated in the acceleration coating process. The method further includes a rotating step.
According to a third aspect of the present invention, the coating method according to the second aspect is characterized in that, in the second aspect, the coating liquid is continuously supplied onto the substrate even in the constant speed rotation step.

The coating method according to claim 4 of the present invention is the coating method according to claim 2 or 3, wherein the substrate is rotated at a constant speed at the first rotation speed in the constant speed rotation step , and then the rotation speed of the substrate is The method further includes a stabilization processing step of rapidly decelerating the rotation speed of the substrate until a second rotation speed lower than the first rotation speed, and then rotating the substrate at a constant speed at the second rotation speed. It is characterized by.
According to these configurations, since the rotation of the substrate starts to accelerate simultaneously with the dropping (wetted liquid) on the substrate, and the dripping is continued while accelerating, the centrifugal force is adjusted according to the spread of the coating liquid (resist). Amplified. For this reason, the amount of coating liquid released to the outside of the substrate is small. In addition, since there is a stabilization processing step at a constant speed after decelerating after the acceleration coating step and the constant speed rotation step, it is possible to mitigate adverse effects due to deviation from the total center of gravity. Therefore, it is not necessary to modify the equipment or install new equipment.

As described above, according to the present invention, it is possible to improve the film thickness uniformity while improving the liquid saving without using dedicated equipment, and to reduce the cost of equipment and raw materials. There is an effect.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a diagram showing processing steps of a coating method in a manufacturing process of a semiconductor device according to an embodiment of the present invention. In the following description, the rotation speed indicates the number of rotations per unit time, and may be simply described as “the number of rotations”. Further, the acceleration indicates an increased number of rotations per unit time, and may be simply referred to as “acceleration”.
1, the wafer 20 is fixed on a spin chuck of a spin coater (not shown), and then the rotation of the wafer 20 is completely stopped and stopped (stationary process P1). .
Next, between the times t1 and t2 shown in FIG. 1, the wafer 20 starts rotating at an acceleration of 30000 rpm / sec or more at the same time as the resist comes into contact with the wafer 20 (acceleration coating process P2).

  In this way, first, a state in which the wafer 20 is completely stationary is provided, and then, a coating method in which the resist comes into contact with the wafer 20 and at the same time the wafer 20 starts rotating at a high acceleration is called a semi-dynamic coating method. In this semi-dynamic coating method, for example, when the reached rotational speed is 6000 rpm, the target rotational speed is reached in 0.2 sec. The resist spreads over the entire surface of the wafer 20, and the surface of the wafer 20 is covered with the resist. An example is shown in FIGS.

FIG. 3 is a diagram showing the relationship between the acceleration and drop amount by the semi-dynamic coating method. The vertical axis represents the diameter of the resist that has spread evenly. The horizontal axis shows acceleration.
Each plot is obtained by plotting the results of changing the dripping amount (0.3 g, 0.35 g, 0.4 g, 0.45 g, 0.5 g) and acceleration of the same kind of resist at an arrival rotational speed of 6000 rpm. is there. It can be seen that the diameter is increased by increasing the acceleration.

FIG. 2 is a graph showing the relationship between the maximum number of rotations achieved by the semi-dynamic coating method and the amount of dripping. The vertical axis represents the diameter of the resist that has spread evenly. The horizontal axis indicates the maximum number of revolutions reached.
Each plot shows the result of changing the dripping amount (0.3 g, 0.35 g, 0.4 g, 0.45 g, 0.5 g) of the same kind of resist and the maximum rotation speed while fixing the acceleration at 30000 rpm / sec. It is a plot.
As shown in FIG. 3, it can be seen that increasing the acceleration increases the resist spreading diameter, and the acceleration at this time is preferably 20000 rpm / sec or more, and more preferably 30000 rpm / sec or more. If the acceleration is lower than this, the centrifugal force may be insufficient even at 0.5 g, and the resist may not spread, resulting in coating unevenness. The acceleration is preferably 40000 rpm / sec or less, more preferably 35000 rpm / sec or less. If the acceleration is higher than this, the substrate to be processed that is vacuum-sucked may come off the chuck and damage the substrate to be processed.

In addition, as shown in FIG. 2, in order to spread the resist without unevenness, the maximum rotation speed is preferably 4000 rpm or more, and more preferably 5000 rpm or more. If the rotational speed is lower than this, the centrifugal force may be insufficient even at 0.5 g, and the resist may not spread, resulting in coating unevenness. Further, the maximum rotation speed is preferably 8000 rpm or less, and more preferably 6000 rpm or less. If the rotational speed is higher than this, if the substrate to be processed is deformed due to the thermal history, the substrate to be processed that is vacuum-sucked may come off the chuck and cause damage to the substrate to be processed.

Thus, according to the present embodiment, the entire surface is thinly covered with the resist dropped in the stage of the acceleration coating step P2, and is the same as the pre-wet using a separate liquid such as an organic solvent in the prior art. The effect of lowering the surface tension is obtained by a resist which is a liquid for forming a film thickness. Further, the dripping liquid is smaller than the conventional liquid saving method.
Further, by first providing a state in which the wafer 20 is completely stationary, and then starting the rotation of the wafer 20 at a high acceleration at the same time as the resist comes into contact with the wafer 20, the centrifugal force can be efficiently increased. Thus, a resist pre-wet film can be formed while suppressing wasteful release of the resist to the outside of the substrate to be processed.

Next, when the target rotational speed is reached, the reached rotational speed is maintained and rotated at a constant rotational speed (speed) between times t2 and t3 shown in FIG. 1 (constant speed rotation process P3).
By doing so, the resist can be spread more efficiently on the substrate to be processed whose critical surface tension is lowered. At this time, even when the process proceeds to the constant speed rotation process P3, the dropping of the resist may be continued. If dripping of the resist is continued, a prewetting effect can be obtained, and further liquid saving can be achieved.

  The rotation speed at this time is preferably 4000 rpm or more, and more preferably 5000 rpm or more. If the rotational speed is lower than this, the centrifugal force may be insufficient even at 0.5 g, and the resist may not spread and uneven coating may occur. Further, the maximum rotation speed is preferably 8000 rpm or less, and more preferably 6000 rpm or less. If the rotational speed is higher than this, when the substrate to be processed is deformed due to the thermal history, the substrate to be processed that is vacuum-sucked may come off the chuck and cause damage to the substrate to be processed.

Thereafter, simultaneously with the end of dropping, as shown between time t3 and time 4 in FIG. 1, the number of rotations of the wafer 20 is rapidly decelerated and rotated at a low speed to form a thick film for obtaining a desired film thickness. (Stabilization process P4).
Here, when the thick film is formed by the above-described method, when the wafer 20 has a center of weight and the center of the spin chuck, for example, the diameter of the wafer 20 is 150 mm, the crystal orientation of the wafer 20 is clarified. There is a straight part (orientation flat) and the center of total weight is shifted by about 0.4 mm. When this is rotated at a rotational speed of 4000 rpm or more, the rotation axis is shaken, affecting the film thickness uniformity in the surface. There is a case.

  With respect to this problem, in-plane uniformity can be improved by optimizing the time and the rotational speed in the stabilization process P4. Further, if the rotational speed and the like are optimized in the stabilization processing step P4, individual recipe adjustments such as a change in the temperature of the resist itself and a change in the environmental temperature around the resist become unnecessary. Also, there is no need to install a position sensor or other equipment to prevent misalignment or to modify the equipment.

  Furthermore, in recent coating apparatuses, an apparatus having a plurality of nozzles in one apparatus has been developed, and it has been necessary to change the temperature of the resist itself, environmental temperature, and humidity individually for each nozzle. Such changes have led to a decrease in production. However, in order to obtain the desired uniformity by providing the stable processing step of the present embodiment, it is only necessary to change the rotation speed and time parameters for each type of resist. There is no need to change temperature or humidity.

  As specific parameters, the rotation speed and time are selected. These parameters have different optimum values depending on the volatilization rate of the solvent to be used (resist is used as various materials), the surface tension and viscosity of the chemical itself. For example, when the main solvent to be used is 2-heptanone, the rotation speed is 1000 to 3000 rpm and the time is 2 to 4 seconds. When the main solvent to be used is ethyl lactate, the rotation speed is 300 to 3000 rpm and the time is 2 It may be set to ˜4 sec.

  The rotation speed at this time is preferably 100 rpm or more, and more preferably 300 rpm or more. If the rotational speed is lower than this, the resist may shrink due to surface tension and the outer peripheral portion may be unevenly coated. Further, the rotation speed is preferably 70% or less, more preferably 50% or less, of the film thickness determination rotation speed between times t4 and t5 shown in FIG. If the rotational speed is higher than this, the film thickness determination is affected, and subsequent film thickness adjustment becomes difficult.

  Thereafter, as a general process, in order to obtain a predetermined film thickness, the film thickness is determined by rotating for a predetermined time at a predetermined rotation speed between times t4 and t5 in FIG. 1 (film thickness determining process P5). Between time t5 and time t1 of 1, the wafer 20 is rotated at a predetermined rotation speed for a predetermined time to remove the resist attached to the back surface, thereby cleaning the back surface of the wafer 20 (back surface cleaning process P6). Then, between times t6 and t7 in FIG. 1, the wafer 20 is dried by rotating at a predetermined rotation speed for a predetermined time in order to dry the solvent on the front surface and the back surface (drying process P7). There is such a series of steps.

Conventionally, these latter half steps (between times t4 and t7 in FIG. 1) require the resist itself to be changed in temperature, environmental temperature, and humidity for each resist used, and moreover, the latter half for each resist. Although it was necessary to change the number of rotations and the rotation time of the process, such a change has led to a decrease in production volume.
However, by providing the stabilization processing step P4 of the present embodiment, if the rotation speed and time parameters are changed for each type of resist, a film thickness having a desired uniformity can be obtained for any resist. I can do it. Therefore, since any resist has a desired uniform film thickness at the time of the latter half of the process, various parameters are shared without change in the latter half of the process (between times t4 and t7 in FIG. 1). be able to.

Here, the film thickness transition for each step in the invented sequence is shown in FIGS.
FIG. 4 is a view showing the film thickness distribution immediately after the acceleration coating process P2 of the coating method of the present embodiment. The vertical axis is the film thickness (unit: Å). The horizontal axis indicates the coordinate position of the center of the wafer 20 measured on a straight line in the X-axis direction. Each plot shows an average value of three sheets subjected to measurement. It can be seen that the graph has a mortar shape where the vicinity of the center is thin.

  FIG. 5 is a view showing the distribution after the end of the stabilization process P4 of the coating method of the present invention. The vertical axis is the film thickness (unit: Å). The horizontal axis indicates the coordinate position of the center of the wafer 20 measured on a straight line in the X-axis direction. Each plot shows the film thickness when the stabilization processing time is shaken as 1, 3, 5 sec. Compared with the mortar type of FIG. 4, the graph is flattened and the film thickness in the vicinity of the center is almost the same regardless of the stabilization processing time. However, the longer the stabilization process, the thinner the outer periphery, and the difference in each condition increases.

  FIG. 6 is a view showing the distribution after the end of the drying step P7 of the coating method of the present invention. The vertical axis is the film thickness (unit: Å). The horizontal axis indicates the coordinate position of the center of the wafer 20 measured on a straight line in the X-axis direction. Each plot shows the film thickness when the stabilization processing time is shaken for 1, 3, 5 seconds. In the graph, the wafer 20 that has been processed with the stabilization processing time varied by 1 and 5 seconds has a mortar shape in which the vicinity of the center is thin and the uniformity is deteriorated. However, it can be seen that the wafer 20 processed in 3 seconds is flat with the balance between the force with which the liquid tries to gather in the center by surface tension and the resist released by the centrifugal force at the outer periphery.

  As described above, if the coating method of the present embodiment is used, the liquid-saving property can be improved by optimizing the acceleration coating process P2 and the constant speed rotation process P3. Furthermore, optimization of the stabilization processing step P4 enables improvement of uniformity, and adjustment of the resist temperature and environmental temperature is unnecessary, so even an apparatus having a plurality of nozzles can be adjusted individually. I can do it.

It is a figure which shows the process process of the coating method in the manufacturing process of the semiconductor device which concerns on embodiment of this invention. It is a figure which shows the relationship between the acceleration by the coating method (semi-dynamic coating method) of this Embodiment, and dripping amount. It is a figure which shows the relationship between the highest rotation speed by the application | coating method (semi-dynamic application | coating method) of this Embodiment, and dripping amount. It is a figure which shows distribution of the film thickness immediately after completion | finish of the constant speed rotation process of the coating method of this Embodiment. It is a figure which shows distribution after completion | finish of the stabilization process of the coating method of this Embodiment. It is a figure which shows distribution after completion | finish of the drying process of the coating method of this Embodiment. It is a figure which shows the conventional application | coating process. It is a figure which shows the other conventional application | coating process.

Explanation of symbols

20 Wafer P1 Static process P2 Accelerated coating process P3 Constant speed rotation process P4 Stabilization process P5 Film thickness determination process P6 Back surface cleaning process P7 Drying process

Claims (4)

In the coating method of rotating the substrate after dropping the coating liquid from above the substrate in a state where the rotation of the substrate is stopped, and applying the coating liquid to the upper surface of the substrate by centrifugal force accompanying the rotation of the substrate,
The substrate starts rotating at the same time as the coating solution comes into contact with the upper surface of the substrate, and the rotation speed of the substrate is set to 20000 rpm / sec or more until the rotation speed of the substrate reaches a first rotation speed of 4000 rpm or more and 8000 rpm or less . A coating method comprising an acceleration coating step of accelerating at an acceleration of 40000 rpm / sec or less .   2. The coating method according to claim 1, further comprising a constant speed rotation step of rotating the substrate at a constant speed at the first rotation speed after accelerating the rotation speed of the substrate in the acceleration coating step. .   3. The coating method according to claim 2, wherein the coating liquid is continuously supplied onto the substrate even in the constant speed rotation step, continuing from the acceleration coating step.   After the substrate is rotated at the first rotation speed at the constant rotation speed in the constant speed rotation step, the rotation of the substrate is performed until the rotation speed of the substrate becomes a second rotation speed lower than the first rotation speed. The coating method according to claim 2, further comprising a stabilization processing step of rapidly decelerating and then rotating the substrate at a constant speed at the second rotation speed.

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