JP2001252631A - Surface cleaning device and surface cleaning method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To regulate the cleanliness of the surface of a work, such as a substrate, to 10-6 to 10-7 molecular layer or less by 'finely cleaning' the surface of the work to a molecular and atomic level. SOLUTION: At least one among steam of high purity and high chemical function, steam containing chemical components of a medicinal liquid and steam containing gas is supplied from a steam introducing port 31, a ejection nozzle 32 and a gas injection nozzle 33 to the surface of the substrate 11 installed within a chamber 10, by which the surface is cleaned. In succession, the surface is subjected to drying to prevent the remaining of water marks on the surface by using the steam described above.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface cleaning apparatus and a surface cleaning method, and more particularly to a "surface purification technology using high-purity and high-performance water vapor" applied to an industrial field in which the function of a product is influenced by a surface cleaning step. And environmental measures technology.

[0002] The major industrial fields are, for example, various electronic industries such as semiconductor device / liquid crystal display device manufacturing, printed circuit board manufacturing, and magnetic disk manufacturing. The present invention promotes “harmony between technology and the environment” by a new surface purification technology using water vapor.

[0003] The present invention contributes to "harmony between technology and the environment" by "technology using 1700 liters of high purity and high chemical function steam generated from 1 liter of water".

[0004]

2. Description of the Related Art Surface cleaning technology in the field of electronics industry includes:
It mainly uses a large-sized apparatus called a wet cleaning system, and relies on multi-step processing using a large amount of ultrapure water and various types of chemicals. As a technology to innovate this, a cleaning technology using a single wafer cleaning system is also being promoted.

However, these cleaning techniques have a heavy burden on the installation area of the cleaning process and a heavy burden on ultrapure water / chemical solution consumption. They have problems that cannot keep up with the progress of product performance.

The "fluid jet method" is a commonly used cleaning technique in the general industrial field. High pressure gas
Liquid fluid or fine particle fluid (ice particles / abrasive particles)
Cleaning-surface peeling-surface polishing is possible by the jet flow, and it is often used when a large-scale on-site cleaning is required such as an aircraft or a vehicle.

[0007] Cleaning methods for spraying steam are also well known.
It is widely used not only in the industrial field but also in the medical and food fields and household cleaning. However, as will be described later, there is a great difference between the cleaning level in this field and the required level in the electronics industry.

[0008]

1. Problems of Surface Cleaning Means Conventional surface cleaning techniques are classified into two cleaning means. Gas cleaning: Also called dry cleaning, a reactive gas, an oxidizing gas, or the like is used. Liquid cleaning: Also called wet cleaning, acid-alkali
Use oxidizing agents, organic solvents, etc.

The present inventors propose a new concept of “purification”. This is because the required level of cleanliness in a field where the function of a product depends on the surface is different from the conventional level of “cleaning” or “cleaning”.

The present inventors propose a new means of "water vapor purification" which is neither "gas cleaning" nor "liquid cleaning".

Steam is inherently pure in the same sense that distilled water is pure. "Purification technology using 1,700 liters of high-purity and high-chemical-performance steam generated from 1 liter of water" is a breakthrough from wastewater problems and a breakthrough from resource- and energy-intensive technologies, that is, realization of environmentally friendly purification technologies. is there.

An object of the present invention is to provide a surface purification apparatus and a surface purification method for purifying the surface of an object to be treated, particularly by using steam or the like having high purity and high chemical function.

Although it does not depend on energy, chemical materials or organic solvents, it utilizes surface purification by the physicochemical action of water vapor.

"Steam 170 generated from one liter of water
The “water vapor removal technology using 0 liters” is a departure from the resource and energy intensive technology, that is, the realization of an environmentally friendly resist film removal technology.

2. Issues of Surface Purification Level Manufacturing processes in the electronics industry are different from other fields in that they are surface processing processes. And there is a technical feature that the surface purification technology affects the performance of the product. This is a special field in which the level of purification of all surfaces, such as the surfaces of process equipment and process equipment components, as well as the process surfaces from substrates to products, becomes increasingly severe with the development of technology generations.

The present inventors have distinguished between "cleaning-" and "purification-". This is because the level of cleaning required for general cleaning is completely different from the level of cleaning required for the electronics industry. Table 1 shows the differences in surface cleanliness levels.

[0017]

[Table 1]

Cleaning is a technique that reaches a “level” from a “level”. For example, on a metal material surface, the roughness of the mechanically polished surface is several tens of μm, and the amount of machining oil is several mg /
It adheres to the level of cm ² . Even when the surface roughness is reduced to about 10 μm by the chemically polished surface, 1 mg / cm ²
Attached to the level. About 3 departures from "level"
If the girder contamination is removed and the "level" is reached, the cleaning objective has been achieved. In the general industrial field, there is no problem in considering this surface to be clean.

On the other hand, in the electronics industry, "level" is the starting point. The presence of several molecular layers of contaminant molecules means that molecules and atoms of the substrate do not exist on the surface, and loses the meaning of making the surface function. Purification is a technology that reaches the "level." This is a technology that reduces pollution by about three orders of magnitude from the “level” and reaches the “level”.

[0020] Nevertheless, depending on the type of contaminant molecules, problems still remain in the surface operation mechanism. For example, super LSI
For the surface of the semiconductor substrate of the next generation, a “level” (10 ⁻⁶ to 10 ⁻⁷ molecular layer) that is about four orders of magnitude lower than the “level” is required.

An object of the present invention is to provide a surface cleaning apparatus and a surface cleaning method that "cleans" the surface to the molecular and atomic level and reduces the surface cleanliness to 10 ^-6 to 10 ^-7 molecular layers or less. It is in.

In the present specification, molecules on the surface
Atomic level “Precise Cleaning-”
-Purification- ”.

3. Issues of Purification Apparatus The present inventors have studied the following issues to configure a surface cleaning apparatus. (1) Basic configuration of the system The configuration of the purification system that treats the surface with water vapor of high purity and high chemical function. (2) Mode of Control of Purification Function Slit etching function of the surface, water mark control function during surface drying, and steam purity control function. (3) Material of the system Material of the chemical corrosion resistance required to generate high-purity steam. (4) Contents of ancillary systems Systematization of physicochemical actions that assists or enhances the steam purification function.

[0024]

Means for Solving the Problems As a result of intensive studies, the present inventors have reached the following aspects of the invention.

The surface cleaning apparatus of the present invention comprises a chemical corrosion-resistant water / chemical / gas supply system for supplying a predetermined amount of water, at least one of a chemical and a gas, respectively, A chemical-corrosion-resistant water vapor supply system for supplying a predetermined amount to the object to be processed, and a substrate moving system on which the object to be processed is installed and which moves the same, steam of high purity and high chemical function, and chemical components of the chemical solution And at least one of water vapor containing the gas is supplied to the object to purify the surface of the object to be processed, and subsequently, the surface of the object is marked with a watermark by using the water vapor. It is characterized by performing drying that does not remain.

One aspect of the surface cleaning apparatus of the present invention includes a high-frequency ultrasonic irradiation mechanism for irradiating high-frequency ultrasonic waves and an ultraviolet irradiation mechanism for irradiating ultraviolet rays.

In one embodiment of the surface cleaning apparatus of the present invention,
The water / chemical liquid / gas supply system supplies pure water to a passage forming body, and the water vapor supply system includes a chemical corrosion resistant and heat conductive passage forming body, an internal pressure control structure, and the passage forming body. It has a surrounding heating body, and supplies pure water vapor of high purity and high chemical function to the surface of the processing object to perform the purification and the drying.

In one embodiment of the surface cleaning apparatus of the present invention,
The water / chemical liquid / gas supply system supplies pure water and the chemical liquid to a passage forming body, respectively, and the water vapor supply system is a chemical corrosion resistant and heat conductive passage forming body, an internal pressure control structure, and A heating element surrounding the passage forming member is provided, and the purification and the drying are performed by supplying a steam containing a chemical component to the surface of the object to be processed.

In one embodiment of the surface cleaning apparatus of the present invention,
The water / chemical liquid / gas supply system supplies pure water and the chemical liquid to a passage forming body, respectively, and the steam supply system comprises a chemical corrosion resistant and heat conductive passage forming body, an internal pressure control structure, and the passage. A heating element surrounding the formed body is provided, and the cleaning and drying are performed by mixing and supplying a chemical component-containing heating chemical solution to the surface of the object to be processed together with the chemical component-containing water vapor.

In one embodiment of the surface cleaning apparatus of the present invention,
The water / chemical / gas supply system supplies pure water to the passage forming body and supplies the gas, and the water vapor supply system comprises a chemical corrosion resistant and heat conductive passage forming body, an internal pressure control structure. And a heating element surrounding the passage forming body, and supplying the gas to the surface of the object to be processed in a mixed or combined use with the steam at room temperature or in a heated state to perform the purification and the drying. Do.

In one aspect of the surface cleaning apparatus of the present invention, the steam supply system has a steam injection mechanism, and the operation of the high-frequency ultrasonic irradiation mechanism and the operation of the ultraviolet irradiation mechanism are superimposed on the operation of the steam injection mechanism. Then, the washing is performed.

The surface cleaning apparatus of the present invention includes a chamber having a substrate loading / unloading mechanism and an atmosphere discharging / introducing mechanism.
The chamber is provided with a chemical corrosion-resistant water, which supplies a predetermined amount of water and at least one of a chemical solution and a gas.
A chemical liquid / gas supply system and a chemical corrosion resistant water vapor supply system for supplying a predetermined amount of water vapor generated from the water to the substrate surface are connected, and high purity and high chemical function water vapor, chemical components of the chemical liquid are connected. And at least one of water vapor containing the gas is supplied to the surface of the substrate installed in the chamber to purify the surface, and then water is applied to the surface using the water vapor. It is characterized in that drying is performed without leaving any marks.

In one embodiment of the surface cleaning apparatus of the present invention,
The chamber has a drive mechanism in which an ejection surface is swept by moving a water vapor ejection nozzle relative to the substrate surface, and the water / chemical liquid / gas supply system includes:
A gas injection mechanism for injecting the gas onto the substrate surface;

One embodiment of the surface cleaning apparatus of the present invention includes a high-frequency ultrasonic irradiation mechanism for irradiating high-frequency ultrasonic waves and an ultraviolet irradiation mechanism for irradiating ultraviolet rays.

One aspect of the surface cleaning apparatus of the present invention is to adjust the three conditions of the internal pressure defined by the internal pressure control structure, the amount of heat supplied to the heating element, and the amount of pure water or chemical solution in a correlated manner. And a mechanism for controlling the steam temperature, the steam pressure, the steam saturation, and the amount of generated steam, and controls the slide etching rate and the slide etching amount of the surface constituting material.

One embodiment of the surface cleaning apparatus of the present invention has a mechanism for controlling the degree of saturation of pure water vapor and the degree of mixing of the heated gas, and controls the watermark on the dry surface.

In one embodiment of the surface cleaning apparatus of the present invention,
The mode of sweeping the jet surface of the steam jet nozzle is a combination of a fixing mechanism and a driving mechanism, the nozzle shape is a combination of a spot nozzle and a line nozzle, the jet angle is variable, and the jet distance is adjustable. .

In one embodiment of the surface cleaning apparatus of the present invention,
The chamber has a heat retaining structure and a heating structure,
This is a mechanism in which the steam introduction temperature and the substrate temperature are stabilized during processing.

In one embodiment of the surface cleaning apparatus of the present invention,
The passage forming member is made of a chemical corrosion resistant material having a thermal conductivity of ¹ Wm ^-1 K ^-1 or more, or a surface of the chemical corrosion resistant material.

In one embodiment of the surface cleaning apparatus of the present invention,
The high-frequency ultrasonic irradiation mechanism has a high-frequency ultrasonic oscillator that oscillates an ultrasonic wave having a frequency of 1 megacycle or more.

In one embodiment of the surface cleaning apparatus of the present invention,
The ultraviolet irradiation mechanism has a function of 5 for water vapor, nitrogen and air.
It has an ultraviolet lamp for irradiating ultraviolet rays having a wavelength whose 0% transmission distance is 2 mm or more.

In one embodiment of the surface cleaning apparatus of the present invention,
The steam supply system has a passage forming body made of a material having chemical corrosion resistance and heat conductivity, and supplies steam having high purity and high chemical function.

According to the surface cleaning method of the present invention, at least one of steam having high purity and high chemical function, steam containing a chemical component of the chemical solution, and steam containing the gas is supplied to the object. Cleaning the surface of the object to be processed, and drying the surface of the object using the water vapor without leaving a watermark.

[0044]

DESCRIPTION OF THE PREFERRED EMBODIMENTS 1. Content of Apparatus Configuration FIG. 1 illustrates a single-wafer type surface steam purification apparatus according to this embodiment.

Single wafer type steam purification chamber: The steam purification chamber has a heat retaining structure and a heating structure, and has a mechanism 10 having a mechanism for stabilizing the steam introduction temperature and the substrate temperature during processing, a mechanism 12 for carrying in and out the substrate 11, and a substrate. support·
The rotating mechanism 13 includes a substrate driving mechanism 14 that sweeps an ejection surface by relatively moving a water vapor ejection nozzle 32 described later, an atmosphere gas introduction mechanism 15, and an exhaust / drainage mechanism 16. Here, the substrate carrying-in / out mechanism 12, the substrate supporting / rotating mechanism 13, and the substrate driving mechanism 14 constitute a substrate moving system.

The steam / gas supply mechanism 20 includes a pure water steam supply system 21 and a chemical component-containing steam supply system 2.
2. A gas supply system 23 and a chemical component-containing solution supply system 26 whose details are omitted. The ultrapure water pump 2 serves as a quantitative supply pump 25 for ultrapure water and a chemical solution.
51 and a chemical liquid pump 252. The chemical component-containing solution supply system 26 can directly mix the chemical component of the chemical solution into the pure water vapor using the pure water vapor supply system 21.

The gas supply system 23 includes the gas cylinder 2
4. It has a heating element 34 and a mixing control mechanism 35, and supplies the gas in a state of being mixed or used in combination with steam at room temperature or in a heated state. The mixing control mechanism 35 is a mechanism that operates when mixing a gas with water vapor.

The pure water steam supply system 21, the chemical component-containing steam supply system 22, and the chemical component-containing solution supply system 26 constitute a chemical corrosion resistant steam supply system. A system for supplying ultrapure water to a pure water steam supply system 21, a system for supplying a chemical solution to a chemical component-containing steam supply system 22, and a gas supply system 23 constitute a chemical / corrosion resistant water / chemical solution / gas supply system. You.

Water vapor and gas introduction mechanism: A water vapor and gas introduction mechanism 30 supplies a water vapor to make contact with the surface of the substrate 11, a water vapor injection nozzle 32 that injects water vapor to the surface of the substrate 11, A gas jet nozzle 33 for jetting to the surface of the substrate 11 is provided. Here, the water vapor inlet 31 and the water vapor injection nozzle 32 constitute a part of a water vapor supply system, and the gas injection nozzle 33 has water, a chemical,
Form a part of the gas supply system. The mode of sweeping the jet surface of the steam jet nozzle 32 is a combination of a fixed mechanism and a driving mechanism, the nozzle shape is a combination of a spot nozzle and a line nozzle, the jet angle is variable, and the jet distance is adjustable. ing.

Heating control system: Heating control system 40
Controls the temperature of the heating element 41 divided by the internal pressure control mechanism (internal pressure control structure) 42. These constitute a part of the steam supply system, and the heating body 41 surrounds the passage forming body having chemical corrosion resistance and heat conductivity. With this heating control system 40,
The ultrapure water and the chemical solution passing through the passage forming body are heated and adjusted to produce desired steam.

Here, the steam temperature, steam pressure, steam pressure, and steam pressure are adjusted by correlating the three conditions of the internal pressure defined by the internal pressure control mechanism 42, the amount of heat supplied to the heater 41, and the amount of pure water or chemical solution supplied. It has a mechanism (not shown) for controlling the degree of saturation and the amount of generated water vapor, and controls the speed and amount of slight etching of the surface constituent material.

Further, the mixing control mechanism 35 has a function of controlling the degree of saturation of pure water vapor and the degree of mixing of the gas heated by the heating element 34, and controls the watermark on the surface of the substrate 11 when drying. I do.

High-frequency ultrasonic irradiation mechanism: The high-frequency ultrasonic irradiation mechanism 50 has a high-frequency ultrasonic oscillator that oscillates ultrasonic waves having a frequency of 1 megacycle or more, and has an ultrasonic irradiation nozzle 51.

Ultraviolet irradiation mechanism: The ultraviolet irradiation mechanism 60
Ultraviolet light is applied to the substrate surface from an ultraviolet lamp 62 inside an ultraviolet lamp house 61 through an ultraviolet window plate 63. UV lamp 62 is 50% of water vapor, nitrogen and air
It irradiates ultraviolet rays having a wavelength of 2 mm or more in transmission distance.

[0055]

EXAMPLES (Example 1) Specific device configuration example Hereinafter, a device configuration example using a chemical corrosion resistant material will be described. Table 2
Then, a passage forming body was formed using a chemical corrosion-resistant material having a thermal conductivity of ¹ Wm ^-1 K ^-1 or more. Capillary resistor has thermal conductivity of 1Wm
^Although a chemical corrosion resistant material of ^-1 K ^-1 or less may be used, the table lists the same material as the passage forming body. An apparatus using amorphous carbon, alumina and silicon carbide has chemical corrosion resistance to all of acids, alkalis, oxidizing agents and organic solvents. Stainless steel can be used for organic solvents, and there is a concentration range applicable to weak alkalis. Cannot be used for acids and oxidizing agents. When forming a fluorinated non-conductive film or an oxidized non-conductive film on the stainless steel surface,
The applicable concentration range for acids, alkalis and oxidizing agents can be expanded. Quartz glass is not applicable to alkalis, but can be used in other cases.

[0056]

[Table 2]

Example 2 Saturated Steam / Superheated Steam Saturated steam or superheated steam was supplied using an electric resistance heater. Table 3 shows an example of control conditions in the following supply mode. Saturated steam: 100 to 160 at an internal pressure of 1 to 6 kg / cm ²
Superheated steam: 100 ° C saturation at an internal pressure of 1 kg / cm ² , 12
Supply of superheated steam at 0 to 160 ° C. As exemplified, it is possible to supply steam having an arbitrary degree of saturation to superheat by controlling the internal pressure.

[0058]

[Table 3]

(Third Embodiment) Internal Pressure Control An embodiment using a thin-tube resistor as a structure for internal pressure control will be described. The pressure loss in the capillary passage is determined by the amount of water vapor and the shape of the capillary resistor. Table 4 exemplifies the pressure loss of the passage forming body and the pressure inside the passage forming body depending on the inner diameter and length of the thin tube, and the steam temperature defined thereby.

[0060]

[Table 4]

Example 4 Chemical Component-Containing Steam The component concentration of chemical component-containing steam supplied using the chemical solution quantitative supply system shown in FIG. 1 was evaluated. A condenser was installed at the steam outlet of the steam supply device to collect a condensate, and the component content concentration was measured. Table 5 compares the chemical component concentrations in the drug substance solution supplied to the metering pump and the condensate. The concentrations of both are always completely identical. In the instantaneous evaporation process in the passage forming body, there can be no transition process from concentration to evaporation to vaporization of the chemical components, and steam having the component content ratio as it is in the drug substance solution can be obtained.

[0062]

[Table 5]

Example 5 Water Vapor Purity / Chemical Corrosion Resistant Material The purity of pure water vapor and water vapor containing a chemical component was evaluated when a chemical corrosion resistant material was used as an apparatus constituent material. A condenser was installed at the steam outlet of the steam supply device to collect a condensate, and impurities were measured by an ICP-mass spectrometer. The ultrapure water and the high-purity chemical used have an impurity concentration of ppb or less. Fluoric acid, potassium hydroxide, and hydrogen peroxide were used as representatives of the acid, alkali, and oxidizing agent. Table 6
Shows the evaluation results. The impurity concentrations in the pure water steam condensate and the chemical component-containing steam condensate are below the ppb level.

[0064]

[Table 6]

Example 6 Gas Mixing A mixed gas of steam and nitrogen gas was supplied using a steam supply device having a gas quantitative supply system shown in FIG. Table 7
An example of mixing and supplying steam and nitrogen gas is shown below.

This is an example in which the internal pressure, supply pressure and supply temperature of steam and nitrogen gas are the same, and the mixing ratio is 1: 1. This gas mixture has a low steam saturation like superheated steam, and has the effect of a dry gas containing steam.

The mixing ratio is arbitrary, and there is an effect that the amount of water vapor is easily expanded by increasing the mixing ratio of the nitrogen gas. The mixing temperature is also arbitrary, and has an effect of easily increasing the steam temperature by the nitrogen gas temperature. In addition, a supply mode can be selected in a wide range, such as a mode in which the steam supply device and the gas quantitative supply system are operated in parallel to simultaneously operate on the processing surface, and a mode in which they operate on different portions of the processing surface.

[0068]

[Table 7]

(Example 7) Purification of organic substances Table 8 shows the results of a purification test for purifying organic substances adhering to the silicon wafer surface. After spraying saturated steam at 120 ° C. for 30 seconds, the organic matter was purified to a monomolecular layer or less. 120 ° C
When ultraviolet irradiation was superimposed on the saturated steam treatment, it was removed to a monomolecular layer after 10 seconds and to a level lower than the detection limit of FTIR measurement after 20 seconds.

[0070]

[Table 8]

Example 8 Purification of Particles Table 9 shows the results of a purification test for particles adhering to the surface of a silicon wafer. Alumina particles (particle diameter 0.3 μm to 0.5
[mu] m) or polystyrene particles (particle diameter 0.6 .mu.m) in a solution containing 10 ⁵ / ml, a silicon wafer (diameter 4
Inches) to allow each particle to adhere. On this surface,
Steam treatment and steam / ultraviolet ray superposition treatment were performed.

Particles: Both the alumina particles and the polystyrene particles were purified to a level lower than the detection limit of the wafer inspection device in 20 seconds.

Lift-off action by slide etching; slide etching is a very small amount of surface dissolution. It is well known that lift-off, that is, the action of slightly dissolving the point of particle attachment and lifting the particles off the surface, is effective in separating the particles from the surface. Water is said to be the largest solvent due to its large polarity. Particularly, the action of dissolving high-temperature water is large, and a sufficient lift-off action is exhibited. For example, the solubility of the SiO ₂ to the water, 100 ° C. is about 100 times the normal temperature in (solubility of SiO ₂ in water: 0.013
% (20 ° C), 1.4% (100 ° C)).

The surface of the silicon wafer is usually a natural oxide film S
iO ₂ . Also, various surface structures are made of the thermal oxide film S
It is configured based on iO ₂ . Even on the metal structure surface, the metal surface is naturally oxidized to form an oxide film. The hot water dissolving power acts on these surfaces.

For the above reasons, the dissolving power of high-temperature steam has a strong lift-off action.

UV action: In the case of polystyrene particles,
Purification was significantly shortened by the steam / ultraviolet radiation superimposition treatment. Also, it was recognized that the superheated steam had a greater purification effect. As shown in the comparative example of Table 9, the irradiation effect of polystyrene particles is low in the case of irradiation with ultraviolet light in normal temperature air.
This is because the transmittance of 191 nm ultraviolet rays in the air is not sufficiently large. 191 nm transmits water vapor well. Here, the advantage of the steam atmosphere is revealed.

[0077]

[Table 9]

(Embodiment 9) Elimination of watermark:
The silicon substrate was purified using a single-wafer surface cleaning device and an ultraviolet treatment device. In the purification step 1, organic substances and particles were purified by hydrofluoric acid / hydrogen peroxide-containing steam treatment under KrI excimer ultraviolet irradiation. Purification step 2
Was subjected to hydrofluoric acid-containing steam treatment under KrI excimer ultraviolet irradiation. In the purification step 3, drying by superheated steam treatment was performed.

Table 10 shows the purification results. Organic substances, metals, particles, and water marks were purified below the detection limit.

Solution of Water Mark: Water mark is a difficult problem as a final finishing problem when cleaning the substrate surface. Even if the cleaning is performed with ultrapure water, water droplets remaining on the surface generate water marks, which hinder the fine circuit structure. It is considered that the process of water droplets drying while dissolving a very small amount of the surface is the cause. Superheated steam treatment completely eliminates this problem. Since superheated steam contains no mist, there is no water mark source. This is the most suitable process for final finishing and drying.

[0081]

[Table 10]

Example 10 Purification of Mask Surface The surface of a mask for semiconductor / liquid crystal production (for lithography) was purified.

Glass substrate purification: In step 1, an alkali and a surfactant were used as purification promoting components. Lift-off action of particles by slide etching of glass surface,
The slide etching accelerating action of the alkali was superimposed, and all foreign substances on the surface of the glass substrate were purified. Organic matter was purified by high-temperature steam. In step 2, the surface monolayer-level surfactant-adsorbed layer was cleaned. In step 3, overheating resulted in a clean dry surface.

Blanks purification: Since chromium oxide forming the surface layer of the chromium oxide film has a non-stoichiometric composition, it is etched by high-temperature steam. Therefore, step 1 was omitted, and the surface was slide-etched by the pure water vapor injection in step 2, and all contamination in the sputtering process could be purified.

Mask purification: By the purification only in step 2, the adhesion of the etching solution component (for example, cerium salt solution) in the wet etching step could be purified. By the superposition of the ultraviolet treatment, the residue of the resist in the resist removing step could be purified.

[0086]

[Table 11]

Example 11 Purification of CMP-Treated Surface The surface of a chemical mechanical polishing (CMP) was purified. Table 12
Shows the processing steps, processing contents and processing time.

Oxide film CMP surface: After polishing the alkaline silica slurry, the steam treatment of Step 1 was directly performed without going through a scrubber treatment using a brush. HF-surfactant was used to promote purification.

After step 1, no slurry particles are measured on the surface. After step 2, no surfactant is detected on the surface.

Al-wiring CMP surface: The same treatment as the oxide film CMP surface treatment was performed, except that an alkaline-surfactant was used for the purification promoting solution. Direct processing without scrubber processing. After step 1, no alumina slurry particles remain on the surface. This is due to the jetting power of water vapor, the action of the accelerator, ie, the slide etching action on the oxide film surface, and the zeta potential effect of the oxide film / alumina slurry particles of the surfactant. After step 2, no surfactant is detected on the surface.

Cu-wiring CMP surface: Al-wiring CMP
The same treatment as for the surface was performed. Similarly, a completely clean surface was obtained by the spraying power of water vapor, the slide etching effect, and the zeta potential effect of the surfactant.

[0092]

[Table 12]

[0093]

According to the present invention, the surface of an object to be processed (for example, a wafer) is purified to a molecular and atomic level by purifying the surface of the object to be processed, particularly by using steam having high purity and high chemical function. Fine purification ”and the surface cleanliness is 10 ^-6 to 10 ^-7
It is possible to have a molecular layer or less.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a single wafer type surface steam purification apparatus according to an embodiment.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Chamber 11 Substrate 12 Substrate loading / unloading mechanism 13 Substrate support / rotation mechanism 14 Substrate driving mechanism 15 Atmospheric gas introduction mechanism 16 Exhaust / drainage mechanism 20 Steam / gas supply mechanism 21 Pure water steam supply system 22 Chemical component containing steam supply system 23 Gas supply system 24 Gas cylinder 25 Quantitative supply pump 26 Chemical component-containing solution supply system 30 Gas introduction mechanism 31 Steam introduction port 32 Steam injection nozzle 33 Gas injection nozzle 34 Heating body 35 Mixing control mechanism 40 Heating control system 41 Heating body 42 Internal pressure control Mechanism 50 High-frequency ultrasonic irradiation mechanism 51 Ultrasonic irradiation nozzle 60 Ultraviolet irradiation mechanism 61 Ultraviolet lamp house 62 Ultraviolet lamp 63 Ultraviolet window plate 251 Pump for ultrapure water 252 Pump for chemical liquid

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/304 651 H01L 21/304 651G 651H (72) Inventor Tadahiro Omi Yonega, Aoba-ku, Sendai, Miyagi Prefecture Bag 2-1-17- 301 F term (reference) 3B201 AA03 AB01 AB34 AB42 BA02 BB13 BB21 BB82 BB85 BB90 BB93 BC01 CB21 CC11 CC21

Claims (19)

[Claims] Claims: 1. Water, at least one of a chemical and a gas
Chemical and corrosion-resistant water, chemical solution,
A gas supply system, a chemical-corrosion-resistant water vapor supply system for supplying a predetermined amount of water vapor generated from the water to the object, and a substrate moving system on which the object is installed and which moves the object. Water vapor of high purity and high chemical function, water vapor containing a chemical component of the chemical solution, and water vapor containing the gas, at least one kind is supplied to the object to be treated to purify the surface of the object, Subsequently, the surface is dried by using the water vapor without leaving a watermark. 2. The surface cleaning apparatus according to claim 1, further comprising: a high-frequency ultrasonic irradiation mechanism for irradiating high-frequency ultrasonic waves; and an ultraviolet irradiation mechanism for irradiating ultraviolet rays. 3. The water / chemical / gas supply system supplies pure water to the passage forming body, and the water vapor supply system includes the passage forming body having chemical corrosion resistance and heat conductivity, an internal pressure control structure, and 2. The cleaning device according to claim 1, further comprising a heating body surrounding the passage forming body, wherein the purification and the drying are performed by supplying pure water vapor having a high purity and a high chemical function to the surface of the processing target. 3. Or the surface purification device according to 2. 4. The water / chemical liquid / gas supply system supplies pure water and the chemical liquid to the passage forming body, respectively, and the water vapor supply system includes a chemical corrosion resistant and heat conductive passage forming body, an internal pressure control. 3. The cleaning device according to claim 1, further comprising a heating body surrounding the structure and the passage forming body, wherein the cleaning and the drying are performed by supplying a steam containing a chemical component to the surface of the processing target. 4. A surface purification device according to claim 1. 5. The water / chemical liquid / gas supply system supplies pure water and the chemical liquid to a passage forming body, respectively, and the water vapor supply system supplies the passage forming body having chemical corrosion resistance and heat conductivity, internal pressure control. It has a heating body surrounding the structure and the passage forming body, and performs the purification and the drying by mixing and supplying a chemical component-containing heating chemical solution to the surface of the object to be processed together with the chemical component-containing steam. The surface cleaning device according to claim 1 or 2, wherein 6. The water / chemical liquid / gas supply system supplies pure water to the passage forming body and supplies the gas, and the water vapor supply system comprises a chemical corrosion resistant and heat conductive passage forming body. Having a heating body surrounding the internal pressure control structure and the passage forming body, supplying the gas to the surface of the object to be processed in a mixed or combined use with the water vapor at room temperature or in a heated state. The surface cleaning apparatus according to claim 1, wherein the cleaning is performed and the drying is performed. 7. The steam supply system has a steam injection mechanism, and the operation of the high-frequency ultrasonic irradiation mechanism and the operation of the ultraviolet irradiation mechanism are superimposed on the operation of the steam injection mechanism.
The surface cleaning apparatus according to claim 2, wherein the cleaning is performed. 8. A chamber having a substrate carrying-in / out mechanism and an atmosphere discharging / introducing mechanism, wherein the chamber is provided with a chemical corrosion-resistant water and a predetermined amount of water and at least one of a chemical solution and a gas. A chemical solution / gas supply system is connected to a chemical corrosion resistant steam supply system that supplies a predetermined amount of water vapor generated from the water to the substrate surface, and high purity and high chemical function water vapor, chemical components of the chemical solution are connected. And at least one of water vapor containing the gas is supplied to the surface of the substrate installed in the chamber to purify the surface, and then water is applied to the surface using the water vapor. A single-substrate surface cleaning apparatus characterized by performing drying without leaving marks. 9. The water / chemical liquid / gas supply system according to claim 9, wherein the chamber has a driving mechanism in which an ejection surface is swept by moving a water vapor ejection nozzle relative to the substrate surface. The surface cleaning apparatus according to claim 8, further comprising a gas injection mechanism that injects the gas to a surface. 10. The surface cleaning apparatus according to claim 9, comprising a high-frequency ultrasonic irradiation mechanism for irradiating high-frequency ultrasonic waves, and an ultraviolet irradiation mechanism for irradiating ultraviolet rays. 11. A steam temperature, a steam pressure, a steam saturation, and a steam pressure, a steam pressure, and a steam pressure are adjusted by correlating three conditions of an internal pressure defined by the internal pressure control structure, an amount of heat supplied to a heating body, and an amount of pure water or a chemical solution supplied. The surface purification apparatus according to any one of claims 3 to 6, further comprising a mechanism for controlling a degree and a generation amount of water vapor, and controlling a sly etching rate and a sly etching amount of the surface constituting material. 12. The surface according to claim 3, further comprising a mechanism for controlling a degree of saturation of pure water vapor and a degree of mixing of the gas in a heated state, and controlling a watermark on a dry surface. Steam purifier. 13. The mode of sweeping the jet surface of the steam jet nozzle is a combination of a fixed mechanism and a driving mechanism, the nozzle shape is a combination of a spot nozzle and a line nozzle, the jet angle is variable, and the jet distance is 10. The surface cleaning apparatus according to claim 9, wherein the mechanism is an adjustable mechanism. 14. The surface cleaning apparatus according to claim 8, wherein the chamber has a heat retaining structure and a heating structure, and is a mechanism that stabilizes a steam introduction temperature and a substrate temperature during processing. 15. The passage forming body has a thermal conductivity of 1 Wm.
^-1 surface cleaning apparatus according to any one of claims 3-6, characterized in that K ^-1 is composed of more chemical corrosion resistant material or chemical corrosion resistant material surface. 16. The surface cleaning apparatus according to claim 2, wherein the high-frequency ultrasonic irradiation mechanism has a high-frequency ultrasonic oscillator that oscillates an ultrasonic wave having a frequency of 1 megacycle or more. 17. The surface according to claim 2, wherein the ultraviolet irradiation mechanism includes an ultraviolet lamp that irradiates an ultraviolet ray having a wavelength having a 50% transmission distance of 2 mm or more to water vapor, nitrogen, and air. Purification device. 18. The steam supply system according to claim 1, further comprising a passage forming body made of a material having chemical corrosion resistance and heat conductivity, and supplying steam having high purity and high chemical function. A surface purification device according to claim 1. 19. At least one of steam having high purity and high chemical function, steam containing a chemical component of the chemical solution, and steam containing the gas is supplied to the object to be processed, and A surface cleaning method, comprising: cleaning a surface; and drying the surface of the object using the water vapor without leaving a watermark.