JP2007098357A - Apparatus and method for photochemistry treatment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus and method for a photochemistry treatment which enable the photochemistry treatment with a high throughput by the enhanced activation efficiency of VUV light with a simple equipment set. <P>SOLUTION: The apparatus for the photochemistry treatment comprises a vacuum ultraviolet ray generating source 1, a housing part 3 which houses the vacuum ultraviolet ray generating source 1, and an activated reaction chamber 2 having a gas introducing port 4 and a gas blowing port 5 wherein a reaction gas 7 introduced through the gas introducing port 4 is activated by a vacuum ultraviolet ray from the vacuum ultraviolet ray generating source 1, and a reaction gas 8 is blown to a substrate 9 to be treated through the gas blowing port 5. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photochemical treatment apparatus and a photochemical treatment method, and in particular, a reaction gas for photochemically performing surface modification and removal of an organic compound adhering to the surface of a semiconductor wafer, carbon nanotube, etc. is efficiently produced. The present invention relates to a photochemical processing apparatus and a photochemical processing method characterized by a configuration for activation.

  Recently, a planar formed product of carbon-based new materials such as carbon nanotubes is expected to develop applications and improve functions as a member for high-performance electronic devices such as sensors and fuel cells.

  Surface cleaning of these carbon-based materials, introduction of chemical functional groups to the surface, and substrate cleaning to remove organic compounds adhering to the surface in the manufacturing process of planar substrates such as semiconductor devices, liquid crystal display devices, and plasma display devices In order to carry out efficiently, the dry method by treatment with reactive gases such as ultraviolet treatment and ozone is often used because of its low environmental load.

  In particular, chemical treatment of carbon materials by irradiation with vacuum ultraviolet rays (VUV) is used to modify physical properties such as chemical modification of the surface and improvement of wettability. Such a VUV reactor is low-pressure mercury. It is known that the UV reaction device such as a lamp has high reactivity and high throughput because the irradiation wavelength is short or high energy.

  On the other hand, because of the high output, the heat generation of the lamp cannot be ignored, and the high heat generation of the lamp causes problems such as a decrease in lamp illuminance and a shortened life of the lamp device, so an active cooling mechanism is necessary. There was also a problem (see, for example, Patent Document 1 or Patent Document 2).

  In such a conventional photochemical processing apparatus with a cooling mechanism, a metal block provided with a water cooling mechanism for cooling a plurality of excimer UV lamps arranged in parallel is provided on the ceiling of the main body case for storing the excimer UV lamp. In addition, a VUV transmission window made of quartz or the like is provided at the bottom of the main body case.

A reactive gas such as O ₂ gas was allowed to flow between the VUV transmission window and a substrate to be processed which was disposed at a position close to several millimeters outside the VUV transmission window, and an active oxidation such as O ₃ was generated by a photochemical reaction. Substrate cleaning is performed using active oxygen.
In this case, N ₂ gas or the like is made to flow in the main body case so that VUV light is not absorbed in the main body case, and air cooling is also performed by N ₂ gas or the like.

On the other hand, in order to process a large substrate to be processed, the excimer UV lamps are accommodated one by one in a protective tube without using the above-mentioned main body case, and a plurality of protective tubes are arranged in parallel, and in the vicinity of each protective tube. It has also been proposed to supply a reaction gas activated by providing a reaction gas outlet to the substrate to be processed uniformly and at a high concentration (see, for example, Patent Document 3).
JP 2004-265770 A JP 2004-221017 A International Publication No. WO2002 / 036259

  However, in the conventional mechanism, the apparatus configuration becomes large, and there is a disadvantage that the apparatus becomes complicated, low in reliability, and high in cost.

  In addition, since VUV light has a large light absorption coefficient in the air and is absorbed within 1 cm to a few cm at most, in Patent Documents 1 and 2 described above, the distance between the substrate to be processed and the body case is to be processed. It must be placed within a few millimeters, at most several centimeters, or a distance close to it over the entire surface of the substrate, but when one of the substrate to be processed or the main body case is tilted, the thickness of the gas layer flowing between them changes asymptotically. Since the concentration of the activated species also changes, there is a problem that uniform processing becomes difficult as the substrate to be processed becomes larger.

  On the other hand, even if the concentration of the activated species is made uniform as in the above-mentioned Patent Document 3, it is still necessary to accurately adjust the gas outlet and the amount of blowout with respect to the substrate to be processed in units of several mm. It is difficult to make the concentration of the generated activated species uniform, and there is a possibility that the photochemical treatment is performed unevenly.

  Furthermore, of the VUV light generated by the excimer UV lamp, only the VUV light emitted immediately below is used effectively. Even if a reflector is provided, the VUV light emitted in the lateral direction activates the reaction gas. Since it does not act effectively, there is a problem that it is inefficient.

  As a result, there is a problem in that the advantage over the conventional low-pressure mercury lamp cannot be fully utilized because the efficiency is not high despite the high-output excimer UV lamp being used.

  Further, in the case of the above-mentioned Patent Document 3, when the wavelength of VUV light is further shortened from 172 nm, quartz glass that is easy to process cannot be used due to its light absorption characteristics. There is a problem that the tube cannot be prepared and cannot be applied to VUV light having a short wavelength of 172 nm or less.

  Accordingly, an object of the present invention is to perform photochemical treatment with high throughput by increasing activation efficiency by VUV light with a simple apparatus configuration.

FIG. 1 is a diagram illustrating the basic configuration of the present invention. Means for solving the problems in the present invention will be described with reference to FIG.
See FIG. 1 In order to solve the above-mentioned problem, the present invention is a photochemical treatment apparatus, which includes a vacuum ultraviolet ray generating light source 1 and a housing 3 for accommodating the vacuum ultraviolet ray generating light source 1, and a gas inlet 4 and a gas outlet 5. The reaction gas 7 introduced from the gas inlet 4 is activated by the vacuum ultraviolet rays from the vacuum ultraviolet ray generation light source 1, and the activated reaction gas 8 is supplied from the gas outlet 5 to the substrate to be processed. 9 is sprayed.

  In this way, the activation reaction chamber 2 is provided, and the reaction gas 8 activated in advance in the activation reaction chamber 2 is blown from the gas outlet 5 to the substrate 9 to be processed, whereby the vacuum ultraviolet ray generating light source 1 and the substrate to be processed are injected. Uniform processing can be performed without requiring the distance between the substrate 9 and the substrate 9 to be opposed to each other with an accuracy of several mm or less over the entire surface of the substrate, thereby simplifying the apparatus configuration.

  In addition, activation efficiency can be increased by activating the reaction gas 7 in the activation reaction chamber 2, thereby enabling photochemical processing to be performed with high throughput.

  In this case, the gas ejection port 5 has a rectangular shape along the major axis direction of the vacuum ultraviolet ray generating light source 1 and scans the substrate 9 to be processed in a direction orthogonal to the major axis direction of the gas ejection port 5. 10 is preferably provided so that the entire surface of the substrate 9 can be processed uniformly.

  Further, a plurality of vacuum ultraviolet ray generating light sources 1 may be arranged in parallel, and a plurality of gas outlets 5 may be provided so as to correspond to the plurality of vacuum ultraviolet ray generating light sources 1, thereby forming a large substrate 9 to be processed. High-throughput and uniform photochemical treatment is possible.

  Moreover, it is desirable to provide the cooling mechanism 6 in the vacuum ultraviolet ray generating light source 1, whereby high output vacuum ultraviolet rays can be generated without causing a decrease in output due to heating, and the activation of the reaction gas 7 is highly efficient. Can be done.

In this case, the cooling mechanism 6 may be provided with a heat sink having a refrigerant duct facing the accommodating portion 3 of the vacuum ultraviolet ray generating light source 1, or the accommodating portion 3 may be provided with the refrigerant gas inlet 4 and the refrigerant gas outlet. In this case, an inert gas such as N ₂ gas that does not absorb vacuum ultraviolet rays is allowed to flow as a refrigerant in the air cooling closed space.

Further, at least the accommodating part 3 of the activation reaction chamber 2 is a transparent member having a high transmittance for vacuum ultraviolet rays, for example, a transmittance of 40% or more, more preferably 60% or more, such as quartz glass, CaF ₂ , or MgF. _It is necessary to configure with a transparent member such as ₂ .

When performing the photochemical treatment using the above-described photochemical treatment apparatus, the reaction gas 7 is a mixed gas obtained by diluting a reaction gas species such as oxygen or ammonia with a gas species inert to vacuum ultraviolet rays such as N ₂ , For example, it is desirable to use a mixed gas diluted to 0.0001 to 10%, more preferably 0.005 to 5%, so that it is at least about 1 cm from the vacuum ultraviolet light source 1 or at a position further away from it. Since the degree of freedom in designing the shape of the activation reaction chamber 2 is increased, the activation efficiency can be increased.

In this case, the reaction gas species may contain a small amount of H ₂ O with respect to the main reaction gas species such as oxygen and ammonia, thereby generating a hydroxy radical (.OH ^* ), Surface modification treatment by mixing action with hydroxy radical (.OH ^* ) becomes possible.

  Further, the substrate 9 to be processed is not particularly limited, and is intended for flat display panels such as semiconductor wafers and liquid crystal panels. In particular, the surface to be processed is chemically stable. Therefore, by applying to a member such as a substrate provided with a carbon nanotube having a slow reaction rate, the surface modification of the carbon nanotube can be performed with high efficiency.

  In the present invention, since the reaction gas is activated in advance by providing an activation reaction chamber, it is possible to efficiently use VUV light absorbed in a distance of less than 1 cm in the atmosphere, thus enabling high-throughput processing. In addition, since the degree of freedom in setting the light source position with respect to the substrate to be processed is increased, the apparatus configuration can be simplified.

The present invention includes a vacuum ultraviolet ray generating light source such as a Xe excimer lamp, and a housing portion that houses the vacuum ultraviolet light generating light source, and also includes a gas introduction port and a gas jet port, and at least the housing portion has a transmittance of 60% for vacuum ultraviolet light. It consists of the above-mentioned activation reaction chamber made of a transparent member such as quartz glass, CaF ₂ , or MgF _2, and O ₂ or NH ₃ as the main reaction gas species is inactivated to vacuum ultraviolet rays such as N ₂ from the gas inlet. A mixed gas diluted to 0.0001% to 10%, more preferably 0.005% to 5% with a simple gas or gaseous substance, and the reaction gas is activated by vacuum ultraviolet rays from a vacuum ultraviolet ray generating light source. It turned ^{_{into, 1 Δ g O 2 * (}} singlet) with blowing activated reactive gas such as [singlet oxygen radicals] from the gas ejection port conforming to the configuration of the vacuum ultraviolet ray generating light source substrate to be processed The Rutotomoni target substrate is provided with a scanning mechanism for scanning in a direction perpendicular to the axial direction of the gas ports.

Here, with reference to FIG.2 and FIG.3, the photochemical processing apparatus of Example 1 of this invention is demonstrated.
See Figure 2
FIG. 2 is a conceptual perspective view of the photochemical processing apparatus according to the first embodiment of the present invention. For example, an activation reaction vessel 12 made of quartz glass is housed in a stainless steel chamber 11 and this activation reaction is performed. The Xe excimer UV lamp 16 is accommodated in the accommodating portion 13 provided on the ceiling portion of the container 12.
In the figure, the both ends of the activation reaction vessel 12 are shown open so that the internal configuration can be easily understood, but both ends are actually closed, and so on. is there.

As the Xe excimer UV lamp 16 in this case, for example, an Xe excimer UV lamp having a light emission length in the major axis direction of 400 mm, generating a vacuum ultraviolet ray having a generation center wavelength λ = 172 nm, and an optical output of 30 mW / cm ² is used. Use.

Further, the activation reaction vessel 12 has a plurality of gas introduction pipes 14 branched according to the length of the Xe excimer UV lamp 16, and a rectangular gas corresponding to the shape of the Xe excimer UV lamp 16 on the lower side. A spout 15 is provided.
Here, three gas introduction pipes 14 are provided on the left and right.

  Further, the Xe excimer UV lamp 16 is provided with a cooling mechanism 17 including a metal block 18 having a refrigerant duct 19, and is fixed and held in the accommodating portion 13 through the metal block 18.

  The chamber 11 is provided with a substrate placement stage 20 that can move in the X and Y directions. The substrate placement stage 20 has a temperature controller 21 for controlling the temperature of the substrate 23 to be processed. A built-in movement mechanism 22 for moving in the XY direction is provided.

See Figure 3
FIG. 3 is an explanatory view of a photochemical treatment process using the photochemical treatment apparatus of Example 1 of the present invention. O ₂ or NH ₃ is gas or gas inert to vacuum ultraviolet rays such as N ₂ from the gas introduction pipe 14. The mixed gas 24 diluted with the gaseous substance is introduced, and the Xe excimer UV lamp 16 is turned on to generate a 172 nm VUV light 25. The VUV light 25 activates O ₂ and NH ₃ to generate ¹ Δ _g O Activated species 26 such as ₂ ^* and NH ₂ ^* are injected from the gas outlet 15 onto the substrate 23 to be processed, and the substrate mounting stage 20 is moved in a direction (X direction) perpendicular to the major axis direction of the gas outlet 15. Photochemical treatment is performed while scanning.
If the length in the Y direction of the substrate 23 to be processed is longer than the light emission length of the Xe excimer UV lamp 16, photochemical processing is performed while scanning in the Y direction.

  As described above, in the first embodiment of the present invention, the activation reaction vessel 12 is provided, the activated species 26 is generated in advance in the activation reaction vessel 12, and the generated activated species 26 is converted into the substrate to be processed. 23, since the substrate to be processed 23 can be installed without worrying about the absorption distance of the VUV light 25, the design freedom of the device configuration is greatly increased and the device configuration is simplified.

Further, since the reaction gas is a mixed gas 24 obtained by diluting a reactive gas species such as O ₂ or NH _{3 with} a gas inert to a vacuum ultraviolet ray such as N ₂ or a gaseous substance, the light absorption distance is increased. As a result, the activation efficiency by light absorption can be increased, and the shape of the activation reaction vessel 12 can be increased, so that the degree of freedom in design is increased.
Further, since the photochemical process is performed while scanning the substrate to be processed, the uniformity of the process is improved.

Next, with reference to FIG. 4, the photochemical processing apparatus of Example 2 of the present invention will be described. The activation reaction vessel in Example 1 is enlarged and a plurality of Xe excimer lasers are arranged. See Figure 4
FIG. 4 is a conceptual perspective view of a photochemical processing apparatus according to Embodiment 2 of the present invention. For example, an activation reaction vessel 30 made of quartz glass is housed in a stainless steel chamber 11 and this activation reaction is performed. A plurality of Xe excimer UV lamps 16 are housed in a housing part 31 provided on the ceiling of the container 30 through a metal block 34 having a refrigerant duct 35.

As the Xe excimer UV lamp 16 in this case, for example, a Xe excimer UV lamp having a light emission length in the major axis direction of 400 mm, generating a vacuum ultraviolet ray having a generation center wavelength λ = 172 nm, and an optical output of 30 mW / cm ² is used. Use.
Here, three Xe excimer UV lamps 16 are used.

In addition, the activation reaction vessel 30 is provided with a plurality of gas introduction pipes 32 branched according to the length of the Xe excimer UV lamp 16, and at a position corresponding to each lower Xe excimer UV lamp 16. A rectangular gas outlet 33 corresponding to the shape of the UV lamp 16 is provided.
Here, three gas introduction pipes 32 are provided on the left and right.

  The chamber 11 is provided with a substrate placement stage 20 that can move in the X and Y directions. The substrate placement stage 20 has a temperature controller 21 for controlling the temperature of the substrate 23 to be processed. A built-in movement mechanism 22 for moving in the XY direction is provided.

  As described above, in the second embodiment of the present invention, since a plurality of Xe excimer UV lamps 16 are provided, the scanning region in the X direction can be narrowed. In addition, the photochemical treatment can be performed in a short time, and the throughput is improved.

Next, with reference to FIG. 5, the photochemical processing apparatus of Example 3 of this invention is demonstrated.
See Figure 5
FIG. 5 is a conceptual perspective view of a photochemical treatment apparatus according to Embodiment 3 of the present invention. For example, an activation reaction vessel 40 made of quartz glass is housed in a stainless steel chamber 11 and this activation reaction is performed. An upper lid member 43 is provided on a concave portion 41 provided on the ceiling of the container 40 to form a pseudo closed space 42. A gas inlet 44 and a gas outlet 45 are provided in the closed space 42, and the Xe excimer UV lamp 16 is provided. To accommodate.

As the Xe excimer UV lamp 16 in this case, for example, a Xe excimer UV lamp having a light emission length in the major axis direction of 400 mm, generating a vacuum ultraviolet ray having a generation center wavelength λ = 172 nm, and an optical output of 30 mW / cm ² is used. Use.

In addition, the activation reaction vessel 40 is provided with a plurality of gas introduction pipes 46 branched on both sides according to the length of the Xe excimer UV lamp 16 and a rectangular shape corresponding to the shape of the Xe excimer UV lamp 16 on the lower side. The gas outlet 47 is provided.
Here, three gas introduction pipes 46 are provided on the left and right.

The Xe excimer UV lamp 16 is passed through the closed space 42 by flowing an inert gas that is not absorbed by the VUV light from the gas inlet 44, for example, a gas or a gaseous substance inert to vacuum ultraviolet rays such as N ₂ gas. Air cooling prevents output drop due to temperature rise.

  The chamber 11 is provided with a substrate placement stage 20 that can move in the X and Y directions. The substrate placement stage 20 has a temperature controller 21 for controlling the temperature of the substrate 23 to be processed. A built-in movement mechanism 22 for moving in the XY direction is provided.

  As described above, in the third embodiment of the present invention, only the cooling mechanism is changed from the indirect cooling of the first embodiment to the direct cooling, and other functions and effects are the same as those of the first embodiment.

Next, with reference to FIG.6 and FIG.7, the photochemical processing apparatus of Example 4 of this invention is demonstrated.
See FIG.
FIG. 6 is a conceptual perspective view of a photochemical treatment apparatus according to Embodiment 4 of the present invention. For example, the activation reaction vessel 50 is housed in a stainless steel chamber 11 and the ceiling of the activation reaction vessel 50 is accommodated. The Xe excimer UV lamp 16 is accommodated in the accommodating part 51 provided in the part.
As the Xe excimer UV lamp 16 in this case, for example, a Xe excimer UV lamp having a light emission length in the major axis direction of 400 mm, generating a vacuum ultraviolet ray having a generation center wavelength λ = 172 nm, and an optical output of 30 mW / cm ² is used. Use.

See FIG.
FIG. 7 is an enlarged view of the main part of the activation reaction container of the photochemical treatment apparatus of Example 4, wherein the main part of the activation reaction container 50 is made of stainless steel, and the housing part 51 is made of stainless steel. It comprises a window member 53 made of CaF ₂ attached to a frame-like member 52, and has a plurality of gas introduction pipes 54 branched according to the length of the Xe excimer UV lamp 16, and a Xe excimer on the lower side. A rectangular gas outlet 55 corresponding to the shape of the UV lamp 16 is provided.
Here, three gas introduction pipes 54 are provided on the left and right.

In this case, although it is difficult to process the shape of CaF ₂ like quartz glass, the basic skeleton is made of stainless steel, and a thin plate-like CaF ₂ processed into a frame member is pasted as a window member. CaF ₂ can be used.

  Further, the Xe excimer UV lamp 16 is provided with a cooling mechanism 17 including a metal block 18 having a refrigerant duct 19, and is fixed and held in the accommodating portion 13 through the metal block 18.

  The chamber 11 is provided with a substrate placement stage 20 that can move in the X and Y directions. The substrate placement stage 20 has a temperature controller 21 for controlling the temperature of the substrate 23 to be processed. A built-in movement mechanism 22 for moving in the XY direction is provided.

Thus, in Example 4 of the present invention, the window member 53 made of CaF ₂ having a smaller light absorption rate of VUV light having a shorter wavelength than quartz glass is provided in the housing part 51 of the Xe excimer UV lamp 16. The transmittance of VUV light is further increased.

In the future, even if the emission wavelength of the excimer UV lamp becomes shorter and absorption of VUV light by quartz glass becomes a problem, it is possible to perform photochemical treatment as it is simply by replacing the excimer UV lamp.
Furthermore, by replacing the window member 53 with a thin plate made of MgF ₂ , it becomes possible to use VUV light having a shorter wavelength.

For example, quartz glass has an optical band gap of 8-9 eV, so it can transmit 172 nm VUV light from a Xe excimer UV lamp, but it can be used as a 140-150 nm Kr ₂ excimer UV lamp or 120-135 nm Ar ₂ excimer UV lamp. However, since the optical band gap of CaF ₂ is 10 eV, 140-150 nm VUV light is transmitted. Furthermore, since the optical band gap of MgF ₂ is 11.8 eV, VUV light of 120-135 nm is To Penetrate.

Next, a fifth embodiment of the present invention relating to the photochemical treatment method will be described. However, since it is performed using the photochemical treatment apparatus shown in FIG.
Here, as a sample, Ni having a thickness of, for example, 25 nm is formed on a p-type silicon wafer having a (100) plane as a main surface by a sputtering method, and then acetylene gas (C ₂ H ₂₎ is formed by a filament CVD method. ) Was used as a raw material and multiwall carbon nanotubes were grown to a length of about 1.5 μm on Ni serving as a catalyst at 650 ° C.

This was previously baked in air at 400 ° C. for 15 minutes to remove flammable impurities other than nanotubes, and then immediately transferred to the photochemical treatment apparatus shown in FIG. A gas obtained by diluting clean air (dust-free air) adjusted to a humidity of about 50% with pure nitrogen is used as a reaction gas, and photochemical treatment is performed for 60 seconds while scanning the sample.
The gas flow rate is 10 L / min for the reaction gas and 60 L / min for the cooling gas.

In this case, since the reaction gas contains a trace amount of H ₂ O of about 0.1 ppm, a carboxyl group (—COOH), a hydroxyl group (—OH), etc. are introduced to the surface of the carbon nanotube, and the surface modification is performed. It is considered that the hydrophilicity is enhanced by quality or surface modification.

That is, the carbon nanotube (CNT) and O ₂ is generated by activating ^{_{1 Δ g O 2 * (Singlet}} ) is reacted,
CNT-C (chemically active site on CNT) + ¹ Δ _g O ₂ ^* (Singlet)
→ CNT-C-OO ・^*
Which reacts with H ₂ O
CNT-C-OO. ^* + H ₂ O → CNT-C-OOH + H.
Thus, it is considered that a carboxyl group is introduced into the surface of the carbon nanotube.

Next, Embodiment 6 of the present invention relating to the photochemical treatment method will be described. However, since it is carried out using the photochemical treatment apparatus shown in FIG.
Here, as a sample, a suspension sample in which multiwall carbon nanotubes generated by an arc discharge method are sufficiently ground in a mortar on a p-type silicon wafer having a (100) plane as a main surface and dispersed in methanol is about 0 in thickness. The one developed and dried to 1 mm was used.

This was previously baked in air at 150 ° C. for 30 minutes to remove residual moisture and volatile components, and then immediately transferred to the photochemical treatment apparatus shown in FIG. A gas obtained by diluting oxygen gas with pure nitrogen is used as a reaction gas, and photochemical treatment is performed for 90 seconds while scanning the sample.
The gas flow rate is 10 L / min for the reaction gas and 20 L / min for the cooling gas.

In this case as well, since the reaction gas contains a very small amount of H ₂ O of about 0.01 ppm or less, a carboxyl group (—COOH) or the like is introduced on the surface of the carbon nanotube, and the surface is modified. Alternatively, surface modification is performed.

Next, Embodiment 7 of the present invention relating to the photochemical treatment method will be described. Here, since it is carried out using the photochemical treatment apparatus shown in FIG.
Here, a PET (polyethylene terephthalate) film having a thickness of 1.5 mm and a planar size of 10 cm × 10 cm was used as a sample.

This is transferred to the photochemical treatment apparatus shown in FIG. 2, and a gas obtained by diluting clean air (dust-free air) adjusted to a humidity of about 50% with pure nitrogen so that the oxygen concentration at 1 atm is 0.5% is a reaction gas. And performing a photochemical treatment for 10 seconds while scanning the sample.
The gas flow rate is 10 L / min for the reaction gas and 20 L / min for the cooling gas.

Also in this case, since the reaction gas contains a trace amount of H ₂ O of about 0.1 ppm, a carboxyl group (—COOH) is present on C (chemically active site on CNT) on the surface of the PET film. ), A hydroxyl group (—OH) and the like are formed, surface modification or surface modification is performed, and surface adhesion is improved.

Next, an eighth embodiment of the present invention relating to the photochemical treatment method will be described. Here, since it is carried out using the photochemical treatment apparatus shown in FIG.
Here, as a sample, Ni having a thickness of, for example, 25 nm is formed on a p-type silicon wafer having a (100) plane as a main surface by a sputtering method, and then acetylene gas (C ₂ H ₂₎ is formed by a filament CVD method. ) Was used as a raw material and multiwall carbon nanotubes were grown to a length of about 1.5 μm on Ni serving as a catalyst at 650 ° C.

After this, remove combustible impurities other than nanotubes and baked 15 minutes at 400 ° C. in advance in air, quickly, and transferred to a photochemical processing apparatus shown in FIG. 2, 1 atm NH ₃ concentration of 0.1 A photochemical treatment is performed while scanning a sample using a gas obtained by diluting NH ₃ gas with pure nitrogen so as to be%.
The gas flow rate is 1 L / min for the reaction gas and 60 L / min for the cooling gas.

In this case, since the reaction gas contains a very small amount of H ₂ O of about 0.01 to 100 ppm, for example, about 0.02 ppm, an amino group (—NH ₂ H) is introduced on the surface of the carbon nanotube. Surface modification or surface modification is performed.

Next, an embodiment 9 of the present invention relating to the photochemical treatment method will be described. However, since it is carried out using the photochemical treatment apparatus shown in FIG.
Here, a polyimide film having a thickness of 0.2 mm and a planar size of 10 cm × 10 cm was used as a sample.

This is transferred to the photochemical treatment apparatus shown in FIG. 2, and a gas obtained by diluting clean air (dust-free air) adjusted to a humidity of about 50% with pure nitrogen so that the O ₂ concentration becomes 0.5% is a reaction gas. And performing a photochemical treatment for 10 seconds while scanning the sample.
The gas flow rate is 10 L / min for the reaction gas and 20 L / min for the cooling gas.

Also in this case, since the reaction gas contains a trace amount of H ₂ O of 0.01 to 10 ppm, for example, about 0.2 ppm, a carboxyl group (—COOH) and a hydroxyl group (—OH) are present on the surface of the polyimide film. ) And the like are formed, and surface modification or surface modification is performed.

Next, an embodiment 10 of the present invention relating to the photochemical treatment method will be described. Here, since it is carried out using the photochemical treatment apparatus shown in FIG.
Here, as a sample, Ni having a thickness of, for example, 25 nm is formed on a p-type silicon wafer having a (100) plane as a main surface by a sputtering method, and then acetylene gas (C ₂ H ₂₎ is formed by a filament CVD method. ) Was used as a raw material and multiwall carbon nanotubes were grown to a length of about 1.5 μm on Ni serving as a catalyst at 650 ° C.
Here, a Kr ₂ excimer UV lamp is used as the excimer UV lamp instead of the Xe excimer UV lamp.

After removal of the combustible impurities other than nanotubes this sample was 15 minutes baking at 400 ° C. in advance in air, quickly, and transferred to a photochemical processing apparatus shown in FIG. 2, 1 atm NH ₃ concentration of 0.1 Using a gas obtained by diluting NH ₃ gas with pure nitrogen so as to become a reaction gas, a photochemical treatment is performed for 8 seconds while scanning the sample.
The gas flow rate is 5 L / min for the reaction gas and 60 L / min for the cooling gas.

In this case, since a very small amount of H ₂ O of less than 0.1 ppm is contained in the reaction gas, an amino group (—NH ₂ ) is introduced on the surface of the carbon nanotube to perform surface modification or surface modification. This improves hydrophilicity.

In Example 10, a shorter wavelength, that is, a higher-energy Kr ₂ excimer UV lamp is used. Therefore, when processing is performed under the same irradiation energy, an Xe excimer UV lamp is used. Processing in a shorter time than the case may be possible.

Next, an eleventh embodiment of the present invention relating to the photochemical treatment method will be described. Here, since it is carried out using the photochemical treatment apparatus shown in FIG.
Here, as a sample, a tetrafluoroethylene [Teflon (registered trademark)] resin plate having a thickness of 1.0 mm and a planar size of 10 cm × 10 cm was used.

This was transferred to the photochemical processing apparatus shown in FIG. 6, and a gas obtained by diluting NH ₃ gas with pure nitrogen so that the 1 atm NH ₃ concentration was 0.2% was used as a reaction gas, and the sample was scanned 15 Photochemical treatment for 2 seconds.
The gas flow rate is 5 L / min for the reaction gas and 30 L / min for the cooling gas.

Also in this case, since a very small amount of H ₂ O of less than 0.1 ppm is contained in the reaction gas, an amino group (—NH ₂ ) is bonded to the surface portion of the Teflon (registered trademark) resin plate, and the surface Modification or surface modification is performed, and hydrophilicity is improved.

Next, Example 12 of the present invention relating to the photochemical treatment method will be described. Here, since it is carried out using the photochemical treatment apparatus shown in FIG. 6, illustration is omitted.
Here, as a sample, Ni having a thickness of, for example, 25 nm is formed on a p-type silicon wafer having a (100) plane as a main surface by a sputtering method, and then acetylene gas (C ₂ H ₂₎ is formed by a filament CVD method. ) Was used as a raw material and multiwall carbon nanotubes were grown to a length of about 1.5 μm on Ni serving as a catalyst at 650 ° C.
Further, here, instead of the Xe excimer UV lamp as the excimer UV lamp, an Ar ₂ excimer UV lamp is used, and MgF ₂ is used as the window member.

The sample after removing combustible impurities other than nanotubes by 15 minutes baking at 400 ° C. in advance in air, quickly, and transferred to a photochemical processing apparatus shown in FIG. 2, 1 atm NH ₃ concentrations 0. A gas obtained by diluting NH ₃ gas with pure nitrogen so as to be 1% is used as a reaction gas, and photochemical treatment is performed for 7 seconds while scanning the sample.
The gas flow rate is 5 L / min for the reaction gas and 30 L / min for the cooling gas.

In this case, since the reaction gas contains a very small amount of H ₂ O of 0.01 to 100 ppm, for example, about 0.02 ppm or less, an amino group (—NH ₂ ) is introduced on the surface of the carbon nanotube. Then, surface modification or surface modification is performed.

In Example 12, since a shorter wavelength, that is, a higher energy Ar ₂ excimer UV lamp is used, when processing is performed so that the irradiation energy has the same condition, an Xe excimer UV lamp, It may be possible to process in a shorter time than when using a Kr ₂ excimer UV lamp.

Next, a thirteenth embodiment of the present invention relating to the photochemical treatment method will be described. Here, since it is carried out using the photochemical treatment apparatus shown in FIG.
Here, a polyimide film having a thickness of 0.1 mm and a planar size of 10 cm × 10 cm was used as a sample.

This was transferred to the photochemical treatment apparatus shown in FIG. 6, and a gas obtained by diluting NH ₃ gas with pure nitrogen so that the 1 atm NH ₃ concentration was 0.1% was used as a reaction gas, and the sample was scanned 7 Photochemical treatment for 2 seconds.
The gas flow rate is 10 L / min for the reaction gas and 30 L / min for the cooling gas.

Also in this case, since a very small amount of H ₂ O of 0.01 to 100 ppm, for example, about 0.02 ppm is contained in the reaction gas, an amino group (—NH ₂ ) or the like is bonded to the surface portion of the polyimide film. And surface modification or surface modification is performed, and the contact angle with respect to the water of a surface falls.

  Although the embodiments of the present invention have been described above, the present invention is not limited to the configurations and conditions described in the embodiments, and various modifications can be made. For example, in each embodiment, a sample is used. As carbon nanotubes grown on a substrate, carbon nanotube powder, or PET film or polyimide film, but not limited to these, surface modification of various inorganic or organic materials including engineering plastics It is applied to surface modification.

  In Examples 1 to 3, the entire activation reaction vessel is made of quartz. However, as in Example 4, the main part may be made of stainless steel and a quartz plate may be used as the window member. Is.

  Further, in the above-described Example 3 and Example 4, only one excimer UV lamp is used, but a plurality of excimer UV lamps are arranged in accordance with the size of the sample to be processed in the same manner as in Example 2 above. Is also good.

In the above-described Examples 1, 2, and 4, N ₂ gas is allowed to flow through the refrigerant duct as a refrigerant. However, the present invention is not limited to N ₂ gas, and air may be allowed to flow, or alternative CFCs may be allowed to flow. In addition, liquid cooling such as water may be used for liquid cooling.

  In each of the above embodiments, an excimer UV lamp is used as the VUV light source. However, the excimer UV lamp is not necessarily used, and an excimer UV laser may be used. Therefore, it is desirable to use a light source that has good luminous efficiency or generates less heat than the amount of light emitted.

Since the power supply unit that supplies power to the excimer light source uses RF (high frequency) power, it is arranged so that the wiring distance from the lamp is as short as possible in order to keep the RF leak rate low. It is desirable.
In addition, it is desirable to design the apparatus so that the distance between the light source and the member to be processed is a relatively short distance, but this can be realized relatively easily by the configuration of the present invention.

  In each of the above embodiments, the surface modification method or the surface modification method is described. However, the present invention is not limited to the surface modification method or the surface modification method. Applicable.

The detailed features of the present invention will be described again with reference to FIG. 1 again.
Again see Figure 1
(Additional remark 1) While providing the vacuum ultraviolet light generation light source 1 and the accommodating part 3 which accommodates the said vacuum ultraviolet light generation light source 1, it has the activation reaction chamber 2 provided with the gas inlet 4 and the gas jet outlet 5, and the said gas inlet 4. A photochemical processing apparatus, wherein the reaction gas 7 introduced from 4 is activated by vacuum ultraviolet light from the vacuum ultraviolet light generation light source 1, and the activated reaction gas 8 is sprayed from the gas outlet 5 onto the substrate 9 to be processed.
(Additional remark 2) While the said gas jet nozzle 5 is a rectangular shape along the major axis direction of the said vacuum ultraviolet ray generation light source 1, the said substrate 9 is the direction orthogonal to the major axis direction of the said gas jet nozzle 5 The photochemical processing apparatus according to appendix 1, further comprising a scanning mechanism 10 that causes the scanning to be performed.
(Supplementary note 3) A plurality of the vacuum ultraviolet ray generation light sources 1 are arranged in parallel, and a plurality of the gas ejection ports 5 are provided so as to correspond to the plurality of vacuum ultraviolet ray generation light sources 1. Photochemical processing equipment.
(Additional remark 4) The photochemical processing apparatus of any one of Additional remark 1 thru | or 3 provided with the cooling mechanism 6 in the said vacuum ultraviolet ray generation light source 1. FIG.
(Additional remark 5) The said cooling mechanism 6 consists of a heat sink provided with the refrigerant | coolant duct provided in the side facing the said accommodating part 3 of the said vacuum ultraviolet ray generation light source 1, The photochemical processing apparatus of Additional remark 4 characterized by the above-mentioned.
(Additional remark 6) The said cooling mechanism 6 consists of the said accommodating part 3 from the closed space for air cooling provided with the refrigerant gas inlet 4 and the refrigerant gas discharge port, The photochemical processing apparatus of Additional mark 4 characterized by the above-mentioned.
(Supplementary note 7) The photochemical treatment according to any one of supplementary notes 1 to 6, wherein at least the accommodating portion 3 of the activation reaction chamber 2 is made of a transparent member having a transmittance of 40% or more for vacuum ultraviolet rays. apparatus.
(Supplementary Note 8) The transparent member is quartz glass, CaF _2, or photochemical treatment of Supplementary Note 7, wherein the consisting of either MgF _2.
(Supplementary note 9) In the photochemical treatment method using the photochemical treatment apparatus according to any one of supplementary notes 1 to 8, the reaction gas 7 is a mixture in which a reaction gas species is diluted with a gas species inert to vacuum ultraviolet rays. A photochemical treatment method characterized by being a gas.
(Supplementary note 10) The photochemical treatment method according to supplementary note 9, wherein the reaction gas species is either oxygen or ammonia.
(Supplementary note 11) The photochemical treatment method according to supplementary note 10, wherein the reactive gas species contains a trace amount of H ₂ O relative to the main reactive gas species.
(Additional remark 12) The said to-be-processed substrate 9 is a board | substrate with which the carbon nanotube used as a to-be-processed object was provided, The photochemical processing method of any one of Additional remarks 9 thru | or 11 characterized by the above-mentioned.

  Typical examples of application of the present invention include surface modification and surface activation by photochemical treatment of a small, low-power device material having a relatively small area of a sample size of about 300 mm or less such as a Si wafer. However, the present invention is also applied to large flat display devices such as large liquid crystal panels and large PDPs, and further to photochemical treatment of large parts such as automobiles.

It is explanatory drawing of the fundamental structure of this invention. It is a conceptual perspective view of the photochemical processing apparatus of Example 1 of this invention. It is explanatory drawing of the photochemical processing process using the photochemical processing apparatus of Example 1 of this invention. It is a conceptual perspective view of the photochemical processing apparatus of Example 2 of this invention. It is a conceptual perspective view of the photochemical processing apparatus of Example 3 of this invention. It is a conceptual perspective view of the photochemical processing apparatus of Example 4 of this invention. It is a principal part enlarged view of the activation reaction container of the photochemical processing apparatus of Example 4.

DESCRIPTION OF SYMBOLS 1 Vacuum ultraviolet light generation light source 2 Activation reaction chamber 3 Accommodating part 4 Gas inlet 5 Gas jet 6 Cooling mechanism 7 Reactive gas 8 Activated reaction gas 9 Substrate 10 Scan mechanism 11 Chamber 12 Activation reaction container 13 Accommodating part Reference Signs List 14 Gas introduction pipe 15 Gas outlet 16 Xe excimer UV lamp 17 Cooling mechanism 18 Metal block 19 Refrigerant duct 20 Substrate placement stage 21 Temperature controller 22 Moving mechanism 23 Substrate 24 Mixed gas 25 VUV light 26 Activated species 30 Activity Conversion reaction vessel 31 Storage portion 32 Gas introduction pipe 33 Gas injection port 34 Metal block 35 Refrigerant duct 40 Activation reaction vessel 41 Recess 42 Closed space 43 Upper lid member 44 Gas introduction port 45 Gas outlet port 46 Gas introduction tube 47 Gas injection port 50 Activation reaction vessel 51 Accommodating portion 52 Frame member 53 Window member 54 Gas introduction pipe 55 Gas outlet

Claims (5)

A vacuum ultraviolet ray generating light source, an accommodating portion for accommodating the vacuum ultraviolet ray generating light source, and an activation reaction chamber having a gas inlet and a gas outlet, and generating the vacuum ultraviolet ray from a reaction gas introduced from the gas inlet A photochemical processing apparatus which is activated by vacuum ultraviolet light from a light source and sprays the activated reaction gas onto the substrate to be processed from the gas ejection port. The gas jet port has a rectangular shape along the long axis direction of the vacuum ultraviolet ray generating light source, and a scanning mechanism for scanning the substrate to be processed in a direction orthogonal to the long axis direction of the gas jet port is provided. The photochemical processing apparatus according to claim 1. 3. The photochemical processing apparatus according to claim 1, wherein a cooling mechanism is provided in the vacuum ultraviolet ray generating light source. The photochemical processing apparatus according to any one of claims 1 to 3, wherein at least the housing portion of the activation reaction chamber is made of a transparent member having a transmittance for vacuum ultraviolet rays of 40% or more. 5. The photochemical treatment method using the photochemical treatment apparatus according to claim 1, wherein the reaction gas is a mixed gas in which a reaction gas species is diluted with a gas species inert to vacuum ultraviolet rays. The photochemical processing method characterized by the above-mentioned.

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