JP6819093B2 - Material manufacturing equipment and material manufacturing method - Google Patents

Description

The present invention relates to a material manufacturing apparatus that irradiates a laser to manufacture a material, and a material manufacturing method.

Conventionally, an ultrahigh pressure (for example, about 100,000 to 200,000 atm) is applied to a target substance, and the target substance is heated to a high temperature (for example, about 1000 ° C. to 1500 ° C.) to undergo a phase transition of the target substance to produce a material. Diamond anvil cells are known. However, diamond anvil cells cannot mass-produce materials because they have a long time to reach an ultrahigh pressure state and a high temperature state.

Therefore, in recent years, a technique for phase-transitioning a target substance by using a plurality of laser irradiation devices that irradiate laser light having a pulse width on the order of nanoseconds has been developed (for example, Non-Patent Document 1). In the technique of Non-Patent Document 1, each laser irradiating device irradiates the target substance with the laser beam stepwise by varying the time for irradiating the laser beam. Then, since pressure is gradually applied to the target substance, the temperature rise of the target substance becomes slow, and the target substance does not melt (or gasify) and does not follow the Hugoniot curve (without following the Hugoniot curve). Can be subjected to a phase transition (phase transition between solid phases).

Keisuke Shigemori, Possibility of Metallic Carbon Generation by High Intensity Laser-Induced Shock Wave, High Pressure Science and Technology Vol.16, NO.3 (2006)

However, the technique described in Non-Patent Document 1 described above requires a plurality of laser irradiation devices, and therefore has a problem that it is too costly to industrially manufacture a material.

Therefore, in view of such a problem, an object of the present invention is to provide a material manufacturing apparatus capable of manufacturing a material at low cost and a material manufacturing method.

In order to solve the above problems, in the material manufacturing apparatus of the present invention, a sacrificial layer composed of a saturable absorber of any one of carbon nanowalls, carbon nanotubes, and graphene is laminated. The processing layer is provided with a pulse laser irradiation unit that irradiates a laser beam having a pulse width of picoseconds or less.
The material constituting the layer to be treated is undergoing a phase transition.

Further, even if it is provided with a holding portion that holds a predetermined gas or a predetermined liquid and arranges a layer to be treated in which the sacrificial layer is laminated in the predetermined gas or the predetermined liquid. Good.

Further, the sacrificial layer is pre-listen saturable absorber may be formed by embedding in a resin or glass.

In order to solve the above problems, in the material manufacturing method of the present invention, a sacrificial layer composed of a layer to be treated containing a saturable absorber of any one of carbon nanowalls, carbon nanotubes, and graphene. A step of irradiating a layer to be treated with a laminated sacrificial layer with a laser beam having a pulse width of picoseconds or less is included, and a material having a phase transition of the materials constituting the layer to be treated is manufactured. To do.

Further, after performing the step of laminating the sacrificial layer and before carrying out the step of irradiating the laser beam, the layer to be treated in which the sacrificial layer is laminated in a predetermined gas or a predetermined liquid. May include the step of arranging.

Further, a step of removing the sacrificial layer after performing the step of irradiating the laser beam may be included.

According to the present invention, it is possible to manufacture a material at low cost.

It is a figure explaining the material manufacturing apparatus. It is a flowchart explaining the process flow of the material manufacturing method. It is a figure which shows the SEM image of GaN. It is a figure which shows the analysis result of XPS of GaN. It is a figure which shows the SEM image of sapphire. It is a figure which shows the analysis result of XPS of sapphire. It is a figure which shows the analysis result of XPS of SOS.

Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The dimensions, materials, other specific numerical values, etc. shown in the embodiment are merely examples for facilitating the understanding of the invention, and do not limit the present invention unless otherwise specified. In the present specification and drawings, elements having substantially the same function and configuration are designated by the same reference numerals to omit duplicate description, and elements not directly related to the present invention are not shown. To do.

(Material manufacturing equipment 100)
1A and 1B are views for explaining the material manufacturing apparatus 100, FIG. 1A is a diagram showing a specific configuration example of the material manufacturing apparatus 100, and FIG. 1B is a diagram to be processed by irradiation with a laser beam. It is a figure explaining the change of a layer 140. In FIG. 1, in order to facilitate understanding, the holding portion 102 and the material to be processed 120 are shown larger than the pulsed laser irradiation portion 110.

As shown in FIG. 1A, the material manufacturing apparatus 100 includes a holding unit 102 and a pulsed laser irradiation unit 110. The holding portion 102 is composed of, for example, a chamber or the like, and holds a predetermined gas inside. Then, the material 120 to be treated, which will be described later, is installed in the holding portion 102, and the material 120 to be treated, which will be described later, is arranged in a predetermined gas. Here, the predetermined gas is air (atmosphere), nitrogen, argon, or the like. Further, the holding portion 102 is provided with a window 102a that transmits the laser light, and the laser light is irradiated to the material 120 to be processed through the window 102a.

The configuration having the holding portion 102 makes it possible to adjust the atmosphere of the material to be processed 120 when irradiating the laser beam described later to a predetermined gas atmosphere and a predetermined pressure (predetermined gas density). .. Further, the holding unit 102 may hold not only the gas but also the predetermined liquid so that the material 120 to be treated is arranged in the predetermined liquid (for example, water).

Pulse laser irradiation unit 110 is, material to be treated 120, following picoseconds pulse width (pico ^{(10 -12)} second order, femto ^{(10 -15)} second order, atto ^{(10 -18)} seconds including the order) Irradiate the laser beam.

The material 120 to be treated is a material in which the substrate 130, the layer 140 to be treated, and the sacrificial layer 150 are laminated in this order. The substrate 130 is made of a material having a higher thermal conductivity than the layer 140 to be treated (for example, sapphire (Al ₂ O ₃ )).

The layer 140 to be treated is a precursor of a material manufactured by the material manufacturing apparatus 100, and is, for example, a solid such as carbon (C), silicon (Si), gallium nitride (GaN), aluminum nitride (AlN), or sapphire. ions by ion implantation _{^{(e.g., H +, H 2 +,}} Ar +, H 2 S + , etc.) is injected solid.

The sacrificial layer 150 is configured to include a nanostructured saturable absorber, for example, carbon nanostructures such as carbon nanowalls (CNW), carbon nanotubes (CNT), graphene, and semiconductor nanostructures. It is composed of nanostructures of materials with band gaps.

As shown in FIG. 1A, in the present embodiment, the pulsed laser irradiation unit 110 irradiates the processed layer 140 with laser light via the sacrificial layer 150. Then, the pressure of the shock wave and the pressure of the plasma generated by the ablation of the layer 140 to be treated (ultra-high pressure of about several hundred GPa in total) are applied to the layer 140 to be treated.

Specifically, as shown in FIG. 1B, when the pulsed laser irradiation unit 110 irradiates the sacrificial layer 150 with the laser beam, a part of the laser beam is absorbed by the saturable absorber constituting the sacrificial layer 150. The remaining laser light is transmitted (passed) through the sacrificial layer 150.

Therefore, the absorbed laser light causes ablation of the sacrificial layer 150. When ablation occurs, plasma of atoms (or molecules) constituting the sacrificial layer 150 is generated, and the plasma generates a shock wave. Then, a pressure is applied to the layer to be processed 140 by this shock wave (indicated by a black-filled arrow in FIG. 1 (b)).

As described above, since the sacrificial layer 150 is composed of nanostructures, the laser beam is deeply incident on the sacrificial layer 150. Therefore, plasma is generated substantially uniformly in the sacrificial layer 150. As a result, strong plasma is generated, and high pressure can be applied to the layer to be processed 140.

Further, by forming the sacrificial layer 150 with carbon nanostructures, the energy of the laser beam can be increased, and a stronger plasma is generated as compared with the sacrificial layer 150 composed of other nanostructures. It becomes possible. This is because the melting point and evaporation point of carbon nanostructures are higher than those of other nanostructures.

On the other hand, the laser light transmitted through the sacrificial layer 150 excites the atoms (or molecules) constituting the layer to be treated 140 to ablate (generate plasma). As a result, the layer 140 to be treated becomes high pressure (indicated by a white arrow in FIG. 1B) and high temperature. That is, the pressure rise in the layer 140 to be treated due to the excitation of atoms and the pressure application due to the shock wave from the sacrificial layer 150 combine to achieve an ultrahigh pressure of about several hundred GPa.

Further, in the layer 140 to be treated, the excited state of atoms can be maintained under an ultrahigh pressure and high temperature environment, so that the phase transition (phase transition between solid phases, structural phase transition) of the materials constituting the layer 140 to be treated occurs. It will be done.

As described above, the processed layer 140 is phase-translated with a simple configuration in which the processed layer 140 is simply irradiated with a laser beam via a sacrificial layer 150 composed of a nanostructured saturable absorber. (Manufactures a material with a phase transition).

For example, there is a possibility that solid metallic hydrogen can be produced by forming the layer 140 to be treated with a solid injected with hydrogen ions. In addition, there is a possibility that solid metal argon can be produced by forming the layer 140 to be treated with a solid injected with argon ions. Further, by forming the layer 140 to be treated with a solid injected with hydrogen sulfide ions, there is a possibility that solid metal hydrogen sulfide can be produced. Therefore, the material manufacturing apparatus 100 may be able to manufacture superconducting substances such as solid metallic hydrogen, solid metallic argon, and solid metal hydrogen sulfide. Further, by forming the layer 140 to be treated with carbon, there is a possibility that super diamond can be produced.

As described above, according to the material manufacturing apparatus 100 according to the present embodiment, there is a possibility that a new substance such as a superconducting substance or a semiconductor material can be manufactured.

Further, by forming the sacrificial layer 150 with carbon nanowalls or carbon nanotubes, it is possible to cause a desired phase transition with respect to the layer to be treated 140. Specifically, carbon nanowalls and carbon nanotubes can control the transmittance of laser light by changing the height (thickness) (ratio of the amount of laser light absorbed by the sacrificial layer 150 to the amount of transmitted light). Can be controlled). For example, by increasing the thickness of the sacrificial layer 150 and irradiating it with a high-energy laser beam, the pressure of the layer to be treated 140 is made higher.

Therefore, by controlling the thickness of the sacrificial layer 150 and the energy of the laser beam irradiated by the pulsed laser irradiation unit 110, the layer 140 to be processed is maintained at the pressure and temperature for phase transition to the target substance. Is possible.

Further, by forming the sacrificial layer 150 with carbon nanowalls, the sacrificial layer 150 can be formed (laminated) on the processed layer 140 by a plasma CVD device or the like regardless of the material of the processed layer 140.

Moreover, the sacrificial layer 150 may be formed by a film in which a saturable absorber having a nanostructure is embedded in a resin (for example, polyimide) or glass. As a result, when the sacrificial layer 150 cannot be formed on the layer 140 to be treated (for example, when the layer 140 to be treated is exposed to a high temperature environment with a plasma CVD device, the layer 140 to be treated is destroyed (for example, ions are injected). Even if it is a solid) or the like), the sacrificial layer 150 can be laminated on the treated layer 140 simply by placing the sacrificial layer 150 on the treated layer 140. Further, when it is desired to partially undergo a phase transition of the layer 140 to be treated, the sacrificial layer 150 may be placed only at a position where the phase transition is desired. Since a film in which a saturable absorber having a nanostructure is embedded in a resin or glass can be produced by an existing technique (for example, Japanese Patent Application Laid-Open No. 2015-118348), detailed description thereof will be omitted here.

(Material manufacturing method)
Subsequently, a material manufacturing method using the material manufacturing apparatus 100 will be described. FIG. 2 is a flowchart illustrating a processing flow of the material manufacturing method.

As shown in FIG. 2, the material manufacturing method includes a laminating step S110, an atmosphere adjusting step S120, a laser beam irradiation step S130, and a removing step S140.

(Laminating step S110)
The laminating step S110 is a step of laminating the sacrificial layer 150 on the layer to be treated 140. The laminating step S110 is, for example, a step of forming the sacrificial layer 150 into the layer to be processed 140 by the plasma CVD apparatus as described above. When the sacrificial layer 150 is a film, the laminating step S110 is a step of placing the sacrificial layer 150 on the layer to be treated 140. In this case, the sacrificial layer 150 (film) may be laminated on the layer to be treated 140 via an adhesive.

(Atmosphere adjustment step S120)
The atmosphere adjusting step S120 is a step of adjusting the atmosphere (gas type, pressure) of the material 120 to be processed by supplying a predetermined gas to the holding unit 102 after accommodating the material 120 to be processed in the holding unit 102. In this way, the material 120 to be treated is arranged in a predetermined gas atmosphere.

By carrying out the atmosphere adjusting step S120, it is possible to adjust the atmosphere of the material 120 to be treated when irradiating the laser beam in the laser light irradiation step S130 described later. Therefore, it is possible to carry out the laser light irradiation step S130, which will be described later, to manufacture a desired material, and to improve the manufacturing efficiency of the manufactured material.

(Laser light irradiation step S130)
The laser light irradiation step S130 is a step in which the pulsed laser irradiation unit 110 irradiates the processed layer 140 with the laser light having a pulse width of picoseconds or less via the sacrificial layer 150.

(Removal step S140)
The removal step S140 is a step of removing the sacrificial layer 150 from the layer to be treated 140. In the removal step S140, the sacrificial layer 150 is removed from the layer to be treated 140 by etching the sacrificial layer 150 using, for example, an ion etching apparatus or an oxygen plasma apparatus. Further, when the sacrificial layer 150 is composed of carbon, the sacrificial layer 150 can be removed by heating in the presence of oxygen (for example, in the atmosphere).

Further, when the sacrificial layer 150 is made of a film, the sacrificial layer 150 can be removed from the processed layer 140 by simply peeling the sacrificial layer 150 from the processed layer 140.

By carrying out the removal step S140, the sacrificial layer 150 that can be an impurity can be removed, and only the phase-transitioned layer 140 to be treated can be produced.

As described above, the material can be manufactured in a short time and at low cost by the material manufacturing method.

(Example)
(1. Lamination of sacrificial layer 150)
A substrate in which the substrate 130 is sapphire and the layer 140 to be treated is made of gallium nitride (5 μm) (hereinafter, simply referred to as “GaN substrate”), and a substrate having only the layer 140 to be treated made of sapphire (hereinafter, simply “” A substrate in which the substrate 130 is sapphire and the layer 140 to be treated is silicon (500 nm) (hereinafter, simply referred to as “SOS substrate”), and carbon nano as a sacrificial layer 150 for each. The wall was formed with a film of 1.4 μm.

Each of the above three types of substrates was installed in a plasma CVD apparatus, and a carbon nanowall was formed under a mixed atmosphere of methane (CH ₄ ), hydrogen (H ₂ ), and argon (Ar). The temperature of the substrate was maintained at 948K during the formation of the carbon nanowall. The film forming time was about 20 to 30 minutes.

(2. Laser irradiation)
A GaN substrate with a carbon nanowall film formed (Example A1), a GaN substrate only (Comparative Example B1), a sapphire substrate with a carbon nanowall film formed (Example A2), and a sapphire substrate only (Comparative Example B2). ), A carbon nanowall film formed on an SOS substrate (Example A3), and only the SOS substrate (Comparative Example B3) were irradiated with one shot of laser light at room temperature and in an atmospheric environment. The wavelength of the laser beam is 800 nm, the pulse width is 100 fs, and the pulse energy is 160 μJ.

(3. Surface analysis)
Scanning electron microscope (SEM) and X-ray photoelectric spectroscope (XPS: PHI 5000 VersaProbe II, ULVAC- It was analyzed by PHI, Inc., Japan). XPS used Al Kα (hν = 1486.6 eV) as the X-ray source. The X-ray beam diameter was 10 μm, and a neutralizing gun was used during the measurement to prevent charge-up. Also, before the XPS analysis, the Ar sputtering used to remove the carbon nanowalls was performed at an acceleration voltage of 4 kV. The sputtering range is 2 × 2 mm ² , and the sputtering rate is 8.77 nm in terms of SiO ₂ .

(4-1. Analysis results for GaN)
FIG. 3 is a diagram showing an SEM image of GaN, FIG. 3A is an SEM image of a laser beam irradiation mark of Comparative Example B1 (GaN substrate only), and FIG. 3B is an Example A1 (GaN). It is an SEM image of a laser beam irradiation mark of a substrate formed by forming a carbon nanowall.

As shown in FIG. 3 (a), the laser beam irradiation trace of Comparative Example B1 has the highest intensity when the beam does not have an accurate Gaussian shape and is slightly off the center (in FIG. 3 (a), The part surrounded by the broken line circle). Moreover, when the white particles shown in FIG. 3A were analyzed by energy dispersive X-ray analysis (EDS), it was confirmed that they were Ga-rich. Since GaN has a property that nitrogen is easily desorbed into the atmosphere at a high temperature, it is considered that only Ga remains due to this.

On the other hand, as shown in FIG. 3 (b), in the laser beam irradiation trace of Example A1, the carbon nanowall was not completely ablated, and the carbon nanowall remained even in the portion having the highest energy. It turned out that there was. In order to investigate the cause of the residual carbon nanowall, the electronic state analysis by XPS was performed.

FIG. 4 is a diagram showing the results of XPS analysis of GaN, FIG. 4A shows the XPS spectrum of the 3d orbital of Ga (gallium), and FIG. 4B shows the XPS spectrum of the 1s orbital of N (nitrogen). Shows the spectrum. In FIG. 4, Comparative Example B1 before laser irradiation is indicated by a chain line, Example A1 after laser irradiation is indicated by a solid line, and Comparative Example B1 after laser irradiation is indicated by a broken line.

First, carbon nanowalls (sacrificial layer 150) were removed by Ar sputtering, and then surface analysis was performed by XPS. As shown in FIG. 4A, the peak of the 3d orbital of Ga in Comparative Example B1 before the laser irradiation is 18.6 eV, and the peak of the 3d orbital of Ga in Comparative Example B1 after the laser irradiation is 18. It was 2 eV, and the peak of the 3d orbital of Ga in Example A1 after the laser irradiation was 19.3 eV.

That is, it was confirmed that the peak of the 3d orbital of Ga in Example A1 after the laser irradiation was shifted to the 0.7 eV high binding energy side from the peak of Comparative Example B1 before the laser light irradiation. Even if Ar sputtering was performed on the GaN substrate for a long time (120 minutes, 1052 nm in terms of SiO ₂ ), the shape of the spectrum of the 3d orbital of Ga and the position of the peak of the 1s orbital of N did not change. It has been confirmed that GaN is stable against sputtering. Further, by arranging GaN under a pressure of 40 to 50 GPa, the peak of the 3d orbital of Ga in the material in which the phase transition from the wurtzite structure to the rock salt structure coincides with the peak of Example A1 after laser irradiation. To do. Therefore, it is considered that the peak shift is not due to Ar sputtering, but due to the phase transition of GaN from the wurtzite structure to the rock salt structure.

On the other hand, it was confirmed that the peak of the 3d orbital of Ga in Comparative Example B1 after the laser irradiation was shifted to the 0.4 eV low binding energy side from the peak of Comparative Example B1 before the laser irradiation. It was found that the peak shift was in the opposite direction to A1. It is considered that this is because, as inferred from the above EDS results, GaN nitrogen was released into the atmosphere by laser irradiation, resulting in a metallic Ga-rich state.

Further, when the peak of the 1s orbital of N was examined, as shown in FIG. 4B, the peak of the 1s orbital of N in Comparative Example B1 before the laser irradiation was 396.0 eV, and after the laser irradiation, the peak was 396.0 eV. The peak of the 1s orbital of N in Comparative Example B1 was 395.7 eV, and the peak of the 1s orbital of N in Example A1 after the laser irradiation was 397.2 eV. Therefore, the shift from the peak of Comparative Example B1 before the laser irradiation is the same as the shift of the peak of the 3d orbital of Ga in both Example A1 after the laser irradiation and Comparative Example B1 after the laser irradiation. It turned out to be. The structure in the range of 390 to 394 eV in the spectrum of the 1s orbital of N is a peak based on the Auger electron of Ga.

(4-2. Analysis results for sapphire)
FIG. 5 is a diagram showing an SEM image of sapphire, FIG. 5 (a) is an SEM image of a laser beam irradiation mark of Comparative Example B2 (sapphire substrate only), and FIG. 5 (b) is an example A2 (sapphire). It is an SEM image of the laser beam irradiation mark (the one which formed the carbon nanowall film on the substrate).

As shown in FIG. 5A, in Comparative Example B2, the surface was only slightly discolored black and no clear laser light irradiation mark could be left (the portion irradiated with the laser light is indicated by a broken line circle. Show). On the other hand, as shown in FIG. 5B, in Example A2, although the carbon nanowall remained, the influence of laser irradiation could be observed.

6A and 6B are diagrams showing the results of XPS analysis of sapphire, FIG. 6A shows the XPS spectrum of the 2p orbital of Al (aluminum), and FIG. 6B shows the XPS of the 1s orbital of O (oxygen). Shows the spectrum. In FIG. 6, Comparative Example B2 before the laser beam irradiation is shown by the alternate long and short dash line, Example A2 after the laser beam irradiation is shown by the solid line, and Example A2 (sputtering time is 160 minutes) after the laser beam irradiation. ) Is indicated by a broken line.

Surface analysis was performed by XPS of Example A2 in which the carbon nanowall (sacrificial layer 150) was removed by Ar sputtering for 200 minutes and Example A2 in which the carbon nanowall was removed by Ar sputtering for 160 minutes.

As a result, as shown in FIG. 6A, the peak of the 2p orbital of Al in Comparative Example B2 before the laser beam irradiation was 76.7 eV, and in Example A2 (spatter time 160 minutes) after the laser beam irradiation. The peak of the 2p orbital of Al was 74.3 eV, and the peak of the 2p orbital of Al in Example A2 (spatter time 200 minutes) after the laser irradiation was 75.1 eV.

Further, as shown in FIG. 6 (b), the peak of the 1s orbit of O in Comparative Example B2 before laser irradiation was 533.4 eV, and that of O in Example A2 (spatter time 160 minutes) after laser irradiation. The peak of the 1s orbit was 531.2 eV, and the peak of the 1s orbit of O in Example A2 (spatter time 200 minutes) after the laser irradiation was 532.0 eV.

That is, the peak of the 2p orbital of Al approaches the peak position of Comparative Example B2 before the laser irradiation from the low binding energy side as the sputtering time increases (as the amount of carbon nanowalls decreases). I understand. The same applies to the peak of the 1s orbit of O. A very large peak shift of 2 eV or more was confirmed for both the peak of the 2p orbital of Al and the peak of the 1s orbital of O. Since it has been confirmed that the peak position of the 1s orbital of C (carbon) derived from carbon nanowall does not change and that the peak shift does not occur even after sputtering for 120 minutes, the above peak shift is sapphire. It is probable that the electronic state of sapphire has changed.

Further, the composition ratios of Al and O were set for each of Comparative Example B2 before laser irradiation, Example A2 after laser irradiation (spatter time 160 minutes), and Example A2 after laser light irradiation (spatter time 200 minutes). Derived. As a result, in Example A2 (sputtering time 200 minutes) after laser irradiation, the composition ratio was almost stoichiometric (Al: 40 at%, O: 60 at%). On the other hand, in Example A2 (sputtering time 160 minutes) after laser irradiation, Al: 46.5 at% and O: 53.5 at%, which are less oxygen than in Example A2 having a sputtering time of 200 minutes. It turned out. In Example A2 (spatter time 160 minutes) after laser light irradiation, the peak shift of the 2p orbital of Al and the peak shift of the 1s orbital of O are oxygen when the temperature becomes high due to the irradiation of the laser light. It is thought that this is because was reduced by carbon and released into the atmosphere.

However, the peak position of the 2p orbital of Al in Example A2 (spatter time 160 minutes) after laser irradiation is 74.3 eV, which is significantly shifted from the peak of Comparative Example B2 before laser irradiation, and the metal Al. The value is close to the peak position (72.8 to 72.9 eV). However, even though oxygen desorption has occurred, since the at% ratio of Al and O is approximately 1: 1, it is unlikely that the cause of such a large peak shift is only oxygen desorption. In the XPS spectrum, the peaks of elements in metallic electronic states generally appear on the low binding energy side, so the above-mentioned large peak shift (peak shift of 2 eV or more) is caused not only by oxygen desorption but also by laser-induced shock waves. Is thought to have acquired metallic properties. It is known that sapphire becomes a metallic amorphous state at 300 GPa.

On the other hand, in Example A2 (sputtering time 200 minutes) after laser irradiation, the peak was largely shifted to the low binding energy side even though the composition ratio was almost stoichiometric. This is thought to be due to the amorphization of sapphire. Since the crystal structure of sapphire at a high pressure of 180 GPa or more has not been reported, it cannot be determined, but if it is amorphized, the layer 140 to be treated is generated by a shock wave by irradiating Example A2 with a laser beam. Can be estimated to have been compressed to about 200 GPa.

(4-3. Analysis results for SOS)
FIG. 7 is a diagram showing the results of XPS analysis of SOS, FIG. 7 (a) shows the XPS spectrum of the 2p orbital of Si (silicon), and FIG. 7 (b) shows the XPS of the 1s orbital of O (oxygen). Shows the spectrum. In FIG. 7, Comparative Example B3 before laser irradiation is indicated by a chain line, Example A3 after laser irradiation is indicated by a solid line, and Comparative Example B3 after laser irradiation is indicated by a broken line.

The carbon nanowall (sacrificial layer 150) was removed by Ar sputtering, and then surface analysis was performed by XPS. As shown in FIG. 7A, the peak of the Si 2p orbital in Comparative Example B3 before the laser irradiation is 98.6 eV, and the peak of the Si 2p orbital in the Comparative Example B3 after the laser irradiation is 99. It was 2 eV, and the peak of the 2p orbital of Si in Example A3 after the laser irradiation was 100.5 eV.

That is, it was confirmed that the peak of the Si 2p orbital in Example A3 after the laser irradiation was 1.9 eV-shifted to the higher binding energy side from the peak of Comparative Example B3 before the laser light irradiation. As a result, it is presumed that the structural phase transition has occurred in Example A3 after the laser irradiation.

Further, as shown in FIG. 7B, the peak of the 1s orbit of O was confirmed in Comparative Example B3 before the laser irradiation and Comparative Example B3 after the laser irradiation, but after the laser irradiation. It could not be confirmed in Example A3. From this, it was confirmed that oxygen was not present in Example A3 after the laser irradiation. In Comparative Example B3 after laser irradiation, a peak of 104 eV was observed in the 2p orbital of Si, so it is considered that oxygen in the atmosphere was taken in by laser irradiation and changed to SiO ₂ .

Although the preferred embodiment of the present invention has been described above with reference to the accompanying drawings, it goes without saying that the present invention is not limited to such an embodiment. It is clear that a person skilled in the art can come up with various modifications or modifications within the scope of the claims, and it is understood that these also naturally belong to the technical scope of the present invention. Will be done.

For example, in the above-described embodiment, the material 120 to be treated in which the substrate 130 is laminated below the layer 140 to be treated (opposite the sacrificial layer 150) has been described as an example. As a result, the heat of the layer 140 to be treated generated when the laser beam is irradiated can be transferred to the substrate 130. Therefore, it is possible to maintain the phase transition state in the layer 140 to be treated. However, when the layer 140 to be treated is composed of a substance having high thermal conductivity (for example, sapphire), the substrate 130 is not essential, and the material 120 to be treated is composed of the layer 140 to be treated and the sacrificial layer 150. It may be configured.

Further, in the above embodiment, the configuration in which the material manufacturing apparatus 100 includes the holding portion 102 has been described as an example. However, when the material 120 to be processed is irradiated with laser light in an air atmosphere, the material manufacturing apparatus 100 does not have to include the holding unit 102.

Further, in the above embodiment, the atmosphere adjusting step S120 and the removing step S140 are carried out, but the atmosphere adjusting step S120 and the removing step S140 are not essential processes.

The present invention can be used in a material manufacturing apparatus that irradiates a laser to manufacture a material, and a material manufacturing method.

S110 Laminating process S120 Atmosphere adjustment process S130 Laser light irradiation process S140 Removal process 100 Material manufacturing equipment 102 Holding unit 110 Pulsed laser irradiation unit 140 Processed layer 150 Sacrificial layer

Claims (6)

A laser beam having a pulse width of picoseconds or less is applied to a layer to be treated in which a sacrificial layer composed of carbon nanowalls, carbon nanotubes, and a saturable absorber of any one of graphene is laminated. Equipped with a pulsed laser irradiation unit
A material manufacturing apparatus that undergoes a phase transition of the materials constituting the layer to be treated. The first aspect of the present invention includes a holding portion that holds a predetermined gas or a predetermined liquid and arranges a layer to be treated in which the sacrificial layer is laminated in the predetermined gas or the predetermined liquid. The material manufacturing apparatus described. The material manufacturing apparatus according to claim 1 or 2 , wherein the sacrificial layer is a saturable absorber embedded in resin or glass. A step of laminating a sacrificial layer composed of carbon nanowalls, carbon nanotubes, and a saturable absorber of any one of graphene on the layer to be treated.
A step of irradiating the layer to be processed on which the sacrificial layer is laminated with a laser beam having a pulse width of picoseconds or less,
Including
A material manufacturing method for manufacturing a material in which the materials constituting the layer to be treated are phase-translated. After performing the step of laminating the sacrificial layer and before carrying out the step of irradiating the laser beam, the layer to be treated on which the sacrificial layer is laminated is arranged in a predetermined gas or a predetermined liquid. The material manufacturing method according to claim 4 , wherein the material manufacturing method includes the step of performing. The material manufacturing method according to claim 4 or 5 , further comprising a step of removing the sacrificial layer after performing the step of irradiating the laser beam.