KR100817371B1 - Processing apparatus - Google Patents

Abstract

The present invention is to provide a treatment apparatus which is different from the conventional treatment with activated oxygen and which suppresses the influence of oxidation on the workpiece. In addition, a processing apparatus using vacuum ultraviolet light, which provides a processing apparatus that enables processing, such as incineration and removal of an ion-implanted resist, that is not possible to obtain a sufficient processing speed by treatment with activated oxygen. For the purpose of

A processing apparatus comprising a light source for emitting vacuum ultraviolet light, a discharge vessel provided with the light source and / or a processing space, and an inlet for introducing a gas activated by irradiation with light, wherein the activated gas is NmHn. (N is a nitrogen atom, H is a hydrogen atom, m, n is an arbitrary natural number), and this NmHn gas is provided with the irradiation means of the vacuum ultraviolet light radiated from the said light source.

Vacuum ultraviolet light, activation, inlet, barrier discharge, processing unit

Description

Processing Unit {PROCESSING APPARATUS}

1 is a conceptual diagram showing a first embodiment of the present invention.

2 is a conceptual diagram illustrating a second embodiment of the present invention.

3 is a conceptual diagram illustrating a third embodiment of the present invention.

4 is a conceptual diagram illustrating a fourth embodiment of the present invention.

5 is a conceptual diagram illustrating a fifth embodiment of the present invention.

6 is a conceptual diagram illustrating a sixth embodiment of the present invention.

7 is a table showing the effect of the amount of ammonia gas of the present invention.

8 is a conceptual diagram showing a conventional processing apparatus.

Explanation of symbols on the main parts of the drawings

1: discharge vessel 2: processing space

3a, 3b, 3c: electrode 4: discharge plasma

4a, 4b: discharge plasma 5: power source for discharge

6a: discharge gas inlet 6b: outlet

7: light extraction window 8: heater

9: to-be-processed object 10a: inlet port

10b: outlet 11: processing device                 

20 processing unit 21 lamp house

22: processing space 23: Xe ₂ excimer lamp

24: discharge plasma 25: power supply for discharge

26a: gas inlet 26b: gas outlet

27: light extraction window 28: heater

29: to-be-processed object 30a: inlet port

30b: outlet

36a, 36b: discharge gas inlet 40: processing apparatus

50 processing apparatus 51 first electrode

52a, 52b: alumina 53: second electrode

54: discharge space 55a: inlet

55b: outlet 56: active species generating chamber

57: active species injection port 60: treatment device

61: light shield plate 70: processing device

80: surface cleaning device 81: lamp house

82: process chamber 83a, 83b: electrode

84: excimer lamp 84a: outer tube

84b: inner tube 85: power source for discharge

86a: oxidative fluid inlet 86b: oxidative fluid outlet

87: light extraction window 88: sample stand                 

89: to-be-processed object

The present invention relates to a processing apparatus using vacuum ultraviolet light. Moreover, in the processing apparatus which activates this processing gas and acts on a to-be-processed object by irradiating a vacuum ultraviolet light to a processing gas, for example, surface modification, dry cleaning, ashing and removal of a resist, and a Si surface It relates to a processing apparatus that can be used for etching and the like.

Background Art Conventionally, a processing apparatus that performs treatment using vacuum ultraviolet light has been widely used in various fields such as surface modification, dry cleaning, painting and removing resists, and the like. When these treatment apparatuses are largely divided, the vacuum ultraviolet light is directly irradiated to the irradiated object to treat the irradiated object by causing a photochemical reaction or the like, and the vacuum ultraviolet light is irradiated to oxygen molecules or the like to activate an active oxygen atom or the like. There may be a case where the object is processed to produce this product.

In particular, in the field of washing and incineration / removal of resist, it is widely used to irradiate this vacuum ultraviolet light to oxygen molecules, generate active oxygen atoms, and to process this irradiated object. As this technique, for example, Japanese Patent Application Laid-Open No. 4-9373 is known as a processing apparatus using a low pressure mercury lamp.

According to this publication, vacuum ultraviolet light with a wavelength of 184 nm emitted from a low pressure mercury lamp as a light source reacts with oxygen to generate ozone, and decomposes this ozone with ultraviolet rays having a wavelength of 245 nm to generate active oxygen atoms, It is described to oxidatively decompose and scatter organic contaminants adhering to the surface. In this case, the light emitted from the low pressure mercury lamp is a resonance line of mercury encapsulated in the low pressure mercury lamp, using both light in the vacuum ultraviolet region (185 nm) and light in the ultraviolet region (254 nm). To do it.

  Here, the mechanism of generating ozone by vacuum ultraviolet light and ultraviolet rays and this cleaning action can be considered as follows.

O ₂ +185 nm light → O (3P) + O (3P)

O ₂ + O (3P) → O ₃

O ₃ + 254 nm light → O ₂ + O (1D)

In this scheme, when 185 nm vacuum ultraviolet light is irradiated to oxygen molecule O ₂ , _two low-energy oxygen atoms O (3P) are produced. Ozone O ₃ is generated when the low-energy oxygen atom O (3P) collides with the oxygen molecule O ₂ . In addition, when the generated ozone O ₃ is irradiated with ultraviolet rays at 254 nm, ozone O ₃ is decomposed to generate oxygen molecules and active oxygen O (1D).

  Moreover, as another example in the process using the conventional vacuum ultraviolet light, the technique of irradiating the oxygen molecule with the vacuum ultraviolet light irradiated from an excimer lamp is known. 8 shows a surface cleaning apparatus having an excimer lamp using a dielectric barrier discharge as a conventional processing apparatus. This surface cleaning apparatus 80 arrange | positions the light extraction window 87 between the lamp house 81 and the process chamber 82. As shown in FIG. In the lamp house 81, a cylindrical outer tube 84a and a cylindrical inner tube 84b are arranged on the same axis, and an electrode 83a is disposed on the inner surface of the inner tube 84b and the outer surface of the outer tube 84a. And 83b, and the excimer lamp 84 which enclosed the gas for discharge was arrange | positioned between this outer side pipe 84a and this inner side pipe 84b. The excimer lamp 84 is applied with a high frequency high voltage from the discharge power source 85. Moreover, the oxidative fluid introduction port 86a and the oxidative fluid discharge port 86b are provided in the process chamber 82 side. In the processing chamber 82, the workpiece 89 is disposed on the sample table 88, and the vacuum ultraviolet light emitted from the excimer lamp 84 side is separated from the surface of the workpiece 89. The oxidative fluid introduced into the processing chamber 82 is irradiated.

As a processing apparatus using such conventional vacuum ultraviolet light, for example, Japanese Patent No. 2948110 is known. According to this publication, there is disclosed a method of oxidizing and cleaning the surface of a treatment product by generating ozone and active oxygen using vacuum ultraviolet light emitted from a dielectric barrier discharge lamp in which xenon is a gas containing a main component. As shown in this publication, oxygen radicals are directly generated by irradiating an oxygen molecule with vacuum ultraviolet light having a wavelength of 172 nm, which is an excimer light emitted from an Xe ₂ excimer lamp using xenon excimer Xe ₂ . In this case, the mechanism for generating active oxygen by the vacuum ultraviolet light can be considered as follows.

O ₂ + 172nm Light → O (3P) + O (1D)

This reaction is to dissolve in a molecular oxygen O ₂ is the oxygen atom O (3P) of the low energy and the active oxygen O (1D) When the vacuum ultraviolet light of the excimer crazy wavelength of 172nm emitted from the Xe ₂ excimer lamp in an oxygen molecule O ₂ josa It is shown.

However, in the treatment with the low-pressure mercury lamp or the excimer lamp, active oxygen is always formed by photoexcitation from oxygen and the treatment is performed, and there is a big problem when the workpiece is difficult to be oxidized. For example, in the case of cleaning the Si surface, SiO ₂ is partially formed under the influence of this active oxygen, which greatly affects characteristics such as contact resistance when forming a semiconductor element. Moreover, the problem that metal oxides, such as copper oxide, form in the metal surface, such as copper, arises. In addition, as described above, since the active oxygen atoms have a very high energy, oxygen atoms invade the object to be treated and deteriorate the object, or absorbed oxygen is later released as an impure gas.

In addition, in the induction and removal of the resist, the resist itself is deteriorated and difficult to decompose when, for example, an ion implantation or the like is applied while the resist is applied, so that the removal rate of the resist is extremely reduced even when active oxygen is formed. there was.

On the other hand, oxygen may not be used as a processing apparatus using vacuum ultraviolet light. For example, Japanese Unexamined Patent Application Publication No. 7-110904 discloses a mixed gas of NH ₃ and B ₃ H ₆ as a reaction gas at 1.9 KPa, and irradiating an ArF excimer laser having a wavelength of 193 nm. When the surface modification of the fluorine resin is carried out, this technique cuts the FC bond of the fluorine resin by irradiating vacuum ultraviolet light to the surface of the irradiated object in an NH ₃ atmosphere, and -NH ₂ groups are formed to improve hydrophilicity.

Moreover, in the processing apparatus using vacuum ultraviolet light, as another example in the case of not using oxygen, the annealing process after formation of the nitride film was made to irradiate ammonia with vacuum ultraviolet light to enable low temperature treatment. -335850. According to this publication, it is disclosed that by irradiating ammonia with ultraviolet rays emitted from a low pressure mercury lamp, ammonia itself is excited and a stable nitride film can be formed only by heating the object to about 500 ° C. This technique is to convey the energy of ultraviolet rays to the object through ammonia to compensate for the shortage of thermal energy, and to promote the formation of the nitride film using N in ammonia.

As a treatment apparatus for irradiating vacuum ultraviolet light without using oxygen as described above, a technique in which the irradiated object and the reactive gas are substituted or laminated on the irradiated object is known, but in the treatment apparatus for irradiating vacuum ultraviolet light, for example, Washing or the like could not be performed without using oxygen.

(Patent Document 1) Japanese Patent Application Laid-Open No. 4-9373

(Patent Document 2) Japanese Patent No. 2948110

(Patent Document 3) Japanese Patent Laid-Open No. 11-335850

The problem to be solved by the present invention is to provide a treatment apparatus which is different from the conventional treatment with activated oxygen and which suppresses the influence of oxidation on the workpiece. It is also an object of the present invention to provide a processing apparatus that uses vacuum ultraviolet light and which does not allow a sufficient processing rate to be obtained by treatment with activated oxygen, for example, a processing apparatus capable of incineration and removal of an ion-implanted resist.

According to the present invention, vacuum ultraviolet light is irradiated to a gas composed of NmHn (N is a nitrogen atom, H is a hydrogen atom, m, n is any natural water), and thus, cleaning with conventional oxygen is performed using this excited NmHn gas. The treatment is carried out by a reaction different from that of the combustion reaction, that is, bonding with oxygen used in the process.

Specifically, when describing a gas consisting of NmHn (N is a nitrogen atom, H is a hydrogen atom, m, n is any natural water), for example, ammonia (NH ₃ ), the ammonia is active when irradiated with vacuum ultraviolet light. NH (a ¹ Δ), NH (X ³ Σ), and H are generated. By using this active NH (a ¹ Δ), NH (X ³ Σ), H, etc., it is possible to suppress the influence of oxygen on the object to be treated by the decomposition of organic matter and the processing of incineration and removal of the resist. It was made.

As a specific structure in the processing apparatus of this invention, the light source which radiates a vacuum ultraviolet light, the discharge container provided with this light source, and / or the process space are arrange | positioned, and the inlet which introduces the gas activated by irradiating light is arrange | positioned. In one processing apparatus, the activated gas is NmHn (N is nitrogen atom, H is hydrogen atom, m, n is any natural number), and the NmHn gas is provided with vacuum ultraviolet light irradiation means radiated from the light source. It is characterized by.

The NmHn gas is ammonia gas, and the partial pressure of the ammonia gas is 0.1 KPa or more and 10 KPa or less.

The light source may be an excimer lamp using a dielectric barrier discharge that generates an Xe ₂ excimer light having a maximum value at a wavelength of 172 nm, a Kr ₂ excimer light having a maximum value at a wavelength of 146 nm, or an Ar ₂ excimer light having a maximum value at a wavelength of 126 nm. It features.

Moreover, after irradiating a vacuum ultraviolet light to the said ammonia gas, this ammonia gas excited by this vacuum ultraviolet light is sprayed on to-be-processed object, It is characterized by the above-mentioned.

In addition, as a means for generating vacuum ultraviolet light, a dielectric barrier discharge using a discharge gas as a rare gas is used, and ammonia is mixed with the discharge gas.

Moreover, you may provide the light shielding means for not irradiating the said vacuum ultraviolet light directly to an irradiated object.

Moreover, in the processing apparatus provided with the light source which radiates a vacuum ultraviolet light, the discharge container provided with this light source, and / or processing space, and the inlet which introduces the gas activated by irradiating light, this processing is activated The gas is ammonia, and the ammonia gas is provided with a means for irradiating the vacuum ultraviolet light emitted from this light source. As this light source, it is a Kr ₂ excimer light having a maximum value at a wavelength of 146 nm or an Ar ₂ excimer having a maximum value at a wavelength of 126 nm. The surface of SiO ₂ is etched using a dielectric barrier discharge that generates light.

Best Mode for Carrying Out the Invention

The processing apparatus of the present invention includes a means for radiating vacuum ultraviolet light, and in the apparatus for irradiating the gas activating the vacuum ultraviolet light, NmHn (N is a nitrogen atom, H is a gas activated by the vacuum ultraviolet light). By using a hydrogen atom, m and n are arbitrary natural waters, it is possible to perform surface modification, dry cleaning, painting and removing resist, etching of Si surface, etc. without affecting oxygen on the object to be treated. will be. In particular, when ammonia gas is used for this activated gas, the following reaction occurs by irradiating Xe ₂ excimer light having a maximum value at a wavelength of 172 nm, for example, and thus, active NH (a ¹ Δ) is generated.

Ammonia + vacuum ultraviolet light → NH (a ¹ △) + H ₂

The activated gas is ammonia gas, and NH _{2 which} is more active than NH (a ¹ Δ) is irradiated by irradiating Kr ₂ excimer light having a maximum value at a wavelength of 146 nm or Ar ₂ excimer light having a maximum value at a wavelength of 126 nm. ³ Σ) and active H are produced.

Light ammonia + 146nm or less → NH (X ³ Σ) + H + H

The specific structure of such a processing apparatus is shown from Example 1 to Example 6.

Example 1

1 shows a first embodiment of the processing apparatus of the present invention. Fig. 1 is a schematic cross-sectional view cut in a plane perpendicular to the electrode axis of cylindrical electrodes 3a, 3b, 3c. The processing apparatus 11 is the discharge vessel (1) and made of a process space (2), the discharge vessel 1 and the light extraction window (7) made of MgF ₂ between the treatment space (2) is arranged . In order to generate Ar ₂ excimer light having a maximum value at a wavelength of 126 nm from the discharge vessel 1, the electrodes 3a, 3b, 3c for dielectric barrier discharge disposed in the discharge vessel 1 are discharged. These electrodes 3a, 3b and 3c are electrically connected to each other, and are provided inside, for example, a quartz glass tube as a dielectric, and a high frequency high voltage is applied between the electrodes. In this embodiment, the light source is the discharge container 1, the light extraction window 7, the electrode for dielectric barrier discharge 3a, 3b, 3c disposed in the discharge container 1, and the discharge container. It consists of Ar gas for light emission introduced in (1). In this discharge vessel 1, since Ar ₂ excimer light having a maximum value is generated at a wavelength of 126 nm, Ar is introduced from the discharge gas inlet 6a and discharged from the outlet 6b. Further, to achieve this by forming the light extraction window (7) as means for irradiating vacuum ultraviolet light to the NmHn gas from a member that passes through the vacuum ultraviolet light such as MgF _2.

On the other hand, the processing object 9 is provided in the processing space 2, and the processing object 9 can be heated by the heater 8. This processing space 2 is provided with an inlet port 10a and an outlet port 10b for introducing a gas activated by irradiation with vacuum ultraviolet light. This activated gas is represented by NmHn (N is a nitrogen atom, H is a hydrogen atom, m, n is any natural number), for example, ammonia (NH ₃ ), hydrazine (N ₂ H ₄ ), and an amino group. And compounds having (-NH ₂ ).

As a 1st Example, the washing | cleaning experiment of the glass substrate for liquid crystal display devices was performed using this processing apparatus 11 shown in FIG. Specific irradiation conditions of light and the like are shown below. The electrodes 3a, 3b, and 3c for dielectric barrier discharge are shown in a circle in the figure, but are cylindrical in shape, and aluminum is inserted into a quartz glass tube having an outer diameter of 20 mm, a thickness of 1 mm, and a length of 250 mm. It was 6 mm. Ar was used as a gas for discharge, Ar pressure in this discharge container 1 was 66.7 KPa, and discharge power was 200W. Discharge plasmas 4a and 4b are generated between the electrodes 3a, 3b, and 3c, and excimer light having a wavelength of 126 nm is emitted from the discharge plasmas 4a and 4b, and the processing space is formed in the light extraction window 7. (2) is investigated. In this processing space 2, ammonia gas NH ₃ is introduced into the inlet port 10a, and Ar excimer light is irradiated onto the ammonia gas NH ₃ to generate active NH (X ³ Σ) and H, and at the same time, Light is directly irradiated to the object 9.

In the present Example, this to-be-processed object 9 is a glass substrate for liquid crystal display devices, and the distance between the to-be-processed object 9 and the light extraction window 7 was 3 mm. The pressure of ammonia NH _{3 in} the processing space 2 was 0.53 KPa, and Ar ₂ excimer light having a wavelength of 126 nm was irradiated. As a result, the glass substrate for liquid crystal display devices could be cleaned in about 20 seconds of processing time.

Example 2

A second embodiment of the present invention is shown in FIG. FIG. 2 is a schematic cross-sectional view cut away from the plane of the excimer lamp 21 that is perpendicular to the lamp tube axis. This second embodiment shows a discharge space 1 for generating Ar ₂ excimer light having a maximum value at a wavelength of 126 nm in FIG. 1. ) Is replaced with a Xe ₂ excimer lamp. Specifically, the processing apparatus 20 includes a lamp house 21 and a processing space 22, and a light extraction window 27 is disposed between the lamp house 21 and the processing space 22. An Xe ₂ excimer lamp 23 is disposed inside the lamp house 21, and the Xe ₂ excimer lamp 23 is a discharge vessel, which has an outer diameter of 26 mm and a thickness of 1 mm, an outer diameter of 16 mm and a thickness of 1 mm. an inner tube disposed in the same axis, and is a Xe ₂ excimer lamp 23 is filled with a Xe gas 53.3KPa the space between the outer tube and the inner tube. The Xe ₂ excimer lamp 23 is electrically connected to the discharge power source 25 to apply a high frequency high voltage between the outer tube and the electrodes disposed in the inner tube, respectively. From the discharge plasma 24 of the Xe ₂ excimer lamp 23, Xe ₂ excimer light having a wavelength of 172 nm is emitted and irradiated to the processing space 22 from the light extraction window 27. In this embodiment, the light source is this excimer lamp 23. Moreover, as a means of irradiating vacuum ultraviolet light to this NmHn gas, it is achieved by constructing the outer tube of this excimer lamp by the synthetic quartz glass which permeate | transmits wavelength 172nm. In addition, the gas inlet 26a and the gas outlet 26b are installed in the lamp house 21 to allow nitrogen to flow in and purge the inside of the lamp house 21 with N ₂ , thereby providing vacuum ultraviolet light. Attenuation is less. The light extraction window 27 is also made of synthetic quartz glass with little attenuation of vacuum ultraviolet light having a wavelength of 172 nm. On the other hand, an object to be processed 29 is provided in the processing space 22, and the object to be processed 29 can be heated by the heater 28. The processing space 22 is provided with an inlet port 30a and an outlet port 30b for introducing, for example, ammonia NH ₃ as NmHn gas.

In this embodiment, the discharge power was tested at 200W as in the case of the first embodiment. The to-be-processed object 29 was quartz glass, the distance between the to-be-processed object 29 and the light extraction window 27 was 3 mm, and the temperature of the to-be-processed object 29 was irradiated at 25 degreeC. The pressure of ammonia NH _{3 in} the processing space 22 was 5.3 KPa. In this case, organic contaminants on the quartz glass could be removed in about 15 seconds. Further, in the present embodiment, since the Xe excimer lamp 23 is a lamp sealed by encapsulating Xe gas, there is also an advantage of obtaining stable light output over a long time.

Example 3

A third embodiment of the present invention is shown in FIG. FIG. 3 is a schematic cross-sectional view cut in the plane parallel to the electrode axis of the cylindrical electrodes 3a, 3b, and 3c. The processing apparatus 40 of this 3rd Example removes the light extraction window in the said 1st Example, and disposes the supply direction of discharge gas to the upper direction through the discharge plasma 4b between the irradiated object 9 in between. It is installed. Supplying the discharge gas of the photo-generated from the discharge gas inlet port (36a, 36b), and supplies the ammonia NH ₃ from the object to be treated (9) ammonia introducing port (10a) of the NH ₃ in the vicinity of the surface. The ammonia gas supplied here may use what was diluted with nitrogen and argon gas. In this processing apparatus, the gas generated by decomposing the discharge gas, the ammonia NH ₃ , and the organic substances scattered on the surface of the object to be processed, for example, is discharged from the discharge port 10b. In this embodiment, the light source is composed of these electrodes 3a, 3b, 3c provided with a dielectric around them, and a light emitting gas introduced around the electrodes. Moreover, this discharge container 1 and the processing chamber 2 are the same member, and consist of the member which shared two functions. As means for irradiating the vacuum ultraviolet light to the NmHn gas, light emitted from the discharge plasma 4b generated between the electrodes 3a, 3b and 3c is supplied directly from the inlet 10a without passing through a window or the like. This is achieved by having the gas irradiated. In addition, since the other structure is the same as that of the 1st Example, description here is abbreviate | omitted.

Thus, according to the structure which does not have a light extraction window, since the absorption loss by this light extraction window is lost, there exists an advantage that an excimer light can be utilized effectively.

Example 4

A fourth embodiment of the present invention is shown in FIG. 4 is a schematic cross-sectional view cut in a plane orthogonal to the direction in which the thickness of the first electrode 51 made of a rectangular plate-shaped metal is visible, that is, in the width direction that is the long side of the rectangle. The processing apparatus 50 in this fourth embodiment is an active species generating chamber 56 for irradiating light to the ammonia gas NH ₃ connected through the light extraction window 7 and the discharge space 54 using the dielectric barrier discharge. ) And an injection hole 57 for injecting active NH (a ¹ Δ), H ₂ , NH (X ³ Σ), and H generated from ammonia gas NH ₃ to the irradiated object 9. The discharge space 54 is a first electrode 51 which covers an alumina 52a having a thickness of 0.5 mm on a SUS plate having a thickness of 1 mm, a height of 100 mm, and a width of 1000 mm, and the second electrode 53 serves as a discharge container. The inner surface is composed of a member covered with alumina 52b having a thickness of 0.5 mm. The discharge distance is 3 mm, and Ar is introduced from the inlet port 55a and discharged from the outlet port 55b in order to generate Ar excimer light having a wavelength of 126 nm in the discharge space 54. The introduction pressure of the Ar in the discharge space 54 is 46.7 KPa. In this embodiment, the light source is composed of a light extraction window 7, a second electrode 53 serving as a discharge vessel, a first electrode 51 covered with alumina 52b, and a gas for discharge. The is achieved by the vacuum ultraviolet light that is configured to the light extraction window (7) as a means for irradiating the gas is NmHn example of a member which transmits light having a wavelength of 126nm, such as MgF _2.

According to this processing apparatus 50, discharge plasma 3 is generated by applying a high frequency voltage to the 1st electrode 51 and the 2nd electrode 53, and Ar excimer light is generated. The Ar excimer light is irradiated to the active species generating chamber 57 through the light extraction window 7 and is activated from NH (a ¹ Δ), H ₂ , NH ( ₃ ), which is active from ammonia NH ₃ introduced from the inlet 10. X ³ Σ), H is generated. The generated active NH (a ¹ Δ), H ₂ , NH (X ³ Σ), H are sprayed over the workpiece 9 from the active species injection port 57 of 1 mm × 1000 mm. By operating the to-be-processed object 9 or a processing apparatus, the whole process of the to-be-processed object 9 can be performed. In addition, in the case of applying a high frequency voltage, various shapes can be used as needed, such as a pulse wave, a square wave, and a sine wave.

Example 5

A fifth embodiment of the present invention is shown in FIG. 5 is a schematic cross-sectional view cut in the direction perpendicular to the direction in which the thickness of the first electrode 51 made of the rectangular plate-shaped metal is visible, that is, the width direction that is the long side of the rectangular plate-shaped metal. In the processing apparatus 60 shown in the fifth embodiment, the light shield plate 61 is provided in the active species generating chamber 57 facing the active species injection port 57 in the fourth embodiment shown in FIG. This is to prevent light from reaching the water to generate active species. In addition, since the other structure is the same as that of FIG. 4, description here is abbreviate | omitted.

Example 6

A sixth embodiment of the present invention is shown in FIG. 6 is a schematic cross-sectional view cut | disconnected in the direction orthogonal to the direction which the thickness of the 1st electrode 51 which consists of a rectangular plate-shaped metal is seen, ie, the width direction which is the long side of this rectangular plate-shaped metal. . The processing apparatus 70 shown in the sixth embodiment removes the light extraction window 7 and the active species generating chamber 56 from the processing apparatus 50 shown in FIG. Moreover, the discharge distance formed by the alumina 52a, 52b provided in the surface of the electrode 51 and the electrode 53 was 3 mm. In addition, the introduction and supplying a mixture of ammonia NH ₃ gas of 12% Ar gas in order to generate an Ar ₂ excimer light from the sphere (55a) to the discharge space (54). When a high frequency voltage is applied to the electrodes 51 and 53 from the power source 5 for discharge, a discharge plasma 4 is formed, and Ar ₂ excimer light is generated. In this embodiment, since ammonia NH ₃ is mixed with Ar gas, the Ar ₂ excimer light is efficiently irradiated to the ammonia NH ₃ itself, and high concentrations of active NH (a ¹ Δ), H ₂ , and NH (X ³ Σ) and H can be generated. In addition, since part of this ammonia NH ₃ can be changed into active species by the discharge plasma 4 formed by the dielectric barrier discharge, the density of the active species becomes more dense. The active NH (a ¹ Δ), H ₂ , NH (X ³ Σ) and H generated in this way are injected from the discharge port 55b toward the object to be processed together with Ar gas, which is a gas for discharge. In this embodiment, the light source is a portion covered with the second electrode 53 serving as a discharge container to form a discharge, the second electrode 53, the first electrode 51 covered with alumina 52a, and a room. It consists of a dedicated gas. In addition, a means for irradiating vacuum ultraviolet light to the NmHn gas, by supplying to configure the light source not through the window member, the mixture gas is mixed with ammonia NH ₃ in Ar gas to the discharge space 54 with a wavelength of 126nm This is achieved by passing ammonia NH ₃ through the discharge plasma 4 generating light.

Example 7

As a seventh embodiment, the structure of the device is the same as the device of Fig. 1 shown in the first embodiment, and the object 9 in Fig. 1 is covered with SiO ₂ of about 2 nm on the surface of the Si wafer. It was made. The distance between this to-be-processed object 9 and the light extraction window 7 was 3 mm, and the partial pressure of ammonia in the process space was 0.5 KPa. Under such conditions, since the pressure of ammonia in the treatment space is relatively low, the amount of 126 nm irradiated to SiO ₂ increases, and SiO ₂ can be etched by the treatment for 100 seconds.

According to the description of claim 1 of the present invention, since the processing such as washing is possible without including oxygen in the gas activated by light irradiation, the influence of oxygen on the object to be treated can be suppressed. In addition, since the gas to be activated is NmHn (N is nitrogen atom, H is hydrogen atom, m, n is any natural number), the generated active species exists in the state of NH molecule. Since the active species composed of NH molecules have a higher molecular weight than oxygen atoms, the active species infiltrates into the object to be treated, such as SiO ₂ , for example, denatures the object or is absorbed onto the surface. Does not cause disharmony to be released.

Further, according to the invention described in claim 2 of the present invention, since the NmHn gas is ammonia, active NH (a ¹ Δ), NH (X ³ Σ), H and the like are generated by irradiating vacuum gas to the gas. As a result, it is possible to perform incineration and removal of organic substances that are difficult to decompose without oxidizing the object to be treated. Since NH (a ¹ Δ) and NH (X ³ Σ) are molecules, they do not penetrate into the object to be treated, so that they can be treated without being released as a gas in a later step or deteriorating the object to be treated. There is an advantage. In addition, since the H generated by the irradiation of vacuum ultraviolet light has a large diffusion coefficient, it is immediately released even if it enters the object to be treated, and thus does not cause any harm, such as generating a gas release in a later step.

Moreover, since the partial pressure of this ammonia gas is 100 Pa or more, mixing of oxygen and water which are impurity gases is few, and it does not oxidize a to-be-processed object. In addition, since the partial pressure of ammonia is 10 kPa or less, the rate at which NH (a ¹ Δ), NH (X ³ Σ), H, etc. collide with ammonia and extinguish it is small, and the efficiency of incineration and removal of organic matters is possible.

To determine the cleaning effect of the partial pressure of ammonia gas NH ^3, for example, it can be carried out by measuring the contact angle of water in a quartz glass optical cleaning. Specifically, the quartz glass (30 mm long, 30 mm wide, 1 mm thick) that has been precisely cleaned in advance is left to stand indoors in the air for 24 hours, and the lower surface of the light extraction window 27 of the irradiation apparatus shown in FIG. The distance to the glass surface was made into 3 mm and 6 mm, the partial pressure of the ammonia gas NH ₃ was changed and irradiated, and the contact angle with water was measured after that. In the light irradiation, Ar was filled with 35 KPa in the discharge vessel to generate Ar plasma between the electrodes, and the emission luminance at the lower surface of the light extraction window 27 was 4.5 mW / cm ² , and the irradiation treatment was performed for 2 minutes under each partial pressure. Was performed. The partial pressure of ammonia gas is NH ₃ was subjected to the measurement of the change, if as shown in Figure 7 in 0.05KPa to 15KPa.

To less than 0.1KPa is, the amount of phosphorus NH (△ ¹ a) of the entire active, NH (X Σ ^3), H is reduced, and could not be sufficient washing. As a result, it can be considered that the contact angle itself becomes large at 0.05 KPa. Further, on the contrary when the ammonia gas NH ₃ when a high partial pressure, greater than the contact angle increased to 10KPa. This is because the ammonia gas NH Since ₃ polyatomic molecules, ammonia gas NH NH (a ¹ △) the partial pressure of higher activity by that when not activated, ammonia gas impact with the NH ₃ in _3, NH (X ³ Σ), It is considered that the effect of dissipation of H, etc. becomes large, and the cleaning effect is lowered. According to these confirmation experiments, it can be said that the partial pressure of the ammonia gas NH ₃ is effective at 0.1 KPa or more and 10 KPa or less. Also preferably, it can be said that there is a more significant effect at 0.5 KPa or more and 5 KPa or less.

Further, according to the invention of claim 3 of the present invention, since the light source that emits vacuum ultraviolet light is Xe ₂ excimer light having a maximum value at a wavelength of 172 nm using dielectric barrier discharge, if the reaction gas is, for example, ammonia gas, the active NH (a ¹ Δ) can be formed. In addition, this light source uses Kr ₂ excimer light having a maximum value at a wavelength of 146 nm or Ar ₂ excimer light having a maximum value at a wavelength of 126 nm, thereby adding active NH (a ¹ Δ) when irradiated with vacuum vacuum light to ammonia gas. Thus, active NH (X ³ Σ) and H are generated, and there is an advantage in that the target object can be efficiently processed. In addition, by using this light source as an excimer lamp using a dielectric barrier discharge, a high efficiency and a predetermined vacuum ultraviolet light can be generated, so that light of an extra wavelength range is not irradiated to the object to be processed and does not cause overheating of the object to be processed. For example, there is an effect that removal of organic substance etc. becomes possible. In addition, since there is no wear and tear of a metal electrode in the form of this light source, it does not pollute a to-be-processed object.

Further, according to the invention described in claim 4 of the present invention, the generated NH (a ¹ Δ), NH (X ³ Σ), H, and the like can be effectively transported to the object to be treated by injection, so that NH (a ¹ Δ), NH (X ³ Σ), H and the like, the utilization rate is improved, as a result, there is an advantage that the processing speed, such as removal of organic matter, improves. In this configuration, the object to be processed can be treated in the air (in normal air), and even when the object is enlarged, the object is easily moved, and the object is continuously processed. There is also an effect that can be easily performed.

According to the invention as set forth in claim 5, as a means for generating vacuum ultraviolet light, a dielectric barrier discharge using a discharge gas as a rare gas is used, and a means in which ammonia is mixed into the discharge gas is used. Excimer light in the vacuum ultraviolet light region generated by the dielectric barrier discharge is efficiently irradiated to ammonia, and part of the ammonia is changed to NH (a ¹ Δ), NH (X ³ Σ), H, etc. by the dielectric barrier discharge. , High density NH (a ¹ Δ), NH (X ³ Σ), H, and the like can be generated, and the removal of organic matters, etc., has the advantage that a fast processing speed can be obtained.

In addition, according to the invention of claim 6, there is an advantage that the irradiated object is not damaged by light by providing a shielding means so that the direct irradiated object is not irradiated.

In addition, according to the invention described in claim 7, the SiO _2, by irradiating an Ar ₂ excimer light having the maximum value in the Kr ₂ excimer light or wavelength 126nm with a maximum at a wavelength of 146nm, while the decomposition of SiO ₂ to Si + SiO, By irradiating NH (a ¹ Δ), NH (X ³ Σ), and H produced by irradiating ammonia with this vacuum ultraviolet light, there is an effect of enabling the etching of SiO ₂ .

Claims (7)

A light source for emitting vacuum ultraviolet light, at least one of a discharge vessel and a processing space including the light source, and an inlet for introducing a gas activated by irradiating light, and the organic material formed on the object to be treated. As a processing device for processing, The activated gas is NmHn (N is a nitrogen atom, H is a hydrogen atom, m, n is any natural number), and means for irradiating the NmHn gas with vacuum ultraviolet light emitted from the light source is provided. The processing apparatus characterized by decomposing and removing said organic substance by irradiating and activating the said light to NmHn gas, and acting on a to-be-processed object. The processing apparatus according to claim 1, wherein the NmHn gas is ammonia gas, and the partial pressure of the ammonia gas is 0.1 KPa or more and 10 KPa or less. The method of claim 1, wherein the light source, Spectral Xe ₂ excimer light having a maximum radiance at a wavelength of 172 nm, Spectral Kr ₂ excimer light having a maximum radiance at a wavelength of 146 nm, or Spectral Ar ₂ excimer light with maximum radiance at wavelength 126 nm It is an excimer lamp using a dielectric barrier discharge to generate a processing apparatus. The said NmHn gas is ammonia gas, After irradiating a vacuum ultraviolet light to this ammonia gas, this ammonia gas excited by this vacuum ultraviolet light is sprayed on to-be-processed object. The method of claim 1, wherein as the means for generating the vacuum ultraviolet light, a dielectric barrier discharge using a discharge gas as a rare gas is used, and ammonia gas for generating active species is mixed with the discharge gas. Processing unit. The processing apparatus according to claim 1, wherein light shielding means is provided so as not to directly irradiate the vacuum ultraviolet light to the irradiated object. A processing apparatus comprising a light source for emitting vacuum ultraviolet light, at least one of a discharge vessel including the light source and a processing space, and an inlet for introducing a gas activated by irradiating light, wherein the activated gas is ammonia, and it is provided with means for irradiating vacuum ultraviolet light radiated from the light source to the ammonia gas, as the light source, the spectrum of the emission luminance of the maximum value at a wavelength of 146nm Kr ₂ excimer light or wavelength radiation of the maximum value to 126nm using a dielectric barrier discharge to generate a spectrum of the Ar ₂ excimer light having the luminance, the processing device, characterized in that the etching of the surface of the SiO _2.

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