JP5102975B2 - Catalytic chemical treatment apparatus and catalytic chemical treatment method - Google Patents

Description

  The present invention relates to a catalytic chemical treatment apparatus and a catalytic chemical treatment method.

There is a Cat-CVD method (catalytic chemical vapor deposition method) as a film forming process that utilizes a catalytic pyrolysis reaction of a raw material gas on the surface of a refractory metal catalyst wire (catalyst body) heated at a high temperature. The decomposition of the source gas can be used not only for the CVD process but also for the surface treatment / modification process of thin films and substrates. For example, a thin film obtained by Cat-CVD or another type of film forming method, or the substrate itself is nitrided in an atmosphere in which NH ₃ is catalytically decomposed, hydrogen is added in an atmosphere in which H ₂ is catalytically decomposed, or Si etching and the like are known. However, in practice, it is often impossible to obtain a practical nitridation amount or a sufficient process speed by simply decomposing the raw material gas with a catalyst wire.

  In general, not only the Cat-CVD method but also a thin film formed by the CVD method contains a considerable amount of light elements in the source gas molecules, which is a property of the film and characteristics of the device using this film. Has a considerable impact on In the case of a plasma CVD-SiN film which is generally formed at a low substrate temperature and a relatively high pressure, this tendency is strong, and H containing up to 1% or more in atomic concentration is contained. There is also. Since it is necessary to release this mixed H to the outside of the film by post-annealing (post-deposition reforming heat treatment), not only the film-forming conditions but also the post-annealing and the conditions are important for controlling the film properties. .

  As a recent important example in which the control of the amount of H in the SiN film by post-annealing has a very large effect on improving the device characteristics, there is a SiN liner layer for forming a “strained Si transistor” corresponding to the 65 nm node and beyond in Si-LSI ( For example, refer nonpatent literature 1). In this case, a plasma CVD-SiN film is typically used, and the amount of H in the film is reduced by post-annealing to increase the stress generated in the liner layer. When bond dissociation / release of medium H is promoted, on the other hand, when the temperature is too high, there is a problem that the lower layer transistor is thermally damaged and the characteristics are impaired. Therefore, there is a case where UV irradiation to the substrate during post-annealing is adopted as one method that can sufficiently obtain the effect of releasing mixed H even at a low temperature at which the characteristics of the lower layer transistor do not deteriorate (for example, to generate a predetermined stress) (for example, Non-patent document 2).

  When UV light having a wavelength (~ <254 nm) having an energy larger than the optical band gap energy (~ 4.9 eV) of SiN is irradiated, the SiN film absorbs this and is photochemically excited to form the film. The bond strength of each atom is reduced, and H is released by dissociation even at a low post-annealing temperature.

  However, the problem still remains even if the post-annealing temperature is lowered by UV irradiation. The mixed H before being released by post-annealing exists in the film while forming Si-H bonds, NH bonds, etc., but on one side, this state is a dangling bond of Si or N in the film ( This is equivalent to terminating / inactivating dangling bonds) by H, and thus contributing to securing the characteristics of the SiN film as an insulator. Therefore, if the Si or N dangling bonds (dangling bonds) left after the H release are newly reconstructed, that is, unless they are recombined with complementary N or Si, the characteristics of the SiN film as an insulator will deteriorate. However, when the post-annealing temperature is lowered, there is a problem that the progress of the reconstruction process tends to be insufficient.

Therefore, the reconfiguration for deactivation and stabilization of the Si and N dangling bonds generated after the mixed H is released is promoted even at a low post-annealing temperature, and the characteristic deterioration after annealing is effective. It is required to be able to prevent it.
(March 2005, NIKKEI NICRODEVUCES (P43)) May 2005 NIKKEI NICRODEVUCES (P57, P60)

  An object of the present invention is to provide a catalytic chemical processing apparatus and a catalytic chemical processing method capable of solving the above-mentioned problems of the prior art and obtaining a practical processing speed and processing effect for a substrate to be processed. It is in.

  In addition to the conventional configuration in which a catalyst body such as tungsten is disposed in the processing chamber, the present inventors have provided a light source that enables light irradiation to the substrate to be processed outside the processing apparatus. Or disposed in a processing apparatus, and as the light source, a wavelength that is absorbed by a substrate being processed or a film on the surface thereof and can excite them solidly photochemically, generally ultraviolet (UV) Using a device that emits light with a wavelength in the light range, it is possible to supply active reactive species (free radicals) generated by contact with the catalyst body to the substrate that is excited by UV irradiation. The present inventors have realized that a sufficient amount of nitridation and a sufficient processing speed can be obtained, and the present invention has been completed.

The catalytic chemical treatment apparatus of the present invention comprises a substrate stage on which a substrate to be treated can be placed, a catalyst body arranged in parallel and opposed to the main surface of the substrate to be treated, and a catalyst body that energizes and heats this catalyst body In a catalytic chemical treatment apparatus including a heating power source, a gas introduction system for introducing a reaction gas for treatment, and an exhaust means, light having a wavelength absorbed by the substrate to be treated is emitted toward the substrate to be treated. A storage container for storing the light source is disposed in the catalytic chemical processing apparatus or outside the catalytic chemical processing apparatus, and a purge gas introduction port for introducing purge gas into the storage container and a purge gas introduced from the purge gas introduction port are stored in the storage container The catalyst body heating power source applies a low potential and a high potential to both ends of the catalyst body so that the low potential is a positive or negative potential with respect to the ground potential. The catalyst body And further comprising a catalyst body potential setting power source for applying a bias voltage.

  In the catalytic chemical treatment apparatus, the substrate to be treated has an optical band gap energy that absorbs UV light having a radiation wavelength emitted from the light source, for example, a plasma CVD method, an LPCVD method, or a catalytic CVD method. The light source is a tube material that transmits UV light having a radiation wavelength (for example, 254 nm and 185 nm) having a photon energy larger than the optical band gap energy (˜4.9 eV) of the SiN film. It is a low-pressure mercury lamp constructed, and this apparatus is characterized in that it is used for performing dehydrogenation and simultaneous post-nitridation (post-annealing) of the SiN film.

Further, in the catalytic chemical treatment apparatus, the substrate to be treated is an H _f O _x film, and this device is used for post-nitriding the substrate to be treated.

Furthermore, in the catalytic chemical treatment apparatus, the substrate to be treated is a H _f O _x film mixed with organic impurities during film formation or a metal nitride film mixed with organic impurities during film formation. It is used for removing organic impurities in the processing substrate.

In the catalytic chemical treatment method of the present invention, the substrate to be treated is transported into the catalytic chemical treatment apparatus, the reaction gas is brought into contact with the catalyst body heated to the decomposition temperature of the reaction gas for treatment, and the light source is accommodated. While purging the interior of the container with a purge gas, a reaction generated from the catalyst body by irradiating light having a wavelength absorbed by the substrate to be processed from the light source through the catalyst body and irradiating the surface of the substrate to be processed. a highly active free radicals, in which absorbs light supplied from the light source is supplied to the surface of the substrate to be processed in a state of being solid photochemically excited, for processing the target substrate surface, wherein A low potential and a high potential are applied to both ends of the catalyst body, a bias voltage is applied to the catalyst body so that the low potential is a positive or negative potential with respect to the ground potential, and thermionic emission from the catalyst body is performed. And light And controls the child release characterized by treating the surface of the substrate to be processed.

In the catalytic chemical treatment method, the substrate to be treated has an optical band gap energy that absorbs UV light having a radiation wavelength emitted from the light source, for example, a plasma CVD method, an LPCVD method, or a catalytic CVD method. An SiN film is used, NH ₃ , H ₂ or a mixed gas of NH ₃ and H ₂ is used as the processing reaction gas, and the optical band gap of the SiN film is used as emitted light from the light source. The surface of the SiN film is dehydrogenated and co-post-nitrided using radiation from a low-pressure mercury lamp composed of a tube that transmits UV light having a radiation wavelength (for example, 254 nm and 185 nm) having a photon energy greater than the energy. It is characterized by processing.

  When a SiN film is used as the substrate to be processed, the substrate temperature during processing is set to 450 ° C. or lower, and post-nitridation is performed together with dehydrogenation of the SiN film. The reason why the substrate temperature is set to 450 ° C. or lower is that the heat resistance of the substrate to be processed is taken into consideration. The lower limit of the substrate temperature is not particularly limited as long as the substrate surface treatment (dehydrogenation and simultaneous post-nitridation treatment) can be performed, and is, for example, about room temperature, preferably about 80 ° C.

When an H _f O _x film is used as the substrate to be processed, the substrate temperature at the time of processing is set to 500 ° C. or lower, and post-nitriding of the H _f O _x film is performed. The reason why the substrate temperature is set to 500 ° C. or less is that the heat resistance of the substrate to be processed is taken into consideration. The lower limit of the substrate temperature is not particularly limited as long as the substrate surface treatment (post nitriding treatment) can be performed, and is, for example, about room temperature, preferably about 80 ° C.

When the substrate to be treated is a H _f O _x film mixed with organic impurities during film formation or a metal nitride film selected from TaN, ZrN, VN, TiN and WN mixed with organic impurities during film formation, The substrate temperature during processing is set to 450 ° C. or lower, and organic impurities in the substrate to be processed are removed. The reason why the substrate temperature is set to 450 ° C. or lower is that the heat resistance of the substrate to be processed is taken into consideration. The lower limit of the substrate temperature is not particularly limited as long as the organic impurities in the substrate can be removed, and is, for example, about room temperature, preferably about 80 ° C. In the case of this organic impurity removal, H ₂ gas is used as a processing reaction gas.

  According to the present invention, there is an effect that it is possible to provide a catalytic chemical processing apparatus and a catalytic chemical processing method capable of obtaining a practical processing speed and processing effect for a substrate to be processed.

  According to the catalytic chemical processing apparatus of the present invention and the catalytic chemical processing method using this apparatus, for example, a Cat-CVD-SiN film obtained in a Cat-CVD chamber having a separate chamber configuration from this processing apparatus, LPCVD, or plasma Application to post-deposition reforming heat treatment (post-annealing) processes such as SiN films obtained by other types of external film forming apparatuses such as CVD has become possible.

  First, an embodiment of the catalytic chemical treatment apparatus according to the present invention will be described, and then the present invention will be further described by comparing the present invention with the background art in detail.

  According to an embodiment of the present invention, as shown in FIG. 1, a substrate stage as a substrate heating susceptor 2 for supporting and heating a substrate to be processed S is installed in the catalytic chemical treatment apparatus 1. Opposite to the susceptor 2, a light source 3 such as a synthetic quartz low pressure mercury lamp (λ = 2537 Å, ˜5 eV: λ = 1849 Å, ˜6 eV) is disposed outside the processing apparatus 1. The light source 3 can emit light having a wavelength absorbed by the substrate to be processed S. An upper part of the processing apparatus 1 is provided with an incident window 4 (made of synthetic quartz) for allowing light emitted from the light source to enter the processing apparatus between the light source 3 and the light source container itself. However, it may be made of a material that reflects light from the light source and has a function as the reflector 5, or a reflector made of such a material may be provided on the inner wall of the container. Light (for example, UV light) emitted from the light source 3 is configured to be irradiated into the processing apparatus 1 with UV light having main emission line wavelengths of 254 nm and 185 nm through the incident window 4. In the case of a low-pressure mercury lamp, in addition to the above emission wavelength, UV light having emission line emission wavelengths such as 313 and 366 nm is also emitted. These wavelengths can also be used for the catalytic chemical treatment of the present invention.

  In the processing apparatus 1, a catalyst body 6 in the form of a mesh or a saddle shape, which is formed of fine wires of a refractory metal such as tungsten, usually having a diameter of less than 1 mm, is formed on the main surface of the substrate S to be processed. The catalyst body is connected to a power source 7 for heating and heating the catalyst body (DC constant current source or the like).

The processing apparatus 1 is provided with a reaction gas introduction port 8, and the storage container of the light source 3 is provided with a purge gas introduction port 9 such as N ₂ .

When carrying out the catalytic chemical treatment method of the present invention using the above-described treatment apparatus, for example, NH ₃ or H ₂ or a mixed gas of NH ₃ and H ₂ is used as a reaction gas, and this reaction gas is used as the treatment apparatus 1. UV that is introduced from the reaction gas inlet 8 provided on the side wall into the processing apparatus, is brought into contact with the catalyst body 6 heated to a predetermined temperature and decomposed, and the generated highly reactive free radicals are supplied from the light source. Supplying the surface of the substrate to be processed S in a state of absorbing light and being excited by solid photochemistry, nitriding treatment (Cat post nitriding treatment (post annealing)) or hydrogen treatment (Cat hydrogen treatment) of the substrate surface, The reaction is performed at a low temperature of 500 ° C. or lower, preferably room temperature to 500 ° C., more preferably 80 to 500 ° C. under UV light irradiation. The UV light is usually applied to the substrate to be processed through the catalyst body.

  FIG. 2 shows another embodiment of the catalytic chemical treatment apparatus according to the present invention. 2, the same components as those in the catalytic chemical treatment apparatus of FIG. 1 are denoted by the same reference numerals, and detailed description thereof is omitted. The processing apparatus 1 shown in FIG. 2 includes a catalyst body potential setting power source (DC power source or the like) 10 for applying a bias voltage to the catalyst body 6 during energization heating. Although FIG. 2 shows an example in which a positive potential is applied with respect to ground, a negative potential with respect to ground may be applied to the catalyst body. Since the catalyst body 6 is simultaneously irradiated with UV light when the substrate to be processed S is irradiated with UV light, thermoelectrons and photoelectrons are emitted from the catalyst body, and such a positive or negative bias potential is applied. By applying it to the catalyst body, its release can be controlled and unintentional discharge can be prevented from occurring in the processing apparatus.

  Next, the relationship between the present invention and the background art will be described.

As described in the background section above, in general, light elements in source gas molecules, for example, SiH ₄ , NH as source gases for SiN film formation, are not limited to Cat-CVD but are formed by a CVD method. _{When 3} is used, a considerable amount of H element is mixed / contained, which has a considerable influence on the film physical properties and the characteristics of the device using this film. In particular, this tendency is strong in a plasma CVD-SiN film which is generally formed at a low substrate temperature of about 400 ° C. or less and a relatively high pressure of about several Torr in order to generate a stable plasma. There may be a case where H as much as 1 percent or more is contained at several concentrations. For this mixed H, it is necessary to decompose the bond in the SiN film by post-annealing at an appropriate temperature and release it outside the film. Is also important for the control of film properties.

  As a recent important example in which the control of the amount of H in the SiN film by post-annealing has a great effect on improving the device characteristics, there is a SiN liner layer for forming a “strained Si transistor” corresponding to the 65 nm node and beyond in Si-LSI. This is because the stress generated in the liner layer covering the entire surface directly above the transistor is increased, thereby generating lattice distortion in the substrate (channel) Si crystal directly below the liner SiN layer which is the key to the process of improving channel mobility. A film in which the amount of H in the film is reduced by post-annealing and the stress is increased, typically a plasma CVD-SiN film is used.

  In this process, in order to obtain a predetermined stress generation, it is necessary to promote the bond dissociation / release of H in the liner SiN layer by setting the post-annealing temperature to a certain level or more. However, there is a problem that the characteristics are damaged due to thermal damage. Therefore, the effect of releasing mixed H can be sufficiently obtained even at a low temperature of about 500 ° C. or less, preferably room temperature to 500 ° C., more preferably 80 to 500 ° C., at which the characteristics of the lower layer transistor do not deteriorate. As a method, UV irradiation to the substrate during post-annealing may be employed.

  The optical band gap energy of SiN is ˜4.9 eV, but when irradiated with UV light of a wavelength (˜ <254 nm) having a larger energy than this, the SiN film absorbs this and is photochemically excited, The bonding force of each atom constituting the film is reduced. In addition to Si—N bonds, which are typical chemical bonds in SiN films, Si—H bonds and N—H bonds, which are incidental bonds involving mixed H, also become unstable and are inherently bonded. These bonds with low energy dissociate even at a low post-annealing temperature, and H is released.

  However, the problem still remains even if the post-annealing temperature is lowered by UV irradiation. The mixed H before being released by the post-annealing is present in the film while forming Si—H bonds, NH bonds, etc. as described above, but on one side, this state is due to Si and N in the film. This is equivalent to the fact that dangling bonds (dangling bonds) are terminated / inactivated by H and thus contribute to securing the characteristics of the SiN film as an insulator. Therefore, if the Si or N dangling bonds (dangling bonds) left after the H release are newly reconstructed, that is, unless they are recombined with complementary N or Si, the characteristics of the SiN film as an insulator will deteriorate. However, when the post-annealing temperature is lowered, there is a problem that the progress of the reconstruction process tends to be insufficient.

The present invention has also been made to solve the above-mentioned contradictory problem in the conventional method. According to the catalytic chemical treatment apparatus having the configuration according to the present invention, a highly active nitriding property in which NH ₃ is simultaneously catalytically decomposed by a catalyst body on a SiN film excited / activated by solid-state photochemistry by UV light irradiation. Since free radicals are supplied from the gas phase, the reconfiguration for deactivation and stabilization of the dangling bonds of Si and N generated after the mixed H is released is promoted even at low post-annealing temperatures. Therefore, it is possible to effectively prevent deterioration of characteristics after annealing.

The state as described above is the effect of nitriding a substrate (thin film) by a nitriding free radical obtained by catalytic decomposition of NH ₃ with a catalyst body, which is conventionally known. It is promoted by irradiating and irradiating and activating by solid photochemical activation.

  In the above description, the effect on the characteristic stabilization post-nitridation at the time of removing H from a SiN film, which is likely to have a high H content, as in the case of a plasma CVD-SiN film, has been described as an example. It may be a SiN film that has been empirically known to contain less H content than plasma CVD-SiN, or not at all, such as Cat-CVD-SiN and high-temperature LPCVD-SiN. . In addition, not only for the purpose of removing H, but also for “post nitridation” for the stoichiometric composition of SiN film that has become Si-excess composition immediately after film formation (as-depo.) Needless to say, this is also effective.

For stoichiometric composition of Si-rich SiN, not only “post-nitridation” but also “extraction of excess Si” can be considered, but the H ₂ gas catalytically decomposed by the catalyst body hydrogenates the excess Si, It is known that it has a strong action of generating “excess Si extraction” that is released out of the SiN film as a gas phase silyl radical (SiH _n (1 ≦ n ≦ 4)).

Therefore, for the purpose of the stoichiometric composition of the Si-rich SiN, a process using not only NH ₃ but also H ₂ or a mixed gas of NH ₃ and H ₂ as a source gas may be used.

  Furthermore, the material to be processed by the apparatus configuration of the present invention is not limited to the above-described SiN film to be dehydrogenated or post-nitrided, as long as it has an optical band gap energy that absorbs irradiated UV light. There is no particular limitation. For example, as a significant example in the device manufacturing process,

(1) Post nitriding such as H _f O _x film (optical band gap energy: 5.8 eV) as a high dielectric constant (High-k) gate dielectric film,

(2) The film is formed by MOCVD (Metal Organic CVD) or MOALD (Metal Organic Atomic Layer Deposition). Removal of C _n H _x (organic matter) from H _f O _x , TaN _x, etc. in which C _n H _x (organic matter) is likely to remain in the film, that is, removal of organic matter in the film by H ₂ that is catalytically decomposed by the catalyst There is.

  In the catalyst body described so far, the reaction gas is usually catalytically decomposed (catalytic decomposition) in a state where a high melting point metal such as tungsten is heated to a high temperature of about 1700 to 2000 ° C. It has already been found that a considerable amount of thermoelectrons are emitted from the catalyst body at this time.

  In the apparatus configuration according to the present invention, since the UV light is irradiated to the catalyst body in which many internal electrons are thermally excited to near the vacuum level, the effective photoelectron emission barrier height is greatly reduced. It is assumed that For this reason, since a large amount of photoelectron emission is superimposed, an unintended discharge may occur in the catalytic chemical treatment apparatus.

  For the purpose of preventing such discharge and making it a pure radical process in which charged particles are not involved, an appropriate polarity, usually a positive bias potential, may be applied to the catalyst body at grounding.

  Conversely, a negative potential that increases / accelerates photoelectrons and thermoelectrons emitted from the catalyst body may be applied to promote / promote the generation of a discharge to form a plasma assist process.

  In a conventional production apparatus, when a processing apparatus using UV light is applied to a film forming process, film formation (deposition) occurs not only on a substrate but also on a UV light incident window, and UV light is emitted. When absorbing film types, the amount of UV light transmitted through the entrance window decreases with the progress of the process, and the process automatically stops, making it impractical as a production apparatus.

However, although the apparatus configuration according to the present invention also uses UV light, the processing apparatus of the present invention does not form a film such as post-nitridation or H ₂ processing of a thin film formed in a separate chamber or apparatus. It is preferable to use it limited to a film) treatment process. Therefore, there is no problem such as the automatic stop of the process as described above, and it can be used as a practical device. Of course, in the case of a film type that does not absorb UV light, it can also be applied to a film forming process.

  According to the present invention, it is possible to provide a catalytic chemical processing apparatus and a catalytic chemical processing method capable of obtaining a practical processing process speed and processing effect for a substrate to be processed. Later, it can be used in necessary technical fields such as film reforming heat treatment.

The block diagram which shows typically the structure of the catalytic chemical treatment apparatus which concerns on one embodiment of this invention. The block diagram which shows typically the structure of the catalytic chemical treatment apparatus which concerns on another embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Catalytic chemical processing apparatus 2 Substrate heating susceptor 3 Light source 4 Incident window 5 Reflector plate 6 Catalytic body 7 Power supply for catalyst body heating 8 Reactive gas inlet 9 Purge gas inlet 10 Power supply for setting catalyst body potential S Processed substrate

Claims (12)

A substrate stage on which a substrate to be treated can be placed, a catalyst body disposed in parallel and opposed to the main surface of the substrate to be treated, a power source for heating a catalyst body that heats the catalyst body by energization, and a reaction for treatment In a catalytic chemical treatment apparatus provided with a gas introduction system for introducing gas and an exhaust means,
A storage container for storing a light source that emits light having a wavelength absorbed by the substrate to be processed toward the substrate to be processed is disposed inside the catalyst chemical treatment apparatus or outside the catalyst chemical treatment apparatus, A purge gas inlet for introducing purge gas and an exhaust outlet for discharging the purge gas introduced from the purge gas inlet from the storage container are provided.
The power source for heating the catalyst body applies a low potential and a high potential to both ends of the catalyst body, and applies a bias voltage to the catalyst body so that the low potential is a positive or negative potential with respect to the ground potential. A catalytic chemical treatment apparatus, further comprising a power source for setting a catalyst body potential.   2. The catalytic chemical treatment apparatus according to claim 1, wherein the substrate to be treated has an optical band gap energy that absorbs UV light having a radiation wavelength emitted from the light source.   The substrate to be processed is a SiN film formed by plasma CVD, LPCVD or catalytic CVD, and the light source has UV light having a radiation wavelength having a photon energy larger than the optical band gap energy of the SiN film. The low-pressure mercury lamp composed of a tube material that permeates water, and the catalytic chemical treatment device is a device used to perform dehydrogenation and simultaneous post-nitridation of the SiN film. 3. The catalytic chemical treatment apparatus according to 2. 3. The catalyst according to claim 1, wherein the substrate to be treated is an H _f O _x film, and the catalytic chemical treatment apparatus is an apparatus used for performing post-nitriding of the substrate to be treated. Chemical processing equipment. The substrate to be treated is a H _f O _x film mixed with organic impurities at the time of film formation or a metal nitride film mixed with organic impurities at the time of film formation, and the catalytic chemical treatment apparatus removes organic impurities in the substrate to be treated. The catalytic chemical treatment apparatus according to claim 1 or 2 , wherein the catalytic chemical treatment apparatus is used for removal. The substrate to be processed is transported into the processing chamber of the catalytic chemical processing apparatus, the reaction gas is brought into contact with the catalyst body heated to the decomposition temperature of the processing reaction gas, and the inside of the storage container for storing the light source is purged with a purge gas. However, the light having a wavelength absorbed by the substrate to be treated is irradiated from the light source to the surface of the substrate to be treated after passing through the catalyst body, and the reaction-active free radicals generated from the catalyst body are irradiated. In the catalytic chemical processing method of absorbing the light supplied from the light source and supplying it to the surface of the substrate to be processed in a state of being solid photochemically excited, and processing the surface of the substrate to be processed,
A low potential and a high potential are applied to both ends of the catalyst body, a bias voltage is applied to the catalyst body so that the low potential is a positive or negative potential with respect to a ground potential, and the thermoelectrons from the catalyst body A catalytic chemical treatment method, wherein the surface of the substrate to be treated is treated by controlling emission and photoelectron emission.   7. The catalytic chemical treatment method according to claim 6, wherein the substrate to be treated has an optical band gap energy that absorbs UV light having a radiation wavelength emitted from the light source. A SiN film formed by plasma CVD, LPCVD or catalytic CVD is used as the substrate to be processed, NH ₃ , H ₂ or a mixed gas of NH ₃ and H ₂ is used as the reaction gas, and As the radiation from the light source, radiation from a low-pressure mercury lamp composed of a tube material that transmits UV light having a radiation wavelength having a photon energy larger than the optical band gap energy of the SiN film is used, and the dehydration of the SiN film is performed. The catalytic chemical treatment method according to claim 6 or 7, wherein the surface is treated by performing elementary and simultaneous post-nitridation.   9. The catalytic chemical treatment method according to claim 8, wherein the substrate temperature during the treatment is set to 450 ° C. or lower, and post-nitridation is performed together with dehydrogenation of the SiN film. 7. A H _f O _x film is used as the substrate to be processed, the substrate temperature at the time of processing is set to 500 ° C. or less, and the surface is treated by post-nitriding the H _f O _x film. Or the catalytic chemical treatment method according to 7. As the substrate to be processed, a H _f O _x film mixed with organic impurities during film formation or a metal nitride film selected from TaN, ZrN, VN, TiN and WN mixed with organic impurities during film formation is used. 8. The catalytic chemical treatment method according to claim 6, wherein the substrate temperature is set to 450 ° C. or less, and organic impurities in the substrate to be treated are removed. The catalytic chemical treatment method according to claim 11, wherein H ₂ gas is used as the reaction gas.

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