JP2005281726A - Plasma deposition method and apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plasma film forming method and an apparatus for realizing high speed film formation while taking advantage of the formation of a high-quality thin film with low temperature and low damage.
A sample that can be rotated on a sample substrate by a plasma film forming apparatus that simultaneously performs film formation by vapor deposition or sputtering physical vapor deposition and plasma irradiation using electron cyclotron resonance. A sample chamber 22 containing a substrate 25, a plasma generation source, and a vapor deposition source are provided. The plasma generation source uses electron cyclotron resonance in the plasma generation chamber 21 connected to the sample chamber 22 by the interaction of a microwave and a magnetic field. The plasma is generated, and the generated plasma is irradiated on the sample substrate 25 rotating in the sample chamber 22 from the inclined direction by using a divergent magnetic field. The vapor deposition source is disposed in the sample chamber 22 that is separated from the rotation center axis of the sample substrate 25 by a predetermined distance, and vaporizes the raw material to grow a thin film on the sample substrate 25.
[Selection] Figure 2

Description

  The present invention relates to a plasma film forming method and an apparatus therefor, and more particularly, a plasma film forming method for forming thin films of various materials on a sample substrate for the purpose of manufacturing electronic devices such as semiconductor integrated circuits and display devices. In particular, the present invention relates to a plasma film forming technique for forming a high-quality metal or metal compound thin film at a low temperature.

  Sputtering is performed by using a plasma generated by electron cyclotron resonance (ECR) and applying voltage to an ECR target placed around the plasma to accelerate and cause ions contained in the plasma to enter the target. A so-called solid source ECR plasma film-forming method that causes a phenomenon and forms a thin film by depositing released target particles on a nearby sample substrate is well known (for example, Patent Document 1 and 2).

  FIG. 1 is a configuration diagram of a conventional solid source ECR plasma film forming apparatus, in which reference numeral 1 denotes a plasma generation chamber, 2 denotes a sample chamber, 3 denotes a plasma extraction window, 4 denotes a sample stage, 5 denotes a sample substrate, and 6 denotes A vacuum pump, 7 is a gas inlet (A), 8 is a gas inlet (B), 9 is a magnetic coil, 10 is a rectangular waveguide, 11 is a microwave, 12 is a microwave introduction window, 13 is a plasma flow, Reference numeral 14 denotes a sputtering power source, 15 denotes an ECR target, and 16 denotes a load lock chamber.

  The plasma generation chamber 1 and the sample chamber 2 are sealed spaces that are isolated from the atmosphere, and are connected via a plasma extraction window 3. In order to form a thin film on the sample substrate 5 placed on the sample stage 4, first, the plasma generation chamber 1 and the sample chamber 2 are evacuated by the vacuum pump 6, and the gas inlet (A) 7 or the gas inlet ( B) Gas is introduced from 8 and maintained at a predetermined pressure. Next, a current is passed through the two magnetic coils 9 placed around the plasma generation chamber 1 to generate a magnetic field, and then a microwave 11 guided to the rectangular waveguide 10 is provided at the bottom of the plasma generation chamber 1. It introduces to the vacuum side through the microwave introduction window 12 formed.

  As a result, electron cyclotron resonance occurs in the plasma generation chamber 1, and ECR plasma is generated. The plasma generated in the plasma generation chamber 1 flows as a plasma flow 13 from the plasma extraction window 3 to the sample substrate 5 along the divergent magnetic field. When the sputtering power supply 14 is turned on and a voltage is applied to the ECR target 15 in this state, ions in the ECR plasma are accelerated toward the ECR target 15, and the atoms constituting the ECR target are released into the vacuum by the ion bombardment. . The particles jumping out from the ECR target 15 travel in all directions and form a thin film on the sample substrate 5.

  Any solid material can be used as the material of the ECR target. Typical examples include silicon, aluminum, titanium, zirconium, carbon, tantalum, molybdenum, tungsten, niobium, and compounds such as STO and PZT. . In addition, when using oxygen or nitrogen in addition to an inert gas such as argon or xenon when forming a film, a compound thin film such as silicon oxide, silicon nitride, or alumina can be formed even when the target is a single metal. it can. When the sample substrate 5 is introduced into the sample chamber 2, first, the sample substrate 5 is placed in the load lock chamber 16, and after sufficiently evacuated, the valve between the sample chamber 5 and the sample chamber 5 is opened and moved.

The greatest feature of ECR plasma film formation is that a high-quality thin film is formed at low temperature and low damage because the thin film grows under irradiation of low energy and high density ions. The energy of ions incident on the substrate along with the divergent magnetic field is as small as 10 to 30 eV and does not damage the substrate. However, this energy is sufficient for surface migration of thin film particles that have reached the substrate. Further, for example, the activation energy for reacting Si and nitrogen is sufficiently large, and a compound thin film such as Si ₃ N ₄ can be formed without heating.

JP-B-1-36693 Japanese Patent Publication No. 63-9588

  However, since a solid target is used as a thin film raw material supply source, it has several drawbacks. The first is that thin film constituent materials are limited. The ECR target needs a certain size as a structure, and it is difficult to form a thin film using a material that is difficult to process in such a shape or a material that reacts with oxygen or moisture in the atmosphere. . As an example, an ECR target with a purity of about 99.9% can be manufactured relatively easily, but a high-purity ECR target with a level of 99.999% is difficult to manufacture except for a few exceptions. Extremely expensive. In addition, a material that reacts with the atmosphere such as fluoride or a material that deteriorates with a slight amount of moisture in the air such as organic EL is difficult to be targeted, and thus is not deposited by sputtering.

  A second drawback is that the density of particles flying onto the film formation substrate is small compared to general vapor deposition or sputtering, and high-speed film formation is not good.

As a film forming apparatus using an ECR plasma flow, there is a CVD type using a gas material as a raw material in addition to the above-described sputtering type. In this method, the thin film material is supplied from a gas such as SiH ₄ or oxygen, and the film formation speed can be made higher than that of the sputtering type, but the selection range of raw materials is small and the thin film material is further limited.

  As described above, the conventional ECR plasma film formation can form a high-quality thin film at a low temperature, but the thin film material to be formed is limited and is not suitable for applications requiring a high film formation speed. There were problems such as.

  The present invention has been made in view of such problems, and its object is to take advantage of the advantages of low-temperature, low-damage, high-quality thin film formation as a feature of film formation using ECR plasma. Another object of the present invention is to provide a plasma film forming method and apparatus for realizing high speed film formation.

  Another object of the present invention is to provide a plasma film forming method and an apparatus for widening the range of thin film materials that can be formed in thin film formation using ECR plasma.

  Furthermore, by combining ECR plasma irradiation using a divergent magnetic field and a general physical vapor deposition method, a plasma film forming method capable of realizing a wide range of uses having new characteristics that has not been obtained so far, and a method thereof To provide an apparatus.

  The present invention has been made to achieve such an object. The invention according to claim 1 is directed to film formation by electron vapor deposition or sputtering physical vapor deposition on a sample substrate, and electrons. A plasma film forming method for simultaneously performing plasma irradiation using cyclotron resonance, wherein plasma is generated using the electron cyclotron resonance by the interaction of a microwave and a magnetic field in a plasma chamber maintained at a reduced pressure, and the plasma And a first step of irradiating the sample substrate rotating in the sample chamber from a tilt direction using a divergent magnetic field, and a sample chamber disposed at a predetermined distance from the rotation center axis of the sample substrate. The second step of vaporizing the raw material from the vapor deposition source or the sputter source and growing the thin film on the sample substrate is performed at the same time.

  The invention according to claim 2 is the invention according to claim 1, wherein the evaporation source is any one of an electron beam evaporation source, a resistance heating evaporation source, an induction heating evaporation source, a Knudsen cell evaporation source, or a laser evaporation source. It is characterized by.

  According to a third aspect of the present invention, in the first aspect of the present invention, the sputter source is disposed in a region where the second step is in the sample chamber and maintained at a higher pressure than other portions. Then, a thin film is grown on the sample substrate using a sputtering method.

  According to a fourth aspect of the present invention, in the first, second or third aspect of the invention, the first step is performed by replacing the rotatable sample substrate disposed in the sample chamber with the sample. The plasma is irradiated on the sample substrate that is moving linearly in the room.

  Further, the invention described in claim 5 is a plasma film forming method for simultaneously performing film formation by vapor deposition or sputtering physical vapor deposition and plasma irradiation using electron cyclotron resonance on a sample substrate. And a plasma generation chamber connected to the sample chamber, and the interaction between the microwave and the magnetic field in the plasma generation chamber To generate plasma using electron cyclotron resonance, and to irradiate the plasma from a tilt direction onto the sample substrate rotating in the sample chamber using a divergent magnetic field; and A vapor deposition source or a sputtering source, which is disposed in the sample chamber separated by a predetermined distance from the rotation center axis and vaporizes the raw material to grow a thin film on the sample substrate, is provided. To.

  The invention according to claim 6 is the invention according to claim 5, wherein the deposition source is any one of an electron beam deposition source, a resistance heating deposition source, an induction heating deposition source, a Knudsen cell deposition source, or a laser deposition source. It is characterized by.

  The invention according to claim 7 is the invention according to claim 5, wherein the sputtering source is provided in a region in the sample chamber where the pressure is maintained higher than other portions. Features.

  The invention described in claim 8 is the film according to claim 5, 6 or 7, wherein the film is linearly movable in the sample chamber instead of the rotatable sample substrate disposed in the sample chamber. A substrate is provided.

  The invention according to claim 9 is the invention according to any one of claims 5 to 8, wherein the plasma flow from the plasma generation source, the vapor flow from the vapor deposition source, or the sputtered particles from the sputtering source. A shutter is provided between the flow and the sample substrate.

  As described above, the present invention basically employs a physical vapor deposition method such as a vapor deposition method or a sputtering method to make the thin film constituent particles incident on the sample substrate and simultaneously irradiate the ECR plasma from other directions. It is a feature. This realizes high-quality thin film deposition at a low temperature and low damage for a wide range of materials, and significantly increases the deposition rate. That is, it is a big difference from the prior art in that film formation by various physical vapor deposition methods such as vapor deposition or sputtering and simultaneous ECR plasma irradiation are performed.

  The present invention simultaneously performs film formation by vapor deposition or sputtering physical vapor deposition and plasma irradiation using electron cyclotron resonance on a sample substrate. A first step of generating plasma using the electron cyclotron resonance due to the interaction between a wave and a magnetic field, and irradiating the plasma from a tilt direction onto a rotating sample substrate in the sample chamber using a divergent magnetic field. And vaporizing the raw material from a deposition source disposed in the sample chamber separated by a predetermined distance from the center axis of rotation of the sample substrate or a sputtering source in a region where the pressure is maintained higher than other portions, and forming a thin film on the sample substrate In addition to realizing the high-quality thin film deposition at low temperature and low damage for a wide range of materials, the deposition speed has been greatly increased. . In addition, film formation by various physical vapor deposition methods such as vapor deposition or sputtering and ECR plasma irradiation can be performed simultaneously.

  Embodiments of the present invention will be described below with reference to the drawings.

  FIG. 2 is a block diagram for explaining the first embodiment of the plasma film-forming apparatus of the present invention. In the figure, reference numeral 21 denotes a plasma generation chamber, 22 denotes a sample chamber, 23 denotes a plasma extraction window, 24 denotes a sample stage, 25 Is a sample substrate, 26 is a vacuum pump, 27 is a gas inlet (A), 28 is a gas inlet (B), 29 is a magnetic coil, 30 is a rectangular waveguide, 31 is a microwave, 32 is a microwave introduction window , 33 is a plasma flow, 34 is a load lock chamber, 35 is a crucible, 36 is a magnetic field, 37 is a filament, 38 is a high voltage DC power source, 39 is thermoelectron, 40 is a raw material, and 41 is a vapor flow.

  An electron beam evaporation source was installed in the sample chamber 22, and a thin film was formed on the sample substrate 25 while irradiating ECR plasma from the plasma generation chamber 21. The plasma generation chamber 21 of the plasma film forming apparatus in the first embodiment is similar to the conventional plasma generation chamber 1 shown in FIG. 1, but the sputtering power source 14 and the ECR target 15 shown in FIG. 1 are omitted. Has been. Instead, an electron beam evaporation source is added in the sample chamber 22.

  The plasma film forming apparatus of Example 1 is a plasma film forming apparatus for performing a plasma film forming method for simultaneously performing film formation by vapor deposition and plasma irradiation using electron cyclotron resonance on a sample substrate 25. It is. A sample chamber 22 containing a rotatable sample substrate 25, a plasma generation source, and a vapor deposition source are provided. The plasma generation source includes a plasma generation chamber 21 connected to the sample chamber 22. Then, plasma is generated using electron cyclotron resonance by the interaction between the microwave and the magnetic field, and the generated plasma is inclined on the sample substrate 25 rotating in the sample chamber 22 using the divergent magnetic field. It is comprised so that it may irradiate from. The vapor deposition source is disposed in the sample chamber 22 that is separated from the rotation center axis of the sample substrate 25 by a predetermined distance, and is configured to vaporize the raw material and grow a thin film on the sample substrate 25.

  In the plasma film forming method using the plasma film forming apparatus having such a structure, a first step of irradiating plasma onto the sample substrate 25 from an inclined direction, and a thin film is grown on the sample substrate 25 by vaporizing the raw material from the vapor deposition source. The second step is performed, and the first step and the second step are performed simultaneously. In the first step, plasma is generated using the electron cyclotron resonance by the interaction between the microwave and the magnetic field in the plasma chamber maintained at a reduced pressure, and this plasma is rotated in the sample chamber using the divergent magnetic field. In the second step, the source material is vaporized from a vapor deposition source disposed in the sample chamber 22 that is separated from the rotation center axis of the sample substrate 25 by a predetermined distance. Thus, a thin film is grown on the sample substrate 25.

  That is, the plasma generation chamber 21 and the sample chamber 22 are sealed spaces that are isolated from the atmosphere, and are connected via the plasma extraction window 23. In forming a thin film on the sample substrate 25 placed on the sample table 24, first, the surface of the sample substrate 25 is irradiated with ECR plasma. For this purpose, the plasma generation chamber 21 and the sample chamber 22 are evacuated by a vacuum pump 26, and a gas is introduced from the gas introduction port (A) 27 or the gas introduction port (B) 28 and maintained at a predetermined pressure. Next, a current is passed through the two magnetic coils 29 placed around the plasma generation chamber 21 to generate a magnetic field, and then a microwave 31 guided to the rectangular waveguide 30 is provided in the lower part of the plasma generation chamber 21. It introduces to the vacuum side through the formed microwave introduction window 32.

  As a result, electron cyclotron resonance occurs in the plasma generation chamber 21, and ECR plasma is generated. The plasma generated in the plasma generation chamber 21 flows as a plasma flow 33 from the plasma extraction window 23 onto the surface of the sample substrate 25 along the divergent magnetic field.

  In order to form a thin film on the sample substrate 25 using an electron beam evaporation source in this state, the following operation is performed. First, a magnetic field 36 oriented perpendicular to the paper surface as shown in FIG. 2 is formed in the vicinity of the water-cooled crucible 35, and the filament 37 is heated by passing an electric current. Next, when the high voltage DC power supply 38 is turned on and a high voltage is applied to the filament, the thermoelectrons 39 generated in the filament flow into the surface of the raw material 40 while being bent by the magnetic field 36 and generate heat. The surface of the raw material is melted and vaporized by this heat to generate a vapor flow 41 and reach the sample substrate 25 to form a thin film. In this way, a thin film grows on the sample substrate 25 while being irradiated with the ECR plasma flow. The vapor flow 41 is usually devised to provide a shielding plate to prevent thin film growth other than the sample substrate.

  By rotating the sample substrate 25 and shifting the center of rotation to an appropriate position from the centers of the ECR plasma flow and the vapor flow, the average incident amount can be made uniform in the substrate plane.

  FIG. 3 is a diagram showing a result of simulating the film thickness distribution of the thin film formed on the sample substrate when the horizontal distance X between the rotation center of the sample substrate and the vapor deposition source is varied. The surface area of the vapor deposition source is assumed to be a circle having a diameter of 20 mm, and the vertical distance Z between this surface and the surface of the sample substrate 25 is fixed to 200 mm. According to FIG. 3, it can be seen that by setting X = 160 mm, a film can be formed with good uniformity in a diameter range of 300 mm.

  FIG. 4 is a diagram showing a case where the vertical distance Z is varied while fixing X = 160 mm. It can be seen that when the distance is shortened, the center becomes concave and when it is separated, the uniformity becomes controllable by changing the distance.

Although not shown in FIG. 2, shutters can be provided individually at the outlets of the ECR plasma stream 33 and the vapor stream 41 to shield only one of them. As a result, it is possible to create a sequence in which the ECR plasma flow is generated first to open the shutter, and the film is started by opening the shutter on the electron beam evaporation source side while the substrate is irradiated with plasma. By irradiating the substrate with ECR plasma, moisture, organic matter, etc. physically adsorbed on the substrate surface can be removed by cleaning, and the effect of improving adhesion to the substrate can be obtained. At this time, when a gas containing oxygen or nitrogen is used, the substrate surface can be oxidized or nitrided with active ECR plasma. For example, when the substrate is a Si wafer, a SiO ₂ or Si ₃ N ₄ film is formed, and the substrate can be used for a MOS capacitor element having stable electrical characteristics at the interface.

  Even when film formation is completed, the effect of modifying the film quality can be expected by closing the shutter on the evaporation source side and irradiating the plasma flow for a while. Of course, if the plasma contains oxygen at this time, the formed thin film can be oxidized. In addition, the film quality can be optimized by changing the strength of the vapor flow and the ECR plasma flow during film formation, but the film quality can also be controlled by opening and closing one or both shutters intermittently. It is possible.

  Although FIG. 2 shows an embodiment using an electron beam evaporation source, the evaporation source may be any mechanism that can be heated and vaporized. For example, a resistance heating evaporation source that heats by supplying current to a boat made of tungsten or BN composite, an induction heating evaporation source having an insulating crucible disposed in a high frequency coil, a Knudsen cell evaporation source, or a laser Even if it is a vapor deposition source, the effect of invention is the same.

  As a vapor deposition material, all solid materials can be used. Typical examples are silicon, aluminum, beryllium, magnesium, titanium, zirconium, hafnium, carbon, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel, In addition to simple metals such as zinc, these alloys, oxides, nitrides, fluorides, chlorides, and organic compounds can also be deposited. In addition, when a reactive gas such as oxygen, nitrogen, or fluorine is used in combination with the film, even if the deposition material is a single metal, in addition to oxides such as silicon oxide, silicon nitride, and alumina, and nitride Any compound thin film can be formed.

  The pressure range of the gas at the time of film formation is almost equal to the range where ECR plasma discharge is possible, but a particularly desirable pressure region is about 0.01 to 0.5 Pa. However, in some cases, the film formation by vapor deposition is preferably lower than the ECR plasma discharge pressure. In that case, an exhaust pump is disposed in the vicinity of the vapor deposition source, and gas introduction is performed from a port on the plasma generation chamber side. Alternatively, a device such as providing a shielding plate between the plasma flow and the vapor flow can be provided.

  As described above, in the first embodiment, a thin film can be formed using a vapor deposition method while irradiating low-energy, high-density ECR plasma. For this reason, in addition to obtaining a high-quality thin film without special substrate heating, the characteristics of the vapor deposition method that a wide range of materials can be formed at high speed remain alive.

  FIG. 5 is a block diagram for explaining Example 2 of the plasma film-forming apparatus of the present invention. In the figure, reference numeral 42 denotes a sputtering power source, 43 denotes a sputtering target, 44 denotes a sputtered particle flow, 45 denotes a gas blowing port, 46. Is a differential pressure adjusting plate, and the other components having the same functions as those in FIG.

  In Example 2, a sputtering source was disposed in the sample chamber 22, and a thin film was formed by sputtering while irradiating the sample substrate 25 with ECR plasma generated in the plasma generation chamber 21. Basically, the vapor deposition source in Example 1 described above is replaced with a sputter target. That is, instead of the vapor deposition source, a sputtering source provided in a region in the sample chamber 22 where the pressure is maintained higher than other portions is provided, and the second step in the first embodiment described above is performed. A sputtering source is disposed in a region in the sample chamber 22 where the pressure is maintained higher than that of other portions, and a thin film is grown on the sample substrate 25 using a sputtering method.

  Although the target is also used in the structure of FIG. 1 described in the prior art, the target in this case is installed at the position of the plasma extraction window 3 so as to surround the plasma.

  For this reason, the accelerated ions that bombard the target are ions in the ECR plasma generated in the plasma generation chamber. On the other hand, in the second embodiment, power is supplied to the sputtering target installed in the sample chamber 22 to newly generate plasma, and the sputtering is performed using ions in the plasma. There is a degree of freedom that a widely used planar magnetron sputtering method can be adopted, and advantages such as easy high-speed film formation can be obtained.

  Since the generation of the ECR plasma is the same as that in the first embodiment, the supply of the thin film material using the sputtering method will be described. In order to start sputtering, it is necessary to introduce gas into the sample chamber 22 in advance and maintain it in a predetermined pressure range. If the plasma generation chamber 21 has already been discharged, the gas is naturally also introduced into the sample chamber 22. In this state, sputtering can be performed simply by turning on the sputtering power supply 42 and supplying power to the sputtering target 43. It is also possible to start and transport the sputtered particle stream 44 onto the sample substrate 25.

  However, although the ECR plasma in the plasma generation chamber 21 can be discharged even at a low pressure of about 0.01 Pa, it is difficult to maintain the discharge at a plasma pressure of a general sputtering target. For this reason, when both of them are performed simultaneously, the pressure around the sputter target 43 needs to be set slightly higher than the plasma generation chamber 21. In general, it is desirable that the pressure be at least about 0.1 Pa. Therefore, the gas introduction into the sample chamber 22 is not performed by the gas introduction port (A) in the vicinity of the sputtering target, but by the gas introduction port (B) 28 on the plasma generation chamber 21 side. 27) or by providing a separate uniform gas outlet 45 around the sputtering target and adding a differential pressure adjusting plate 46 to maintain the pressure difference. The position of the gas outlet 45 is not necessarily the position shown in FIG. 5, and the same effect can be obtained if the position is closer to the sputtering target than the plasma generation chamber 21.

  As for the film formation distribution on the substrate, a highly uniform distribution can be obtained by appropriately setting the positional relationship between the sample substrate and the sputter target in the same manner as in the first embodiment. If a magnet is arranged on the back side of the sputtering target to perform magnetron sputtering, ionization is promoted and the film formation rate is greatly improved. The power source may be either DC or RF, and in addition, DC pulses with various frequencies may be used. If the sputtering target has a negative bias of several hundreds V to several kV with respect to the surroundings, the positively ionized gas particles impact the target, and the target material jumps out toward the sample substrate.

  Sputter target materials include silicon, aluminum, beryllium, magnesium, titanium, zirconium, hafnium, carbon, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel, zinc, etc. Alloys, oxides and nitrides are possible. In addition, if a reactive gas such as oxygen, nitrogen, or fluorine is used in combination with an inert gas such as argon, helium, neon, krypton, or xenon during film formation, silicon oxide can be used even when the sputtering target is a single metal. In addition to oxides and nitrides such as silicon nitride and alumina, any compound thin film can be formed.

  When a compound thin film such as an oxide is formed, reactive sputtering can be performed by using a metal target and adding oxygen or the like to an inert gas. If the conditions are set appropriately at this time, so-called metal mode film formation is possible in which an oxidation reaction is performed on the surface of the sample substrate while the target surface is not oxidized. In general, the sputtering efficiency of metal on the target surface is often much higher than that of oxide, and metal mode film formation has the advantage that the film formation rate can be increased.

  In this way, the thin film grows on the sample substrate 25 while being irradiated with the ECR plasma flow. Similar to the first embodiment described above, various processes can be performed by switching between irradiation of the ECR plasma flow and sputtering film formation by installing a shutter.

  FIG. 6 is a block diagram for explaining Example 3 of the plasma film-forming apparatus of the present invention. In the figure, reference numeral 47 is a film substrate, 48 is a delivery roll, 49 is a take-up roll, and the others are the same as FIG. Components having functions are denoted by the same reference numerals. An example in which the sample substrate 25 is not a circular substrate but a thin film substrate is shown.

  Instead of the rotatable sample substrate 25 arranged in the sample chamber 22, a film substrate 47 that can move linearly in the sample chamber 22 is provided, and the first step in the first embodiment described above is the sample chamber. The plasma is irradiated onto the sample substrate 25 which is moving linearly within 22.

  The material of the film may be various plastics, thin metal foils, or anything else. Here, the plasma generation chamber 21 and the vapor deposition source have the same structure as that of the first embodiment described above, and only the substrate holding mechanism is changed from the substrate rotation method to the roll-to-roll method. In order to form a thin film on the film substrate 47, the film substrate 47 is moved by rotating the feed roll 48 and the take-up roll 49 while the plasma stream 33 and the vapor stream 41 are irradiated. The film thickness attached to the film substrate 47 can be controlled by the power and rotation speed of the vapor deposition source. Since film formation is performed while moving the film substrate 47, only plasma flow irradiation is performed first, and when film formation is performed while plasma irradiation is subsequently performed, the vapor flow is limited using a shielding plate or the like, Only the plasma hits the front end of the film substrate 47 in the traveling direction.

  In the third embodiment, the feed roll 48 and the take-up roll 49 are installed in the sample chamber 22, but these can be placed on the atmosphere side. In that case, in order to keep the sample chamber 22 in a vacuum, it is necessary to use a structure that sufficiently absorbs the pressure difference from the atmosphere using the working exhaust.

  When the width of the film substrate 47 is small, even if a cylindrical plasma generation chamber 21 as shown in the third embodiment and an evaporation source having a structure close to a point source are used, the thin film formed on the substrate The film thickness uniformity is sufficiently good. However, when the width of the film substrate 47 is, for example, about 30 cm or more, uniform film formation cannot be performed. In such a case, the shape of the plasma generation chamber 21 may be a rectangular parallelepiped to increase the width of the plasma flow, and at the same time, the vapor deposition source may be linear and long. The cross section of the plasma generation chamber 21 and the vapor deposition source in that case is, for example, the same arrangement as in FIG. 6, and the irradiation region of the plasma flow 33 and the vapor flow 41 on the film substrate 47 is an ellipse that is long in the direction perpendicular to the paper surface. Or it becomes a shape close to a rectangle.

  Such film formation while moving the film substrate linearly is suitable not only for the roll-to-roll method but also for a square substrate such as glass for liquid crystal. In that case, a belt, a roller, a chain, etc. are installed at both ends of the square substrate and moved in the horizontal direction. Of course, as a film forming method, not only vapor deposition but also various sputtering methods can be applied to a film substrate or a glass substrate.

It is a block diagram of the conventional solid source ECR plasma film-forming apparatus. It is a block diagram for demonstrating Example 1 of the plasma film-forming apparatus of this invention. It is the figure which showed the result of having simulated the film thickness distribution of the thin film formed in a sample board | substrate when changing the horizontal distance X of the rotation center of a sample board | substrate, and a vapor deposition source. It is the figure which showed the case where X = 160mm was fixed and the vertical distance Z was varied. It is a block diagram for demonstrating Example 2 of the plasma film-forming apparatus of this invention. It is a block diagram for demonstrating Example 3 of the plasma film-forming apparatus of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Plasma production chamber 2 Sample chamber 3 Plasma extraction window 4 Sample stand 5 Sample substrate 6 Vacuum pump 7 Gas inlet (A)
8 Gas inlet (B)
9 Magnetic coil 10 Rectangular waveguide 11 Microwave 12 Microwave introduction window 13 Plasma flow 14 Sputtering power source 15 ECR target 16 Load lock chamber 21 Plasma generation chamber 22 Sample chamber 23 Plasma extraction window 24 Sample stage 25 Sample substrate 26 Vacuum pump 27 Gas inlet (A)
28 Gas inlet (B)
29 Magnetic coil 30 Rectangular waveguide 31 Microwave 32 Microwave introduction window 33 Plasma flow 34 Load lock chamber 35 Crucible 36 Magnetic field 37 Filament 38 High voltage DC power supply 39 Thermoelectron 40 Raw material 41 Vapor flow 42 Sputter power supply 43 Sputter target 44 Sputtered particles Flow 45 Gas outlet 46 Differential pressure adjustment plate 47 Film substrate 48 Delivery roll 49 Winding roll

Claims (9)

A plasma film forming method for simultaneously performing film formation by vapor deposition or sputtering physical vapor deposition and plasma irradiation using electron cyclotron resonance on a sample substrate,
Plasma is generated using the electron cyclotron resonance due to the interaction between the microwave and the magnetic field in the plasma chamber maintained at a reduced pressure, and the plasma is applied to the rotating sample substrate in the sample chamber using the divergent magnetic field. A first step of irradiating from an inclined direction;
Simultaneously performing a second step of evaporating a raw material from a vapor deposition source or a sputtering source disposed in the sample chamber separated from the rotation center axis of the sample substrate by a predetermined distance and growing a thin film on the sample substrate. A plasma film forming method characterized by the above.   The plasma deposition method according to claim 1, wherein the deposition source is any one of an electron beam deposition source, a resistance heating deposition source, an induction heating deposition source, a Knudsen cell deposition source, and a laser deposition source.   The second step is characterized in that a sputtering source is arranged in a region in the sample chamber where the pressure is maintained higher than other portions, and a thin film is grown on the sample substrate using a sputtering method. The plasma film-forming method according to claim 1.   The first step irradiates the plasma onto the sample substrate that is linearly moved in the sample chamber, instead of the rotatable sample substrate disposed in the sample chamber. The plasma film-forming method as described in 1, 2 or 3. A plasma film forming apparatus for performing a plasma film forming method for simultaneously performing film formation by vapor deposition or sputtering physical vapor deposition and plasma irradiation using electron cyclotron resonance on a sample substrate. And
A sample chamber containing a rotatable sample substrate;
A plasma generation chamber connected to the sample chamber; in the plasma generation chamber, plasma is generated using electron cyclotron resonance by interaction of a microwave and a magnetic field, and the plasma is generated using the divergent magnetic field. A plasma generation source for irradiating the sample substrate rotating in a room from an inclined direction;
A plasma, comprising: a vapor deposition source or a sputter source disposed in the sample chamber at a predetermined distance from the rotation center axis of the sample substrate, vaporizing the raw material, and growing a thin film on the sample substrate. Deposition device.   The plasma deposition apparatus according to claim 5, wherein the deposition source is any one of an electron beam deposition source, a resistance heating deposition source, an induction heating deposition source, a Knudsen cell deposition source, and a laser deposition source.   6. The plasma film-forming apparatus according to claim 5, wherein the sputtering source is provided in a region in the sample chamber that is maintained at a higher pressure than other portions.   8. A plasma film forming apparatus according to claim 5, further comprising a film substrate that can move linearly in the sample chamber, instead of the rotatable sample substrate disposed in the sample chamber. .   9. A shutter is provided between the plasma flow from the plasma generation source, the vapor flow from the vapor deposition source or the sputtered particle flow from the sputtering source, and the sample substrate, respectively. The plasma film forming apparatus according to any one of the above.

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