KR100324499B1 - Thin film formation method by laser ablation or high voltage discharge plasma CVD or laser ablation combined with high voltage discharge plasma CVD - Google Patents

Abstract

In the thin film forming method such as the laser ablation method, the plasma CVD method, or the combination method of the two methods according to the present invention, the laser beam 2 generated from the excimer or yag laser 1, which is a laser source, is used. Particles (laser plume 7) protruding from the surface when the fixed target 6 located in the vacuum chamber 5 are irradiated by condensing with the lens 3 and using an optical device called a driving reflector 4. A laser ablation method for forming a thin film on the substrate 9 located on the substrate heater 8, a plasma zone generated by applying a high voltage between the cathode 10 and the anode 11 made of a material to be sputtered ( Plasma CVD method for forming a thin film on the substrate 9 installed on the anode 11 located in the center of 12), the two methods are specially combined so that the above two deposition processes are performed at the same time. group (9) A method of forming a thin film such as a thin film device, wherein the plasma density is increased during the deposition process of the above three methods to increase the excitation efficiency and the deposition rate to form a thin film such as a thin film of good quality. In addition, the method may further include applying an electromagnetic field generated from the electromagnet 14 to the laser plume zone or plasma zone surrounded by the special high temperature heat-treated glass reactor 13.

Description

Thin film formation method by laser ablation or high voltage discharge plasma CVD or laser ablation combined with high voltage discharge plasma CVD}

The present invention relates to a thin film forming method such as a laser ablation method, a high voltage discharge plasma CVD method, a thin film device by a combination method of the above two methods. In more detail, when forming a thin film such as a thin film device in the gas atmosphere to be reacted by the three methods of the present invention, generated from the electromagnet in the laser plume zone or plasma zone surrounded by a special high temperature heat treatment glass reactor The present invention relates to a method of forming a thin film such as a high quality thin film device in a shorter time by inducing an increase in plasma density by Lorentz's law by increasing the excitation efficiency, the deposition rate, and the efficiency by applying an electron field.

Conventionally, in order to form a thin film such as a thin film device on a substrate, the above-described laser ablation method or plasma CVD method is mainly used under a reaction gas atmosphere at a constant pressure. When a thin film such as a thin film device is grown by a laser ablation method or a plasma CVD method under an existing gas atmosphere, it is known that a thin film having a relatively high quality can be obtained. On the other hand, in spite of the advantages of the above two methods, the structure of the device is simple and relatively high quality thin film can be obtained. Although the trend is being applied to the formation of thin films, such as thin-film devices by a combined method combined method has not been announced yet.

1, 2 and 3 are schematic diagrams showing a process of forming a thin film such as a thin film device by a laser ablation method, a plasma CVD method, and a mixing method combining them, respectively, as shown in FIG. In the laser ablation method of the laser beam, the laser beam 2 generated from the laser 1, which is a laser generation source, is condensed by the lens 3, irradiated onto the target 6, and particles protruded by the laser beam 2 irradiation. Field 7 is formed on a substrate 9 located above the substrate heater 8 to form a thin film such as a thin film device. As shown in FIG. 2, in the conventional plasma CVD method, when a high voltage is applied between two electrodes 10 and 11 spaced apart from each other, a large number of particles are emitted from the cathode 10, and these particles are transferred to the substrate heater 8. The thin film, such as a thin film device, is deposited on the substrate 9 positioned on the substrate 9). In addition, as shown in FIG. 3, in the mixing method by combining the two methods, the above process is simultaneously performed and deposited on the substrate 9 positioned on the anode 11 to form a thin film such as a thin film device. Let's go.

However, the method of forming a thin film such as a thin film device on the substrate using the conventional methods described above is the simplest structure when depositing the particles emitted by irradiating a laser beam on the target on the substrate, the emitted carbon particles Despite their merits of high kinetic energy, crystallization can be achieved at low substrate temperatures, they have the limitation of not being able to obtain high-quality thin films such as thin film devices with a uniform thickness over a large area. Thin films such as thin film devices obtained by the method are superior in quality to the laser ablation method, but have a disadvantage in that the production cost is high due to the long time required to obtain them.

The present invention is to solve the above problems of the prior art, an object of the present invention is to form a thin film, such as a thin film device on a substrate by a laser ablation method, plasma CVD method, a combination method of the two methods, In order to overcome the various problems, the present invention is to provide a method for maximizing the excitation efficiency, deposition rate and deposition efficiency with a device specially designed in the present invention to form a thin film of the best quality thin film device in a short time It is a technical task.

According to the Lorentz's law, the small particles present in the electromagnetic field rotate while rotating like a solenoid in a predetermined direction under the influence of the magnetic field, and thus the path of the particles is longer, and the collision probability between the particles becomes larger than without the magnetic field. As the probability increases, the excitation probability increases the density of particles with high kinetic energy, and thus, the present invention has been completed.

1 is a schematic view of a thin film formation process by a conventional laser ablation method

Figure 2 is a schematic diagram of a thin film formation process by a conventional high voltage discharge plasma CVD method

Figure 3 is a schematic diagram of a thin film formation process by a conventional mixing method of the two methods combined

Figure 4 is a schematic view of the thin film formation process by the laser ablation method of the present invention

5 is a schematic view of a thin film formation process by the high voltage discharge plasma CVD method of the present invention

Figure 6 is a schematic diagram of a thin film formation process by the mixing method of the laser ablation method and the plasma CVD method of the present invention

Figure 7 is a detailed view of the electromagnet for generating magnetic field of the present invention

* Explanation of symbols for main parts of the drawings

1: laser source (excimer, yag laser) 2: laser beam

3: condenser lens 4: driving reflector

5: vacuum chamber 6: target

7: laser plum 8: substrate heater

9: substrate 10: cathode wood

11: anode 12: plasma zone

13: glass reactor 14: electromagnet for magnetic field generation

14a: magnetic field core 14b: coil

In order to achieve the above object, a thin film forming method such as a laser ablation method according to the present invention, a plasma CVD method under a reaction gas, a combined method of combining the two methods, excimer or yag that is a laser source When the laser beam 2 generated from the laser 1 is condensed by the lens 3 and irradiated to the target 6 located in the vacuum chamber 5 by using an optical device called a driving reflector 4 from the surface thereof, A laser ablation method of forming a thin film on the substrate 9 on which the protruding particles (laser plume 7) is placed on the substrate heater 8, and a cathode 10 and an anode (i.e., made of a material to be sputtered) 11) the two deposition processes described above using two methods, plasma CVD, which forms a thin film on the substrate 9 installed on the anode 11 located at the center of the plasma zone 12 generated by applying a high voltage. In the method of forming a thin film such as a thin film device on the substrate 9 placed on the anode 11 so that the crystals are simultaneously formed, the excitation efficiency and the deposition rate are induced by inducing an increase in plasma density during the deposition process of the above three methods. The method further includes applying an electromagnetic field generated from the electromagnet 14 to the laser plume zone or plasma zone surrounded by a special high temperature heat-treated glass reactor 13 so as to form a thin film such as a high quality thin film device. The present invention provides a method for inducing a reactive gas atom to be supplied close to a substrate on which a thin film such as a thin film device is formed in order to effectively perform its function on the substrate and to increase the generation efficiency of the atomic gas. It is preferable to use special guide tubes.

Hereinafter, a method of forming a thin film such as a thin film device according to a preferred embodiment of the present invention will be described.

Embodiment A target positioned in the vacuum chamber 5 using an optical device called a driving reflector 4 by concentrating a laser beam 2 generated from an excimer or a yag laser 1, which is a laser generation source, into a lens 3 6) the laser enclosed by the high temperature heat-treated glass reactor 13 when forming a thin film on the substrate 9 positioned on the substrate heater 8 (laser plume 7) protruding from the surface when irradiated The electromagnetic field generated from the electromagnet 14 was applied to the plum zone to induce an increase in plasma density by Lorentz's law to form a thin film such as a high quality thin film device in a shorter time. In order to exert its function and to increase the efficiency of generating gas atoms, it is possible to supply the reaction gas to the substrate where the thin film such as thin film device is formed. In order to apply the electromagnetic field generated from the electromagnet 14 to the laser plume zone, the small charged particles existing in the electromagnetic field rotate like a solenoid in a predetermined direction under the influence of the magnetic field (Lawrence law). It increases the density of particles with high kinetic energy by prolonging the particle propagation path, prolonging the time that charged particles stay in the plasma zone and improving the collision probability between the particles than without the magnetic field. By applying an electron field to the laser plume zone and the plasma zone enclosed by the high temperature special heat-treated glass reactor 13 to achieve crystallization even at low substrate temperature, the plasma density is increased by Lorentz's law to generate the excitation efficiency, deposition rate and Increased efficiency improves quality thin film device in less time A thin film of light is formed. The following description is made with reference to the accompanying drawings. FIG. 1 is a schematic view of a thin film formation process by a conventional laser ablation method, and FIG. 2 is a thin film formation process by a conventional high voltage discharge plasma CVD method. 3 is a schematic view of a thin film formation process by a conventional mixing method of the two methods, FIG. 4 is a schematic view of a thin film formation process by the laser ablation method of the present invention, and FIG. 5 is a high voltage discharge plasma CVD method of the present invention. Fig. 6 is a schematic view of the thin film formation process, and Fig. 6 is a schematic view of the thin film formation process by the mixing method of the laser ablation method and the plasma CVD method of the present invention, and Fig. 7 is a detailed view of the electromagnet for generating the magnetic field of the present invention. Excimer, yag laser) (1), laser beam (2), condenser lens (3), driving reflector (4), vacuum chamber (5), target (6), laser plume (7), substrate heater (8) , Substrate (9), cathode 10, the anode 11, the plasma zone 12, the glass reactor 13, the magnetic field generating electromagnet 14, the magnetic iron core 14a, and the coil 14b. As shown in Figs. 5 and 6, the present invention is a substrate 9 formed in the inner center of the vacuum chamber, an anode (substrate holder) 11 formed below the substrate 9, and the anode 11 A reaction gas guide tube 13 for supplying a reaction gas formed at a lower portion to the plasma zone, a laser plume 7 formed on the substrate 11 to form a thin film, and the laser plume 7 formed thereon, and a laser A plasma zone 12 which is a target cathode 10 irradiated by the beam 2, a support for supporting the target 6, and a place for forming a thin film between the target 6 and the substrate 9. And a glass reactor 13 surrounding the plasma zone 12, a magnetic field generating electromagnet 14 formed outside the glass reactor 13, and the vacuum chamber. A laser generating source 1 formed at one end of the laser beam to emit a laser beam 2, a condenser lens 3 for condensing the laser source, and a driving reflector for reflecting the focused laser to the surface of the target ( 4) and a vacuum pump formed on one side of the reverse side, and FIG. 7 relates to the magnetic field generating electromagnet 14, wherein a square magnetic iron core having a space in which a reactor is located at one end of an iron core magnetic circuit ( 14a) is insulated with an insulating material and then wound by a predetermined number of turns with a coil 14b. The substrate 9 includes Si, (100) or (111) having a crystal plane of (100) or (111). As the Ni substrate, the fixed target and the laser beam were arranged to face each other at intervals of about 20 to 200 mm according to the energy and the size of the laser beam, and a high temperature inside the plasma does not require a separate substrate heater installed in the conventional apparatus.The operating method of the above apparatuses is about 30 minutes by washing the surface of the target object (Si or Ni, etc.) to form a thin film with alcohol or acetone with an ultrasonic cleaner, holding the target holder in the vacuum chamber, and then vacuuming. After pumping the chamber into a constant vacuum with a pump, argon gas is injected into the chamber to a certain pressure, and a relatively low voltage is applied between the two electrodes so that plasma is formed only on the surface of the object, and the object surface is plasma cleaned (separately In addition, after the pumping is performed so that the inside of the chamber is a constant vacuum with a vacuum pump, the reaction gas is injected into the chamber to a predetermined pressure, and then the laser light generated from the laser source is driven. Irradiates a fixed target (6) located in the vacuum chamber, and rotates the driven reflector (4). Alternatively, the linear motion of the laser beam causes the spot path of the laser beam to be circular (oval) or straight (cross) on the target 6 to protrude high energy carbon particles from the surface of the target 6 while simultaneously applying a high voltage between the two electrodes. Applied to cause the discharge plasma to be generated throughout the reactor to excite the reaction gas supplied to the inside of the glass reactor 13 with the reaction gas supply tube to mix with the carbon particles, and from the electromagnet 14 formed in the laser plume zone. The generated electromagnetic field causes small charged particles existing in the electromagnetic field to rotate while moving like a solenoid in a certain direction under the influence of the magnetic field, thus lengthening the path of the particles, and improving the probability of collision between the particles than in the absence of a magnetic field. Increasing the density of particles with high kinetic energy, allowing crystallization at low substrate temperatures Applying an electromagnetic field in the laser plume zone and the plasma zone enclosed by a glass reactor (13) to heat treatment rules to thereby deposit a thin film on the object surface.

In the present invention, the laser plume zone and plasma in a special high temperature heat-treated glass reactor located in the center of the vacuum chamber are used to compensate for the disadvantages of the above methods and to improve the excitation efficiency, deposition efficiency, deposition rate, etc. under the gas atmosphere to be reacted. By applying the electromagnetic field generated from the newly designed electromagnet to the zone, the plasma density in the reactor is significantly increased by Lorentz's law, which improves the excitation efficiency and the thin film deposition rate. Thin film is to be formed. In addition, the laser ablation method, the plasma CVD method, and the blending method newly combined in the present invention may be applied to other kinds of materials, such as hard coating (for example, electronic materials, cutting tools, etc.) on a material surface. It is designed to be effectively applied to thin film manufacturing. In particular, recently, a diamond thin film manufacturing method that has gained great attention as a flat panel display device by providing a thin film that does not use the field emission tip, which is the most important in manufacturing a field emission device (FED), etc. It can also be applied.

Claims (9)

In the thin film formation method by the laser ablation method, the high voltage discharge plasma CVD method, or the mixing method of the two methods, the laser beam 2 generated from the excimer or the yag laser 1, which is a laser source, is focused on the lens 3 When the target 6 located in the vacuum chamber 5 is irradiated using an optical device called a driving reflector 4, the particles (laser plumes 7) protruding from the surface thereof are placed on the substrate heater 8. (9) a laser ablation method for forming a thin film on The electromagnetic field generated from the electromagnet 14 is applied to the laser plume zone surrounded by the high temperature heat-treated glass reactor 13 to induce an increase in the plasma density according to the Lorentz law, thereby increasing the excitation efficiency, the deposition rate, and the efficiency. A thin film formation method using a laser ablation method, a high voltage discharge plasma CVD method, a mixture of two methods, characterized in that a thin film is formed using an electromagnetic field according to (14). The method of claim 1, wherein the reactive gas atoms can be supplied close to the substrate where a thin film such as a thin film device is formed in order to efficiently react the functions of the reactive gas atoms on the substrate and increase the generation efficiency of the reactive gas atoms during the deposition process. Guide tube to guide, The process of applying the electromagnetic field generated from the electromagnet 14 to the laser plume zone allows small charged particles existing in the electromagnetic field to rotate while moving like a solenoid in a predetermined direction under the influence of the magnetic field, thereby lengthening the path of the particles. Laser surrounded by heat-treated glass reactor 13 to improve the collision probability between particles, that is, the excitation probability, to increase the density of particles with high kinetic energy, and to crystallize even at low substrate temperature than without magnetic field. The laser ablation method, the high voltage discharge plasma CVD method, which forms an thin film by increasing the excitation efficiency, the deposition rate, and the efficiency by inducing an increase in the plasma density according to the Lorentz law by applying an electromagnetic field to the plume zone and the plasma zone. Thin film formation method by mixing two methods. In the thin film forming apparatus by the laser ablation method, the high voltage discharge plasma CVD method, or the mixing method of the two methods, the substrate 9 provided in the inner center of the vacuum chamber and the anode (substrate holder) formed under the substrate 9 (11), a reaction gas guide tube 13 for supplying a reaction gas provided under the anode 11, a laser plume 7 formed on the substrate 11 to form a thin film, and the laser plume ( 7) and a place for forming a thin film between the cathode (10) irradiated by the laser beam (2), the support for supporting the target (6), and the target (6) and the substrate (9) A phosphorus plasma zone 12, a glass reactor 13 surrounding the plasma zone 12, a magnetic field generating electromagnet 14 formed outside the glass reactor 13, and a lower end of the vacuum chamber. And a laser generating source 1 for emitting a laser beam 2, and the laser generating source A laser ablation method and a high voltage, comprising a condenser lens 3 for condensing, a driving reflector 4 for reflecting the condensed laser and irradiating the target surface, and a vacuum pump provided on one side of the condenser; Thin film forming apparatus by discharge plasma CVD method, a mixture of two methods. The magnetic field generating electromagnet (14) according to claim 3, wherein the outside of the rectangular magnetic iron core (14a) having a predetermined length of pores formed so that the reactor is located at one end of the iron core magnetic circuit circuit is insulated with an insulating material. A thin film forming apparatus comprising a laser ablation method, a high voltage discharge plasma CVD method, and a mixing method of the two methods, characterized in that the coil 14b is wound around a predetermined number of turns. In the method of operating the thin film forming apparatus by the laser ablation method, the high voltage discharge plasma CVD method, or the mixing method of the two methods, the surface of the object (Si or Ni, etc.) to form the thin film with alcohol or acetone is about 30 using an ultrasonic cleaner. After washing for about a minute, holding the object holder in the vacuum chamber, and pumping the inside of the chamber with a constant vacuum with a vacuum pump, Ar gas is injected into the chamber to a certain pressure, and the two electrodes to form a plasma only on the surface of the object. Plasma cleaning the surface of the object by applying a relatively low voltage between them (no separate object heating step is required), and then pumping the inside of the chamber with a constant vacuum with a vacuum pump, and then injecting the reaction gas into the chamber to a certain pressure. Then, the laser light generated from the laser source is passed through the vacuum reflector optical device to the vacuum chamber. The target 6 is irradiated to the fixed target 6 located at the position, and the driving reflector 4 is rotated or linearly moved so that the spot path of the laser beam becomes a circular (ellipse) or a straight (cross) shape on the target 6. The carbon particles protrude from the surface and at the same time a high voltage is applied between the two electrodes so that a discharge plasma is generated throughout the reactor, and the reaction gas is supplied to the inside of the glass reactor 13 through the reaction gas supply tube. Excited and mixed with the carbon particles, and the electromagnetic field generated from the electromagnet 14 formed in the laser plume zone and the plasma zone causes small charged particles existing in the electromagnetic field to rotate while moving like a solenoid in a predetermined direction under the influence of the magnetic field. By lengthening the particle path, the collision probability (excitation probability) between the particles can be improved more than if the magnetic field does not exist. It increases the density of particles with kinetic energy and deposits on the surface of the target object by applying an electromagnetic field to the laser plume zone and plasma zone surrounded by the heat-treated glass reactor 13 to achieve crystallization even at low substrate temperature. A method of operating a thin film forming apparatus by a laser ablation method, a high voltage discharge plasma CVD method, and a mixing method of two methods. delete delete delete 4. The substrate 9 according to claim 3, wherein the substrate 9 is a Si substrate having a crystal plane of (100) or (111), or a Ni substrate having (100) or (111), depending on the energy of the fixed target and the laser beam and the substrate size. A thin film forming apparatus using a laser ablation method, a high voltage discharge plasma CVD method, and a mixing method of the two methods, which are arranged to face each other at intervals of ˜200 mm.