JP2009016800A - Manufacturing method of semiconductor device, and substrate cleaning apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a semiconductor device and an apparatus for cleaning a substrate, which can prevent breakage of patterns on a substrate surface and prevent occurrence of water marks. <P>SOLUTION: In the manufacturing method of the semiconductor device having a cleaning step of cleaning a substrate surface while rotating the substrate, the cleaning step comprises a step (Step S16) of cleaning the substrate surface by supplying a cleaning liquid to the substrate, a step (Step S18) of rinsing the substrate surface after the cleaning by supplying a rinsing water containing pure water to the substrate, and a step (Step S22) of drying the substrate after the rinsing, wherein in the rinsing step of the substrate surface, HF is added to the rinsing water. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a semiconductor device manufacturing method and a substrate cleaning apparatus.

  As one of the substrate cleaning apparatuses, a spin type single substrate cleaning apparatus is known. In this type of substrate cleaning apparatus, for example, dilute hydrofluoric acid (DHF) is supplied to the rotating substrate surface to clean the substrate surface, and then rinse water, which is pure water, is supplied to the rotating substrate surface. The DHF remaining on the surface is washed away, and then the substrate is rotated at a high speed in a state where the supply of the rinse water is stopped, the rinse water on the substrate surface is shaken off, and the substrate is dried (for example, Patent Document 1).

JP 2002-164316 A

  As described above, a method of rotating the substrate at a high speed, shaking off the rinse water on the substrate surface, and drying the substrate is called spin drying. Specifically, in spin drying, moisture is removed by centrifugal force caused by rotation, and a small amount of remaining moisture is dried in a nitrogen atmosphere. As another drying method, there is also known a method called rotagoni drying in which IPA (isopropyl alcohol) vapor is supplied to the center side from the rinsing water supply unit and the rinsing water is IPA-substituted.

  The present inventors have found that the pattern on the substrate surface may be destroyed in the above-described spin drying. This is considered to occur due to the large surface tension of water. It was also discovered that a watermark may occur on the substrate surface. On the other hand, in Rotagoni drying, it is difficult to set conditions such as rotation of the substrate and supply of IPA vapor, and it is not used as a mass production means.

  An object of the present invention is to provide a method of manufacturing a semiconductor device and a substrate cleaning apparatus that can prevent the pattern on the substrate surface from being destroyed and can prevent the generation of a watermark.

  According to one aspect of the present invention, in the method of manufacturing a semiconductor device having a cleaning process of cleaning the substrate surface while rotating the substrate, the cleaning process supplies the cleaning liquid to the substrate to clean the substrate surface. And a step of supplying rinse water containing pure water to the substrate to rinse the substrate surface after the cleaning, and a step of drying the substrate after the rinse. In the step of rinsing the surface, a method for manufacturing a semiconductor device is provided in which HF is added to the rinse water.

  According to another aspect of the present invention, a support that supports the substrate, a rotating mechanism that rotates the support, a supply system that supplies cleaning liquid, rinse water containing pure water, and HF to the substrate, While rotating the support by supporting the substrate, the cleaning liquid is supplied to the substrate to clean the surface of the substrate, and the rinse water is supplied to the substrate to rotate the substrate. A controller that controls the rotation mechanism and the supply system so that the substrate surface after cleaning is rinsed, and then the substrate is dried and HF is added to the rinse water during the rinsing. A substrate cleaning apparatus is provided.

  According to the present invention, it is possible to prevent the pattern on the substrate surface from being destroyed, to prevent the generation of a watermark, and to improve the yield of the semiconductor device.

Next, embodiments of the present invention will be described with reference to the drawings.
1 and 2 show a substrate cleaning apparatus 10 according to a first embodiment of the present invention. The substrate cleaning apparatus 10 has a cleaning apparatus main body 12, and a cleaning chamber 14 is configured by being surrounded by the substrate cleaning apparatus main body 12. In the cleaning chamber 14, a support 18 that horizontally supports a substrate 16 such as a semiconductor wafer is disposed. The support 18 is connected to a rotation mechanism 20 made of a motor or the like via a rotation shaft 21, and the substrate 16 that is horizontally supported is rotated by the rotation mechanism 20.

  The periphery of the support 18 is surrounded by a cover 22. As will be described later, the cover 22 is configured to receive a chemical liquid flying from the substrate 16 when the substrate 16 is rotated by the support 18.

  As shown in FIG. 2, a substrate loading / unloading port 24 is formed on the side surface of the cleaning apparatus main body 12. A gate valve 26 is provided at the substrate loading / unloading port 24, and the substrate loading / unloading port 24 is opened and closed by the gate valve 26. Further, a substrate transfer machine 27 for transferring the substrate 16 to the support 18 through the substrate carry-in / out port 24 is provided.

  A first nozzle 28 and a second nozzle 30 are inserted into the cleaning chamber 14 described above. The first nozzle 28 and the second nozzle 30 are horizontally arranged such that their respective tips extend to near the center of the substrate 16 supported by the support 18. The first nozzle 28 is connected to a cleaning liquid supply unit 32 that supplies a cleaning liquid made of DHF, for example, via a control valve 32 a that controls the supply of the cleaning liquid, and the cleaning liquid is supplied from the first nozzle 28 to the substrate 16. Supplied to the center of the. The second nozzle 30 is connected to a rinsing water supply unit 34 that supplies rinsing water made of pure water and a replacement liquid supply unit 36 that supplies replacement liquid via a control valve 38 that controls the supply of rinsing water and replacement liquid. The second nozzle 30 is connected, and rinse water or replacement liquid is supplied to the center of the substrate 16. Accordingly, a cleaning liquid supply system is mainly configured by the first nozzle 28, the cleaning liquid supply unit 32, and the control valve 32a, and a rinse water supply system is mainly configured by the second nozzle 30, the rinse water supply unit 34, and the control valve 38. The replacement liquid supply system is mainly configured by the second nozzle 30, the replacement liquid supply unit 36, and the control valve 38, and the supply system is configured by the cleaning liquid supply system, the rinse water supply system, and the replacement liquid supply system. The

  The replacement liquid is rinse water, that is, a liquid having a surface tension smaller than that of pure water, and can be mixed with rinse water. For example, methanol, ethanol, isopropyl alcohol (IPA), n-propyl alcohol, ethylene glycol, 2-methyl Any of 2-propanol, a mixture thereof, or a mixture of these diluted with pure water. Since the replacement liquid also functions as rinse water, the rinse water composed of pure water may be referred to as first rinse water, the replacement liquid may be referred to as second rinse water, and both may be simply referred to as rinse water.

  The water supply unit 40 opens around the inner upper portion of the cover 22 described above, and the other end is connected to a pure water supply unit 42 that supplies water made of pure water so that water can be supplied to the inner surface of the cover 22. It has become. The water supply unit 40 is provided with a control valve 42a that controls the supply of pure water. The pure water supply unit 42 may be shared with the rinse water supply unit 34.

  A drain pipe 44 for discharging water supplied to the cover 22 is connected to the lower surface of the cover 22, and the drain pipe 44 extends to the outside of the substrate cleaning apparatus main body 12, and passes through the drain pipe 44. Then, the water in the cover 22 is discharged.

A drying gas supply pipe 46 is connected to the upper portion of the substrate cleaning apparatus main body 12. A drying gas supply unit 48 is connected to the other end of the drying gas supply pipe 46. The drying gas supply pipe 46 is provided with a control valve 48a for controlling the supply of the drying gas. For example, nitrogen (N ₂ ) is used as the drying gas. Further, an exhaust pipe 50 for discharging the drying gas is connected to the lower part of the substrate cleaning apparatus main body 12.

The controller 52 includes a computer, and is controlled by the rotation of the support 18 by the rotation mechanism 20, opening / closing of the substrate loading / unloading port 24 by the gate valve 26, loading / unloading of the substrate 16 by the substrate transfer machine 27, and the control valve 32a. Supply of DHF by the first nozzle 28, supply of rinse water or replacement liquid by the second nozzle 30 controlled by the control valve 38, supply of pure water from the water supply unit 40 controlled by the control valve 42a, control valve The supply of nitrogen (N ₂ ) from the drying gas supply pipe 46 controlled by 48a is controlled.

  Next, a method for cleaning a substrate will be described as one step of a semiconductor device (device) manufacturing process using the substrate cleaning apparatus 10 having the above-described configuration.

FIG. 3 is a flowchart showing a control flow by the controller 52.
First, in step S10, the substrate loading / unloading opening 24 is opened by the gate valve 26, and the substrate 16 on which the pattern is formed is loaded into the cleaning chamber 14 by the substrate transfer device 27.

  In the next step S 12, the substrate transfer machine 27 is further controlled to support (set) the substrate 16 on the support 18, and the substrate loading / unloading port 24 is closed by the gate valve 26.

  In the next step S <b> 14, the rotation of the substrate 16 is started by rotating the support 18 through the rotation shaft 21 by the rotation mechanism 20.

  In the next step S <b> 16, as shown in FIG. 4, while maintaining the rotation of the substrate 16, DHF is supplied from the first nozzle 28 toward the center of the substrate 16 to clean the surface of the substrate 16.

  In the next step S18, as shown in FIG. 5, while the rotation of the substrate 16 is maintained, the supply of DHF from the first nozzle 28 is stopped, the rinse water supply side of the control valve 38 is opened, and the replacement liquid The side is closed, and pure water (first rinse water) as rinse water is supplied from the second nozzle 30 toward the center of the substrate 16 to wash away DHF remaining on the substrate surface.

In the next step S20, while maintaining the rotation of the substrate 16, the rinsing water supply side of the control valve 38 is gradually closed, and the replacement liquid side is gradually opened. As shown in FIG. Ethanol or the like (second rinse water) as a replacement liquid is supplied toward the center of the substrate 16 to replace the pure water on the substrate with ethanol or the like. In this case, when the replacement liquid can be mixed with water, it is not always necessary to replace 100%, and part of the rinse water can be replaced with the replacement liquid.
In step S <b> 20, water is supplied from the water supply unit 40 to the inner surface of the cover 22. As a result, the risk of combustion caused by ethanol or the like blown to the inner surface of the cover 22 can be reduced. The water supplied to the inner surface of the cover 22 is discharged to the outside through the drain pipe 44.

In the next step S22, as shown in FIG. 7, while the rotation of the substrate 16 is maintained, the supply of the rinse water and the replacement liquid from the second nozzle 30 is stopped, and the ethanol on the substrate is centrifuged by the rotation. Sift out with force. In this step S22, the cleaning chamber 14, the cleaning chamber 14 by supplying N ₂ as a drying gas through the drying gas feed pipe 46 and a N ₂ atmosphere the drying gas supply unit 48, the N _The substrate 16 is dried in _two atmospheres.
The water supply from the water supply unit 40 to the inner surface of the cover 22 may be performed only in the replacement process in step S20. However, in order to further improve safety, the water supply is continuously performed in the drying process in step S22. It may be. That is, water may be supplied to the inner surface of the cover 22 at least while ethanol or the like flies from the substrate 16 to the cover 22.

In the next step S24, the rotation of the substrate 16 is stopped by stopping the rotation of the support 18 by the rotation mechanism 20. Further, N ₂ in the cleaning chamber 14 is exhausted.

  According to the next step S 26, the substrate loading / unloading port 24 is opened by the gate valve 26, and the substrate 16 is unloaded from the cleaning chamber 14 by the substrate transfer machine 27. Thereafter, the film is transferred to another apparatus, for example, an epitaxial growth apparatus, and processing such as film formation is performed.

  According to the present invention, in order to dry the substrate, the rinse water is replaced with a liquid having a surface tension smaller than that of the rinse water such as alcohol, and then drying is performed. Compared to the surface tension of water, 72.75 mN / m (20 ° C.), for example, the surface tension of ethanol is as small as 22.55 mN / m (20 ° C.). The force becomes as small as about 1/3, and pattern destruction due to surface tension can be prevented. Further, according to the present invention, when the rinse water is replaced with alcohol or the like, organic substances on the substrate surface can be removed by the action of alcohol or the like. Furthermore, according to the present invention, when water on the substrate surface is replaced with a combustible chemical solution such as alcohol, water is supplied to the cover that receives the chemical solution flying from the rotating substrate, thereby reducing the risk of combustion. be able to.

  FIG. 8 shows a substrate cleaning apparatus 10 according to the second embodiment of the present invention. This second embodiment is different from the first embodiment in that a hydrogen fluoride (HF) supply unit 54 is connected to the second nozzle 30 via a control valve 38, that is, as a supply system. Further, a difference is that a hydrogen fluoride supply system is provided. Then, in step S20 described above, control is performed so that this HF is added to the final rinse liquid that replaces pure water with ethanol or the like. The HF to be added is extremely dilute, and preferably the HF concentration in the final rinsing solution is 1 to 1000 ppm.

  Thus, the reason for adding extremely dilute HF to the final rinse is to prevent the generation of watermarks without destroying the substrate pattern when the substrate is dried. The watermark is a pattern in which impurities such as dissolved silica contained in the water droplets remain on the surface when the water evaporates. When HF is added to the final rinse solution, impurities such as dissolved silica that cause this watermark can be changed to a substance with a high vapor pressure. By vaporizing the high vapor pressure, The substrate can be dried without generating.

By the way, it has been confirmed that the concentration of dissolved silica in pure water is about 0.1 to 10 ppt or less. With the current technology, this level of silica inevitably remains in pure water. Alcohol such as IPA is often used after being diluted with pure water. In this case, this level of silica is also dissolved in IPA diluted with pure water, that is, IPA solution. That is, when an alcohol such as IPA diluted with pure water is used as a replacement solution, silica is dissolved in the final rinse solution.
Considering the concentration of this dissolved silica, in order to stabilize and remove the dissolved silica (change to a substance having a high vapor pressure), the concentration of HF added to the IPA solution needs to be at least 1 to 1000 ppm. When the HF concentration is less than 1 ppm, the contact probability between HF and silica is lowered, and dissolved silica cannot be sufficiently removed. On the other hand, if the HF concentration is higher than 1000 ppm, the etching rate of the film is generated and the film formed on the substrate surface is etched. That is, when the HF concentration is set to a value within this range, the dissolved silica can be sufficiently removed without etching the film formed on the substrate surface.
In consideration of wastewater treatment, the HF concentration is preferably 1 to 10 ppm. If the HF concentration is set to a value within this range, the dissolved silica can be sufficiently removed without etching the film formed on the substrate surface, and further, no waste water treatment is required.

  In the present embodiment, the rinsing water supply system (first rinsing water supply system), the replacement liquid supply system (second rinsing water supply system), and the HF supply system are configured as shown in FIG. Also good. That is, in FIG. 9, the second nozzle 30 is connected to the rinse water supply unit 34 via the control valve 38. The second nozzle 30 is branched on the upstream side, and the branched line is connected to the blending device 60. The blending device 60 and the replacement liquid supply unit 36 are connected via a pipe 62, and a flow rate regulator 64 and a valve 66 are provided in the pipe 62. The blending device 60 and the HF supply unit 54 are connected via a pipe 61, and the pipe 61 is provided with a flow rate regulator 63 and a valve 65. In the blending device 60, the HF concentration in the replacement liquid is adjusted by blending the replacement liquid and the HF whose flow rates are controlled by the flow rate regulator 64 and the flow rate regulator 63, respectively. If the supply system is configured in this way, the controllability of the HF concentration in the replacement liquid can be easily ensured, and the extremely dilute HF concentration can be easily adjusted.

In the second embodiment, HF is added. However, the present invention is not limited to this, and the impurity that causes the watermark can be changed to a substance having a high vapor pressure. For example, hydrogen chloride (HCl), aqueous ammonia (NH ₄ OH), or the like can be used instead of HF.

  In the first embodiment and the second embodiment, after washing with DHF in step S16, pure water as the first rinse water is supplied to the substrate 16 in step S18, and in step S20, the second water is supplied. Although the example which supplies ethanol etc. as rinse water with respect to the board | substrate 16 was demonstrated, step S18 which rinses with a pure water can also be abbreviate | omitted. That is, after washing with DHF, rinsing with a chemical solution such as ethanol can be performed without rinsing with pure water. This will be described with reference to FIG. Here, a case where IPA diluted with pure water (hereinafter, diluted IPA) is used as a chemical solution will be described.

  FIG. 10A shows a cleaning flow corresponding to the cleaning flow of the first embodiment, and FIG. 10B omits step S18 for performing pure water rinsing in the cleaning flow of FIG. 10A. The washing flow is shown. FIG. 10C shows a cleaning flow corresponding to the cleaning flow of the second embodiment, and FIG. 10D shows step S18 for performing pure water rinsing in the cleaning flow of FIG. The omitted cleaning flow is shown. 10A shows an example of performing washing with DHF → rinsing with pure water → rinsing with diluted IPA → drying, and FIG. 10B shows washing with DHF → rinsing with diluted IPA → drying. FIG. 10 (c) shows an example in which washing with DHF → rinsing with pure water → rinsing with diluted IPA added with HF → drying is performed, and FIG. 10 (d) shows a case with DHF. In this example, washing, rinsing with diluted IPA added with HF, and drying are performed. As shown in FIG. 10B and FIG. 10D, even when rinsing with pure water is omitted, the same effects as the cleaning in the first embodiment and the cleaning in the second embodiment are obtained. It is done.

[Example]
The substrate on which the pattern was formed was cleaned by the respective cleaning flows of FIGS. 10A, 10B, 10C, and 10D. The cleaning flows in FIGS. 10A and 10B are performed using the substrate cleaning apparatus of the first embodiment, and the cleaning flows in FIGS. 10C and 10D are the substrate cleaning of the second embodiment. Performed using the apparatus. The diluted IPA rinses in FIGS. 10 (a) and 10 (b) are performed with an IPA concentration of 20%, and the HF-added diluted IPA rinses in FIGS. 10 (c) and 10 (d) have an IPA concentration of 20%. %, HF concentration was 500 ppm.
As a result, as shown in FIG. 11, the pattern formed on the substrate was not broken when it was cleaned by the cleaning flow of FIGS. 10 (a) and 10 (b). In addition, when the cleaning was performed by the cleaning flow shown in FIGS. 10C and 10D, the pattern formed on the substrate was not broken and no watermark was generated.

  According to one aspect of the present invention, in the method of manufacturing a semiconductor device having a cleaning process of cleaning the substrate surface while rotating the substrate, the cleaning process supplies the cleaning liquid to the substrate to clean the substrate surface. And a step of supplying rinse water containing pure water to the substrate to rinse the substrate surface after the cleaning, and a step of drying the substrate after the rinse. In the step of rinsing the surface, a method for manufacturing a semiconductor device is provided in which HF is added to the rinse water.

  Preferably, the concentration of HF in the rinse water is 1-1000 ppm.

  Preferably, the concentration of HF in the rinse water is 1 to 10 ppm.

  Preferably, the cleaning liquid contains HF, and the concentration of HF in the rinse water is lower than the concentration of HF in the cleaning liquid.

  Preferably, the rinse water includes any of methanol, ethanol, isopropyl alcohol, n-propyl alcohol, ethylene glycol, 2-methyl-2-propanol, or a mixture thereof.

  Preferably, a cover is provided around the substrate to receive the cleaning liquid or the rinsing water flying from the substrate when the substrate rotates, and at least during the rinsing water flying from the substrate, the cover Supply pure water to the part where the rinse water flies.

  Preferably, the step of rinsing the substrate surface includes supplying a first rinse water containing pure water to the substrate, and containing pure water to the substrate, and methanol, ethanol, isopropyl alcohol. , N-propyl alcohol, ethylene glycol, 2-methyl-2-propanol, or a mixture of these is supplied, and the first rinse water on the substrate surface is supplied to the second rinse water. And HF is added to the second rinse water.

  Preferably, the step of rinsing the substrate surface includes a step of supplying a first rinse water containing pure water to the substrate, and a step tension containing pure water to the substrate than that of the first rinse water. Supplying a small second rinsing water to replace the first rinsing water on the substrate surface with the second rinsing water, and HF is added to the second rinsing water.

  According to another aspect of the present invention, a support that supports the substrate, a rotating mechanism that rotates the support, a supply system that supplies cleaning liquid, rinse water containing pure water, and HF to the substrate, While rotating the support by supporting the substrate, the cleaning liquid is supplied to the substrate to clean the surface of the substrate, and the rinse water is supplied to the substrate to rotate the substrate. A controller that controls the rotation mechanism and the supply system so that the substrate surface after cleaning is rinsed, and then the substrate is dried and HF is added to the rinse water during the rinsing. A substrate cleaning apparatus is provided.

  Preferably, the controller controls the supply system so that the concentration of HF in the rinse water is 1 to 1000 ppm.

  Preferably, the controller supplies a first rinsing water containing pure water to the substrate during the rinsing, and then contains pure water to the substrate and includes methanol, ethanol, isopropyl. Supplying a second rinse water containing alcohol, n-propyl alcohol, ethylene glycol, 2-methyl-2-propanol, or a mixture thereof; and supplying the first rinse water on the substrate surface to the first rinse water. The supply system is controlled such that HF is added to the second rinse water while substituting with two rinse water.

  Preferably, the rinse water includes any one of methanol, ethanol, isopropyl alcohol, n-propyl alcohol, ethylene glycol, 2-methyl-2-propanol, or a mixture thereof, and further, when the substrate is rotated. A cover for receiving the cleaning liquid or the rinsing water flying from the substrate, and a water supply unit for supplying pure water to the cover, and the controller covers the cover at least while the rinsing water flies from the substrate. The water supply unit is controlled so as to supply pure water to a portion where the rinse water flies.

  According to still another aspect of the present invention, in the method of manufacturing a semiconductor device having a cleaning process of cleaning the substrate surface while rotating the substrate, the cleaning process supplies the cleaning liquid to the substrate to clean the substrate surface. Rinsing water on the substrate surface by supplying rinsing water to the substrate to wash away the cleaning liquid on the substrate surface, supplying a liquid having a surface tension smaller than that of the rinsing water to the substrate, There is provided a method for manufacturing a semiconductor device, comprising: replacing at least a part of the substrate with the liquid; and drying the substrate after replacing the rinse water with the liquid.

  Preferably, the liquid is one of methanol, ethanol, isopropyl alcohol, n-propyl alcohol, ethylene glycol, 2-methyl-2-propanol or a mixture thereof.

  According to still another aspect of the present invention, a support that supports the substrate, a rotation mechanism that rotates the support, a cleaning liquid, rinse water, and a liquid having a surface tension smaller than that of the rinse water with respect to the substrate. While rotating the supply means for supplying and the support that supports the substrate, the substrate surface is cleaned by supplying a cleaning liquid to the substrate, and rinse water is supplied to the substrate by supplying rinsing water to the substrate. The rotating mechanism and the supply so that the cleaning liquid is washed away, the liquid is supplied to the substrate, and at least a part of rinse water on the substrate surface is replaced with the liquid, and then the substrate is dried. And a controller for controlling the means.

  Preferably, the controller further includes a cover that receives the chemical liquid flying from the substrate when the substrate is rotated by the support, and a water supply unit that supplies water to at least a portion of the cover where the chemical liquid flies. The water supply unit is controlled so as to supply water to the cover when at least the rinse water is replaced with the liquid.

  Preferably, the controller further includes a cover that receives the chemical liquid flying from the substrate when the substrate is rotated by the support, and a water supply unit that supplies water to at least a portion of the cover where the chemical liquid flies. The water supply unit is controlled to supply water to the cover at least when the rinse water is replaced with the liquid and when the substrate is dried.

  Preferably, the controller further includes a cover that receives the chemical liquid flying from the substrate when the substrate is rotated by the support, and a water supply unit that supplies water to at least a portion of the cover where the chemical liquid flies. The water supply unit is controlled so as to supply water to the cover at least while the liquid flies off the substrate.

  According to still another aspect of the present invention, there is provided a substrate cleaning method including a cleaning step of cleaning a substrate surface while rotating the substrate, wherein the cleaning step supplies a cleaning liquid to the substrate to clean the substrate surface. Rinsing water on the substrate surface by supplying rinsing water to the substrate to wash away the cleaning liquid on the substrate surface, and supplying a liquid having a surface tension smaller than that of the rinsing water to the substrate. There is provided a substrate cleaning method comprising a step of replacing at least a part of the substrate with the liquid, and a step of drying the substrate after replacing the rinse water with the liquid.

  Preferably, in the step of supplying a liquid having a surface tension smaller than that of the rinsing water to the substrate and replacing at least a part of the rinsing water on the surface of the substrate with the liquid, an extremely dilute HF is added. Use the final rinse solution.

  Preferably, the HF concentration in the final rinse liquid is 1000 ppm or less.

  Preferably, the HF concentration in the final rinse solution is 100 ppm or less.

  Preferably, the HF concentration in the final rinse solution is 10 ppm or less.

  Preferably, the HF concentration in the final rinse solution is 1 ppm or less.

  Preferably, HCl is added instead of HF.

Preferably, NH ₄ OH is added instead of HF.

According to still another aspect of the present invention, there is provided a method of manufacturing a semiconductor device having a cleaning step of cleaning a substrate surface while rotating the substrate, wherein the cleaning step supplies a cleaning liquid to the substrate to supply the substrate surface. A step of supplying a rinsing water added with HF, HCl or NH ₄ OH to the substrate to wash away the cleaning liquid on the surface of the substrate, and a step of drying the substrate. A manufacturing method is provided.

1 is a cross-sectional view showing a substrate cleaning apparatus according to a first embodiment of the present invention. It is a side view showing a substrate cleaning device and a substrate transfer machine concerning a 1st embodiment of the present invention. It is a flowchart which shows the control flow by the controller in the 1st Embodiment of this invention. It is the top view and side view which show the state of the board | substrate cleaning apparatus of the DHF cleaning process in the 1st Embodiment of this invention. It is the top view and side view which show the state of the board | substrate cleaning apparatus of the rinse process in the 1st Embodiment of this invention. It is the top view and side view which show the state of the board | substrate cleaning apparatus of the substitution process in the 1st Embodiment of this invention. It is the top view and side view which show the state of the board | substrate cleaning apparatus of the drying process in the 1st Embodiment of this invention. It is sectional drawing which shows the board | substrate cleaning apparatus which concerns on the 2nd Embodiment of this invention. It is sectional drawing which shows a part of substrate cleaning apparatus which concerns on the 3rd Embodiment of this invention. It is a flowchart which shows the washing | cleaning flow in the 1st Embodiment and 2nd Embodiment of this invention. It is an experimental result in the washing | cleaning flow of the 1st Embodiment and 2nd Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Substrate cleaning apparatus 12 Substrate cleaning apparatus main body 14 Cleaning chamber 16 Substrate 18 Supporting tool 20 Rotating mechanism 22 Cover 27 Substrate transfer machine 28 First nozzle 30 Second nozzle 40 Water supply unit 52 Controller

Claims (12)

In a manufacturing method of a semiconductor device having a cleaning step of cleaning a substrate surface while rotating the substrate,
The washing step includes
Supplying a cleaning liquid to the substrate to clean the substrate surface;
Supplying rinse water containing pure water to the substrate to rinse the substrate surface after the cleaning;
Drying the substrate after the rinsing,
In the step of rinsing the substrate surface, HF is added to the rinse water.   The method for manufacturing a semiconductor device according to claim 1, wherein a concentration of HF in the rinse water is 1 to 1000 ppm.   The method for manufacturing a semiconductor device according to claim 1, wherein the HF concentration in the rinse water is 1 to 10 ppm.   2. The method of manufacturing a semiconductor device according to claim 1, wherein the cleaning liquid contains HF, and the concentration of HF in the rinse water is lower than the concentration of HF in the cleaning liquid.   2. The semiconductor according to claim 1, wherein the rinse water includes one of methanol, ethanol, isopropyl alcohol, n-propyl alcohol, ethylene glycol, 2-methyl-2-propanol, or a mixture thereof. Device manufacturing method.   Around the substrate, a cover is provided for receiving the cleaning liquid or the rinse water that flies from the substrate when the substrate rotates. At least while the rinse water flies from the substrate, the rinse water of the cover is 6. The method of manufacturing a semiconductor device according to claim 5, wherein pure water is supplied to the flying portion. The step of rinsing the substrate surface includes:
Supplying a first rinse water containing pure water to the substrate;
Second rinse water containing pure water and containing any one of methanol, ethanol, isopropyl alcohol, n-propyl alcohol, ethylene glycol, 2-methyl-2-propanol, or a mixture thereof. And replacing the first rinse water on the substrate surface with the second rinse water,
2. The method of manufacturing a semiconductor device according to claim 1, wherein HF is added to the second rinse water. The step of rinsing the substrate surface includes:
Supplying a first rinse water containing pure water to the substrate;
Supplying the second rinse water containing pure water and having a surface tension smaller than that of the first rinse water to the substrate, and replacing the first rinse water on the substrate surface with the second rinse water; Have
2. The method of manufacturing a semiconductor device according to claim 1, wherein HF is added to the second rinse water. A support for supporting the substrate;
A rotation mechanism for rotating the support;
A supply system for supplying cleaning liquid, rinse water containing pure water, and HF to the substrate;
While rotating the support by supporting the substrate, the cleaning liquid is supplied to the substrate to clean the surface of the substrate, and the rinse water is supplied to the substrate to rotate the substrate. A controller that controls the rotating mechanism and the supply system so as to rinse the substrate surface after cleaning, and then dry the substrate and add HF to the rinse water during the rinsing;
A substrate cleaning apparatus comprising:   The substrate cleaning apparatus according to claim 9, wherein the controller controls the supply system so that a concentration of HF in the rinse water is 1 to 1000 ppm.   The controller supplies first rinsing water containing pure water to the substrate during the rinsing, and then contains pure water to the substrate and includes methanol, ethanol, isopropyl alcohol, n Supplying a second rinsing water containing one of propyl alcohol, ethylene glycol, 2-methyl-2-propanol, or a mixture thereof, and the first rinsing water on the substrate surface to the second rinsing water; The substrate cleaning apparatus according to claim 9, wherein the supply system is controlled so as to add HF to the second rinse water. The rinse water includes methanol, ethanol, isopropyl alcohol, n-propyl alcohol, ethylene glycol, 2-methyl-2-propanol, or a mixture thereof,
A cover for receiving the cleaning liquid or the rinse water flying from the substrate when rotating the substrate;
A water supply unit for supplying pure water to the cover,
10. The substrate according to claim 9, wherein the controller controls the water supply unit to supply pure water to a portion of the cover where the rinse water flies at least while the rinse water flies from the substrate. Cleaning device.

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