JP2000103607A - Apparatus and method for generating excited nitrogen - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide both an apparatus for generating an excited nitrogen so that the object of a reaction can freely be selected by generating a pure excited nitrogen-containing nitrogen without mixing an impurity from a wall surface of a vacuum container or a discharge electrode therein and solely feeding the resultant nitrogen and a method therefor. SOLUTION: Nitrogen gas fed from a gas introduction port 10 is solidified on the surface of a gas cooling surface 9 provided in a vacuum container 2 to form a nitrogen aggregate layer 20 and a laser 12 for exciting the nitrogen and a laser 13 for ablasion are introduced through a laser introduction window 11 in the order mentioned into the vacuum container 2 to irradiate the nearly same position of the solid nitrogen layer 20. Thereby, nitrogen ablasion particles 21 containing a large amount of the excited nitrogen are released.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus and a method for producing excited ionic or radical nitrogen that can be used for forming a thin film of a nitrogen compound or for nitriding a material surface.

[0002]

2. Description of the Related Art A nitrogen compound thin film can be obtained by depositing on a substrate while reacting nitrogen with boron, niobium, silicon or the like, or a material having preferable characteristics can be obtained by impregnating the surface with nitrogen. Since nitrogen is an inert gas and has low reactivity, when it is used for forming a nitrogen compound thin film or nitriding reaction of the material surface, it is converted into active excited nitrogen in ionic or radical state and then supplied to the reaction field. It is preferred to accelerate the reaction process.

As a method of generating such excited nitrogen, a method of converting nitrogen gas into plasma by high-frequency discharge, microwave discharge, or the like has been widely used. The reaction is promoted to form a nitrogen compound thin film. However, the method using plasma has a drawback that the region where excited nitrogen is generated is widened, so that impurities from these materials tend to be mixed by acting on the wall surface of the vacuum vessel and the discharge electrode.

There is also a method of obtaining a nitride thin film by laser ablation of a constituent material in a nitrogen gas atmosphere. However, nitrogen deficiency can be sufficiently compensated even if film formation is performed at a relatively high nitrogen partial pressure. However, impurities such as oxygen and carbon slightly remaining in the film forming apparatus are mixed into the film, and a problem remains in terms of film quality.

Japanese Patent Application Laid-Open No. 6-248438 discloses a method of forming a semiconductor thin film on a substrate by performing laser ablation using a II-VI group semiconductor element adsorbed with nitrogen gas as a target. In this method, a target made of a semiconductor constituent element is cooled in a vacuum vessel, nitrogen is adsorbed on the surface thereof, and a laser is irradiated to the target to ablate the semiconductor constituent element. Then, the nitrogen activated by the laser is scattered along with the ablation particles of the semiconductor constituent element target, and the ablation particles and the active nitrogen are simultaneously supplied on the substrate to form a nitrogen-doped semiconductor thin film.

In this method, activated nitrogen is generated in the vicinity of the substrate, so that a high concentration of nitrogen can be added to the compound deposited on the substrate by acting before the active nitrogen is deactivated. A similar method can be used for forming a nitrogen compound thin film. However, the laser ablation method using a nitrogen adsorbent as a target can obtain activated nitrogen.However, the reaction conditions of the excited nitrogen are limited due to the scattering of the mixed nitrogen with the target ablation substance. Cannot be freely selected.

[0007]

The problem to be solved by the present invention is to generate pure excited nitrogen-containing nitrogen in which impurities from the wall surface of the vacuum vessel and from the discharge electrode are not mixed, and supply it alone. Accordingly, it is an object of the present invention to provide an excited nitrogen generator and a method for performing a nitridation reaction by freely selecting a reaction target.

[0008]

In order to solve the above-mentioned problems, an excited nitrogen generator according to the present invention comprises a vacuum vessel, a laser generator for exciting nitrogen and a laser generator for ablation, and a gas provided in the vacuum vessel. The nitrogen gas supplied from the gas inlet is solidified on the surface of the cooling surface to form a solid nitrogen layer, and a laser for nitrogen excitation and a laser for ablation are introduced into the vacuum vessel through a laser introduction window, and a solid nitrogen layer is formed. Irradiation is performed at substantially the same position. The nitrogen excitation laser generator preferably generates a laser in the ultraviolet light range, and more preferably an excimer laser. Further, it is preferable that the ablation laser generator generates a pulse laser in a visible light region or an ultraviolet light region.
More preferably, it is a G laser device.

In order to solve the above-mentioned problems, a method for generating excited nitrogen according to the present invention comprises supplying a nitrogen gas into a evacuated vacuum vessel and solidifying the nitrogen gas on a cooling surface to form a solid nitrogen layer. The solid nitrogen layer is irradiated with a laser for exciting nitrogen, and then the irradiation position is irradiated with a laser for ablation to ablate the nitrogen component. Note that the thickness of the solid nitrogen layer is preferably set to such an extent that the material of the cooling surface is not eroded by the laser for ablation. Preferably, the laser for nitrogen excitation is a laser in the ultraviolet region, and the laser for ablation is a pulse laser in the visible or ultraviolet region. It should be noted that an ablation laser mainly having a second harmonic of a YAG laser can be used.

Furthermore, a second ablation laser generator is provided, and another laser introduction window, a target support board, and a thin film deposition substrate are further provided, and a laser generated by the second ablation laser generator is separated. Irradiation on the target support board may be performed through a laser introduction window. According to the above configuration, ablation particles of the reaction target are generated near the excited nitrogen and the nitrogen reactant is deposited on the substrate, so that a high-quality thin film can be formed.

According to the excited nitrogen generation method of the present invention, nitrogen, which has conventionally been regarded as an atmospheric gas when forming a nitride film by laser ablation, is cooled to a very low temperature by itself and aggregated.
This is a new method of solidifying and using it as a target. According to the excited nitrogen generating apparatus and method of the present invention, nitrogen is efficiently excited when a condensed layer is formed with an appropriate thickness on a cryogenic local cooling surface provided in a vacuum vessel. Irradiate laser to generate excited nitrogen, accumulate in the aggregate, and irradiate the ablation laser to the part of the nitrogen aggregate layer that is excited while the excited state is maintained, so that only the nitrogen aggregate is ablated, Nitrogen aggregates containing a large amount of excited nitrogen are released as ablation particles,
Excited nitrogen with less contamination of residual gas and impurities generated from walls can be supplied to the reaction site. Furthermore, a target of an object reacting with nitrogen and a substrate on which a thin film is deposited are provided in a vacuum vessel, and a nitrogen component is ablated and the reaction object is ablated, so that a generated nitrogen reactant is deposited on the substrate. You can also.

The present inventors have found that when a laser beam having a large photon energy, such as an excimer laser in the ultraviolet region, is irradiated on the aggregated nitrogen, nitrogen molecules in a ground state are dissociated into an atomic state and excited. It is also known that the same laser also generates excited state nitrogen molecules. However, depending on the commonly used ultraviolet laser, excited nitrogen is only generated in the nitrogen aggregate and cannot be taken out of the aggregate. On the other hand, it has been confirmed by the present inventors that nitrogen aggregates can be ablated and emitted by irradiating a pulse laser having a large peak intensity in a visible light region where the thermal effect is not so large. However, even when a visible light laser is applied to the nitrogen aggregate, the ability to excite nitrogen is low because the photon energy is small.

On the basis of the above findings obtained as a result of earnest studies, the present inventors cooled and aggregated nitrogen gas to form a nitrogen-aggregated layer having an appropriate thickness. Irradiates an excitation laser beam such as an ultraviolet excimer laser to excite nitrogen to excite it, and before extinguishing the excited nitrogen, irradiates a portion with much excited nitrogen with a visible light laser with strong peak intensity to ablate only the nitrogen aggregation layer portion By doing
The invention of an apparatus and a method capable of obtaining a large amount of nitrogen containing a large amount of nitrogen in an excited state and containing few impurities has been achieved.

Incidentally, the nitrogen aggregate once in an excited state is deactivated with a predetermined time constant even after the irradiation of the excitation laser is completed. A mixture of molecular nitrogen atoms can be obtained. In addition, the amount of impurities such as oxygen remaining under a high vacuum is reduced, and excited nitrogen is generated under the high vacuum. Obtainable.

[0015]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments with reference to the drawings. FIG. 1 is a block diagram showing one embodiment of the excited nitrogen generator of the present invention, FIG. 2 is a perspective view showing a main part of the present embodiment, FIG. 3 is a graph explaining the operation of the laser for nitrogen excitation in the present invention, FIG. 4 is a graph showing the operation of the laser for ablation, FIG. 5 is a graph illustrating the effect of the present invention, FIG. 6 is a block diagram showing a second embodiment of the present embodiment, and FIG. It is a block diagram showing the 3rd aspect.

[0016]

FIG. 1 is a block diagram showing a configuration of an excited nitrogen generator according to one embodiment of the present invention, and FIG. 2 is a perspective view showing a main part of the present embodiment. As shown in FIGS. 1 and 2, the vacuum chamber 2 of the excited nitrogen generator 1 is connected to a vacuum pump 3 and can be evacuated. Two small refrigerators, that is, a coagulation refrigerator 5 inserted from the side of the vacuum chamber 2 are attached to perform cryogenic cooling.

The main part of the excited nitrogen generator 1 is disposed inside a cryopanel 8 installed at the center of the vacuum chamber 2. The exhaust refrigerator 4 is provided with a first stage 6 which is cooled to about 80K and a second stage 7 which is cooled to about 10K, and a cryopanel 8 made of copper is attached to the first stage 6. The cryopanel 8 shields heat from the surroundings, adsorbs residual gas such as moisture and oxygen, and maintains the environment in the vacuum chamber 2.

The distal end of the coagulation refrigerator 5 is disposed near the second stage 7 and cooled to about 10K at the distal end thereof.
Stage 9 is provided. In addition, nitrogen gas nozzle 1
0 extends near the third stage 9 so that nitrogen gas can be supplied near the stage surface. Also,
The vacuum chamber 2 has a laser introduction window 11, from which two types of laser beams, a laser 12 for nitrogen excitation and a laser 13 for ablation, are introduced, and pass through a laser transmission hole 30 provided in the cryopanel 8, Irradiation is performed on the surface of the third stage 9 of the coagulation refrigerator 5.

The nitrogen excitation laser 12 is emitted from the first laser generator 14, reflected vertically by the mirror 15, condensed by the lens 16, transmitted through the laser introduction window 11, and passed through the third stage 9 in the vacuum chamber 2. Focus on the surface. The ablation laser 13 is a second laser generator 17.
Then, the light is vertically reflected by the total reflection mirror 18, passes through the mirror 15, passes through the same optical path as the nitrogen excitation laser 12, and is focused on the surface of the third stage 9. The irradiation timing of these lasers is controlled by the control device 19.

When the excited nitrogen is generated by the excited nitrogen generator 1 of the present embodiment, the exhaust refrigerator 4 and the vacuum pump 3
Is operated, the inside of the vacuum chamber 2 is sufficiently cooled to, for example, about 20K, and the vacuum chamber 2 is evacuated to about 1 × 10 ⁻⁷ Torr, and the coagulation refrigerator 5 is operated.
The stage 9 is cooled to, for example, 20K or less. Next, when nitrogen gas is supplied from the nitrogen gas nozzle 10, the third stage 9 is started.
Since the temperature of the surface is sufficiently low, nitrogen aggregates 20 are formed on the surface. When the nitrogen agglomerate layer 20 is appropriately developed, if the nitrogen excitation laser 12 having an appropriate pulse time length is irradiated an appropriate number of times, nitrogen in an excited state is generated in the agglomerate.

Thereafter, when the ablation laser 13 is irradiated to the place where excited nitrogen is generated, nitrogen atoms and nitrogen molecules in the excited state are released from the nitrogen aggregate as ablation particles 21. Although the thickness of the nitrogen aggregate is reduced in the portion where the nitrogen is released, a dent is generated. The next laser irradiation may be performed after new nitrogen gas is aggregated and compensated. By slightly moving the laser or optically shifting the laser irradiation position, the laser irradiation can be repeated in a short time.

The nitrogen excitation laser 12 is preferably an excimer laser that generates light in the ultraviolet region, for example, an ArF excimer laser having a wavelength of 193 nm and a pulse width of 14 nsec, or a KrF having a wavelength of 248 nm and a pulse width of 14 nsec.
An excimer laser can be used. FIG. 3 shows the results of observing a change in the amount of excited nitrogen while irradiating a nitrogen aggregate with each laser using a 193 nm wavelength ArF excimer laser and a 248 nm wavelength KrF excimer laser as nitrogen excitation lasers. The amount of excited nitrogen is shown by measuring the emission intensity of green light having a wavelength of 523 nm, which is known as α emission and is generated when the excited nitrogen atom transitions to the ground state.

As can be seen from FIG. 3, when the nitrogen excitation laser is irradiated on the nitrogen aggregate, the amount of the excited nitrogen increases exponentially. At this time, the irradiation energy density of the ArF excimer laser was 1.2 J / cm ² , and even though it was smaller than 3.0 J / cm ² of the KrF excimer laser, the photon energy was high, so that more nitrogen was excited. I understand. After the irradiation with the nitrogen excitation laser, the ablation laser is applied to the same place while the excited nitrogen remains.
According to the above findings, when laser irradiation is interrupted, the amount of excited nitrogen decreases in accordance with an exponential relaxation curve. The half-life is estimated to be about 20 seconds, and it is easy to secure an amount of excited nitrogen that can be used even after 60 seconds have elapsed.

Incidentally, when the excitation laser irradiation is restarted after the nitrogen excitation is interrupted, a phenomenon has been observed in which the once reduced amount of excited nitrogen recovers to the original level in a very short time. It is considered that this is because a stable intermediate product having a long lifetime remains in the nitrogen aggregate and transitions to an excited state with a small amount of excitation energy. The nitrogen excitation method in the present embodiment irradiates a laser for excitation to a localized area where nitrogen is aggregated at high density as an aggregate, so that the photon energy of the laser can be efficiently used. Molecules can be easily excited and dissociated through multiphoton absorption processes.

The ablation laser 13 is required to be a pulse laser having a high peak intensity. If the wavelength of the ablation laser 13 is in the infrared region, the ablation is not performed properly due to thermal effects, so that the reaction of forming nitride to be deposited and the process of injecting nitrogen into the cooled thin film surface are efficiently performed. Disappears. Therefore, it is preferable to select a laser in the visible or ultraviolet region as the laser 13 for ablation.

As a laser for ablation, a YAG laser mainly composed of double harmonics is used.
It was confirmed by experiments that the excited state nitrogen agglomerates can be efficiently ablated using a YAG laser having a nm and a pulse width of 5 to 8 nsec. Since the fundamental wave of the YAG laser is in the infrared light region at 1.064 μm, a large amount of ablation particles can be obtained by using a wavelength of 532 nm, which is the second harmonic, to avoid thermal effects.

FIG. 4 is a graph showing the relationship between the irradiation peak intensity on the horizontal axis and the ablation particle generation amount of nitrogen aggregates on the vertical axis. As can be seen from the figure, when the irradiation peak intensity is smaller than 125 MW / cm ² , ablation of the nitrogen aggregate does not occur. On the other hand, 1250 MW / cm ²
If it is larger, the amount of generated nitrogen increases, but the underlying material on which the aggregates are placed is ablated together, so that the generated nitrogen contains impurities. From this result, YAG
It has been found that it is preferable to select the laser irradiation peak intensity in the range of 125 to 1250 MW / cm ² .

The thickness of the nitrogen agglomerate layer 20 needs to be such that the laser beam does not reach the surface of the third stage 9 when irradiating the laser for ablation. It is preferable that it is above. If the layer thickness of the nitrogen aggregate 20 is too large, a portion where the aggregate density is small adheres to the surface, which may cause a phenomenon that the efficiency of excitation and ablation is rather deteriorated.

FIG. 5 is a graph showing the amount of nitrogen ablation particles generated by irradiating the laser for ablation and then irradiating the laser for ablation in the present embodiment, as compared with the case of irradiating only the laser for ablation. It is. A KrF excimer laser was used as a laser for exciting nitrogen, and a YAG laser was used as a laser for ablation. It can be seen that in the case of ablation with a YAG laser after irradiation with a laser for nitrogen excitation, the amounts of both nitrogen atoms and nitrogen molecules are larger than in the case of irradiation with only a YAG laser.

As described above, the nitrogen agglomerate layer formed by cooling is irradiated with a laser for exciting nitrogen, and is irradiated with a laser for ablation before the excited nitrogen is deactivated. Release
By supplying this to a reaction field, a nitrogen compound thin film and a nitriding reactant can be efficiently produced. The thin film forming substrate and the object of the nitriding reaction can be set in the same vacuum chamber so that a more efficient reaction can be performed. Further, according to the excited nitrogen generator of the present embodiment, it is easy to control the nitrogen supply amount, and in particular, it is possible to control even the ratio of the excited nitrogen.

FIG. 6 is a block diagram showing another embodiment of the present embodiment. The only difference from the embodiment shown in FIG. 1 is that the laser for nitrogen excitation and the laser for ablation are introduced from different laser introduction windows, respectively. Therefore, only the differences will be described. Note that, in the figure, elements having the same functions as those in FIG.

In the excited nitrogen generator 1 of this embodiment, the nitrogen excitation laser 12 is converged by the lens 16, passes through the first laser introduction window 11, and irradiates the nitrogen aggregate layer 20. The ablation laser 13 is converged by the lens 23 for the ablation, passes through the second laser introduction window 22, and irradiates the nitrogen aggregate layer 20. As described above, since the two lasers are guided and focused by different optical systems independent of each other, it is necessary to devise a method of applying the two lasers to the same position of the nitrogen aggregate. Since it is sufficient to assemble the best optical system for each without the need for optical path adjustment, there is an advantage that the design and adjustment are easy when viewed comprehensively.

FIG. 7 is a block diagram showing still another embodiment of the present embodiment. The difference from the embodiment shown in FIG. 1 is that a target of a reaction target to be further deposited is set inside a vacuum chamber, and another ablation laser for ablating the target can be irradiated. At this point, the target material can be ablated together with the generation of excited nitrogen, and a nitrogen compound thin film can be formed immediately in a vacuum chamber. Also in this embodiment, only the differences will be described, and the description of the elements having the same functions as those in FIG. 1 will be omitted by retaining the same reference numerals.

The excited nitrogen generator 1 of this embodiment includes a target support board 24 and a thin film deposition substrate 25 in addition to the third stage 9 for stacking nitrogen aggregates in the vacuum chamber 2. A third laser introduction window 27 for introducing an ablation laser 26 is provided. The second ablation laser 26 is adjusted so that it is generated by the third laser generator 28, converged by the focusing lens 29, passes through the third laser introduction window 27, and is focused on the target support board 24. . Third stage 9 and target support board 24
Are arranged at positions facing the thin film deposition substrate 25.

Using the excited nitrogen generator 1 of this embodiment, Nb
In the case of forming an N film, niobium Nb, which is a substance to be subjected to a nitridation reaction, is adhered onto the target support plate 24, and the excited nitrogen aggregate 20 and the substance to be reacted formed by the above-described procedure are respectively subjected to the ablation laser 13, 26 to ablate simultaneously. Then, both substances can be supplied as ablation particles onto the thin film deposition substrate 25 made of, for example, silicon Si, and an NbN film is formed on the substrate.

Since Nb has a strong gettering action and absorbs a large amount of impurities such as oxygen and moisture in the residual gas, Nb
Obtaining a membrane was said to be difficult. However, according to this embodiment, since nitrogen is handled as an aggregate, the nitridation reaction of Nb is performed in the presence of a large amount of excited nitrogen while maintaining the atmosphere in the film forming apparatus at an extremely low pressure. Therefore,
The NbN film formed according to the present embodiment has an extremely small content of impurities such as oxygen and carbon and a large amount of nitrogen as compared with an NbN film obtained by a conventional method of ablating Nb in a nitrogen atmosphere. High quality film quality was achieved.

A boron nitride BN film can also be formed by using the excited nitrogen generator 1 of this embodiment. B by conventional method
When the N film is formed, nitrogen is dissociated on the target surface due to laser irradiation during the film formation, and only boron tends to re-solidify on the substrate. Only a black BN film was obtained. When a BN film is formed by using the excited nitrogen generator 1 of this embodiment, boron B or boron nitride BN is attached on the target support plate 24, and the excited nitrogen aggregate 20 and B
Alternatively, the BN targets are simultaneously ablated using the respective ablation lasers 13 and 26. Then, when B or BN re-coagulates on the substrate 25, the excited nitrogen contributes to the reaction, so that nitrogen deficiency is improved and a high-quality transparent BN film is formed.

As described above, in the excited nitrogen generating apparatus of this embodiment, the thin film deposition substrate is disposed at a position opposite to the nitrogen aggregation position, and the high purity and high density excited nitrogen generated by the apparatus is disposed on the substrate surface. Is supplied, a higher quality nitrogen mixture thin film can be produced. In the embodiment, an example is described in which an ArF excimer laser or a KrF excimer laser is used as the nitrogen excitation laser. However, it is needless to say that other lasers may be used as long as they include components that easily excite nitrogen. Absent. Further, the laser for ablation can be similarly applied as long as the laser has sufficient performance for ablation. Further, it goes without saying that various substances such as Si ₃ N ₄ and CN _x are also applicable to the thin film and the nitriding reactant formed by the reaction of nitrogen.

[0039]

As described above, the excited nitrogen generating apparatus and the excited nitrogen generating method of the present invention make it possible to supply much higher purity and higher density of excited nitrogen for the thin film forming step and the nitridation reaction.

[Brief description of the drawings]

FIG. 1 is a block diagram showing one embodiment of an excited nitrogen generator according to the present invention.

FIG. 2 is a perspective view illustrating a main part of the present embodiment.

FIG. 3 is a graph showing a change in the amount of excited nitrogen when a nitrogen excitation laser is irradiated on a nitrogen aggregate in the present invention.

FIG. 4 is a graph showing a relationship between an irradiation peak intensity of an ablation laser and an ablation particle generation amount of a nitrogen aggregate in the present invention.

FIG. 5 is a graph comparing nitrogen ablation particle amounts when a nitrogen excitation laser and an ablation laser are used and when only an ablation laser is used in the present invention.

FIG. 6 is a block diagram illustrating a second mode of the present embodiment.

FIG. 7 is a block diagram illustrating a third mode of the present embodiment.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Excited nitrogen generator 2 Vacuum chamber 3 Vacuum pump 4 Exhaust refrigerator 5 Coagulation refrigerator 6 First stage 7 Second stage 8 Cryopanel 9 Third stage 10 Nitrogen gas nozzle 11, 22, 27 Laser introduction window 12 Nitrogen excitation Laser 13 ablation laser 14 first laser generator 15 mirror 16, 23, 29 lens 17 second laser generator 18 total reflection mirror 19 controller 20 nitrogen aggregate layer 21 ablation particles 24 target support plate 25 thin film deposition substrate 26 Second Ablation Laser 28 Third Laser Generator 30 Laser Transmission Hole

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Kenichi Fukatsu 2085-16 Uenoyama, Fukasawa-cho, Nagaoka City, Niigata Prefecture F-term in Laser Application Engineering Laboratory Co., Ltd. 4K029 BA58 CA04 DB20 5F103 AA10 BB09 BB23 DD30 NN01 NN07 RR06

Claims (12)

[Claims] 1. An excited nitrogen generator comprising: a vacuum container having a laser introduction window, a gas inlet, and a gas cooling surface; a nitrogen excitation laser generator; and an ablation laser generator. The cooling surface is in the vacuum vessel and solidifies nitrogen gas supplied from the gas inlet to form a nitrogen aggregate layer, which is generated by the laser generator for nitrogen excitation and the laser generator for ablation, respectively. An excited nitrogen generator, wherein a laser is arranged to irradiate substantially the same position of the nitrogen aggregate layer through the laser introduction window. 2. The excited nitrogen generator according to claim 1, wherein the laser generator for exciting nitrogen emits a laser in an ultraviolet light region. 3. The excited nitrogen generator according to claim 1, wherein said nitrogen excitation laser generator is an excimer laser device. 4. The excited nitrogen generator according to claim 1, wherein the laser generator for ablation generates a pulse laser in a visible light range or an ultraviolet light range. 5. The excited nitrogen generator according to claim 1, wherein the laser generator for ablation is a YAG laser device. 6. A second laser generator for ablation, and another laser introduction window provided in the vacuum vessel;
The apparatus further includes a target support board provided in the vacuum vessel and a thin film deposition substrate, and a laser generated by the second ablation laser generator irradiates the target support board via the further laser introduction window. The excited nitrogen generator according to any one of claims 1 to 5, wherein the apparatus is arranged as follows. 7. A nitrogen gas is supplied into a vacuum container evacuated, and the nitrogen gas is solidified on a cooling surface to form a nitrogen aggregate layer. The nitrogen aggregate layer is irradiated with a laser for exciting nitrogen. ,
Thereafter, the irradiation position is irradiated with an ablation laser to ablate the nitrogen component, thereby producing an excited nitrogen. 8. The excited nitrogen generating method according to claim 7, wherein the thickness of the nitrogen aggregate layer is set so that the material of the cooling surface is not eroded by the ablation laser. 9. The method according to claim 7, wherein the laser for exciting nitrogen is a laser in an ultraviolet light region. 10. The method for generating excited nitrogen according to claim 7, wherein the laser for ablation is a pulse laser in a visible light region or an ultraviolet light region. 11. The ablation laser is a YAG laser.
The method according to any one of claims 7 to 10, wherein the method mainly comprises a second harmonic of a laser. 12. Nitrogen produced by providing a target of an object reacting with nitrogen and a substrate on which a thin film is to be deposited in the vacuum vessel, ablating a nitrogen component and ablating the target with a second ablation laser. The method according to any one of claims 7 to 11, wherein a reactant is deposited on the substrate.