JP2003037095A - Apparatus and method for treating substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus and a method for treating a substrate capable of treating a surface of the substrate with ozone water uniformly on the surface of the substrate. SOLUTION: The apparatus for treating the substrate treats the Sa surface of the substrate S with the ozone water L. The apparatus comprises a holding means 1 for holding the substrate S, an ozone water nozzle 5 for supplying the ozone water L to the surface Sa of the substrate S held by the means 1, and ozone supply means 7, 9 for supplying ozone O3 to a downstream of an ozone water stream formed by supplying the water L from the nozzle 5 to the surface Sa of the substrate S held by the means 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate processing method and a substrate processing apparatus, and in particular, for treating a semiconductor substrate, a glass substrate of a liquid crystal display device, a glass substrate for a photomask, a substrate for an optical disk, or the like with ozone water. Substrate processing method and substrate processing apparatus.

[0002]

2. Description of the Related Art In the manufacturing process of semiconductor devices, as semiconductor devices are miniaturized and highly integrated, particles (fine particles) attached to semiconductor substrates (so-called wafers) in the manufacturing process, metal contamination, organic contamination, etc. However, it has come to have a great influence on the yield and characteristics of the device. For example, the adhesion of particles causes an oxide film withstand voltage defect or a wiring short circuit, and metal contamination or organic matter contamination causes an oxide film withstand voltage defect or a junction leak defect.

However, the manufacturing process of a semiconductor device is
Since most of them are generation sources of particles, metal impurities, and organic pollutants, it is necessary to keep the front surface and the back surface of the semiconductor substrate clean throughout the manufacturing process in order to improve the device yield and its characteristics. .
Therefore, in each manufacturing process, a semiconductor substrate cleaning step is appropriately performed.

In the manufacturing process of semiconductor devices,
A resist that is an organic film is used in processes such as lithography, etching, and ion implantation, and after the completion of each process, a process of peeling and removing the resist from the semiconductor substrate is performed.

In recent years, in the cleaning process and the peeling / removing process, a wet process has become mainstream from the viewpoint of increasing the diameter of a semiconductor substrate and reducing the cost.

In the wet processing of such a semiconductor substrate, chemicals such as ammonia water, hydrochloric acid, sulfuric acid and hydrogen peroxide, chemicals obtained by mixing these, and further aqueous solutions thereof are used as treatment liquids. For example, sulfuric acid and hydrogen peroxide solution are mixed in a stock solution and a mixed solution (hereinafter referred to as sulfuric acid / hydrogen peroxide mixture) is used for cleaning for the purpose of removing organic substances and for removing and removing the organic film (resist). 80 ℃ ~
A method of treating at a high temperature of 150 ° C., a method of treating with fuming nitric acid, a method of treating at a high temperature of about 80 ° C. using an organic stripping solution mixed with an amine and the like are performed.

However, the above processing method has the following problems. For example, the treatment with sulfuric acid / hydrogen peroxide is
Operability is poor because it is a high-temperature treatment using a high-concentration chemical solution. Furthermore, in addition to the cost of the chemicals themselves, the cost for waste liquid treatment is high, which increases the running cost. This also applies to the treatment using highly reactive fuming nitric acid and the treatment using an organic stripping solution which is a high temperature process.

Therefore, ozone-dissolved water obtained by dissolving ozone in pure water (hereinafter referred to as ozone water) is used as a treatment liquid for cleaning for removing organic substances and for removing and removing the organic film (resist). Is starting to appear. In the wet treatment using ozone water, ozone water itself is relatively inexpensive, and the cost of waste liquid treatment is not necessary because ozone in ozone water is naturally decomposed.

However, the substrate treatment using ozone water is less reactive than the treatment using sulfuric acid / hydrogen peroxide mixture. Therefore, when ozone is dissolved in pure water, the ozone pressure is increased to increase the ozone concentration, and the temperature is lowered to keep the ozone solubility high, thereby ensuring the ozone concentration in the ozone water and improving the reaction efficiency. We are trying to improve

In substrate processing using such ozone water, a rotation processing apparatus as shown in FIG. 5 is used.
This rotation processing device includes a rotation chuck 101 that rotates and holds the substrate S, and an ozone water nozzle 105 that supplies ozone water L to the substantially central portion of the substrate S that is rotated and held by the rotation chuck 101. When this rotation processing device is used, the substrate S rotated and held by the rotation chuck 101 is
By supplying the ozone water L from the ozone water nozzle 105 to the top, the ozone water L flows from the center of the substrate S toward the outer peripheral direction by the centrifugal force due to the rotation of the substrate S, and the entire surface of the substrate S is treated with the ozone water L. .

In addition to such a rotation processing device,
Japanese Unexamined Patent Publication No. 2000-37671 discloses a method and apparatus for treating the surface of a substrate in a closed container filled with ozone water in order to effectively utilize ozone that is difficult to dissolve in water.

[0012]

However, ozone dissolved in pure water has a low concentration of about 250 ppm even when ozone is pressurized to several atmospheric pressure to be dissolved.

For this reason, in the rotation processing apparatus as shown in FIG. 5, the substrate S from the tip of the ozone water nozzle 105.
The ozone in the ozone water L supplied to the center of the substrate S is consumed by the surface treatment near the center of the substrate S before the ozone water L reaches the periphery of the substrate S. For this reason,
A sufficient amount of ozone cannot reach the peripheral portion of the substrate S. Therefore, on the surface of the substrate S,
The treatment efficiency of the ozone water L in the peripheral portion is lower than that in the central portion, and uniform ozone water treatment cannot be performed on the entire surface of the substrate S.

This is also the case with the treatment method and treatment apparatus disclosed in Japanese Patent Laid-Open No. 2000-37671. The ozone concentration in the ozone water becomes lower at a position farther from the ozone water supply unit. Uniform ozone water treatment cannot be performed on the entire surface of the substrate.

Therefore, an object of the present invention is to provide a substrate processing method and a substrate processing apparatus capable of performing uniform ozone processing on the entire surface of the substrate.

[0016]

The present invention for achieving the above object is a substrate processing apparatus for treating the surface of a substrate with ozone water, and is provided with a holding means for holding the substrate and the holding means. The ozone supply means is provided together with the ozone water supply means for supplying ozone water to the surface of the held substrate. The ozone supply means supplies ozone to the downstream side of the ozone water flow formed by the ozone water supply means supplying ozone water to the surface of the substrate held by the holding means.

The present invention is also a substrate processing method for treating the surface of a substrate with ozone water. By supplying ozone water to the surface of the substrate to be treated, an ozone water stream is formed on the surface of the substrate, and ozone water is generated. It is characterized in that ozone is supplied to the ozone water stream downstream of the supply unit.

In the substrate processing apparatus and the substrate processing method as described above, ozone water is supplied to the surface of the substrate to be processed to form an ozone water stream, and the ozone water stream is supplied to the ozone water stream downstream of the ozone water supply unit. Ozone is supplied.
Therefore, even if ozone is consumed by the reaction with the substrate surface on the upstream side of the ozone water flow, ozone is supplied and melts into the ozone water on the downstream side of the ozone water flow.
Therefore, the ozone concentration in the ozone water on the downstream side of the ozone water flow is secured. Therefore, the ozone concentrations of the ozone water on the upstream and downstream sides of the ozone water flow on the substrate surface are made uniform.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The substrate processing apparatus and the substrate processing method of the present invention will be described in detail below based on the embodiments thereof. Incidentally, the present invention, in the manufacturing process of semiconductor devices and liquid crystal display devices, and other substrate products, using ozone water, to remove the resist film formed on a substrate such as a semiconductor substrate or a liquid crystal substrate, A substrate processing apparatus and a substrate processing method for removing metal contaminants and organic contaminants attached to the surfaces of these substrates, and further for forming an oxide film on the surfaces of these substrates. In each of the following embodiments, the present invention will be described by exemplifying a case where a surface of a semiconductor substrate (substrate) is treated with ozone water.

FIG. 1 is a schematic configuration diagram showing an example of a substrate processing apparatus used in the substrate processing method of the embodiment.

The substrate processing apparatus shown in this figure comprises a holding means 1 for holding a substantially circular substrate S. The holding means 1 is provided with a support member (edge clamp ring) 3 for fixing the substrate S by pressing the edge of the substrate S from each direction toward the center direction of the substrate S, for example. The first surface (hereinafter, referred to as the front surface) Sa that is and the second surface (hereinafter, referred to as the rear surface) Sb that is the back surface side thereof are configured to be fixed in a non-contact state. Thereby, the back surface Sb of the substrate S can also be cleaned. However, when it is not necessary to consider the back surface cleaning of the substrate S, the holding means 1 holds the vacuum chuck type,
Further, any form such as a guide pin type utilizing centrifugal force may be used.

The holding means 1 is a so-called rotary chuck, which is provided at the tip of a rotary shaft 4 which is rotated by the power of a motor (not shown) and which holds the substrate S fixedly held by the holding means 1. It is configured to be rotatable while keeping the surface Sa horizontal.

Above the holding means 1 as described above, at a position on the central portion of the substrate S fixedly held by the holding means 1,
A supply end of an ozone water nozzle 5 serving as an ozone water supply unit and a supply end of a deionized water nozzle (not shown) are arranged, and ozone water L and pure water are supplied onto the central portion of the substrate S. Is configured. Although not shown here, ozone water generating means is connected to the ozone water nozzle 5 via a supply pump. The ozone water producing means produces ozone water L in which the solubility of ozone (O ₃ ) in pure water is increased by pressurizing the ozone atmosphere.

A supply end 71 of the ozone gas nozzle 7 for supplying ozone O ₃ is arranged above the holding means 1 so as to surround the supply end of the ozone water nozzle 5. The ozone gas nozzle 7 is connected to the ozone gas generator 9, and its supply end 71 is arranged so as to face the entire surface of the substrate S held by the holding means 1 except for the central portion thereof, and the ozone is showered to the substrate S. Ozone ₃ is discharged in a circular pattern. The ozone gas nozzle 7, the ozone gas generator 9, and the mass flow controller provided in the ozone gas nozzle 7 constitute ozone supply means. Further, ozone O ₃ is introduced into the supply end 71 of the ozone gas nozzle 7 from a plurality of positions so that ozone O ₃ is supplied from each part of the supply end 71 at a uniform pressure. .

In FIG. 2, the supply end 7 of the ozone gas nozzle 7 is shown.
1 is a plan view of the surface A on which the ozone supply port 71a is arranged, as viewed from the chuck (1) side, in which ozone O ₃ is discharged. As also shown in this figure, the supply end 71 of the ozone nozzle
Is formed into a donut-shaped shower head having a circular outer periphery, and a plurality of gas supply ports 71a are formed in an array on the surface A facing the chuck (1) side. Then, the supply end 51 of the ozone water supply nozzle 5 is arranged at the center opening of the donut shape.

Here, in particular, the plurality of gas supply ports 71a are
It is arranged on the surface A of the supply end 71 so that the ozone supply amount per unit area to the surface of the substrate S held and supported by the holding means 1 is constant. That is, it is assumed that the plurality of gas supply ports 71a are arranged on the surface A with a uniform opening area per unit area.

For this reason, for example, as shown in FIG. 2, on the surface A at the supply end 71, along the radial direction, which is allocated at an equal angle from the center of the surface A (here, the supply end 51 of the ozone water supply nozzle 5). Thus, when a plurality of gas supply ports 71a having the same opening diameter are arranged, the distance between the gas supply ports 71a is reduced as the position is closer to the outer periphery of the surface A. In other words, when the surface A is divided into fan-shaped portions that are equiangularly distributed at the center, and the inside of the fan-shaped portion is divided into the same area from the center, the gas having the same opening area is supplied to each of the sections having the same area. Place the mouth 71a. This allows
Ozone O ₃ is supplied to the surface of the substrate S so that the supply amount per unit area is constant.

Further, for example, as shown in FIG. 3, on the surface A at the supply end 71 of the ozone nozzle, concentric circles arranged at regular intervals from the center of the surface A (here, the supply end 51 of the ozone water supply nozzle 5). When arranging a plurality of gas supply ports 71a having the same opening diameter on the upper side, a larger number of discharge port 71a are arranged on a concentric circle located on the outer periphery of the surface A. That is, when the surface A is divided into concentric circles arranged at regular intervals from the center, and the donut surfaces located between the concentric circles are also divided into the same area in the circumferential direction, the same area is formed in each section. Gas supply port 71a having an opening area of
To place. As a result, ozone O ₃ is supplied to the surface of the substrate S so that the supply amount per unit area becomes constant.

Further, as shown in FIG. 4, for example, on the surface A at the supply end 71, along the radial direction that is equiangularly distributed from the center of the surface A (here, the supply end 51 of the ozone water supply nozzle 5). When arranging a plurality of gas supply ports 71a at equal intervals in the radial direction, the opening diameter of the gas supply port 71a is increased as the position is closer to the outer periphery of the surface A. In other words, when the surface A is divided into fan-shaped portions that are equally divided at the center thereof, and the inside of the fan-shaped portion is divided at regular intervals from the center, each of the opening areas having the same ratio as the area ratio of each section in the fan-shaped portion is formed. The gas supply port 71a is arranged. As a result, ozone is supplied to the surface of the substrate S so that the supply amount per unit area becomes constant.

In the above, the configuration in which the gas supply port 71a is arranged using the θ coordinate system with respect to the surface A has been described.
The gas supply ports 71a may be evenly arranged on the surface A using an xy coordinate system.

In the substrate processing apparatus configured as described above, when ozone water L is supplied from the ozone water nozzle 5 to the substrate S rotated and held by the holding means 1, the surface Sa of the substrate S is A centrifugal force generated by the rotation of the substrate S forms an ozone water flow from the center of the substrate S toward the peripheral direction. By supplying ozone O ₃ from the supply end 71 of the ozone gas nozzle 7 in such a state, ozone O ₃ is supplied over the entire surface Sa of the substrate S.

For this reason, ozone is consumed by the reaction with the surface Sa of the substrate S on the upstream side of the ozone water flow (that is, near the center of the substrate S), and the ozone water L whose ozone concentration is lower than the ozone water L is on the downstream side of the ozone water flow. The ozone supplied from the ozone gas nozzle 7 is melted (that is, near the center of the substrate S to the peripheral side). As a result, a decrease in the ozone concentration in the ozone water on the downstream side of the ozone water flow is suppressed. Therefore, the ozone concentration of the ozone water on the upstream side and the downstream side (that is, the center and the peripheral edge of the substrate S) of the surface of the substrate S is made uniform.

Further, in particular, ozone O ₃ is supplied to the surface of the substrate S so that the supply amount per unit area is constant. Therefore, ozone O ₃ consumed on the upstream side of the surface of the substrate S is replenished on the entire downstream side. Therefore, the ozone concentration in the ozone water flow is made uniform over the entire surface of the substrate S.

Here, removal and cleaning of organic substances using ozone water and formation of an oxide film are rate-controlled by the amount of ozone supplied to the treated surface. Therefore, as described above, the ozone concentration in the ozone water flow is made uniform over the entire surface of the substrate S, so that the ozone O ₃ can uniformly act on the surface of the substrate S, Substrate S
It is possible to perform a uniform ozone water treatment on the entire surface. As a result, specifically, when the organic film on the substrate S is removed by the ozone water treatment, the removal rate of the organic film on the entire surface of the substrate S becomes uniform, and the organic film remaining on the peripheral portion of the substrate S is prevented. As a result, efficient processing can be performed. Similarly, even when an oxide film is formed on the surface of the substrate S by ozone water treatment or when the surface of the substrate S is cleaned, the processing speed on the entire surface of the substrate S becomes uniform, and efficient processing can be performed. It will be possible.

[0035]

As described above, according to the present invention, by supplying ozone to the ozone water flow on the downstream side of the ozone water supply unit, the ozone water flow is formed on the substrate surface on the upstream side. Ozone consumed by the reaction can be replenished on the downstream side to make the ozone concentration of ozone water uniform on the upstream side and the downstream side of the ozone water flow on the substrate surface. As a result, it becomes possible to uniformly apply ozone to the surface of the substrate and perform uniform ozone water treatment on the entire surface of the substrate.

[Brief description of drawings]

FIG. 1 is a configuration diagram showing an example of a substrate processing apparatus of the present invention.

FIG. 2 is a plan view showing an arrangement example of gas supply ports in an ozone nozzle.

FIG. 3 is a plan view showing another example of arrangement of gas supply ports in the ozone nozzle.

FIG. 4 is a plan view showing still another example of the arrangement of gas supply ports in the ozone nozzle.

FIG. 5 is a configuration diagram showing an example of a conventional substrate processing apparatus.

[Explanation of symbols]

1 ... Holding means, 5 ... Ozone water nozzle (ozone water supply means), 7 ... Ozone gas nozzle (ozone supply means), 71
a ... Gas supply port, L ... Ozone water, S ... Substrate, Sa ... Surface

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02F 1/13 101 G02F 1/13 101

Claims (6)

[Claims] 1. A substrate processing apparatus for treating the surface of a substrate with ozone water, comprising holding means for holding the substrate, and ozone water supply means for supplying ozone water to the surface of the substrate held by the holding means. And an ozone supply unit for supplying ozone to the downstream side of the ozone water flow formed by the supply of ozone water from the ozone water supply unit on the substrate surface held by the holding unit. Substrate processing equipment. 2. The substrate processing apparatus according to claim 1, wherein the ozone supply unit is provided with a gas supply port so that a supply amount of ozone per unit area of the substrate surface held by the holding unit is constant. A substrate processing apparatus, wherein the substrate processing apparatus is provided. 3. The substrate processing apparatus according to claim 1, wherein the holding unit is a rotary chuck that rotatably supports the substrate. 4. A method of treating a substrate surface with ozone water, comprising supplying ozone water to the substrate surface to be treated to form an ozone water stream on the substrate surface, and supplying the ozone water. A method for treating a substrate, characterized in that ozone is supplied to the ozone water flow on the downstream side of the section. 5. The substrate processing method according to claim 4, wherein the ozone is supplied so that the supply amount per unit area of the substrate surface is constant. 6. The substrate processing method according to claim 4, wherein the ozone water stream is formed by rotation of the substrate.