JP2588971B2 - Laser deposition method and apparatus - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] A laser vapor deposition method for irradiating an object to be irradiated with a laser to generate a laser-induced plasma therein, and evaporating a substance released from the object to be irradiated onto a substrate Related to the device.

[Prior Art] Conventionally, various films, particularly thin films, have been used in antireflection films for optical components such as camera lenses and surface coatings for decorative articles. In recent years, with the miniaturization and high performance of various devices in the field of electronics, thin films have been widely used in wiring of semiconductor devices, ICs, LSIs and the like, magnetic recording materials, and the like.

In addition, as the research on thin films progresses, various unique effects such as tunnel effect are obtained by thinning, and further thinning the material changes the structure of the material itself. It has been found that new functions can be achieved. For this reason, the importance of films is increasing in various fields.

Here, as a film manufacturing technique, a film material particle is evaporated in a high vacuum, a vacuum evaporation method of depositing the evaporated particle on a substrate, or a target (irradiated object) is irradiated with ions to form a target surface. There is a sputtering method in which atoms and molecules are evaporated and deposited on a substrate, and an appropriate method is adopted depending on the type of a film to be formed.

Then, in the conventional film generation, there is known a method in which vapor deposition is performed by utilizing the effects of plasma and ions. This is because, by using plasma and ions, (a) the surface of the substrate on which the film is formed can be cleaned, the adhesion can be improved, and (b) physical properties such as the crystallinity of the formed film can be controlled. This is because effects such as being able to be performed can be obtained.

As a method for positively utilizing the effects of such plasma and ions, (A) an ion plating method in which evaporated particles are ionized in plasma, accelerated by an electric field, and then adhered onto a substrate; Cluster ion beam method in which clusters consisting of about 1000 molecules are formed by heat, ionization of these clusters, and accelerated vapor deposition. (C) Ion beam method in which irradiated ions formed in an ionization chamber are irradiated on a target. (D) Ions. There is a method such as an ion beam enhanced deposition method of evaporating by a beam and ionizing an evaporant to adhere to a substrate.

[Problems to be Solved by the Invention] However, the above (A) ion plating method,
(C) In the ion beam method, particles to be deposited are evaporated and ionized by gas plasma or discharge of an inert gas such as argon. For this reason, it cannot be used in a high vacuum, and there is a problem that impurities contained in the film cannot be reduced sufficiently. That is, an impurity is contained in the inert gas and may be mixed in, or the inert gas itself may be mixed as an impurity in the film.

In (A) the ion plating method, (B) the cluster ion beam method, and (D) the ion beam enhanced deposition method, an evaporation source for evaporating a deposition material and an ionization section are separately formed. However, there has been a problem that the entire apparatus becomes large.

Furthermore, in any of the above methods (A) to (D), the ionic valency of the film constituent material to be deposited is almost monovalent, and the ionic valence of the film-forming substance is unique among polyvalent ions. It could not be manufactured. Further, there are considerable restrictions on the materials to be deposited, and a film of a desired material cannot be formed.

In addition, in the case of a multilayer film in which a plurality of films are stacked or a mixed film in which a film is formed in a state where a plurality of materials are mixed, a separate evaporation source is required for each material to be evaporated. However, there is a problem that it becomes large-scale.

A laser vapor deposition method for condensing and irradiating a laser beam onto an irradiation object disposed in a vacuum to evaporate the irradiation object and depositing the evaporated particles on a substrate is also disclosed in, for example,
This is disclosed in, for example, JP-A-59-116373. However, even in such a laser vapor deposition method, there is no means for selecting the ion valence of the particles to be evaporated, and a film having a desired configuration cannot be formed.

The present invention has been made to solve the above problems, and has as its object to provide a laser vapor deposition method and apparatus capable of controlling a film configuration to a desired one.

[Means for Solving the Problems] The invention of claim (1) is the first invention of the present invention, in which an object to be irradiated is arranged in an airtightly formed decompression container, and a laser beam is applied to the object to be irradiated. And irradiate it to generate laser-induced plasma containing mono- and poly-valent ions, electrons, and neutral atoms of the irradiation object having a spatial and temporal distribution in physical and chemical states. And discharging the emitted material, and selecting an emitted material from the emitted material toward a predetermined angle range and depositing the selected material on the substrate.

Further, the invention of claim (2) is the second invention of the present invention, characterized in that a substance emitted at a predetermined range of emission rate is selected from the emitted substances and is deposited on the substrate.

The invention of claim (3) is the third invention of the present invention, and is a pressure reducing container formed airtight and capable of holding the inside in a reduced pressure state, and provided inside the pressure reducing container and emitted by irradiation with laser light. An irradiation object holder that holds an irradiation object that emits an object, a laser beam emitted from a laser oscillator is collected and irradiated to the irradiation object, and the physical state of the emission material released from the irradiation object and An optical system for generating laser-induced plasma having a spatial and temporal distribution in a chemical state, a substrate holder for holding a substrate on which an emission emitted from the object is deposited, an object holder and a substrate holder And a selective permeation means provided in an intermediate discharge flow passage for selectively passing a substance emitted in a predetermined direction from the substances emitted from the irradiation object.

[Operation] The first to fourth inventions of the present invention have the above-described configuration. When performing vapor deposition, first, an irradiation target that emits a deposition substance is attached to an irradiation target holder. A substrate on which a film is to be formed is attached to a substrate holder. Next, the gas in the hermetic container is sucked out by, for example, a vacuum pump or the like, and the inside of the hermetic container is maintained at a predetermined reduced pressure.

Then, the object to be irradiated is irradiated with laser light from a laser oscillator. Here, as the laser oscillator, one that emits pulsed laser light such as an excimer laser or a continuous wave laser with chopper ring is preferable. The laser light is condensed on the surface of the irradiation object by an optical system such as an optical lens, and a predetermined high energy laser irradiation is performed.

By the laser irradiation, ions (including multivalent), electrons, and neutral atoms are released from the irradiation object, and laser-induced plasma is generated in the atmosphere. The density of the laser-induced plasma can be easily adjusted depending on the degree of light collection of the optical system.

Then, the emission material emitted from the irradiation object scatters around, but a part of the emission material fly toward the substrate and adhere to the surface of the substrate.

Here, in the present invention, the emission attached to or deposited on the substrate is determined by the physical state of the emission such as the velocity and mass, the type of the emission (monovalent and polyvalent ions, electrons, neutral atoms, etc.). Etc.), the emission which is deposited on the substrate can be controlled.

Therefore, a film having a desired component and structure can be deposited on the substrate.

[Effects of the Invention] As described above, according to the laser deposition method and apparatus according to the present invention, the crystal structure and the like of the deposited film can be controlled by utilizing the effects of plasma and ions by laser light.

In addition, a film having a novel structure selectively using polyvalent ions, which has not been obtained conventionally, can be obtained.

According to a third aspect of the present invention, the vapor deposition control means is provided in an emission distribution passage intermediate the object holder and the substrate holder, and only the one emitted in a predetermined direction from the objects emitted from the object is provided. Are selectively passed means for selectively passing through.

As the selective transmission means of the third invention, for example, a shielding plate having an opening or a shielding plate having an opening is repeatedly opened and closed at predetermined time intervals in the passage of the release logistics, and the discharge passing therethrough at a predetermined time is performed. A filter or the like that selects only an object is conceivable.

The control of the vapor deposition in the third invention can be performed as follows.

That is, a spatial selection means, for example, a shielding plate having an opening is provided in the emission flow path from the irradiation target to the substrate. Then, among the emission substances emitted from the irradiation object, those reaching the surface of the substrate are limited to those passing through the opening.

The emission material emitted from the irradiation object depends on the chemical state such as its type (multivalent ions, monovalent ions, neutral particles, clusters, fine particles, and electrons), and the physical state such as velocity and mass, and radiation. The directions and the like are different, and based on this, a spatial component distribution of the radiant is generated. Therefore, spatial selection can be performed by a shield plate or the like, and the configuration of the deposited film can be controlled. For example, the ratio of crystallinity such as α phase and β phase of the tungsten vapor deposition film can be controlled by this spatial selection.

In addition, a speed filter that rotates a disk having an opening at a predetermined angle is disposed on a path from an object to be irradiated to a substrate, and only emission that reaches the speed filter at a predetermined time can be selected. That is, when the object is irradiated with the laser, the irradiation object arrives at the speed filter in order from the irradiation object with the highest speed. Therefore, if the speed filter is opened in synchronization with the laser irradiation and opened only at a predetermined time after the laser irradiation, it is possible to select only the emission having a speed corresponding to this time. For example, by using molybdenum as an irradiation object, fine particles can be removed or only monovalent ions can be selected.

A fourth invention of the present invention is characterized in that the vapor deposition control means is a control means for controlling a rate and an amount in accordance with the state of the compound in the discharge.

As the vapor deposition control means of the fourth invention, for example, an applied voltage control means for applying a predetermined voltage between the object to be irradiated and the substrate can be considered.

According to the fourth aspect, the crystallinity and the like of the deposited film can be controlled by controlling the speed and amount in accordance with the chemical state of the emitted substance emitted from the irradiation object. For example, if a voltage is applied so that the potential of the irradiation object becomes a positive or negative value with respect to the substrate, an electric field is formed in the moving path of the emission object, and ions or other charged objects are accelerated or accelerated by this electric field. Slow down. Therefore, the speed and amount are changed according to the chemical state of the emission adhering to the substrate, thereby changing the crystal structure of the film formed on the substrate surface. Therefore, physical properties such as the crystal structure of the deposited film can be controlled by changing the applied voltage between the irradiation target and the substrate.

For example, when tungsten is used as the irradiation object and the potential of the irradiation object is -1 kV or lower or 1 kV or higher, an amorphous film can be formed on the substrate. A tungsten film with good crystallinity can be obtained.

[Effects of Other Inventions] As described above, according to the laser deposition method and apparatus according to the present invention, while utilizing the effects of plasma and ions by laser light, spatial selection means and temporal selection means As shown in FIG. 2, the crystal phase ratio, the crystal structure, and the like of the deposited film can be controlled using a speed control means and the like.
For this reason, a film having a desired crystal phase ratio and crystal structure can be obtained with a simple structure, and a film having a novel structure selectively using polyvalent ions, which has not been obtained conventionally, can be obtained. Therefore, the film according to the present invention is expected to be widely used in various fields in a variety of fields, exhibit new functions, and contribute to enhancing the functions of various devices.

Example An example of a laser deposition method and apparatus according to the present invention will be described below with reference to the drawings.

First Embodiment A laser deposition apparatus according to a first embodiment of the present invention will be described with reference to FIGS.

FIG. 1 is a configuration diagram of a first embodiment, in which an airtight container 10 is formed of a sealed pressure-resistant container, and the inside thereof is shielded from an external space. A vacuum pump 12 is connected to the hermetic container 10 via a pressure regulator 14, and by driving the vacuum pump 12, the inside of the hermetic container 10 can be brought into a reduced pressure state. In a normal case, a pressure detector (not shown) is provided to detect the pressure inside the airtight container 10, and the pressure regulator 14 is controlled to maintain the inside of the airtight container 10 at a predetermined pressure. For this reason, the inside of the airtight container 10 can be brought into a predetermined reduced pressure state by the vacuum pump 12 and the pressure regulator 14.

Further, a gas source 20 is connected to the hermetic container 10 via a valve 16 and a flow regulator 18. Therefore, a desired gas from the gas source 20 can be introduced into the airtight container 10 at a predetermined flow rate. Therefore, the inside of the airtight container 10 can be maintained in a predetermined gas atmosphere state.

The laser oscillator 30 emits a predetermined laser beam 32. For example, an excimer laser that oscillates a pulse laser is used. Then, the laser light 32 is condensed by the condenser lens 34.
After passing through the (optical system), the light is guided into the airtight container 10 through the transmission window 36 provided in the airtight container 10.

On the other hand, a rotary table 40 is provided in the airtight container 10, and the irradiation target 42 is held on the rotary table 40. That is, a secondary motor 44 is fixed to the rotary table 40, and an irradiation object holder 46 is fixed to a main shaft of the secondary motor 44. Then, the irradiation object holder 46
The object to be irradiated 42 is fixed to the substrate.

Therefore, when irradiating the object 42 with the laser light 32 by the condenser lens 34, the irradiation power density (energy density) of the laser light irradiated on the object 42 is adjusted by adjusting the store distance in the condenser lens 34. Can be adjusted. This makes it possible to control the amount and composition of the emitted substance emitted from the irradiation target 42, for example, the ion amount of the discharged substance containing multivalent ions and the ratio of the multivalent ions. In the present invention, plasma is generated in this atmosphere by irradiating the object 42 with laser light,
This plasma density can also be adjusted by adjusting the laser beam irradiation power density.

Further, the motor 44 is driven to rotate the irradiation target holder 46 in order to prevent the irradiation target 42 from being concentratedly damaged by the laser irradiation. That is, by rotating the irradiation object holder 46, the irradiation object 42 is rotated, and the laser light condensed by the condenser lens 34 is sequentially irradiated to each part of the irradiation object 42, thereby preventing concentrated damage. Can be.

Further, by rotating the rotary table 40 about its rotation axis, the laser beam from the condenser lens 34 and the object 42
Angle can be changed. Therefore, it is possible to control the scattering direction of the emission material emitted from the irradiation object 42.

A substrate holder 50 is disposed at a position facing the irradiation target 42 in the hermetic container 10.
A substrate 52 on which a film is formed by vapor deposition is mounted.

Here, in this embodiment, a shielding plate 60 which is a selective transmission unit as a vapor deposition control unit is provided on the front side of the substrate 52. The shielding plate 60 is provided with an opening 62, and the emission released from the irradiation target 42 can be limited to only the one passing through the opening 62. That is, it is possible to spatially limit the passage through which the discharged material is circulated, and to select the discharged material discharged in a predetermined direction. Therefore, the substrate
The substance deposited on the surface of 52 is limited to only those released from the irradiated object 42 in the direction of the opening 62. The emission components emitted from the irradiation target 42 have a predetermined spatial distribution, and the emission of the desired component can be selected according to the position of the opening 62 of the shielding plate 60. Can be deposited.

The irradiation object holder 46 and the substrate holder 50 are provided with temperature controllers 70 and 72, respectively, so that the temperatures of the irradiation object 42 and the substrate 52 can be controlled to desired ones.

As described above, in the laser vapor deposition apparatus of the embodiment, when the laser beam 32 is condensed and irradiated on the irradiation target 42, laser-induced plasma is generated here, and the emission target is released from the irradiation target 42. You. The emission includes neutral particles, clusters, droplet particles, fine particles, ions including these multiply charged ions, electrons, and the like. These emissions are injected in a predetermined direction according to their components. Therefore, the emission released from the irradiation target 42 has a spatial distribution according to the component. Therefore, a desired component can be selected by the operation of the turntable 40 and the position of the opening 62.

Example 1 Next, an example of an experimental result of actually performing a deposition process using the apparatus of the first example will be described.

In this example, the irradiation target 42 is tungsten (W),
The substrate 52 is made of glass, and the laser oscillator 30 is made of a KrF excimer laser (wavelength 249 nm, pulse width 16 nsec, pulse energy 250 m
J), a laser repetition cycle of 25 Hz, a total of 30,000 pulses of irradiation pulses for the irradiation target 42, a laser irradiation area of 6 × 10 ⁻³ cm ² for the irradiation target 42, a rotation speed of the motor 44 of 20 rpm,
The incident angle of the laser beam 32 to the irradiation object 42 is 45 °, the temperature of the irradiation object 42 and the substrate 52 is room temperature, and the air pressure in the hermetic container 10 is 1
× 10 ^-5 Torr or less.

The distance between the irradiation target 42 and the substrate 52 is 30 mm,
Was disposed so as to be in close contact with the substrate 52.

The laser beam 32 is condensed and irradiated on the irradiation object 42, where laser-induced plasma is generated. Then, neutral particles, clusters, ions including multiply-charged ions, and electrons are emitted from the irradiation target 42 toward the periphery thereof. Then, the emitted material flies toward the substrate 52 and is deposited on the substrate 52.

Here, in front of the substrate 52, a shielding plate 60 having an opening 62 is provided.
Is arranged. Since the spatial distribution (emission direction) of the ions in the plasma varies depending on the valence, selecting a specific direction according to the position of the opening 62 allows each valence reaching the substrate (for example, monovalent, divalent, trivalent, etc.). ) Can be controlled.

FIG. 2 shows an X-ray diffraction result of the tungsten vapor deposited film thus deposited on the substrate 52. In the figure, the horizontal axis is the X-ray incident angle 2θ, and the horizontal axis is the diffracted X-ray intensity.

Thus, when the size of the opening 62 is 30 mm (the solid angle is
0.663 steradian), the tungsten vapor deposition film is composed of α phase and β
It has a peak at the incident angle corresponding to the phase, and α-phase and β-phase crystals are mixed. On the other hand, when the size of the opening 62 is set to 5 mm (solid angle is 0.022 steradians), only a component having a particularly high ion (including multiply charged ion) amount and plasma density among the discharged substances is deposited. Therefore, the tungsten vapor-deposited film has an α-phase single phase. As described above, the size of the opening 62 is used, and only a specific component can be selected by using the spatial distribution of the components of the emission. Therefore, it is understood that the physical properties of the film can be controlled by this example.
Note that CoKα was used as the X-ray source.

The tungsten film thus obtained is, for example, an IC
It is used as a wiring material for etc. In general, it is known that the α phase of tungsten has a smaller specific resistance than the β phase and is preferable as a wiring material. The α phase has a higher melting point than the β phase, and can be used as a surface coat film for heat-resistant parts. When using a tungsten film, its crystallinity and crystal structure are factors that govern conductivity, heat resistance, and corrosion resistance, and the apparatus of this embodiment that can control this is very important in the use of a tungsten film. Can play a role.

Experimental Example 2 Next, the results of an experiment performed under different conditions using the apparatus of the present embodiment will be described. In this example, as shown in FIG. 3, the irradiation object 42 was of a split type made of copper (Cu) and iron (Fe). The substrate 52 is made of glass, and the laser oscillator 32 is made of an ArF excimer laser (wavelength 193 nm, pulse width 16 nse
c, pulse energy 200 mJ), repetition cycle 25 Hz, total number of irradiation pulses 30,000, laser irradiation area 6 × 10 ^-3 cm ² , laser height 32 and irradiation angle of irradiation object 42 45 degrees, irradiation object 42 and substrate The temperature of 52 was room temperature, and the air pressure in the hermetic chamber 10 was 1 × 10 ⁻⁵ Torr or less.

The laser beam 32 is irradiated on the irradiation object 42 under such conditions to generate laser-induced plasma. Then
From the irradiated object 42, an emission composed of iron, copper, an emission, its ions (including multiply-charged ions), electrons, and the like is generated alternately. This is because the irradiated object 42 is made of both iron and copper as shown in FIG. 3, and the rotation of the motor 44 irradiates the iron and copper alternately. Then, the irradiation target 42
By controlling the rotation speed, multilayer films having various configurations can be formed. That is, the film thickness is determined by the irradiation time. However, if the rotation speed of the irradiation object 42 is increased, the number of times that iron and copper are alternately irradiated increases, the number of layers of the film increases, and the thickness of each layer increases. Becomes smaller.

In FIG. 4, the size of the opening 62 is 5 mm,
The X-ray analysis results are shown in the case where the distance of 2 is 30 mm, the shielding plate 60 is brought into close contact with the substrate 52, the irradiation target 42 is rotated at various speeds, and a multi-layered film of iron and copper is formed on the substrate.

As can be seen from the figure, changing the rotation speed
When there are 1840 layers, 460 layers, 92 layers, and 20 layers, there is a considerable change in the configuration of the iron and copper multilayer film. That is, the irradiation target 42
The crystal structure of the multilayer film changes in accordance with the rotation speed of.
Further, regarding iron, it is understood that the ε phase, which can be obtained only in a high-temperature and high-pressure state, is stably present in the multilayer film, and a film having a unique configuration is formed. The total thickness of the deposited film is the same as 1380 °.

Furthermore, if the irradiation target 42 is of two or more types, a plurality of mixed films can be formed according to the material, and the division ratio (area ratio) of the irradiation target 42 is appropriately selected. This makes it possible to easily control the mixing ratio of the multilayer film.

As described above, according to the first embodiment, it is possible to select a substance to be vapor-deposited from among the substances emitted from the irradiation object 42,
A desired deposited film can be formed.

In addition, when a reactive gas is introduced from the gas source 20 into the hermetic container 10 and vapor deposition is performed in the reactive gas, the reactivity between the ion containing multivalent ions of the discharged substance and the gas can be increased, and Can be performed on the substrate by reactive vapor deposition.

In addition, as the irradiation object 42, various metal alloys, ceramics, alumina, organic materials, liquids or gases which are adsorbed on another solid surface, and the like can be used.
This allows various emissions to be obtained and the desired film to be formed.

Further, in the present embodiment, since the temperature control device 70 is provided, the temperature of the irradiation target can be maintained at a predetermined temperature. Therefore, it is possible to prevent cracks or the like of the irradiation object due to a rapid rise in temperature, and to prevent evaporation of a target gas or liquid from a solid material that has adsorbed the gas or liquid. Further, by controlling the temperature of the substrate, the crystal structure of the film can be controlled.

In general, a multilayer film can obtain various physical properties that are not found in a substance existing in nature by selecting and controlling a lamination method, a material to be laminated, a mixing ratio, and the like. Also, if a multilayer film having new physical properties can be obtained, a completely new function is exhibited.

Further, a multilayer film having special magnetic properties can be used as a magneto-optical recording material by using this to enhance the perpendicular anisotropy.

Second Embodiment Next, a second embodiment will be described with reference to FIGS.

FIG. 5 is a block diagram of the second embodiment, in which the same members as those in the first embodiment are denoted by the same reference numerals, and description thereof will be omitted.

What is characteristic in the second embodiment is that, as selective permeation means, which is a vapor deposition means, the opening / closing and shielding are repeated at predetermined time intervals between the specific irradiation object 42 and the substrate 52, and only the emission material which is worth a predetermined time at a predetermined time is used. Speed filter 80 which is the filter to select
That is, The speed filter 80 includes a motor 82 and a rotating disk 84, and an opening 86 having a predetermined opening angle is formed in the rotating disk 84.

That is, in this example, as shown in FIG. 5 and FIG. 6, a sector-shaped opening 86 having an angle θ is formed in the rotating disk 84. Then, the speed filter 80 has a rotating disc 84,
The shielding plate 60 is provided so as to be located near the substrate 52 side.

Further, in this example, the entire object such as the irradiation object 42 and the substrate 52 is placed on the rotary table 40. However, by the rotation of the rotary table 40, the angle of the laser beam 32 with respect to the irradiation target 42 can be adjusted, and the irradiation target to be directed to the substrate 52 can be spatially selected.

In such an apparatus, a pulse laser beam is condensed and irradiated on the irradiation object 42 by a pulse laser oscillator 30 such as an excimer laser. Then, similarly to the first embodiment, the irradiation target 42
, And emits a laser-induced plasma. Then, of the discharged substances, those scattered in the direction of the substrate 52 pass through a predetermined opening 62 of the shielding plate 60.

Here, in the present embodiment, the speed filter 80 is disposed behind the shielding plate 60, and the rotating disk 84 of the speed filter 80 is rotated in synchronization with the pulse generation cycle of the laser oscillator 30. Therefore, the time distribution of the emission can be selected by the speed filter 80, and a desired component can be selected.

That is, by selecting the width (opening angle θ) of the opening 86 of the rotating disk 84 of the speed filter 80, the number of rotations, the diameter, the repetition period of the pulse laser, the distance from the irradiated object 42 to the speed filter 80, and the like. In addition, it is possible to select only a specific rate of the emission emitted from the irradiation target 42, and to achieve the selection of the component using the temporal component distribution in the emission.

Here, assuming that the velocity of the emitted matter (particles) emitted from the irradiation target 42 is v (cm / sec) and the distance from the irradiation target 42 to the speed filter 80 is d (cm), A time ta required for the discharged matter to reach the velocity filter 80 can be expressed as follows.

ta = d / v On the other hand, if the rotation speed of the rotating disk 82 in the speed filter 80 is ω (rpm) and the angle of the opening 86 is θ (deg), 1
The time tp during which the emission emitted from the irradiation target 42 by the irradiation of the pulsed laser light 32 can pass through the speed filter 80 can be expressed as follows.

tp = (60 / ω) ・ θ / 360 And 32 repetition periods T (pulses / sec) of laser light
And the rotation cycle ω (rpm) of the speed filter 80 are the same, the time tp is as follows.

tp = θ / 360T Therefore, if the time ta until the emission reaches the speed filter 80 and the time tp during which the emission can pass through the speed filter 80 are set to be equal, only the emission group having the speed v or higher can be obtained. Can be selected and deposited on the substrate 52.

For this purpose, the distance d from the irradiation target 42 to the speed filter 80 may be set as in the following equation.

d = (1/360) · v · θ / T The selection using the spatial component distribution by the opening 62 of the shielding plate 60 is the same as in the first embodiment.

In the above description, the irradiation laser is pulse-shaped, but may be continuous. In this case, the configuration of FIG. 6 is changed as shown in FIG. That is, when the laser is of continuous oscillation, a plurality of rotating disks 84 are used in the configuration of the speed filter 80, and the one shown in FIG. 7 is mounted as the speed filter 80 in FIG.

That is, in this example, as shown in FIG. 7, a sector-shaped opening 86 having an angle θ is formed in the rotating disk 84.
The speed filter 80 is provided such that the rotating disk 84 is located near the shield plate 60 on the substrate 52 side.

Further, in this example, the entire object such as the irradiation object 42 and the substrate 52 is placed on the rotary table 40. However, by the rotation of the rotary table 40, the angle of the laser beam 32 with respect to the irradiation target 42 can be adjusted, and the irradiation target to be directed to the substrate 52 can be spatially selected.

In such devices, CW such as high-power CO ₂ laser
The CW laser light is condensed and irradiated on the irradiation object 42 by the laser oscillator 30. Then, similarly to the first embodiment, the emitted material is released from the irradiated object 42, and the laser-induced plasma is generated here. Then, of the discharged substances, those scattered in the direction of the substrate 52 pass through a predetermined opening 62 of the shielding plate 60.

Here, in the present embodiment, a speed filter 80 composed of a plurality of rotating disks is disposed behind the shielding plate 60.

That is, the opening of the first rotating disk 84 of the speed filter 80
By selecting the width (opening angle θ) of 86, the number of rotations, the diameter, the distance from the irradiated object 42 to the speed filter 80, etc., a continuous emitted object with various speeds emitted from the irradiated object 42 The particle bundle 100 is cut out from the inside by the first rotating disk 84. Emissions with various velocities are present in the particle bundle 100. Higher velocities within the time of flight until reaching the second rotating disk 106 come first, and those with lower velocities come later. The bundle 102 extends spatially as shown and has a particle distribution according to the spatial velocity component. This particle bundle 10
2 is selected by selecting the opening 108 (opening angle θ ') of the second rotating disk 106, the number of rotations and its delay time, the diameter, the distance between the first rotating disk 84 and the second rotating disk 106, and the like. Only a specific velocity of the particle bundle 102 can be selected, and a component-selected particle bundle such as the particle bundle 104 is obtained. It should be noted that the rotation speed of the second rotating disk is the same as that of the first rotating disk, or that multiplication thereof is efficient.

By using a plurality of rotating disks in this way, it is possible to select a specific velocity component in the emitted material even in the case of continuous oscillation of the laser, as in the case of pulse oscillation.

As described above, the laser light of the present embodiment may be pulsed or continuous, and in this embodiment, the laser light is condensed and irradiated on the irradiation object, and the emitted material is distributed. The passage is limited spatially and temporally, and discharges discharged in a predetermined direction at a predetermined time are selected.

Experimental Example An experimental result performed using the apparatus of the second embodiment will be described.

In this example, the object to be irradiated 42 is molybdenum (Mo),
The substrate 52 is made of glass, and the laser oscillator 30 is made of a KrF excimer laser (wavelength 249 nm, pulse width 16 nsec, pulse energy 250 m
J), the inside of the hermetic container 10 is 1 × 10 ⁻⁵ Torr or less, the laser pulse repetition cycle is 20 pulses / sec, the irradiation angle of the laser beam 52 to the irradiation object 52 is 45 °, the total irradiation pulse is 30,000 pulses, The irradiation area on the irradiation target 42 was 6 × 10 ⁻³ cm ² , the rotation speed of the irradiation target 42 was 20 rpm, and the temperature of the irradiation target 42 was room temperature.

When vapor deposition is performed under these conditions, the velocity distribution of the particles constituting the emission is as shown in FIG. 7, and therefore, the object to be irradiated is irradiated with a laser pulse in the velocity filter 80. If a radiant is passed only after a predetermined time has passed since then, a radiant that passes through the velocity filter 80 can be selected. That is, if the speed filter 80 is set to a time that is much shorter than the time when the irradiation target 42 is irradiated with the laser beam 32, only multiply-charged ions can be selected. You can choose.

Here, the diameter of the opening 62 of the shielding plate 60 is 20 mm, the diameter of the rotating disk 84 of the speed filter 80 is 30 mm, the opening angle θ of the opening 86 of the rotating disk is 5 °, the number of rotations is 1200 rpm, The distance d from 42 to the speed filter 80 is 34.7 mm, the distance between the irradiation target 42 and the substrate 52 is 40 mm, and the shielding plate 60 is positioned in front of the speed filter.
The experiment was conducted by setting it at a position of 2 mm.

Then, by synchronizing the pulse of the laser beam 32 with the rotation of the speed filter 80, the emission can pass through the speed filter 80 only for a predetermined time (0.7 msec) from when the irradiation of the irradiation target 42 is started. Becomes Therefore, only the emission having a speed of 5 × 10 ³ co / sec or more passes through the speed filter 80 corresponding to the time that can pass.

As is clear from FIG. 8, since the speed of the fine particles is low, if the above-described speed filter 80 is provided, the fine particles in the vapor-deposited film should be significantly reduced. Therefore,
Experiments of vapor deposition were performed for the case where the speed filter 80 was provided and the case where the speed filter 80 was not provided, and the density of the fine particles was described.

When the speed filter 80 is provided, the particle density is 65
It was / mm ^2.

The density of the fine particles without the speed filter 80 is
2.4 × 10 ³ pieces / mm ² .

From this, it is understood that the velocity filter 80 of this experimental example can effectively remove fine particles.
In addition, the number of these fine particles is
It measured using the SEM (scanning electron microscope) photograph.

Third Embodiment Next, a third embodiment will be described with reference to FIGS.

FIG. 9 is a block diagram of the third embodiment. The same members as those in the first and second embodiments are denoted by the same reference numerals, and the description thereof will be omitted.

What is characteristic in the third embodiment is that, as the vapor deposition control means, there is provided an applied voltage control means which is a control means for controlling the speed, type and amount in accordance with the chemical state of the emitted material, and the irradiation object 42 and the substrate 52 are provided. That is, a predetermined voltage was applied during this period.
That is, the applied voltage control means includes, for example, the switch 90,
The irradiation target 42 is constituted by a positive variable voltage power supply 92 or a negative variable voltage power supply 94. A voltage is applied to the irradiation object 42 by the applied voltage control means, and the substrate 52 is connected to the ground. Therefore, the irradiation object 42 can be set to a predetermined positive or negative potential with respect to the substrate 52. Further, since the output voltage values of the power supplies 92 and 94 are variable, the irradiation target 42 can be set to a desired electric range.

Then, of the laser-induced plasma generated by the laser light 32 by setting the irradiation target 42 to a predetermined potential by the power supplies 92 and 94, the emission in the predetermined direction selected by the opening 62 of the shielding plate 60 is included. Charged particles can be controlled. That is, if the potential of the irradiation target 42 is set to the positive side, the ions emitted from the irradiation target 42
The ions accelerated by the electric field that has been positively raised in between, and the ions emitted are decelerated by setting the negative side. If such an electric field is formed, the acceleration will differ depending on the valence of the ions, and the amount of the ions will also be limited. Therefore, whether or not it is an ion, the speed and the amount when colliding with the substrate 52 according to the valence of the ion are different,
By controlling the potential of the irradiation object, physical properties such as crystallinity of a deposited film deposited on the substrate 52 can be suppressed.

That is, in the present embodiment, a predetermined voltage is applied between the irradiation target and the substrate, and the speed, type, and amount are selected according to the chemical state of the emission emitted from the irradiation target in a predetermined direction. is there.

Experimental Example Next, an experimental result performed using the device of the third embodiment will be described. In this example, the irradiation object 42 is tungsten (W), the substrate 52 is glass, and the laser oscillator 30 is Kr.
F excimer laser (wavelength 249 nm, pulse width 16 nsec, pulse energy 250 mJ), the degree of vacuum in the hermetic container 10 is 1 × 10 ^-5 T
less than orr, the pulse laser repetition cycle is 25 pulses / sec,
The irradiation angle of the laser beam on the irradiation target 42 is 45 °, the total number of irradiation pulses is 30,000 pulses, the laser irradiation area on the irradiation target 42 is 6 × 10 ⁻³ cm ² , the rotation speed of the irradiation target 42 is 20 rpm,
The temperature of the irradiation target 42 was room temperature, the temperature of the substrate 52 was room temperature, and the distance between the irradiation target 42 and the substrate 52 was 30 mm.

Then, under such conditions, the speed and amount of the charged particles in the selectively permeated emission were controlled by setting the potential of the irradiation target 42 to −1 kV to 1 kV.

FIG. 9 shows the results of X-ray analysis of the tungsten deposition film obtained by this experiment. Thus, when no voltage is applied to the irradiation target 42, the tungsten film has a strong crystallinity. However, when the potential of the irradiation object 42 was set to a negative value and the voltage was increased, the crystallinity of the tungsten vapor-deposited film gradually decreased and became amorphous at -1 kV. When the potential of the irradiation target 42 is set to the positive side and the potential is increased, the crystallinity is improved up to around 300 V, but the crystallinity is reduced when the potential exceeds 300 V. When the potential reached 1 kV, the tungsten film became amorphous.

Note that the above experimental results are obtained when the temperature of the substrate 52 is set to room temperature.
When the potential of the irradiation object 42 is in the range of −3 kV to 3 kV, the substrate 52
All of the deposited films deposited on top became crystalline.

As described above, by applying a voltage between the irradiation target 42 and the substrate 52 and controlling the laser-induced plasma, the substrate
It is possible to control the crystal structure of the deposited film formed on 52. The physical properties of the tungsten film largely depend on the crystal structure as described above. In general, it is known that by making the film amorphous, the hardness of the film can be increased, and a film suitable for abrasion and heat resistant coating can be formed.

Further, it is known that improving the crystallinity means exhibiting properties more suitable for the wiring material. By controlling the crystal structure of the film as in this embodiment, films having various physical properties can be obtained. In the third embodiment, the aperture 60 adopted in the first embodiment can be combined.

Further, in the third embodiment, the speed filter 80 employed in the second embodiment can be combined.

[Brief description of the drawings]

FIG. 1 is a configuration diagram showing a main part configuration of a first embodiment of a laser vapor deposition apparatus according to the present invention, FIG. 2 is a characteristic diagram of X-ray diffraction of a tungsten film in the first embodiment, FIG. FIG. 4 is a diagram showing an X-ray diffraction characteristic of the Fe—Cu film according to the embodiment, and FIG. 5 is a diagram illustrating a second example of the laser evaporation apparatus according to the present invention. FIG. 6 is an explanatory diagram for explaining the configuration of the embodiment, FIG. 7 is an explanatory diagram showing another configuration of the embodiment, FIG. FIG. 9 is a configuration diagram showing a main part configuration of a third embodiment of the laser vapor deposition apparatus according to the present invention, and FIG. 10 is a diagram showing the X of the tungsten film in the third embodiment. It is a characteristic view of a line diffraction. 10 Airtight container 30 Laser oscillator 32 Laser light 34 Condensing lens (optical system) 42 Irradiated object

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Noboru Takayanagi 1 Toyota Town, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation (56) References JP-A-56-169228 (JP, A) JP-A-2-311307 (JP, A) JP-A-64-39371 (JP, A) JP-A-60-243270 (JP, A) JP-A-64-17002 (JP, A)

Claims (4)

(57) [Claims] 1. An object to be illuminated made of a metal is placed in an airtightly formed decompression container, and a laser beam is condensed and irradiated onto the object to be illuminated. A laser-induced plasma containing mono- and multi-charged ions, electrons, and neutral atoms of the irradiation object having a temporal and temporal distribution is generated, and the emission material is released. A laser vapor deposition method characterized in that a substance emitted toward a solid angle range is selected and vapor-deposited on a substrate. 2. The laser vapor deposition method according to claim 1, wherein said solid angle is within 0.022 steradians. 3. An object to be irradiated is placed in an airtight decompression vessel, and the object to be irradiated is condensed and irradiated with a laser beam. Generates a laser-induced plasma containing monovalent and multiply-charged ions, electrons, and neutral atoms of the irradiation object having a temporal distribution, emits the emission, and moves the emission toward a predetermined angle range from the emission. A laser vapor deposition method characterized in that a material that is emitted and emitted at an emission speed within a predetermined speed range is selected and evaporated on a substrate. 4. A depressurized container which is formed in an airtight manner and is capable of holding the inside in a decompressed state, and holds an object to be irradiated which is provided inside the depressurized container and which is made of a metal which emits an emitted material by irradiation with a laser beam. Irradiates the irradiated object holder with the laser beam emitted from the laser oscillator, irradiates the irradiated object with the laser beam, and spatially and temporally changes the physical state and chemical state of the released object from the irradiated object. An optical system for generating a laser-induced plasma having a distribution; a substrate holder for holding a substrate on which the emission material emitted from the irradiation object is deposited; and an emission flow passage intermediate the irradiation object holder and the substrate holder. And a selective means for selectively passing only those emitted in a direction of a predetermined solid angle with respect to the irradiated object from among the emitted materials emitted from the irradiated object, and Evaporation equipment.