JP2002018379A - Thin film peeling method, thin film peeling apparatus, and method of manufacturing electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thin film, particularly a photoresist, which is used for a thin film process substrate and needs to be peeled off from the substrate after process processing, and most of them are deteriorated or adhered to hardly removed materials. It is difficult to remove the cage. For stripping, a large amount of expensive high-temperature, high-concentration chemical solution and a device with large power consumption such as O2 ashing were required. SOLUTION: After irradiating the substrate with ozone gas, water vapor and ultraviolet rays, the substrate is finished and rinsed with ozone water or pure water rinse, so that a thin film which cannot be peeled off can be peeled off with high quality. In addition, a thin chemical solution was sprayed or a wet cleaning was applied to the hard-to-remove thin film containing inorganic material, achieving a low energy, chemical solution reduction, and an inexpensive stripping process.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for removing a thin film from the surface of an object to be cleaned. The present invention also relates to a method for manufacturing an electronic device having such a thin film peeling method as a part of the process.

[0002]

2. Description of the Related Art Thin film processing is a very important step, not limited to semiconductors and mounting substrates. Thin films are often used in, for example, photo processes, but it is necessary to peel the thin films from those substrates after the process is completed. However, the photoresist and the like after the completion of the process are deteriorated by etching, ion implantation, and the like. In a semiconductor requiring a high-definition pattern, an organic / inorganic compound or mixture (sidewall polymer) is deposited on the pattern side wall. It is also done and is very difficult to remove. As a method for removing the thin film of the photoresist or the side wall polymer, O ₂ ashing in vacuum dry processing, hot sulfuric acid stripping, organic stripping liquid, and the like are frequently used.

[0003]

However, in the case of a cleaning method using a chemical solution, there is a problem that the chemical solution itself is very expensive. In addition, it is necessary to use a large amount of harmful substances that cause environmental pollution or adversely affect the human body, and special treatment is required for treating a large amount of drainage and exhaust gas.

[0004] In the case of the stripping method using plasma, a special device is required for controlling discharge for generating stable plasma and for electrode equipment, which makes the whole device complicated and increases the cost and obtains uniform discharge. This makes it difficult to remove the thin film, and there is a problem that the peeled foreign matter is re-adhered to the substrate and re-contaminated.

As a stripping apparatus using ozone gas and water vapor, for example, JP-A-5-304126 and JP-A-11-219926 disclose a thin film removing apparatus and a process using a process of water vapor, ozone and additives. I have. However, with the disclosed apparatus and process, it is possible to strip organic substances, but it is difficult to strip inorganic substances. Further, there is a problem that even an organic substance, which has been altered by ion implantation or the like, cannot be stripped at all, and even if it can be stripped, the stripping rate is very slow. Further, Japanese Patent Application Laid-Open No. 5-259139 discloses a cleaning device using water vapor, ozone and ultraviolet rays. However, this device is designed for single-wafer processing, and is not suitable for mass production.
There is a problem that only a very limited amount of organic substances can be removed.

[0006]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made to solve the above-mentioned problems, and an object of the present invention is to reduce the influence on the human body and the environment, and at a low cost. An object of the present invention is to provide a method and an apparatus for removing a thin film from a surface of an object to be cleaned at a high rate, and a method for manufacturing an electronic device having the method for removing a thin film as a part of a process.

[0007]

(1) A method of peeling a thin film from a substrate surface by supplying an ozone gas and water vapor while irradiating the surface of the substrate to be treated with ultraviolet rays. It is characterized by having.

[0008] Therefore, the bonding of organic substances in the thin film on the substrate surface can be broken by the irradiation of ultraviolet rays, and the organic film can be decomposed with ozone gas and water vapor. Therefore, various thin films can be efficiently removed from the surface of the object to be cleaned at a high rate with little effect on the human body and environment and at low cost.

[0009] Steam can be generated by superheating water in a steam generation chamber. Ozone gas can be generated by an ozone gas generator.

(2) The thin film peeling method of the present invention comprises a first step of peeling a thin film from a substrate surface by supplying an ozone gas and / or water vapor while irradiating the surface of the substrate to be treated with ultraviolet rays. And a second step of cleaning the substrate surface with ozone water or pure water in this order.

[0011] Therefore, the bonding of organic substances in the thin film on the substrate surface can be broken by the irradiation of ultraviolet rays, and the organic film can be decomposed with ozone gas and / or water vapor. Therefore, various thin films can be efficiently removed from the surface of the object to be cleaned at a high rate with little effect on the human body and environment and at low cost.

In order to more effectively remove the thin film from the substrate surface, it is preferable to heat the substrate to a temperature higher than the boiling point of water and uniformly irradiate the substrate surface with ultraviolet rays together with water vapor.
By irradiating the surface of the substrate with ultraviolet rays, various chemical bonds of organic substances in the thin film are broken, and the decomposition action of the thin film is promoted. In addition, the surface of the thin film is modified to exhibit hydrophilicity. As a result, the water vapor is easily adsorbed on the surface of the thin film. As a result, the decomposition reaction of the thin film proceeds rapidly, and the water vapor is adsorbed over the entire surface of the substrate.

(3) In the thin film peeling method of (1) or (2), it is preferable to irradiate ultraviolet rays having a wavelength of 180 nm to 400 nm. This is to promote the decomposition of organic substances and reduce problems such as irradiation distance and absorption by water vapor.

(4) The thin film peeling method of (2) preferably further comprises a third step of spraying a first chemical solution onto the substrate surface before or after the first step. In semiconductors, a combination of organic and inorganic compounds and a mixture (sidewall polymer) are deposited on the pattern side walls during dry etching, and ozone gas, water vapor,
In addition to ultraviolet rays, a chemical solution for removing inorganic and organic compounds and mixtures is required. By spraying a chemical solution for removing the side wall polymer at the time of the above-described ozone gas, water vapor, or ultraviolet treatment in which the substrate is heated, the heating energy can also be effectively applied. Depending on the composition of the side wall polymer, the deposition thickness, etc., it is possible to select whether the treatment is performed before or after the ozone gas, water vapor, and ultraviolet treatment.

(5) The thin film peeling method of (2) preferably further comprises a fourth step of cleaning the substrate surface with a second chemical between the first step and the second step. . The sidewall polymer can also be removed by immersion cleaning or spin cleaning of a chemical solution.

(6) The thin film peeling method of (4) preferably further comprises a fourth step of cleaning the substrate surface with a second chemical between the first step and the second step. .

This is because, if a chemical solution is appropriately selected according to the type of the thin film, the thin film removal cleaning can be more effectively performed. As a result, the entire surface of the substrate can be effectively and uniformly removed. After performing the above method, the substrate is subsequently washed with functional water such as ozone water, rinsed, and dried to complete the process.

(7) In the thin film peeling method according to the above (4) or (6), the first step and / or the third step is performed while the substrate is heated to a temperature of room temperature or higher and 250 ° C. or lower. Is preferred.

(8) In the thin film peeling method according to (7), the temperature is preferably 40 ° C. or higher.
C. or higher, more preferably 110.degree. C. or higher.

(9) In the thin film peeling method according to the above (4), (6), (7) or (8), the first step and / or the third step may be performed while the substrate is isolated from the outside air. It is preferred to do so.

(10) In the thin film peeling method of the above (9), it is preferable that the first step and / or the third step be performed in a pressure atmosphere of 1 atm or more and 3 atm or less. .

As described above, by performing the thin film peeling treatment in a heated and pressurized atmosphere, a chemical solution, ozone gas or the like penetrates into the thin film on the substrate surface, and the decomposition reaction of the thin film proceeds more quickly. Peeling becomes possible.

(11) In the thin film peeling method according to any one of the above (4) to (10), the first chemical solution or the second chemical solution may be composed of an aliphatic polycarboxylic acid and a salt thereof, and an aminopolycarboxylic acid. And at least one or more chemical solutions selected from the group consisting of:

(12) In the thin film peeling method of the above (11), the concentration of the first chemical solution or the second chemical solution is preferably 0.001 to 10 wt%, and
It is more preferable that the content be from 01 to 1 wt%.

(13) In the thin film peeling method according to any one of the above (2) to (12), the ozone water contains carboxylic acids, aliphatic polycarboxylic acids and salts thereof, and aminopolycarboxylic acids and salts thereof. It is preferable that at least one or two or more chemical solutions selected from the group consisting of

(14) In the thin film peeling method of (13), the concentration of the chemical contained in the ozone water is
It is preferably 0.001 to 1 wt%.

(15) In the method for removing a thin film according to any one of the above (9) to (14), after the first step is performed, in the step of taking out the substrate to the outside air, the used ozone gas is decomposed by ultraviolet rays to be harmless. Can be

(16) In the thin film peeling method according to any one of the above (2) to (15), the temperature of the ozone water is room temperature, and the concentration of ozone contained in the ozone water is 60 ppm or more. Is preferably 80 ppm or more, more preferably 100 ppm or more.

(17) In the thin film peeling method according to the above (16), the ozone water contains 0.001 to 1 acetic acid.
It is preferable that the content is contained by wt%.

(18) The thin film peeling apparatus of the present invention is a thin film peeling apparatus capable of peeling a thin film from a substrate surface, and is a hermetically sealed washing pot for processing a substrate to be processed. Can be shut off, and the substrate can be taken in and out,
It is characterized by comprising a sealed washing pot capable of heating the substrate to room temperature or higher, supplying water vapor, ozone gas and / or chemical mist to the substrate, and irradiating the substrate with ultraviolet light, and at least one washing tank. And

(19) It is preferable that the thin film peeling apparatus of the above (18) is provided with a substrate holding mechanism which enables a batch processing mode capable of simultaneously processing a plurality of substrates. This is because the throughput can be increased as compared with an apparatus that performs single-wafer processing. Half pitch processing is possible for the interval between the objects to be cleaned, and the processing of the objects to be cleaned can be performed more effectively than at a normal pitch.

(20) In the thin film peeling apparatus of (18), it is preferable that the ultraviolet irradiation means includes at least one high-pressure mercury lamp.

(21) In the thin film stripping apparatus of (18), an ozone water producing apparatus capable of supplying room temperature ozone water in which 1 to 120 ppm of ozone gas is dissolved is connected to the cleaning tank. Is preferred.

(22) In the thin film stripping apparatus of (21), it is preferable that a circulating device for circulating ozone water in the cleaning tank is further provided. This is because by circulating the ozone water, the concentration of the ozone water itself can be increased and maintained, and the thin film can be more effectively peeled off. Also, it is possible to reduce the amount of ultrapure water or chemical solution used and the amount of electricity used, as compared to always producing new ozone water, thereby reducing the manufacturing cost.

(23) In the thin film peeling apparatus according to the above (18), the cleaning tank contains at least one member selected from the group consisting of aliphatic polycarboxylic acids and salts thereof, and aminopolycarboxylic acids and salts thereof. It is preferable that a chemical liquid supply device capable of supplying an aqueous solution to which two or more chemical liquids are added is attached.

(24) In the thin film peeling apparatus according to any one of the above (21) to (23), it is preferable to include a sealing device for sealing the cleaning tank.

(25) It is preferable that the thin film stripping apparatus according to any one of the above (21) to (24) further includes a bubbling apparatus for bubbling ozone gas into the cleaning tank. This is because the action of stirring the surface of the substrate at the same time as increasing the concentration of the ozone water works, and the thin film separation and removal can be performed more effectively. The bubble size during bubbling is 70 μm or less, more preferably 50 μm or less. When bubbling the ozone gas, the washing tank is sealed to prevent the ozone gas dissolved in the ozone water from being discharged out of the tank, so that a decrease in the concentration of the ozone water can be minimized. Thus, the thin film separation and removal can be performed more effectively.

(26) In the thin film stripping apparatus of the above (18), the washing tank comprises a washing tank using ozone water, an aliphatic polycarboxylic acid and a salt thereof, and an aminopolycarboxylic acid and a salt thereof. A washing tank using at least one kind or two or more kinds of chemical solutions selected from the group.

(27) In the thin film peeling apparatus according to any one of the above (18) to (26), it is preferable that the inner surface of the closed washing pot is subjected to a surface treatment for efficiently reflecting ultraviolet rays. .

(28) In the thin film peeling apparatus of the above (27), it is preferable that the inner surface of the closed washing pot is subjected to a mirror surface treatment for efficiently reflecting ultraviolet rays. This is because it is necessary to reflect ultraviolet rays efficiently in the closed washing pot because the processing mode is a batch type. In particular, by making the inside of the washing pot mirror-finished or embossed, irregular reflection of ultraviolet rays can be effectively obtained, and ultraviolet rays can be evenly applied between the objects to be washed even at a half pitch. For this reason, thin film peeling can be performed effectively in batch processing.

(29) In the thin film peeling apparatus according to any one of the above (18) to (28), it is preferable that the closed washing pot is provided with a nozzle for spraying ozone gas and water vapor from the same nozzle.

(30) In the thin film peeling apparatus according to any one of the above (18) to (29), it is preferable that the closed washing pot is further provided with, for example, a pressurizing means for pressurizing the closed washing pot. The pressure is, for example, 1.0 to 5.0 atm, preferably 1.0 to 3.0 atm, more preferably 1.0 to 3.0 atm.
2.0 atm.

(31) A method of manufacturing an electronic device according to the present invention includes a step of peeling a thin film formed on a substrate surface by any one of the thin film peeling methods (1) to (17). And

Depending on the type of thin film to be removed and the process to be applied, the type and presence or absence of a chemical solution used in a cleaning pot or a subsequent cleaning tank, the appropriate concentration ratio with ozone gas or water vapor, the presence or absence of ozone water cleaning, etc. Choose properly. Since an optimal processing step can be selected, the processing time can be reduced, and the present invention can be applied to all steps. For this reason, it is possible to greatly reduce the cleaning of a chemical solution that is problematic for the human body and the environment. Further, unlike a high-cost plasma method, a thin film can be peeled off from the substrate surface at low cost without significantly affecting the human body and environment.

[0045]

FIG. 1 is a view showing a preferred embodiment of a thin film removing apparatus according to the present invention. The thin film removing apparatus can be hermetically sealed, and includes a cleaning chamber 1 for storing an object 7 to be cleaned stored in a cassette 8, a steam generating chamber 2a for generating steam, and an ozone generating apparatus 5 for generating ozone.
a, an ozone water cleaning tank 12, an ultrapure water rinsing tank 16a, a dryer 17 and the like.

An ultraviolet irradiation lamp 6 is provided in the interior of the cleaning chamber 1 above the object 7 to be cleaned.
The wavelengths such as nm and 365 nm are irradiated. The ultraviolet irradiation wavelength is preferably 365 nm or less, but more preferably an ultraviolet irradiation lamp having a peak at 254 nm. Further, an exhaust 10 and a drain 11 are provided below the washing pot 1. The inside of the cleaning pot 1 is subjected to a surface treatment after electrolytic polishing in order to efficiently reflect ultraviolet rays irregularly. For example, GoldEP treatment (Shinko Pantech) or quartz coating may be applied.

The temperature in the washing pot 1 is preferably 150 ° C. or more (more preferably 180 ° C. or more). As a method for heating the cleaning pot 1, a method using a hot plate 9 for heating the entire cleaning pot 1 to a temperature of 80 to 150 ° C., and the object to be cleaned itself using infrared radiation heat obtained from an ultraviolet irradiation lamp 7 Or a method using both the hot plate 9 that heats the entire washing pot 1 to a temperature of 80 to 150 ° C. and the object itself to be heated using infrared radiation heat from the ultraviolet irradiation lamp 7. .

The washing pot 1 and the steam generation chamber 2a are connected via a steam supply pipe 2b. Further, the ultrapure water 2c stored in the steam generation chamber 2a is kept at 20 to 100 ° C.
The hot plate 3 for heating to the temperature of is provided. Then, the ultrapure water in the steam generating chamber 2a is heated to the above temperature by the hot plate 3 to generate steam,
Steam is supplied into the washing pot 1 through the steam supply pipe 2b at a vapor pressure. Further, the washing pot 1 has an ozone gas supply pipe 5 connected to a flow path of an ozone gas generator 5a.
b is connected. Further, the cleaning solution 1 is supplied with the chemical solution 4c stored in the chemical solution supply container 4a into the cleaning device 1 via the chemical solution supply pipe 4b.

The ozone water cleaning tank 12 is connected to an ozone water supply pipe 13b connected to an ozone water supply device 13a. The ozone water washing tank can circulate the ozone water by switching the switching valve 14 so that the ozone water flows into an overflow state through the pipe 13d and through the pipe 13c. further,
The chemical liquid 15c stored in the chemical liquid supply tank 15a can be injected by the chemical liquid injection pump through the injection pipe 15b. An ozone gas bubbling device 18 is provided at the bottom of the ozone water cleaning tank 12 so that ozone gas can be bubbled. Ozone gas is supplied from the ozone generator 5a to the ozone gas bubbling device 1 via the ozone gas supply pipe 5b.
8 is supplied.

(Embodiment 1) An embodiment of the present invention is shown in FIG. The object 7 to be cleaned from which the thin film is removed is a Si substrate used in the semiconductor process, and is the one immediately after the hole is formed in the interlayer insulating film by dry etching. Specifically, the interlayer film in which a hole is formed is an SiO2 system, an Al wiring is provided at the bottom of the hole, and a composite polymer of CFx and an inorganic compound is adhered and remains on the inner wall of the hole. Shows a state in which an anti-reflection film (Barc) and a KrF excimer resist remain thereon. The purpose of this embodiment is to remove the polymer, Barc, and KrF excimer resist.

The lid of the cleaning pot 1 of FIG. 1 was opened, and 52 Φ8 inch Si substrates 7 were set up at half pitch. The lid is closed again, the Si substrate 7 is shut off from the outside air, and the inert gas (N ₂ ) 19 is exhausted from the exhaust 10 while being replaced by the inert gas (N ₂ ) at ₂ L / min. While operating the ultraviolet irradiation device 6, the Si substrate 7 is
Heated to ° C. This time, the ultraviolet irradiation device 6 is a high-pressure mercury lamp 3
I use a book.

After the temperature of the Si substrate 7 is stabilized at 120 ° C., the ozone gas
The ozone gas 5c of 25 to 360 g / Nm3 is generated by the ozone gas generator 5a, and the steam 2c at a flow rate of 1 L / min and 90% RH is passed through the ozone gas supply pipe 5b.
And supplied to the washing tank 1 at 50 mL / min through the steam supply pipe 2b. At this time, the exhaust 10 was squeezed, the inside of the washing pot 1 was pressurized to 2.5 atm, and held for 10 minutes.
After processing the i-substrate, supply of ozone gas 5c and water vapor 2c, stopping of the washing tank heating device 9 and inert gas 19
/ Minute to the washing pot 1 for 1 minute to replace
Minutes still. At this time, the ultraviolet irradiation device 6 was turned on to decompose the residual ozone gas. The substrate temperature is 40 ℃
And dropped out. The lid of the cleaning pot 1 was opened, and the Si substrate 7 was taken out. At this time, the anti-reflection film (Barc) and the KrF excimer resist were almost completely removed from the Si substrate 7, but some of the residue and the polymer still remained.

Next, 52 Si substrates 7 were immersed in the ozone water washing tank 12 filled with 100 ppm ozone water to which 0.01% by weight of oxalic acid was added by the chemical liquid supply device 15a while maintaining the half pitch at 52 sheets. Subsequently, the lid 12a is closed and the ozone gas bubbler 18 causes the ozone gas concentration 325 to 325.
Bubbling ozone gas 5c of 360 g / Nm3,
A high concentration ozone gas was filled in the lid on the ozone water liquid level. As a result, the rate of ozone gas desorption from ozone water could be reduced. This was maintained for 10 minutes, and then the Si substrate 7 was transferred to the rinsing bath 16a, rinsed for 10 minutes, and finally dried by the dryer 17.

As a result of observing the processed substrate 7 with an SEM, the resist, the Barc residue, and the polymer remaining when the substrate 7 was taken out by the cleaning pot 1 were completely removed. In the cleaning pot 1, although a strong resist and Barc can be almost removed, a residue is generated due to the gas phase treatment. Therefore, by subsequently treating with oxalic acid-added ozone water, a high level of removal performance could be obtained by the oxalic acid chelating effect, the decomposition by ozone water, and the rinsing action. In the hole cross section observation, no corrosion of the hole (interlayer film) itself or the Al wiring at the hole bottom was observed at all.

The processing time in the cleaning tank 1 was changed from 10 minutes to 1 minute, and the resist and Barc removal rates were confirmed to be 6000 A / min.

(Embodiment 2) In Embodiment 1, the removal of the polymer was mainly oxalic acid added to the ozone water washing tank 12, but it can also be sprayed in the washing pot 1.

The lid of the cleaning pot 1 shown in FIG. 1 was opened, and 52 Φ8 inch Si substrates 7 were set up at half pitch. The lid is closed again, the Si substrate 7 is cut off from the outside air, and the inert gas (N2) 19 is exhausted from the exhaust 10 while flowing at a rate of 2 L / min. While operating the irradiation device 6, the Si substrate 7 is
Heated to ° C. This time, the ultraviolet irradiation device 6 is a high-pressure mercury lamp 3
I use a book.

After the temperature of the Si substrate 7 is stabilized at 120 ° C., while the high-pressure mercury lamp is kept on, oxalic acid 0.01
The wt% solution was sprayed from 4b at 50 mL / min for 1 minute. Subsequently, an ozone gas 5c having an ozone gas concentration of 325 to 360 g / Nm3 is generated by the ozone gas generator 5a, and the flow rate is 1 L / min and 90% through the ozone gas supply pipe 5b.
RH steam 2c was generated in 2a and supplied to the washing tank 1 at 50 mL / min through a steam supply pipe 2b. At this time,
The exhaust 10 is squeezed, and the inside of the washing pot 1 is pressurized to 2.5 atm.
After holding for 10 minutes as it is, treating the Si substrate, then supplying ozone gas 5c and water vapor 2c, stopping the washing pot heating device 9 and flowing the inert gas 19 into the washing pot 1 at 2 L / min for 1 minute to replace the same. Rested for 1 minute. At this time, the ultraviolet irradiation device 6 was turned on to decompose the residual ozone gas. Further, the substrate temperature was lowered to 40 ° C., and the substrate was taken out. The lid of the cleaning pot 1 was opened, and the Si substrate 7 was taken out. At this time,
Although the anti-reflection film (Barc) and the KrF excimer resist were almost removed from the Si substrate 7, some of the remaining residue was present. However, unlike Example 1, no polymer remained, and the polymer was completely removed by spraying with oxalic acid.

Next, acetic acid 0.0
The 52 Si substrates 7 were immersed in an ozone water cleaning tank 12 filled with 100 ppm ozone water to which 1 wt% was added, while maintaining a half pitch. Subsequently, the cover 12a is closed, and the ozone gas concentration 325 to 360 is
The ozone gas 5c of g / Nm3 was bubbled, and the lid on the surface of the ozone water was filled with high-concentration ozone gas. As a result, the rate of ozone gas desorption from ozone water can be greatly reduced, and the ozone concentration can be maintained at a higher level than in Example 1 by adding a scavenger of acetic acid. Hold for 10 minutes as it is, and then transfer to rinse tank 16a.
The i-substrate 7 was transferred, rinsed for 10 minutes, and finally dried by the drier 17.

As a result of observing the processed substrate 7 with an SEM, the resist and the Barc residue remaining when the substrate 7 was taken out by the cleaning pot 1 were completely removed. In the hole cross-section observation, no damage was observed on the hole (interlayer film) itself, but corrosion was observed on the Al wiring at the bottom of the hole.

(Example 3)
The temperature of the Si substrate 7 in the cleaning vessel 1
℃, 40 ℃, room temperature, and the same experiment was carried out, the resist was 6000 A / min at 120 ℃, and Ba
The rc removal rates were 4700 A / min and 3200 A, respectively.
/ Min, 2200 A / min. At a temperature of 40 ° C. or lower, non-uniformity of the substrate processing due to condensation of water vapor was observed. However, although the removability of the polymer was not enough at room temperature, 4
It was good at 0 ° C., and there was no corrosion of Al at all. Therefore, it was found that the removal of the resist and Barc by ozone gas / water vapor was good at high temperature, but the removal of polymer by oxalic acid (considering Al corrosion) was good at 40 ° C.

(Embodiment 4) Embodiment 4 is different from Embodiment 1 in that the pressurizing of the cleaning pot 1 is not performed. When treated at normal pressure, the removal rate was 35 ° C at 120 ° C.
It dropped to 00 A / min. Also, if you do not pressurize,
Power for heating the cleaning pot 1 and the Si substrate 7 (the cleaning pot heating device 9
, Etc.). Pressurization was found to be effective in promoting removal and reducing energy.

(Embodiment 5) Embodiment 5 differs from Embodiment 1 in the ultraviolet irradiation lamp. In this case, when a low-pressure mercury lamp having the same output was used, the removability of the resist and Barc became very poor (removal rate 500 A / min) and became non-uniform.
Only the portion near the lamp had a removal rate of 5000 A / min. This is probably because the low wavelength was absorbed by ozone gas or water vapor.

(Embodiment 6) Embodiment 6 is different from Embodiment 1 in that the high-pressure mercury lamp is turned off at the same time when the processing in the washing pot 1 in Embodiment 1 is completed (supply of ozone gas and water vapor is stopped, and the washing pot heating device is stopped). . In Example 1, the ozone gas could be decomposed in one minute by the replacement of the inert gas and in one minute of quiescence, but in this example, the replacement of the inert gas for 10 minutes or more was required. From this, it was found that the throughput can be improved by effectively using the ultraviolet irradiation.

(Embodiment 7) Embodiment 7 of the present invention relates to Embodiment 1.
Ozone water concentration in the ozone water cleaning tank 12 at 80 p
pm, 60 ppm, 40 ppm, and 0 ppm. At this time, the remaining resist, barc, and polymer remaining up to 80 to 40 ppm were completely removed in the same manner as 100 ppm by the treatment for 10 minutes. However, 0 ppm had a slight residual, indicating that ozone water was necessary for post-treatment of the washing tank.

(Embodiment 8) In the semiconductor process, there are many processes in which adhesion of a polymer is small. The third step and the fourth step could be omitted for the implant resist. Example 8 will be described below.

The object 7 to be cleaned for removing the thin film is a Si substrate used in a semiconductor process, and As is applied to the resist surface by 1E.
Those implanted at the concentrations of 13, 1E14 and 1E15 were evaluated for peeling.

The lid of the cleaning pot 1 shown in FIG. 1 was opened, and 52 Φ8 inch Si substrates 7 were set up at a half pitch. The lid is closed again, the Si substrate 7 is cut off from the outside air, and the inert gas (N2) 19 is exhausted from the exhaust 10 while flowing at a rate of 2 L / min. While operating the irradiation device 6, the Si substrate 7 is
Heated to ° C. This time, the ultraviolet irradiation device 6 is a high-pressure mercury lamp 3
I use a book.

After the temperature of the Si substrate 7 is stabilized at 120 ° C., the ozone gas
The ozone gas 5c of 25 to 360 g / Nm3 is generated by the ozone gas generator 5a, the flow rate is 1 L / min through the ozone gas supply pipe 5b, and the steam 2c of 90% RH is generated by 2a and the flow rate is 50 mL / min through the steam supply pipe 2b. In minutes. At this time, the exhaust 10 was throttled, and
The inside is pressurized to 2.5 atm and kept as it is for 10 minutes.
The substrate was processed, and then the supply of ozone gas 5c and water vapor 2c, the cleaning device 9 was stopped, and the inert gas 19 was supplied at 2 L /
After 1 minute, it was flown into the washing tank 1 for 1 minute to replace the container, and then left still for 1 minute. At this time, the ultraviolet irradiation device 6 is lit,
The remaining ozone gas was decomposed. Further, the substrate temperature was lowered to 40 ° C., and the substrate was taken out. Open the lid of the cleaning pot 1 and remove the Si substrate 7
Was taken out. At this time, most of the resist remained.

Next, 52 Si substrates 7 were immersed in an ozone water cleaning tank 12 filled with 100 ppm ozone water to which nothing was added while maintaining a half pitch. Subsequently, the lid 12a is closed, and the ozone gas
The ozone gas 5c of 25 to 360 g / Nm3 was bubbled to fill the lid on the surface of the ozone water with high-concentration ozone gas. As a result, the rate of ozone gas desorption from ozone water could be reduced. This is maintained for 10 minutes, then the Si substrate 7 is transferred to the rinsing tank 16a, and rinsed for 10 minutes.
Finally, it was dried in the dryer 17.

As a result of observing the processed substrate 7 with an SEM, the resist remaining when the substrate 7 was taken out by the cleaning pot 1 was completely removed for all concentrations of 1E13, 1E14 and 1E15.

[0072]

According to the present invention, a more efficient cleaning process can be selected by preparing a recipe according to the type and state of a thin film, and all the thin films can be removed by one apparatus. Can be. In addition, since the structure and operation are performed as described above, the thin film on the surface of the object to be cleaned is quickly and uniformly removed. The apparatus and method according to the present invention can be used, for example, in a manufacturing process of a semiconductor device, a liquid crystal device, and an electronic device, for example, by removing an ion implantation resist after an ion implantation process, or by a conventional technique such as plasma ashing, SPM processing, and organic peeling. It is an alternative.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a configuration of an apparatus used to carry out a method for removing a thin film from a surface to be cleaned according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Washing pot 2a Steam generator 2b Steam supply line 2c Pure water or ultrapure water 3 Steam generator heating device 4a Chemical solution supply device 4b Chemical solution supply line 4c Supply chemical solution 5a Ozone gas generator 5b Ozone gas supply line 5c Ozone gas supply 6 Ultraviolet irradiation device 7 Object to be cleaned 8 Cassette 9 Cleaning room heating device 10 Exhaust 11 Drain 12 Ozone water cleaning tank 12a Ozone water cleaning device lid 13a Ozone water production device 13b Ozone water supply line 13c Ozone water circulation line 13d Ozone water drain 14 Switching valve 15a Chemical solution supply device 15b Chemical solution supply line 16a Rinse tank 16b Ultrapure water 17 Dryer 18 Ozone gas bubbler 19 Inert gas

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/304 645 H01L 21/304 645D 645B 647 647A (72) Inventor Toshitaka Nakajima 3-chome, Yamato, Suwa-shi, Nagano Prefecture No. 3-5 Seiko Epson Corporation (72) Inventor Takeshi Sunagawa 3-3-5 Yamato Suwa-shi, Nagano Prefecture Seiko Epson Corporation (72) Inventor Hironori Suzuki 3-35 Yamato Suwa-shi, Nagano Prefecture Seiko Epson Corporation (72) Inventor Mafumi Muramatsu 3-3-5 Yamato, Suwa City, Nagano Prefecture Seiko Epson Corporation F Term (Reference) 3B116 AA03 AB01 AB44 BB02 BB82 BB89 BC01 CC01 CC03 CC05 CD11 3B201 AA03 AB01 AB44 BB02 BB13 BB82 BB89 BB92 BB93 BB96 BC01 CB15 CC01 CC11 CC21 CD11

Claims (31)

[Claims] 1. An ozone gas and a water vapor are supplied while irradiating a surface of a substrate to be treated with an ultraviolet ray.
A thin film peeling method, comprising a step of peeling a thin film from a substrate surface. 2. A first step of supplying an ozone gas and / or water vapor while irradiating an ultraviolet ray to a surface of a substrate to be treated, thereby removing a thin film from the substrate surface, and applying ozone water or pure water to the substrate surface. A second step of washing with
In this order. 3. The method for stripping a thin film according to claim 1, wherein ultraviolet light having a wavelength of 180 nm to 400 nm is irradiated. 4. The thin film peeling method according to claim 2, further comprising a third step of spraying a first chemical solution onto the substrate surface before or after the first step. . 5. The thin film peeling method according to claim 2, further comprising a fourth step of cleaning the substrate surface with a second chemical between the first step and the second step. Thin film peeling method. 6. The thin film peeling method according to claim 4, further comprising a fourth step of cleaning the substrate surface with a second chemical between the first step and the second step. Thin film peeling method. 7. The thin film peeling method according to claim 4, wherein the first step and / or the third step are performed while the substrate is heated to a temperature of room temperature or higher and 250 ° C. or lower. Thin film peeling method. 8. The method according to claim 7, wherein the temperature is 40 ° C. or higher. 9. The thin film peeling method according to claim 4, 6, 7, or 8, wherein the first step and / or the third step includes:
A thin film peeling method, wherein the method is performed in a state where the substrate is isolated from the outside air. 10. The method for stripping a thin film according to claim 9, wherein the first step and / or the third step is performed at a pressure of not less than 1 atm.
A method of peeling a thin film, wherein the method is performed in a pressure atmosphere of not more than an atmospheric pressure. 11. The thin film peeling method according to claim 4, wherein the first chemical solution or the second chemical solution is an aliphatic polycarboxylic acid and a salt thereof, and an aminopolycarboxylic acid and a salt thereof. A thin film peeling method comprising at least one or two or more chemical solutions selected from the group consisting of: 12. The thin film peeling method according to claim 11, wherein the concentration of the first chemical solution or the second chemical solution is 0.0.
A thin film peeling method characterized by being in the range of 01 to 10 wt%. 13. The method for removing a thin film according to claim 2, wherein the ozone water includes a carboxylic acid, an aliphatic polycarboxylic acid and a salt thereof, and an aminopolycarboxylic acid and a salt thereof. A thin film peeling method comprising at least one kind or two or more kinds of chemicals selected from the group consisting of: 14. The thin film peeling method according to claim 13, wherein the concentration of the chemical contained in the ozone water is 0.0
A thin film peeling method characterized in that the amount is from 01 to 1 wt%. 15. The method for removing a thin film according to claim 9, wherein after the first step is performed, in the step of taking out the substrate to the outside air, the used ozone gas is detoxified by ultraviolet rays to render it harmless. A thin film peeling method characterized by the above-mentioned. 16. The thin film peeling method according to claim 2, wherein the temperature of the ozone water is room temperature,
And a method of peeling a thin film, wherein the concentration of ozone contained in the ozone water is 60 ppm or more. 17. The thin film peeling method according to claim 16, wherein the ozone water contains 0.001 to 1 wt% of acetic acid. 18. A thin film peeling apparatus capable of peeling a thin film from a substrate surface, wherein the sealed cleaning pot for processing a substrate to be processed, wherein the substrate can be shielded from outside air.
The substrate can be taken in and out, the substrate can be heated above room temperature,
A sealed washing pot capable of supplying water vapor, ozone gas and / or chemical fog to the substrate, and capable of irradiating the substrate with ultraviolet light;
A thin film peeling device comprising at least one washing tank. 19. The thin film peeling apparatus according to claim 18, further comprising a substrate holding mechanism that enables a batch processing mode capable of simultaneously processing a plurality of substrates. 20. The thin film peeling apparatus according to claim 18, wherein the ultraviolet irradiation means includes at least one high-pressure mercury lamp. 21. The thin film stripping apparatus according to claim 18, wherein an ozone water producing apparatus capable of supplying room temperature ozone water in which 1 to 120 ppm of ozone gas is dissolved is connected to the cleaning tank. A thin film peeling device characterized by the above-mentioned. 22. The thin film peeling apparatus according to claim 21, further comprising a circulation device for circulating ozone water in the cleaning tank. 23. The thin film peeling apparatus according to claim 18, wherein the cleaning tank includes at least one member selected from the group consisting of aliphatic polycarboxylic acids and salts thereof and aminopolycarboxylic acids and salts thereof. A thin film peeling device, which is provided with a chemical solution supply device capable of supplying an aqueous solution to which more than two types of chemical solutions are added. 24. The thin-film stripping apparatus according to claim 21, further comprising a sealing device for sealing the cleaning tank. 25. The thin-film stripping apparatus according to claim 21, further comprising a bubbling apparatus for bubbling ozone gas into the cleaning tank. 26. The thin film stripping apparatus according to claim 18, wherein the cleaning tank includes a cleaning tank using ozone water,
At least one selected from the group consisting of aliphatic polycarboxylic acids and salts thereof and aminopolycarboxylic acids and salts thereof
A thin film peeling apparatus, comprising: a cleaning tank using one or more kinds of chemical solutions. 27. The thin film peeling apparatus according to claim 18, wherein an inner surface of the closed washing pot is
A thin film peeling device, which has been subjected to a surface treatment for efficiently reflecting ultraviolet light. 28. The thin film peeling apparatus according to claim 27, wherein an inner surface of the closed cleaning pot is subjected to a mirror surface treatment for efficiently reflecting ultraviolet rays. 29. The thin-film stripping apparatus according to claim 18, wherein the hermetic washing tank has a nozzle for spraying ozone gas and water vapor from the same nozzle. apparatus. 30. The thin film peeling apparatus according to claim 18, further comprising a pressurizing means for pressurizing the closed washing pot. 31. A method for manufacturing an electronic device, comprising a step of peeling a thin film formed on a substrate surface by the thin film peeling method according to any one of claims 1 to 17.