JP2002110605A - Substrate treating method and device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a device with which the throughput can be increased by reducing the treatment time of substrates by ozonic water. SOLUTION: The substrate treating device is provided with an ozonation bath 12 which contains low-temperature ozonic water, having a high density of dissolved ozone and in which substrates W are immersed for treatment, a hot purified water bath 48, which contains hot purified water heated to a high temperature and in which the substrates W are immersed and are heated and a substrate-transfer means, which transfers the substrates W between the hot purified water bath 48 and the ozonation bath 12.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a semiconductor wafer,
The present invention relates to a substrate processing method for immersing a substrate such as a glass substrate for a liquid crystal display device and an electronic component in ozone water in which ozone is dissolved, and a substrate processing apparatus used for performing the method.

[0002]

2. Description of the Related Art In a semiconductor device manufacturing process, for example, ozone water obtained by dissolving ozone in pure water is used for the purpose of decomposing and removing organic substances such as a resist attached to the surface of a substrate, for example, a silicon wafer. Then, the wafer is immersed in the ozone water for processing.

FIG. 6 is a schematic diagram showing an example of the configuration of a conventional substrate processing apparatus using ozone water. This substrate processing apparatus is provided with a processing tank 12 in which ozone water is contained and a wafer W is held by a wafer holder 14 and immersed in the ozone water.

The processing tank 12 has a liquid supply port 16 at a lower part and an overflow part 18 from which liquid overflows at an upper part. Further, the processing tank 12 is provided with an overflow liquid receiving section 20, and the liquid overflowing from the overflow section 18 above the processing tank 12 flows into the overflow liquid receiving section 20. .
An overflow liquid discharge pipe 22 is connected to the bottom of the overflow liquid receiving section 20 so as to communicate therewith, and the overflow liquid discharge pipe 22 is connected to a drain discharge pipe 24. A drain port 26 is formed at the bottom of the processing tank 12.
A drain pipe 28 in which a drain valve 30 is inserted is connected and connected, and the drain pipe 28 is connected to the drain drain pipe 24.

Further, a liquid supply port 16 at a lower portion of the processing tank 12 is provided.
Is connected to a liquid supply pipe 32 in which an open / close control valve 34 is interposed. The liquid supply pipe 32 has an open / close control valve 38 and a flow control valve 40 connected to a pure water supply source. The open / close control valve 4 is connected to an inserted pure water supply pipe 36 and an ozone water supply source such as an ozone water generator.
The ozone water supply pipes 42 each having the interposed 4 are connected to each other. In a so-called one-bus type substrate processing apparatus as shown in FIG. 6, a mixing valve is usually provided in the liquid supply pipe 32, and the mixing valve is connected to supply tanks of different types of chemical liquids. A plurality of chemical solution supply pipes are connected, and it is configured such that pure water sent through the pure water supply pipe 36 and each chemical solution can be mixed and supplied into the processing tank 12. Its illustration and description are omitted in this document.

In the substrate processing apparatus having the structure shown in FIG. 6, when decomposing and removing organic substances such as resist adhered to the surface of the wafer W with ozone water, the ozone water supply pipe 42 is connected to the liquid supply pipe 32. The ozone water is supplied to the liquid supply port 16 of the processing tank 12 through the through-hole, the ozone water flows into the processing tank 12, and the inside thereof is filled with the ozone water.
The ozone water overflows from the overflow portion 18 at the upper part of 2 and flows into the overflow receiving portion 20. Alternatively, ozone water is supplied from the ozone water supply pipe 42 to the liquid supply port 16 of the processing tank 12 through the liquid supply pipe 32 into the processing tank 12 filled with pure water, and the ozone water flows into the processing tank 12. Then, pure water is pushed out from the overflow portion 18 on the upper portion of the processing tank 12 with ozone water, the inside of the processing tank 12 is replaced with ozone water, and the inside of the processing tank 12 is filled with ozone water and overflows on the upper portion of the processing tank 12. The state is such that ozone water overflows from the section 18 and flows into the overflow receiving section 20. In this state, the wafer W is immersed in the ozone water, or the wafer W stored in the processing tank 12 before the supply of the ozone water into the processing tank 12 is immersed in the ozone water, and Organic substances on the surface of the wafer W are decomposed and removed by the oxidizing action.

When the processing of the wafer W with the ozone water is completed, the supply of the ozone water is stopped, and pure water is supplied from the pure water supply pipe 36 to the liquid supply port 16 of the processing tank 12 through the liquid supply pipe 32 to process the wafer W. Pure water is allowed to flow into the tank 12, and the ozone water is pushed out from the overflow portion 18 on the upper part of the processing tank 12 with the pure water, and the inside of the processing tank 12 is replaced with pure water. So that the pure water overflows from the overflow portion 18 at the upper part of the treatment tank 12 and flows into the overflow receiving portion 20. Alternatively, the drainage valve 30 is opened to allow the ozone water in the processing tank 12 to flow out from the drainage port 26, and the drainage pipe 2
8 to quickly discharge the ozone water,
Pure water is supplied to the inside, so that the inside of the processing tank 12 is filled with the pure water, and the pure water overflows from the overflow section 18 on the upper part of the processing tank 12 and flows into the overflow receiving section 20. In this state, the wafer W is immersed in pure water and washed. When the washing is completed, the wafer W is carried out of the processing tank 12.

[0008]

As described above, in the process of decomposing and removing organic substances from the surface of a substrate using ozone water, the reaction rate R between ozone and the organic substances in ozone water is determined as follows.
Is represented by R = k × C × T (k: reaction constant, C: dissolved ozone concentration, T: processing temperature). Therefore, the reaction rate R increases as the dissolved ozone concentration C increases and the treatment concentration T increases.

However, the dissolved ozone concentration C and the processing temperature T
Is in an opposite relationship. That is, if the processing temperature T (liquid temperature of ozone water) is increased in order to increase the reaction rate R, the solubility of ozone decreases, and the dissolved ozone concentration C
Becomes small, and the reaction rate R decreases. On the other hand, if the liquid temperature of the ozone water is lowered in order to increase the dissolved ozone concentration C to increase the reaction rate R, the processing temperature T decreases, and the reaction rate R decreases. When the substrate is processed by supplying ozone water at normal temperature from the ozone water generator into the processing tank, the reaction rate R does not change because the dissolved ozone concentration decreases. As described above, it is impossible to increase the reaction rate R by increasing both the dissolved ozone concentration C and the processing temperature T.

Therefore, conventionally, the reaction rate between the ozone and the organic matter in the ozone water cannot be increased beyond a certain limit, so that the processing time of the substrate with the ozone water becomes longer and the throughput becomes lower. There was a problem.

The present invention has been made in view of the above circumstances, and provides a substrate processing method capable of shortening the processing time of a substrate with ozone water and increasing throughput. It is an object of the present invention to provide a substrate processing apparatus capable of suitably performing the method.

[0012]

The invention according to claim 1 is
In a substrate processing method of immersing a substrate in ozone water in which ozone is dissolved, the substrate processing method includes a substrate heating step of heating the substrate, and a substrate processing step of immersing the heated substrate in ozone water to perform processing. Features.

According to a second aspect of the present invention, there is provided an ozone treatment tank in which ozone water in which ozone is dissolved is accommodated, and a substrate is immersed in the ozone water for treatment, and ozone is supplied to the ozone treatment tank. In a substrate processing apparatus provided with a water supply unit, a heat treatment tank containing a liquid heated to a high temperature and being heated by immersing the substrate in the liquid,
A substrate transfer means for transferring a substrate between the heat treatment tank and the ozone treatment tank is further provided.

According to a third aspect of the present invention, there is provided an ozone treatment tank for storing ozone water in which ozone is dissolved and treating the substrate by immersing the substrate in the ozone water, and supplying ozone water to the ozone treatment tank. And a water supply means, the substrate processing apparatus provided with a plurality of the ozone treatment tank, a heat treatment tank containing a liquid heated to a high temperature, the substrate is immersed in the liquid and heated. A substrate transfer means for sequentially transferring a substrate from one ozone treatment tank to the heat treatment tank and from the heat treatment tank to the next ozone treatment tank is further provided.

According to a fourth aspect of the present invention, there is provided a processing tank in which ozone water in which ozone is dissolved is accommodated and a substrate is immersed in the ozone water for processing, and an ozone water supply for supplying the ozone water into the processing tank. Means for heating a substrate disposed outside the processing tank and heating the substrate, and a substrate for transferring the substrate between the position where the heating means is disposed and the processing tank. And transport means.

According to a fifth aspect of the present invention, there is provided a processing tank in which ozone water in which ozone is dissolved is stored and a substrate is immersed in the ozone water for processing, and a first ozone for supplying ozone water into the processing tank. In a substrate processing apparatus comprising: a water supply unit; and a drainage unit that discharges a liquid from the processing tank.
A first liquid supply unit configured to supply a liquid heated to a high temperature into the processing tank; and a second liquid supply unit configured to supply a liquid heated to a high temperature from an upper portion of the processing tank to a surface of a substrate housed in the processing tank. Liquid supply means and second ozone water supply means for supplying ozone water in which ozone is dissolved from the upper part of the processing tank to the surface of the substrate accommodated in the processing tank are further provided.

According to the substrate processing method of the first aspect of the present invention, even if the heated substrate is immersed in low-temperature ozone water, the temperature of the substrate does not immediately decrease. Below, the ozone in the ozone water reacts with the organic matter on the substrate surface. Therefore, by preparing ozone water with a high dissolved ozone concentration at a low temperature, and immersing a high-temperature substrate in the ozone water and treating,
By increasing both the dissolved ozone concentration and the processing temperature, the reaction rate between ozone and organic substances can be increased. Therefore, the processing time of the substrate with ozone water can be shortened.

In the substrate processing apparatus according to the second aspect of the present invention, the substrate is immersed and heated in a liquid heated in a high temperature and contained in a heat treatment tank, and the heated substrate is transferred by the substrate transfer means. When transported to the ozone treatment tank and immersed in ozone water contained in the ozone treatment tank for processing,
Even if the substrate is immersed in low-temperature ozone water, the temperature of the substrate does not decrease immediately. Therefore, on the surface of the substrate,
Under high temperature conditions, the ozone in the ozone water reacts with the organic matter on the substrate surface. Therefore, ozone water having a high dissolved ozone concentration at a low temperature is prepared and supplied into an ozone treatment tank by an ozone water supply means, and a substrate heated in a heat treatment tank is immersed in the ozone water for treatment. The reaction between the ozone and the organic substance is performed in a state where both the concentration and the processing temperature are high, and the reaction speed increases. Therefore, the processing time of the substrate with ozone water is shortened. Then, until the organic matter is completely removed from the surface of the substrate,
While the substrate is transferred between the heat treatment tank and the ozone treatment tank by the substrate transfer means, for example, an ozone treatment tank → a heat treatment tank → an ozone treatment tank, a heat treatment tank → an ozone treatment tank → a heat treatment tank → ozone treatment Heating the substrate in the heat treatment tank and the ozone water in the ozone treatment tank while transporting the substrate in a tank or ozone treatment tank → heat treatment tank → ozone treatment tank → heat treatment tank → ozone treatment tank. The processing may be repeated.

In the substrate processing apparatus according to the third aspect of the present invention, the substrate is immersed in a liquid which is heated to a high temperature and accommodated in a heat treatment tank and heated, and the heated substrate is transferred by the substrate transfer means. When transported to the ozone treatment tank and immersed in ozone water contained in the ozone treatment tank for processing,
Even if the substrate is immersed in low-temperature ozone water, the temperature of the substrate does not decrease immediately. Therefore, on the surface of the substrate,
Under high temperature conditions, the ozone in the ozone water reacts with the organic matter on the substrate surface. Therefore, ozone water having a high dissolved ozone concentration at a low temperature is prepared and supplied into an ozone treatment tank by an ozone water supply means, and a substrate heated in a heat treatment tank is immersed in the ozone water for treatment. The reaction between the ozone and the organic substance is performed in a state where both the concentration and the processing temperature are high, and the reaction speed increases. Therefore, the processing time of the substrate with ozone water is shortened. Then, until the organic matter is completely removed from the surface of the substrate,
While sequentially transferring the substrate from one ozone treatment tank to the heat treatment tank and from the heat treatment tank to the next ozone treatment tank by the substrate transfer means, for example, the first ozone treatment tank → the heat treatment tank → the second Ozone treatment tank, first heat treatment tank → first ozone treatment tank → second heat treatment tank → second ozone treatment tank, or first ozone treatment tank → first heat treatment tank →
Heating the substrate in the heat treatment tank and treating the substrate with ozone water in the ozone treatment tank while transporting the substrate in the order of the second ozone treatment tank → the second heat treatment tank → the third ozone treatment tank. May be repeated.

In the substrate processing apparatus according to the present invention, the substrate is heated by the heating means provided outside the processing tank, and the heated substrate is transferred to the processing tank by the substrate transferring means. When the substrate is immersed in the ozone water contained in the processing tank for processing, the temperature of the substrate does not immediately decrease even if the substrate is immersed in the low-temperature ozone water. Therefore, on the surface of the substrate, the ozone in the ozone water reacts with the organic matter on the substrate surface under high temperature conditions.
Therefore, when the ozone water having a high dissolved ozone concentration is prepared at a low temperature by the ozone water supply means and supplied into the processing tank, and the substrate heated by the heating means is immersed in the ozone water for processing, the dissolved ozone concentration is reduced. The reaction between the ozone and the organic substance is performed in a state where both the processing temperature is high, and the reaction speed increases. Therefore, the processing time of the substrate with ozone water is shortened. Until the organic matter is completely removed from the surface of the substrate, the substrate is transported by the substrate transport means between the arrangement position of the heating means and the processing tank, for example, processing tank → heating means → processing tank, Heating means → treatment tank → heating means →
While transporting the substrate such as a processing tank or a processing tank → a heating means → a processing tank → a heating means → a processing tank, the heating of the substrate by the heating means and the processing of the substrate by the ozone water in the processing tank are repeated. do it.

In the substrate processing apparatus according to the fifth aspect of the present invention, the substrate accommodated in the processing tank is brought into contact with the liquid heated to a high temperature supplied from the second liquid supply means or the second liquid supply means. Heated to a high temperature and supplied to the processing tank and immersed in the liquid contained in the processing tank, or heated by the first liquid supply means and supplied to the processing tank. It is heated by being immersed in a liquid. The substrate in the processing tank heated as described above is supplied into the processing tank by the first ozone water supply means and immersed in the ozone water contained in the processing tank to be processed, or the second ozone water is supplied. The treatment is performed by contacting with the ozone water supplied from the supply means or by being supplied into the treatment tank by the second ozone water supply means and immersed in the ozone water contained in the treatment tank. At this time, even if the substrate is immersed in low-temperature ozone water or comes into contact with low-temperature ozone water, the temperature of the substrate does not decrease immediately. Therefore, on the surface of the substrate, the ozone in the ozone water reacts with the organic matter on the substrate surface under high temperature conditions. Therefore, by the first ozone water supply means,
Ozone water having a high dissolved ozone concentration is prepared at a low temperature and supplied into a processing tank, and a heated substrate is immersed in the ozone water for processing. Concentration ozone water is prepared and supplied into the processing tank, and the ozone water is brought into contact with the heated substrate or the heated substrate is immersed in the ozone water for processing. The reaction between the ozone and the organic substance is performed in a high state, and the reaction speed increases. Therefore, the processing time of the substrate with ozone water is shortened. Until the organic matter is completely removed from the surface of the substrate, the liquid is supplied from the processing tank by the liquid discharging means, the liquid is supplied from the second liquid supplying means, and the ozone water is supplied from the first ozone water supplying means. The supply, the supply of the liquid by the first liquid supply unit, and the supply of the ozone water by the second ozone water supply unit may be sequentially performed, and the heating of the substrate and the treatment of the substrate with the ozone water may be repeated.

It should be noted that claims 2, 3, and 5
As the “liquid” described in (1), a liquid heated to 40 ° C. to 150 ° C. is considered. Specifically, a mixture of pure water and hydrochloric acid, a mixture of pure water and acetic acid, a mixture of pure water and sulfuric acid, a mixture of pure water and hydrogen peroxide, a mixture of pure water and phosphoric acid, or Only pure water is mentioned. In the case of pure water only, that is, in the case of warm pure water, washing of the heat treatment tank becomes unnecessary,
Inexpensive.

[0023]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A preferred embodiment of the present invention will be described below with reference to FIGS.

FIG. 1 is a schematic diagram showing an example of the configuration of a substrate processing apparatus used to carry out the substrate processing method according to the present invention. This apparatus includes a substrate processing unit 10 and a substrate heating unit 46. Among these, the configuration of the substrate processing unit 10 is the same as the above-described conventional substrate processing apparatus using ozone water shown in FIG. Although not shown, the apparatus is provided with a wafer transfer mechanism for transferring the wafer W between the substrate processing unit 10 and the substrate heating unit 46.

The substrate heating section 46 includes a hot pure water tank 48 in which hot pure water heated to a high temperature, for example, near the boiling point is accommodated, and the wafer W is held by the wafer holder 14 and immersed in the hot pure water. . The hot pure water tank 48 corresponds to the heat treatment tank of the present invention, and has a hot pure water supply / discharge port 50 at a lower part and an overflow part 52 from which hot pure water overflows at an upper part. Further, the hot pure water tank 48 is provided with an overflow water receiving portion 54, and the hot pure water overflowing from the overflow portion 52 above the hot pure water tank 48 flows into the overflow water receiving portion 54. . One end of a hot pure water circulation pipe 56 is connected to and connected to the bottom of the overflow water receiving portion 54, and the other end of the hot pure water circulation pipe 56 communicates with the hot pure water supply / discharge port 50 of the hot pure water tank 48. It is connected.

A pump 58, a hot pure water circulation pipe 56,
A heater 60 and a filter 62 are provided therebetween. The hot-purified water circulation pipe 56 is branched in the middle, and a pure water supply pipe 66 connected to a pure water supply source and having an open / close control valve 68 interposed therein, and a switch valve 72. Are connected to each other.

In the substrate heating section 46, hot pure water heated to a predetermined temperature is constantly circulated between the inside of the hot pure water tank 48 and the hot pure water circulation pipe 56. And hot pure water tank 4
The wafer W is heated by being immersed in the hot pure water in the wafer 6 for a predetermined time.

Next, an example of a processing operation for decomposing and removing an organic substance such as a resist attached to the surface of the wafer W using the substrate processing apparatus having the above-described configuration will be described.

First, in the substrate processing section 10, the inside of the ozone treatment tank 12 is filled with ozone water by the above-described operation, and the ozone water overflows from the overflow section 18 on the upper part of the ozone treatment tank 12 and overflows. In the state of flowing into the part 20,
The first processing of the wafer W is performed by immersing the wafer W in ozone water in the ozone processing tank 12. At this time, the ozone water supply source prepares ozone water having a high dissolved ozone concentration at a low temperature, and supplies the ozone water from the ozone water supply pipe 42 to the liquid supply port 16 of the ozone treatment tank 12 through the liquid supply pipe 32. The ozone treatment tank 12 is filled with ozone water having a high dissolved ozone concentration.

When the first processing of the wafer W is completed, the wafer W is lifted from the ozone water in the ozone processing tank 12 and
The wafer W is transferred to the substrate heating section 46 by the wafer transfer mechanism. Then, in the substrate heating unit 46, the wafer W is immersed in the high-temperature hot pure water accommodated in the hot pure water tank 48 for a predetermined time and heated.

Subsequently, the wafer W is lifted out of the hot pure water in the hot pure water tank 48, and the heated wafer W is transferred to the substrate processing unit 10 again by the wafer transfer mechanism. And
In the substrate processing section 10, the heated wafer W is immersed again in ozone water having a high dissolved ozone concentration in the ozone processing tank 12, and the second processing of the wafer W is performed. At this time,
Even if the heated wafer W is immersed in low-temperature ozone water, the temperature of the wafer W does not decrease immediately. Therefore, on the surface of the wafer W, the ozone having a high dissolved concentration reacts with the organic substance under a high temperature condition, and the reaction speed increases. Therefore, the processing of the wafer W with the ozone water proceeds promptly.

When the temperature of the wafer W decreases to, for example, near normal temperature while the wafer W is immersed in the low-temperature ozone water in the ozone processing tank 12, the wafer W is moved into the ozone processing tank 12. The wafer W is lifted out of the ozone water, and is transferred to the substrate heating unit 46 again by the wafer transfer mechanism. Then, in the substrate heating section 46, the wafer W is immersed again in high-temperature hot pure water in the hot pure water tank 48 and heated. When the wafer W is heated to a high temperature, the wafer W is lifted out of the hot pure water in the hot pure water tank 48, the heated wafer W is transported again to the substrate processing unit 10 by the wafer transport mechanism, and the heated wafer W is again transported. The third processing of the wafer W is performed by immersing the wafer W in ozone water having a high dissolved ozone concentration in the ozone processing tank 12. The heating of the wafer W and the processing of the wafer W as described above are repeated until organic substances are completely removed from the surface of the wafer W.

When the processing of the wafer W with the ozone water is completed, the supply of the ozone water into the ozone processing tank 12 is stopped, and the pure water is supplied into the ozone processing tank 12 as described above. The inside of the tank 12 is filled with pure water, and the pure water overflows from the overflow part 18 at the upper part of the ozone treatment tank 12 and flows into the overflow receiving part 20. The wafer W is rinsed with water by immersing the wafer W therein. When the washing is completed, the wafer W is removed from the ozone treatment tank 1.
After being lifted from the inside and dried, it is carried out of the apparatus.

The results of a series of processes described above in which hot pure water at 90 ° C. was stored in the hot pure water tank 48 and evaluated were as follows: the reaction rate was improved about 5 times as compared with the conventional process.

In the above description, first, the wafer W is once treated with ozone water having a low dissolved ozone concentration at a low temperature.
Thereafter, the wafer W is transferred from the substrate processing unit 10 to the substrate heating unit 4.
6, the wafer W is heated with hot pure water. First, the wafer W is transferred to the substrate heating unit 46 and heated by the substrate heating unit 46, and then the wafer W is heated by the substrate heating unit. The wafer W may be transported from the substrate processing unit 46 to the substrate processing unit 46, and the first processing of the wafer W with ozone water having a low temperature and a high dissolved ozone concentration may be performed.

When the above-described series of processes is performed under pressure, the dissolved ozone concentration of ozone water can be further increased, and the boiling point of a solution such as pure water can be increased to increase the process temperature. It is preferable because the height can be increased.
Further, for the purpose of generating OH radicals having a high reaction rate with organic substances in ozone water, megasonic irradiation, addition of hydrogen peroxide solution, ultraviolet irradiation, radiation irradiation and the like may be used in combination with the treatment with ozone water. Also, in order to prolong the half-life of ozone water, acid with low pH (hydrochloric acid, hydrofluoric acid, etc.)
Addition of carbonic acid and bicarbonate ions to carbonic acid and carboxylic acid to scavenger OH radicals (consumable substance)
May be added.

FIG. 2 is a schematic diagram showing another configuration example of the substrate processing apparatus. In this apparatus, a plurality of substrate processing units 10a and 10b and substrate heating units 46a and 46b each having the same configuration as the substrate processing unit 10 and the substrate heating unit 46 of the apparatus shown in FIG. Not shown,
From the first substrate processing unit 10a to the first substrate heating unit 46a
From the first substrate heating section 46a to the second substrate processing section 10
b, from the second substrate processing unit 10b to the second substrate heating unit 4
6b is provided with a wafer transfer mechanism for sequentially transferring wafers W to 6b.

An example of the processing operation of the wafer W using the substrate processing apparatus having the configuration shown in FIG. 2 will be briefly described. First, in the first substrate processing section 10a, the substrate processing of the apparatus shown in FIG. By the same operation as in the unit 10, the first processing of the wafer W with ozone water having a low dissolved ozone concentration at a low temperature is performed. When the first processing of the wafer W is completed, the wafer W is lifted out of the ozone water in the ozone processing tank 12, and the wafer W is moved to the first position by the wafer transfer mechanism.
To the substrate heating unit 46a. Then, in the first substrate heating section 46a, the substrate heating section 4 of the apparatus shown in FIG.
6, the wafer W is heated with high-temperature hot pure water.

Subsequently, the wafer W is lifted out of the hot pure water in the hot pure water tank 48, and the heated wafer W is transferred to the second substrate processing section 10b by the wafer transfer mechanism. Then, in the second substrate processing unit 10b, the heated wafer W is immersed in ozone water having a high dissolved ozone concentration in the ozone processing tank 12, and the second processing of the wafer W is performed. At this time, on the surface of the wafer W, a high dissolved concentration of ozone reacts with an organic substance under a high temperature condition, and the processing of the wafer W with ozone water proceeds promptly.

When the temperature of the wafer W decreases while the wafer W is immersed in the low-temperature ozone water in the ozone processing tank 12, the wafer W is pulled up from the ozone water in the ozone processing tank 12, The wafer W is transferred to the second substrate heating section 46b by the wafer transfer mechanism. And the second
In the substrate heating section 46 of FIG.
8 and immersed in high-temperature hot pure water and heated. Wafer W
Is heated to a high temperature, the wafer W is pulled up from the hot pure water in the hot pure water tank 48, and the heated wafer W is transferred to the next substrate processing unit (not shown) by the wafer transfer mechanism.
The heated wafer W is immersed again in ozone water having a high dissolved ozone concentration in the ozone treatment tank 12, and the third processing of the wafer W is performed.

As described above, the heating of the wafer W and the processing of the wafer W are repeated while the wafer W is alternately transported to the substrate processing section and the substrate heating section. When the organic matter is completely removed from the surface of the wafer W, pure water is supplied into the last ozone treatment tank 12 in which the processed wafer W is stored, and the wafer W is washed with water. When the washing is completed, the wafer W
Is taken out of the ozone treatment tank 12, dried, and then carried out of the apparatus.

In the apparatus shown in FIG. 2, a substrate processing section 10a is provided at the head position, and after processing the wafer W once with low-temperature ozone water having a high dissolved ozone concentration, the wafer W is heated. The wafer W is transported to the section 46a and heated with hot pure water. However, a substrate heating section is provided at the top position, and after the wafer W is heated by the substrate heating section, the wafer W is transferred to the substrate processing section. The wafer W may be transported to perform the first processing of the wafer W with ozone water having a low temperature and a high dissolved ozone concentration.

Next, FIG. 3 is a schematic view showing another example of the configuration of the substrate processing apparatus. This apparatus includes a substrate processing section 74 having the same configuration as the substrate processing section 10 of the apparatus shown in FIG. 1, and a heater such as a halogen lamp or a (far) infrared heater is provided immediately above the ozone processing tank 12. Container 78
Is provided, and includes a wafer transfer mechanism (not shown) for transferring the wafer W between the substrate processing unit 74 and the heating unit 76.

An example of the processing operation of the wafer W using the substrate processing apparatus having the configuration shown in FIG. 3 will be briefly described. First, in the substrate processing section 74, the processing in the substrate processing section 10 of the apparatus shown in FIG. By the same operation as in the case, the first processing of the wafer W with ozone water having a low dissolved ozone concentration at a low temperature is performed. After the first processing of the wafer W,
The wafer W is pulled up from the ozone water in the ozone processing tank 12, the wafer W is moved to the heating section 76 by the wafer transfer mechanism, and the wafer W is heated by the heater 78 in the heating section 76. When the heating of the wafer W is completed, the heated wafer W is transferred to the substrate processing unit 7 by the wafer transfer mechanism.
4, the heated wafer W is immersed again in ozone water having a high dissolved ozone concentration in the ozone treatment tank 12,
The second processing of the wafer W is performed. At this time, on the surface of the wafer W, a high dissolved concentration of ozone and an organic substance react under high temperature conditions, and the wafer W
Will proceed promptly.

When the temperature of the wafer W decreases while the wafer W is immersed in the low-temperature ozone water in the ozone processing tank 12, the wafer W is lifted from the ozone water in the ozone processing tank 12, The wafer W is moved again to the heating section 76 by the wafer transfer mechanism, and the wafer W is heated by the heater 78. When the wafer W is heated and becomes high temperature again, the heated wafer W is moved again to the substrate processing unit 74 by the wafer transfer mechanism, and the heated wafer W is again returned to the ozone water having a high dissolved ozone concentration in the ozone processing tank 12. And the third processing of the wafer W is performed. The heating of the wafer W and the processing of the wafer W as described above
Repeat until organics are completely removed from the surface of the.

When the processing of the wafer W with the ozone water is completed, the supply of the ozone water into the ozone processing tank 12 is stopped, and pure water is supplied into the ozone processing tank 12 so that the wafer W is removed from the ozone processing tank 12. Is immersed in pure water to wash the wafer W with water. When the washing is completed, the wafer W is lifted out of the ozone treatment tank 12, dried, and carried out of the apparatus.

In the above description, first, the wafer W is first treated with ozone water having a low dissolved ozone concentration at a low temperature.
After that, the wafer W is moved to the heating unit 76, and the wafer W is heated by the heater 78.
The wafer W may be heated by the heating unit 76, and thereafter, the wafer W may be moved to the substrate processing unit 74 to perform the first processing of the wafer W with low-temperature ozone water having a high dissolved ozone concentration.

In the substrate processing apparatus shown in FIG. 3, the heating section provided directly above the ozone processing tank 12 in the substrate processing section 74 may have a configuration as shown in FIG.
In the apparatus shown in FIG. 4, a plurality of heating fluid blowing nozzles 82 are disposed above the ozone treatment tank 12, and each of the blowing nozzles 82 is connected to hot pure water or heated steam or nitrogen heated to a high temperature. A heating unit 80 is configured by being connected to a heating fluid supply pipe 84 connected to a supply source of a heating fluid such as an inert gas such as a gas and having an opening / closing control valve 86 interposed therebetween.

Further, in the apparatus shown in FIG.
When the cover 90 is opened and closed, the wafer W
Is housed in a processing chamber 88 which can carry in and carry out the wafer and can be sealed. Although not shown, inside the processing chamber 88,
A wafer transfer mechanism for transferring the wafer W between the inside of the ozone processing tank 12 of the substrate processing unit 74 and the position of the blowing nozzle 82 of the heating unit 80 is provided. Also,
A gas-liquid discharge port 92 is formed at the bottom of the processing chamber 88, and a gas-liquid discharge pipe 94 is connected to the gas-liquid discharge port 92 so as to communicate therewith. The gas-liquid discharge pipe 94 has an open / close control valve 98.
A drain pipe 96 having a through hole and an exhaust pipe 100 having an opening / closing control valve 102 and connected to a vacuum pump 104 communicate with each other.

In the apparatus shown in FIG. 4, hot pure water or heated steam heated to a high temperature is blown from the blowing nozzle 82 of the heating unit 80 to the surface of the wafer W,
The wafer W is heated. Then, the hot pure water blown out from the blowing nozzle 82 and flowing down to the inner bottom of the processing chamber 88 is discharged from the processing chamber 88 through the drain pipe 96. Further, the steam is discharged from the processing chamber 88 to the exhaust pipe 1.
Exhausted through 00. The device shown in FIG. 4 differs from the device shown in FIG. 3 only in the configuration of the heating unit.
The processing operation itself is the same.

FIG. 5 is a schematic view showing still another example of the configuration of the substrate processing apparatus. In FIG. 5, the components denoted by the same reference numerals as those used in FIGS. 1 to 4 and 6 have the same functions as the respective components of the device described so far. Is omitted.

The apparatus shown in FIG. 5 is provided with a pure water heating bypass pipe 106 which branches off from the pure water supply pipe 36, joins the pure water supply pipe 36 again, and communicates with the liquid supply pipe 32. An opening / closing control valve 108 and a heater 110 are provided in the bypass pipe 106, respectively. The open / close control valve 3 inserted in the pure water supply pipe 36
8 is closed, and the on-off control valve 1 inserted in the bypass pipe 106 is closed.
08, the pure water supplied from the pure water supply source flows into the bypass pipe 106 and is heated to a high temperature while passing through the heater 110, and the heated hot pure water is supplied from the bypass pipe 106 The liquid is supplied to the liquid supply port 16 of the ozone treatment tank 12 through a pipe 32,
Can be filled with warm pure water.

Further, a plurality of blowing nozzles 112 for blowing the liquid toward the inside of the ozone treatment tank 12 are provided above the ozone treatment tank 12. Each blowing nozzle 11
2 is connected to an upper liquid supply pipe 114 in communication therewith. The upper liquid supply pipe 114 is connected to a supply source of hot pure water heated to a high temperature, and is provided with an open / close control valve 118 interposed therebetween. 116, and an ozone water supply pipe 120 connected to an ozone water supply source for preparing and supplying ozone water having a high dissolved ozone concentration at a low temperature and having an opening / closing control valve 122 interposed therebetween.
Are connected respectively.

An example of a processing operation for decomposing and removing organic substances attached to the surface of the wafer W using the substrate processing apparatus having the configuration shown in FIG. 5 will be described.

In a state where the wafer W is stored in the ozone treatment tank 12, first, the opening / closing control valve 118 inserted in the hot pure water supply pipe 116 is opened, and the blowing nozzle is passed from the hot pure water supply pipe 116 through the upper liquid supply pipe 114. The hot pure water heated to a high temperature is supplied to 112. Then, hot pure water is blown from the blowing nozzle 112 toward the wafer W in the ozone processing tank 12, and the hot pure water is further stored in the ozone processing tank 12 (at this time, the drain valve 3 inserted into the drain pipe 28).
0 is closed), and the wafer W is heated by immersing the wafer W in the hot pure water. At this time, the wafer W may be heated by blowing hot pure water from the blowing nozzle 112 toward the wafer W in the ozone treatment tank 12 with the drain valve 30 kept open.

When the wafer W is heated by the hot pure water,
The open / close control valve 118 inserted into the hot pure water supply pipe 116 is closed to stop the supply of the hot pure water, and the drain valve 30 is opened to quickly drain the hot pure water in the ozone treatment tank 12. When the hot pure water is discharged from the ozone treatment tank 12, the drain valve 30
Is closed, and the open / close control valve 4 inserted in the ozone water supply pipe 42 is closed.
4, the ozone water having a low dissolved ozone concentration is supplied from the ozone water supply pipe 42 to the liquid supply port 16 of the ozone treatment tank 12 through the liquid supply pipe 32, and the ozone water flows into the ozone treatment tank 12. And fill it with ozone water,
The ozone water overflows from the overflow portion 18 at the top of the ozone treatment tank 12 and flows into the overflow receiving portion 20. Thus, the wafer W is immersed in the ozone water, and the first processing of the wafer W is performed. At this time, on the surface of the wafer W, a high dissolved concentration of ozone reacts with an organic substance under a high temperature condition, and the processing of the wafer W with ozone water proceeds promptly.

When the temperature of the wafer W decreases while the wafer W is immersed in the low-temperature ozone water in the ozone processing tank 12, the opening / closing control valve 44 inserted in the ozone water supply pipe 42. Is closed to stop the supply of the ozone water into the ozone treatment tank 12, and the drain valve 3 inserted into the drain pipe 28 is closed.
0 is opened, and the ozone water in the ozone treatment tank 12 is rapidly drained. When the ozone water is discharged from the ozone treatment tank 12, the drain valve 30 is closed. Then, on the wafer W
Next, in order to improve the reaction rate difference below, it is necessary to open the on-off control valve 108 inserted in the bypass pipe 106 while closing the on-off control valve 38 inserted in the pure water supply pipe 36. As a result, heated pure water is supplied from the bypass pipe 106 to the liquid supply port 16 of the ozone treatment tank 12 through the liquid supply pipe 32.
And the inside of the ozone treatment tank 12 is filled with warm pure water.
Then, the wafer W is heated by being immersed in the hot pure water in the ozone treatment tank 12.

When the wafer W is heated by hot pure water,
Open / close control valve 1 inserted into pure water heating bypass pipe 106
08 is closed, the supply of hot pure water into the ozone treatment tank 12 is stopped, and the drain valve 30 is opened to quickly drain the hot pure water from the ozone treatment tank 12. When the hot pure water is discharged from the ozone treatment tank 12, the drain valve 30 is closed, and the open / close control valve 122 inserted in the ozone water supply pipe 120 is opened to remove the ozone water having a high dissolved ozone concentration at a low temperature. Water supply pipe 12
0 to the blowing nozzle 11 through the upper liquid supply pipe 114
Supply to 2. Then, ozone water is blown from the blowing nozzle 112 toward the wafer W in the ozone processing tank 12,
Ozone water is stored in the ozone treatment tank 12. Then, the wafer W is processed for the second time by immersing the wafer W in ozone water in the ozone processing tank 12.

When the second processing of the wafer W is completed, the opening / closing control valve 122 inserted in the ozone water supply pipe 120 is closed to stop the supply of the ozone water to the blowing nozzle 112.
The drainage valve 30 inserted in the drainage pipe 28 is opened to quickly drain the ozone water in the ozone treatment tank 12. When ozone water is discharged from the ozone treatment tank 12, the drain valve 30
Close.

Thereafter, if necessary, the above-mentioned operations are repeated to completely remove organic substances from the surface of the wafer W.
When the processing of the wafer W with the ozone water is completed, pure water is supplied into the ozone processing tank 12 to wash the wafer W, and when the washing is completed, the wafer W is pulled up from the ozone processing tank 12 and dried. After that, it is carried out of the device.

By using the apparatus shown in FIG. 5 to supply hot pure water and ozone water alternately from the upper and lower parts of the ozone treatment tank 12 as described above, the reaction rate difference between the upper and lower parts of the wafer W can be reduced. Can be improved. In addition, it is preferable to add a swing operation of the wafer W during the processing.

[0062]

According to the substrate processing method of the present invention, the processing time of the substrate with ozone water can be shortened and the throughput can be improved.

By using the substrate processing apparatus of each of the inventions according to claims 2 to 5, the method of the invention according to claim 1 can be suitably performed, and the processing time of the substrate with ozone water can be shortened. Thus, the throughput can be improved.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a configuration of a substrate processing apparatus used to carry out a substrate processing method according to the present invention.

FIG. 2 is a schematic view showing another example of the configuration of the substrate processing apparatus used to carry out the substrate processing method according to the present invention.

FIG. 3 is a schematic diagram showing still another configuration example of the substrate processing apparatus used to carry out the substrate processing method according to the present invention.

FIG. 4 is a schematic diagram showing still another configuration example of the substrate processing apparatus used for performing the substrate processing method according to the present invention.

FIG. 5 is a schematic view showing still another configuration example of the substrate processing apparatus used to carry out the substrate processing method according to the present invention.

FIG. 6 is a schematic view showing an example of a configuration of a conventional substrate processing apparatus using ozone water.

[Explanation of symbols]

10, 10a, 10b, 74 Substrate processing section 12 Ozone treatment tank 14 Wafer holder 16 Liquid supply port 18, 52 Overflow section 20 Overflow liquid receiving section 22 Overflow liquid discharge pipe 24 Drain discharge pipe 26 Drain ports 28, 96 Drain Liquid pipe 30 drain valve 32 liquid supply pipe 34, 38, 44, 68, 72, 86, 98, 102,
108, 118, 122 Open / close control valve 36 Pure water supply pipe 40 Flow rate regulating valve 42, 120 Ozone water supply pipe 46, 46a, 46b Substrate heating section 48 Hot pure water tank 50 Hot pure water supply / discharge port 54 Overflow water receiving section 56 For hot pure water circulation Pipe 58 Pump 60, 110 Heater 62 Filter 64 Branch pipe 66 Pure water supply pipe 70 Drain discharge pipe 76, 80 Heating unit 78 Heater 82, 112 Blow-out nozzle 84 Heating fluid supply pipe 88 Processing chamber 90 Cover 92 Gas-liquid discharge port 94 Gas-liquid discharge pipe 100 Exhaust pipe 104 Vacuum pump 106 Bypass pipe for heating pure water 114 Upper liquid supply pipe 116 Hot pure water supply pipe W Wafer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02F 1/1333 500 G02F 1/1333 500 H01L 21/027 H01L 21/30 572B 21/306 21/306 A ( 72) Inventor Kazumi Kanemoto 4-chome Tenjin Kitamachi 1-chome, Horikawa-dori-Terauchi, Kamigyo-ku, Kyoto F-term (reference) 2H088 FA21 FA24 FA30 HA01 2H090 JC06 JC08 JC19 5F043 AA37 BB25 CC16 DD07 DD30 5F046 MA02 MA03 MA10

Claims (5)

[Claims] 1. A substrate processing method in which a substrate is immersed in ozone water in which ozone is dissolved for processing, wherein a substrate heating step of heating the substrate, and a substrate processing step of immersing the heated substrate in ozone water for processing. And a substrate processing method. 2. An ozone treatment tank for containing ozone water in which ozone is dissolved and treating the substrate by immersing the substrate in the ozone water, and an ozone water supply means for supplying the ozone water into the ozone treatment tank. In a substrate processing apparatus provided with: a heat treatment tank that contains a liquid heated to a high temperature and is heated by being immersed in the liquid, and the substrate is interposed between the heat treatment tank and the ozone treatment tank. A substrate processing apparatus, further comprising: a substrate transport unit configured to transport the substrate. 3. An ozone treatment tank for containing ozone water in which ozone is dissolved and treating the substrate by immersing the substrate in the ozone water, and an ozone water supply means for supplying the ozone water into the ozone treatment tank. In the substrate processing apparatus provided, a plurality of the ozone treatment tanks are provided, and a heat treatment tank that accommodates a liquid heated to a high temperature, is immersed in the liquid, and heated by heating the substrate, is provided. A substrate processing apparatus, further comprising a substrate transfer means for sequentially transferring a substrate to the heat treatment tank from the heat treatment tank to the next ozone treatment tank. 4. A processing tank for storing ozone water in which ozone is dissolved and for processing a substrate by immersing the substrate in the ozone water, and an ozone water supply means for supplying ozone water into the processing tank. In the substrate processing apparatus, a heating unit disposed outside the ozone processing tank to heat the substrate, and a substrate transfer unit configured to transfer the substrate between the position where the heating unit is disposed and the processing tank, A substrate processing apparatus further provided. 5. A processing tank for storing ozone water in which ozone is dissolved, wherein the substrate is immersed in the ozone water for processing, a first ozone water supply means for supplying ozone water into the processing tank, A substrate processing apparatus comprising: a liquid discharging unit configured to discharge a liquid from a processing tank; a first liquid supply unit configured to supply a liquid heated to a high temperature into the processing tank; Second liquid supply means for supplying a liquid heated to a high temperature from the upper part of the processing tank to the surface of the substrate; ozone water in which ozone is dissolved from the upper part of the processing tank to the surface of the substrate housed in the processing tank And a second ozone water supply means for supplying the water.