JP4707403B2 - Plasma processing method and apparatus by pulse division supply and plasma CVD method - Google Patents

Description

  The present invention relates to a plasma processing method and apparatus suitable for performing film formation, etching or surface modification on a large area substrate used in the field of liquid crystal.

  Today, the demand for large-sized, high-quality, low-priced liquid crystal displays and organic electroluminescence display panels is increasing, and the increase in the size of the mother glass used for production thereof is accelerating. Along with this, in the process of manufacturing devices on a substrate, in the process steps such as film formation around the plasma, etching, surface modification, etc., increasing the processing area and in-plane uniformity of processing performance are important issues. ing.

The current state of such plasma processing will be described by taking film formation by plasma CVD as an example.
The thin films deposited on the substrate are typically amorphous silicon (a-Si), silicon nitride (SiNx), silicon oxide (SiOx), silicon oxynitride (SiOxNy), and n-doped amorphous silicon (n + a-Si). Can be fisted.

  When these thin films are formed on a substrate, the plasma CVD apparatus converts the gas into plasma using high-frequency power. However, the larger the size of the electrode that supplies high-frequency power, the more the standing wave generated on the electrode affects the in-plane uniformity of the electric field strength distribution, and hence the plasma density. It is known to lead to deterioration.

  At the same time, the larger the size of the substrate used, the larger the size of the electrode, the larger the vacuum chamber in which the electrode and the substrate holder are arranged, and the higher the high-frequency power supplied to the plasma. Since the relative size is reduced, it is also known that the influence of plasma on the current distribution flowing from the substrate holder on which the substrate is placed to the ground potential via the vacuum chamber wall cannot be ignored.

  In order to solve such problems, conventionally, an electrode for supplying high-frequency power is divided into a central portion and a peripheral portion, and the distance between the electrode and the substrate holder in the central portion and the peripheral portion of the electrode can be adjusted to make plasma. A plasma CVD apparatus has been proposed in which the distribution is adjusted and the film thickness distribution is made uniform (see Patent Document 1).

  Further, the electrode is divided into a plurality of small electrodes so that the distance between the electrode and the substrate holder is continuous at the boundary between the divided electrodes, and the high-frequency power supplied to each small electrode is adjusted, thereby A plasma processing apparatus that makes the thickness distribution uniform has also been proposed (see Patent Document 2).

  However, the apparatus described in Patent Document 1 has a problem that plasma becomes unstable and a thin film cannot be formed uniformly because the boundary between the central part and the peripheral part of the electrode is discontinuous.

  Further, the reaction product easily adheres to and peels from the interface between the electrodes, so that it becomes a source of particles in the apparatus and a source of abnormal discharge, resulting in a problem that the yield of the product is lowered.

Therefore, the inventors first supplied high-frequency power to a plurality of portions of the electrode, and set the electrode substrate holder to a shape in which the distance between the electrode and the substrate holder changes continuously at least in the peripheral portion. It has been proposed to configure opposing surfaces and to set the film forming pressure in the vacuum chamber in accordance with the shape of the surface of the electrode facing the substrate holder (see Patent Document 3). As a result, the film forming gas can be uniformly converted to plasma on the substrate, and a thin film having a uniform film thickness of the reaction product can be formed.
Japanese Patent Laid-Open No. 10-289881 JP 2003-68651 A Japanese Patent Application No. 2004-315714

  In the invention described in Patent Document 1 and Patent Document 2, since the boundary between the central portion and the peripheral portion of the electrode is discontinuous, the plasma becomes unstable and a thin film can be formed uniformly. In addition, the reaction product easily adheres to and peels off from the interface between the electrodes, and as a result, it becomes a source of particles in the apparatus and a source of abnormal discharge, resulting in a decrease in product yield. The problem is to be solved based on a concept different from the previously proposed invention.

  These problems are not limited to film formation by plasma CVD, but are common to etching and surface modification processes using plasma.

  Therefore, an object of the present invention is to provide a plasma processing method and apparatus capable of solving such problems associated with the prior art and performing uniform plasma processing on a large area substrate.

In order to achieve the above object, a plasma processing apparatus according to the first invention of the present invention comprises:
A substrate holder for placing a large-area substrate in the vacuum chamber; an electrode that is opposed to the substrate holder and is larger than the outer dimension of the substrate placed on the substrate holder; and means for introducing a gas into the vacuum chamber; Provided,
In addition, high-frequency power supply means for supplying a plurality of pulse-modulated high-frequency power to a plurality of spaced apart positions of the electrode is provided,
The high-frequency power supply means is configured so that each of the plurality of pulse-modulated high-frequency powers propagates entirely on the electrode surface.
According to another feature of the present invention, a substrate holder for placing a large-area substrate, an electrode facing the substrate holder, and a means for introducing gas into the vacuum chamber are provided in the vacuum chamber. ,
In addition, high-frequency power supply means for supplying a plurality of pulse-modulated high-frequency power to a plurality of spaced apart positions of the electrode is provided,
High-frequency power supply means is configured to propagate the plurality of pulse-modulated high-frequency powers respectively on the surface of the electrodes,
The frequency of the high frequency power is in the range of 13 MHz to 30 MHz;
The high-frequency power supply means includes means for adjusting a relative phase difference of pulse modulation of the plurality of pulse-modulated high-frequency powers.
A plasma processing apparatus is provided.

  In the plasma processing apparatus according to the first aspect of the present invention, the frequency of the high-frequency power may be in the range of 13 MHz to 30 MHz.

  The high-frequency power supply means may include means for adjusting the relative phase difference of the pulse modulation of the plurality of pulse-modulated high-frequency powers.

  Further, the position for supplying the high-frequency power is set at an adjustable distance (Ka, Kb) from the electrode end.

  Preferably, the output duty ratio of the pulse modulation may be in the range of 30% to 70%.

  In one embodiment of the present invention, the positions where the high frequency power is supplied are two positions on the electrode which are separated from each other, and the relative phase difference of the pulse modulation of the high frequency power supplied to the two positions is 180 °. It is. In this case, the high-frequency power supply means includes two high-frequency power sources and one pulse oscillator that performs pulse modulation on the high-frequency power of each high-frequency power source and controls the phase so that the relative phase difference between the high-frequency powers becomes a predetermined value. And may be configured. The pulse oscillator may be configured with a divided pulse modulation function that makes two types of pulse modulation outputs divided in time so that the high-frequency powers of the two high-frequency power sources do not interfere with each other.

    In another embodiment of the present invention, the positions for supplying the high-frequency power are four positions on the electrode that are spaced apart from each other, and among the four positions, the positions of the high-frequency power supplied to the two positions that are opposed to the left and right or the top and bottom, respectively. The relative phase difference of the pulse modulation is 180 °. In this case, the high-frequency power supply means pulse-modulates the four high-frequency power sources and the high-frequency power of each high-frequency power source, and at the two positions on the electrode that are opposed to the left and right or up and down. And a single pulse oscillator configured to generate two types of pulse-modulated outputs that are time-divided so that the supplied high-frequency power does not interfere with each other.

  In the plasma processing apparatus according to the first aspect of the present invention, the frequency of pulse modulation may be in the range of 1 kHz to 500 kHz.

In the plasma processing method according to the second aspect of the present invention, a substrate holder for placing a large area substrate in a vacuum chamber and an electrode larger than the outer dimension of the substrate placed on the substrate holder facing the substrate holder are provided. A gas is introduced into the vacuum chamber, and a plurality of pulse-modulated high-frequency powers are supplied to spaced positions on the electrode, and a plurality of pulse-modulated high-frequency powers are separated on the electrode surface onto the electrode surface. It is characterized in that processing is performed on the large-area substrate by generating plasma and generating plasma entirely.

  In the plasma processing method according to the second aspect of the present invention, the frequency of the high frequency power can be set in a range of 13 MHz to 30 MHz.

  In the plasma processing method according to the second aspect of the present invention, the relative phase difference of the pulse modulation of a plurality of pulse-modulated radio frequency powers can be adjusted.

  In the plasma processing method according to the second aspect of the present invention, the position on the electrode for supplying the high frequency power can be adjusted.

  In the plasma processing method according to the second aspect of the present invention, the pulse modulation output duty ratio can be adjusted in the range of 30% to 70%.

  In one embodiment of the plasma processing method according to the second aspect of the present invention, the positions where the high frequency power is supplied are two positions on the electrode which are separated from each other, and the pulse modulation of the high frequency power supplied to the two positions is relative to each other. The relative phase difference of the pulse modulation of the high frequency power is adjusted so that the typical phase difference becomes 180 °.

  In another embodiment, the positions for supplying the high-frequency power are four positions on the electrode that are spaced apart from each other, and pulse modulation of the high-frequency power that is supplied to two positions of the four positions opposed to the left and right or up and down respectively. The relative phase difference of the pulse modulation of the high frequency power is adjusted so that the relative phase difference of becomes 180 °.

  In the plasma processing method according to the second aspect of the present invention, the frequency of pulse modulation can be adjusted in the range of 1 kHz to 500 kHz.

In the plasma CVD method according to the third aspect of the present invention, a substrate holder for placing a large-area substrate and an electrode larger than the outer dimension of the substrate placed on the substrate holder facing the substrate holder are provided in a vacuum chamber. Introducing a film-forming gas into the vacuum chamber, supplying a plurality of pulse-modulated high-frequency powers to positions spaced apart from the electrodes, and applying a plurality of pulse-modulated high-frequency powers to spaced positions on the electrodes It is characterized in that it is propagated as a whole and plasma is generated to perform processing on a large area substrate.

  In the plasma CVD method according to the third aspect of the present invention, the film quality of the thin film deposited on the large area substrate is controlled by adjusting the frequency of pulse modulation.

  In the present specification, the term “large area substrate” means a substrate having an arbitrary shape having a size of 1 m × 1 m or more in length and width and a length of a long side or a long diameter of 1 m or more.

  In the plasma processing apparatus according to the first aspect of the present invention, the high-frequency power supply means is configured to propagate the plurality of pulse-modulated high-frequency powers respectively on the electrode surfaces, so that the electrodes and the substrate Provided is a plasma processing apparatus capable of obtaining a favorable electric field strength distribution with a holder, generating uniform plasma on a substrate, and performing uniform plasma processing on a large area substrate. Will be able to.

  In the plasma processing method according to the second aspect of the present invention, a plurality of pulse-modulated high-frequency powers are supplied to spaced positions on the electrode, and a plurality of pulse-modulated high-frequency powers are spaced on the electrode. Since power is propagated entirely on the electrode surface to generate plasma and processing is performed on the large area substrate, a good electric field strength distribution between the electrode and the substrate holder can be obtained. Thus, uniform plasma can be generated on a large-area substrate having a vertical and horizontal length of 1 m × 1 m or more, and uniform plasma treatment can be performed.

  In the plasma CVD apparatus according to the third aspect of the present invention, a substrate holder for placing a large-area substrate and an electrode facing the substrate holder are provided in the vacuum chamber, a film forming gas is introduced into the vacuum chamber, Supplying a plurality of pulse-modulated high-frequency power to positions spaced apart from the electrode, and generating a plasma by propagating the plurality of pulse-modulated high-frequency power to the spaced positions on the electrode entirely on the electrode surface; Since processing is performed on a large-area substrate, a good electric field strength distribution between the electrode and the substrate holder can be obtained, and the film forming gas can be uniformly converted to plasma on the substrate. The reaction product can be uniformly formed on a large-area substrate.

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

  FIG. 1 shows a plasma CVD apparatus according to an embodiment of the present invention. In FIG. 1, reference numeral 1 denotes a vacuum chamber, and a substrate holder 2 that functions as an anode and an electrode 3 that functions as a cathode are disposed inside the vacuum chamber 1 so as to face each other. The substrate holder 2 is attached to the bottom wall of the vacuum chamber 1, includes a heater 4 inside, and a large area substrate 5 is placed on the upper surface of the substrate holder 2.

  The electrode 3 is attached to the top wall of the vacuum chamber 1 via an insulating member 6. The outer dimension of the electrode 3 is configured to be larger than the outer dimension of the large-area substrate 5 placed on the substrate holder 2. In this embodiment, the electrode 3 includes a shower head 3a and a shower plate 3b. The shower head 3 a is connected to a gas supply source (not shown) via the film forming gas supply port 7. Inside the shower head 3a, a plurality of diffusion plates 3c are arranged at intervals, and each diffusion plate 3c is provided with a number of through holes 3d.

  The shower plate 3b includes a number of gas discharge holes 3e. As a result, the gas supplied from the gas supply source (not shown) to the inside of the shower head 3a through the gas supply port 7 is a large number of through holes 3d in the plurality of diffusion plates 3c arranged inside the shower head 3a. And diffused and mixed through the gaps between the diffusion plates 3c and supplied from a large number of gas discharge holes 3e in the shower plate 3b toward the large area substrate 5 on the substrate holder 2.

  The substrate holder 2 can be moved up and down by a lifting mechanism (not shown), whereby the distance from the electrode 3 can be adjusted, and the distance between the substrate holder 2 and the electrode 3 can be changed during film formation and cleaning. To be. In this case, the lifting mechanism also carries a large-area substrate 5 to be processed from the outside to the inside of the vacuum chamber 1 and a transfer operation when the processed large-area substrate 5 is unloaded from the inside of the vacuum chamber 1 to the outside. It can also be used for raising and lowering the substrate.

  As shown in FIG. 1, high-frequency power is supplied to the two parts of the electrode 3 through two high-frequency power sources each including a crystal oscillator 8 and a high-frequency amplifier 9, a matching unit 10 and a feeding member 11, respectively. The Each power supply member 11 is insulated from the vacuum chamber 1 by an insulating member 13. The vacuum chamber 1 and the substrate holder 2 are connected to the ground potential. The pulse oscillator 12 is configured to pulse-modulate the high-frequency power of each high-frequency power source and arbitrarily adjust the output duty ratio and phase difference of the pulse modulation.

  Although not shown, the vacuum chamber 1 has a gas introduction system for introducing gas into the vacuum chamber 1 from an external film forming gas supply source, and a vacuum exhaust system for exhausting the vacuum and exhausting the gas in the vacuum chamber 1. Is provided.

  In the operation of the apparatus of FIG. 1 configured as described above, high-frequency power from two high-frequency power sources (8, 9) that are respectively pulse-modulated and phase-controlled by the pulse oscillator 12 is transmitted via the matching unit 10 and the power supply member 11. When supplied to the two parts of the electrode 3, the supplied high-frequency power propagates to the entire surface layer of the electrode 3 facing the substrate holder 2, and enters the vacuum chamber 1 from an external gas supply source (not shown). The gas introduced into is converted into plasma in the vacuum chamber 1 by capacitively coupled glow discharge using the substrate holder 2 as an anode and the electrode 3 as a cathode. On the other hand, the large area substrate 5 is heated to a predetermined temperature in advance by a heater 4 built in the substrate holder 2. As a result, the reaction product of the plasma gas reaches the surface of the large-area substrate 5 and a desired thin film having a good film thickness distribution is formed on the substrate 5.

    In the apparatus of FIG. 1, the two left and right parts of the electrode 3 to which high frequency power is supplied from each of the two high frequency power supplies (8, 9) are preferably the center on the electrode 3 as shown in FIG. It can be set on the axis. Further, as shown in FIG. 3, the pulse oscillator 12 has a divided pulse modulation function for generating two types of time-divided pulse modulation outputs so that the high-frequency powers of the two high-frequency power sources do not interfere with each other. The waveform shown in FIG. 3 is the most preferable example in which the influence on the disturbance of the electric field intensity distribution due to plasma interference is small in the two-point supply.

  For example, if the output duty ratio of the two types of pulse modulation is set in the range of 30% to 50% and the phase difference is set to 180 °, the average output of the high frequency power supply 8 can be divided and output equally.

 FIG. 4 shows another embodiment of the present invention. In this case, as shown in the drawing, high frequency power is supplied to the four portions A1, B1, A2, and B2 of the electrode 3. The relative pulse modulation phase difference between the four outputs is controlled by one pulse oscillator 12. In FIG. The pulse oscillator 12 also has a function of controlling the phase difference of the pulse modulation in the two-divided output. In the embodiment shown in FIG. 4, it is of course possible to provide a phase control device that controls the phase difference between the electrodes 3 by independently supplying all the pulse-modulated high-frequency power supplied to the electrode 3. The pulse-modulated high frequency output supplied to the four parts A1, B1, A2, and B2 of the electrode 3 by the action of the pulse oscillator 12 is supplied to the two parts A1 and B1 of the electrode 3 as shown in FIG. The pulse-modulated high-frequency output is divided in time so as not to interfere with each other, and the pulse-modulated high-frequency output supplied to the remaining two parts A2 and B2 of the electrode 3 is the two parts A1 and B1 of the electrode 3. Similarly to the pulse-modulated high-frequency output supplied to, it is generated so as to be time-divided so as not to interfere with each other.

  Next, the present invention will be further described based on a simulation in the case where a SiNx film is formed on a large area substrate.

  When the distance between the flat electrode or shower plate 3 having an outer dimension of 2500 mm × 2200 mm and the substrate holder 2 having the same outer dimension was set to 20 mm, the electric field intensity distribution was simulated.

The pulse-modulated high-frequency power is supplied to each of the centers A and B at the short-side end of the electrode 3, the frequency of the high-frequency power is 10 to 30 MHz, the number of pulse frequency drums is 1 kHz to 500 kHz, and the pulse modulation output duty Is 30% to 50%, the phase difference of pulse modulation is 180 °, and the power density per unit area of the electrode is 0.05 to 3.0 W / cm ² . Calculated with a 1/4 model. Ka and Kb indicate distances from the electrode end to the positions A and B on the electrode 3, respectively. If the above parameter range is used as a condition, the plasma generated by the high-frequency power supplied to the position A on the electrode 3 and the plasma generated by the high-frequency power supplied to the position B on the electrode 3 must interfere with each other at the same time. Therefore, the time-averaged electric field intensity distribution relating to the generation of plasma is obtained by superimposing the electric field intensity distribution when the high frequency power is supplied only to the part A and the electric field intensity distribution when the high frequency power is supplied only to the part B. be able to.

  FIG. 6 shows the calculation result when the frequency of the high frequency power is 27.12 MHz and Ka = Kb = 0. In the simulation, the same result is obtained within the range of the pulse frequency and the output modulation duty of the pulse modulation. In FIG. 6, the origin 0 on the horizontal axis corresponds to the center of the short side of one side of the electrode, and the electric field intensity distribution on the long side, that is, the center line in the 2500 mm direction is shown. The electric field strength on the vertical axis is an arbitrary unit.

  From the calculation result of the electric field strength distribution of FIG. 6, the simulation result of the film thickness distribution of the thin film formed when the large-area substrate 3 is 2.4 m × 2.2 m is ± 20%, and is separately simulated. The film thickness distribution is better than ± 40% when high-frequency power is supplied to one central electrode point. It is shown that the disturbance of the electric field intensity distribution at one point supply is smoothed by the superposition of two point supply.

  Next, an example in which a SiNx film is formed using the plasma CVD apparatus according to the embodiment shown in FIG. 1 and the film thickness distribution in the substrate is verified will be described.

As conditions, the frequency of the high frequency power is 27.12 MHz, the pulse frequency is 100 kHz, the output duty of the pulse modulation is 50%, the phase difference of the pulse modulation is 180 °, and the power density per unit area of the electrode is 0.5 W / cm ^2. It was. Ka = Kb≈0. As the film forming gas, a mixed gas composed of monosilane (SiH ₄ ), ammonia (NH ₃ ) and nitrogen (N ₂ ) was used, and the film forming pressure (discharge pressure) was set to 200 Pa. The substrate temperature was 300 ° C. The external dimensions of the electrode 3 were 2.5 m × 2.4 m for comparison. The distance between the electrode 3 and the substrate holder 2 was 20 mm. Regarding the substrate 5, a small glass having a thickness of 0.7 mm was placed in a range of 2.4 m × 2.2 m on the substrate holder to form a substrate. The measurement result of the film thickness distribution was ± 17%. The tendency of the improvement of the film thickness distribution suggested by the calculation in the actual film formation was confirmed.

  Note that the film thickness distribution result in this example shows that the influence of the standing wave generated on the electrode 3 is remarkable as inferred from the relationship between the frequency of the high frequency and the size of the electrode. By adjusting, a more preferable film formation distribution can be obtained. Specifically, this is performed by optimizing the distance K from the electrode end portion of the high-frequency power supply position. The apparatus configuration can be implemented by providing means capable of moving the high-frequency power supply unit on the electrode 3 or changing the connection position as a structure in which a plurality of supply units are provided in advance.

  FIG. 7 shows the electric field strength distribution result by simulation when Ka = Kb = 400 (mm). From the calculation result of the electric field strength distribution of FIG. 7, the result of simulating the film thickness distribution of the thin film formed when the large-area substrate 5 is 2.4 m × 2.2 m is less than ± 5%, and the supply position It was shown that the smoothing by superimposing can be optimized by adjusting the above to obtain a good electric field strength distribution and, more particularly, a film thickness distribution.

  The film thickness distribution was 5% in the result of performing the film formation of SiNx and verifying the film thickness distribution in the substrate. Compared with the simulation result, the film thickness distribution in the actual film forming apparatus is relatively poor, but this is largely due to the asymmetry in the structure of the actual apparatus.

  By adjusting the electric power supply position, adjusting the pulse modulation duty adjustment range in the range of 30% to 70%, or changing the electric field strong product distribution by adjusting the phase difference of the pulse modulation. The film thickness distribution can be further improved by correcting the disturbance of the electric field distribution. Needless to say, this is also effective in an actual apparatus that supplies high-frequency power to four locations.

  Next, in the example of SiNx film formation, the result of film formation of SiNx by changing the frequency of pulse modulation will be described.

  FIG. 8 shows the case where pulse modulation is not applied (CW) and the frequency of pulse modulation is changed to 500 kHz, 100 kHz, 10 kHz, 5 kHz, and 1 kHz under the same conditions for the time-average high-frequency output supplied to the electrodes. The film forming speed obtained is shown. When the frequency of the pulse modulation is 10 kHz or less, the film forming speed is remarkably reduced, but at 500 kHz, it is only slightly reduced.

  FIG. 9 shows the refractive index of the obtained SiNx film. Although the refractive index of the film depends on the frequency of pulse modulation, the refractive index increases when the frequency is 10 KHz or less, and the film quality with a refractive index of 1.86 or less that is normally obtained by plasma CVD using a high frequency without pulse modulation is This is obtained when the frequency of pulse modulation is 500 kHz.

  From these results, it is clear that the frequency of pulse modulation has an influence on the SiNx film forming process. Specifically, it is determined that the higher the frequency, the more the nitriding of Si is promoted and the refractive index is increased. Is done. In other words, the film quality can be adjusted by adjusting the frequency of pulse modulation.

  In this embodiment, the distance between the electrode and the substrate holder is 20 mm. However, the distance between the electrode and the substrate holder can be 10 mm as the distance between the electrode and the substrate holder. More preferably, it is in the range of ˜20 mm. Further, plasma cleaning can be performed by introducing a predetermined gas with the distance between the electrode and the substrate holder being 25 mm or more.

  The film forming conditions in which the experiment was performed were a film forming pressure of 200 Pa. However, in the region where the film forming pressure is 100 Pa or less (for example, 10 Pa to 100 Pa), plasma tends to diffuse toward the vacuum chamber wall, and the outer periphery of the electrode It is known that the plasma density increases. In this case, it is expected that the uniformity of the time-averaged electric field distribution and the uniformity of the plasma on the entire surface of the large area substrate are particularly improved by adjusting the supply position of the high-frequency power.

  The present invention can naturally be applied to materials other than the exemplified film forming materials.

  In the above description, the plasma CVD apparatus for forming a thin film on a large substrate has been exemplified. However, the present invention can be applied to a plasma cleaning apparatus and an etching apparatus.

1 is a schematic sectional view showing a plasma CVD apparatus according to an embodiment of the present invention. The schematic diagram which illustrates the high frequency electric power supply means in the plasma CVD apparatus shown in FIG. The figure which shows the example of a waveform of two types of pulse modulation outputs in the high frequency electric power supply means of the plasma CVD apparatus of FIG.1 and FIG.2. The schematic diagram which shows the high frequency electric power supply means by another embodiment in this invention plasma CVD apparatus. The figure which shows the example of a waveform of four types of pulse modulation outputs in the high frequency electric power supply means of the plasma CVD apparatus of FIG. The graph which shows the electric field strength distribution on the longitudinal direction center line of the electrode at the time of supplying high frequency electric power to two edge parts which an electrode opposes. The graph which shows the electric field strength distribution on the longitudinal centerline of an electrode at the time of supplying high frequency electric power to two site | parts which were each 400 mm away from the two edge parts which an electrode opposes according to this invention. The graph which shows the pulse modulation frequency dependence of the film-forming speed of SiNx. The graph which shows the pulse modulation frequency dependence of the refractive index of SiNx.

Explanation of symbols

1: Vacuum chamber 2: Substrate holder 3: Electrode 4: Heater 5: Large area substrate 6: Insulating member 7: Deposition gas supply port 8: Crystal oscillator 9: High frequency amplifier 10: Matching device 11: Feeding member 12: Pulse oscillator 13: Insulating member

Claims (22)

In the vacuum chamber, a substrate holder for placing a large-area substrate, an electrode facing the substrate holder, and means for introducing gas into the vacuum chamber,
In addition, high-frequency power supply means for supplying a plurality of pulse-modulated high-frequency power to a plurality of spaced apart positions of the electrode is provided,
High-frequency power supply means is configured to propagate the plurality of pulse-modulated high-frequency powers respectively on the surface of the electrodes ,
The frequency of the high frequency power is in the range of 13 MHz to 30 MHz;
The plasma processing apparatus, wherein the high-frequency power supply means includes means for adjusting a relative phase difference of the pulse modulation of the plurality of pulse-modulated high-frequency powers . A substrate holder for placing a large-area substrate in the vacuum chamber; an electrode larger than the outer dimension of the substrate placed on the substrate holder opposite to the substrate holder; and means for introducing gas into the vacuum chamber; Provided,
In addition, high-frequency power supply means for supplying a plurality of pulse-modulated high-frequency power to a plurality of spaced apart positions of the electrode is provided,
High-frequency power supply means is configured to propagate each of the plurality of pulse-modulated high-frequency powers on the electrode surfaces as a whole.
A plasma processing apparatus. The plasma processing apparatus according to claim 2 , wherein the frequency of the high-frequency power is in a range of 13 MHz to 30 MHz . The plasma processing apparatus according to claim 2, wherein the high-frequency power supply unit includes a unit that adjusts a relative phase difference of pulse modulation of the plurality of pulse-modulated high-frequency powers . The plasma processing apparatus according to any one of claims 1 to 3, wherein a position for supplying the high-frequency power is separated from an electrode end by an adjustable distance (Ka, Kb) . The plasma processing apparatus according to any one of claims 1 or 4-5 outputs the duty ratio of the pulse modulation is characterized in that in the range of 30% to 70%. The positions where the high frequency power is supplied are two spaced apart positions on the electrode, and the relative phase difference of the pulse modulation of the high frequency power supplied to the two positions is 180 °. The plasma processing apparatus according to any one of claims 1 to 6 . The high-frequency power supply means includes two high-frequency power supplies and a pulse oscillator that modulates the high-frequency power of each high-frequency power supply and controls the phase so that the relative phase difference of the high-frequency power becomes a predetermined value. The plasma processing apparatus according to claim 7 . 9. The pulse oscillator according to claim 8, wherein the pulse oscillator has a divided pulse modulation function that makes two types of pulse modulation outputs divided in time so that high-frequency power from each high-frequency power source does not interfere with each other. Plasma processing equipment. The positions for supplying the high-frequency power are four positions on the electrode that are spaced apart from each other, and the relative positions of the pulse modulation of the high-frequency power that are respectively supplied to two positions of the four positions that are opposed to the left and right or up and down. The plasma processing apparatus according to claim 1, wherein the phase difference is 180 ° . The high-frequency power supply means pulse-modulates four high-frequency power supplies and the high-frequency power of each high-frequency power supply, and the high-frequency power is supplied to two positions on the electrode that are opposed to the left and right or up and down. The plasma processing apparatus according to claim 10 , further comprising: one pulse oscillator configured to generate two types of pulse-modulated outputs that are time-divided so that power does not interfere with each other . The plasma processing apparatus according to any one of claims 1 to 11, wherein a frequency of the pulse modulation is in a range of 1 kHz to 500 kHz . A substrate holder for placing a large-area substrate in a vacuum chamber and an electrode larger than the outer dimension of the substrate placed on the substrate holder opposite to the substrate holder are provided, gas is introduced into the vacuum chamber, and the electrode A plurality of pulse-modulated high-frequency power is supplied to the spaced apart positions on the electrode, and a plurality of pulse-modulated high-frequency powers are propagated entirely on the surface of the electrode to generate plasma. Then, the plasma processing method is characterized in that processing is performed on the large-area substrate . The plasma processing method according to claim 13 , wherein the frequency of the high-frequency power is in a range of 13 MHz to 30 MHz . The plasma processing method according to claim 13 or 14 , wherein a relative phase difference of the pulse modulation of the plurality of pulse-modulated high-frequency powers is adjusted . The plasma processing method according to claim 13 , wherein a position on the electrode that supplies the high-frequency power is adjusted . The plasma processing method according to claim 15 or 16 , wherein an output duty ratio of the pulse modulation is adjusted in a range of 30% to 70% . The high-frequency power is supplied so that the positions where the high-frequency power is supplied are two spaced apart positions on the electrode, and the relative phase difference of the pulse modulation of the high-frequency power supplied to the two positions is 180 °. The plasma processing method according to claim 13 , wherein a relative phase difference of the pulse modulation is adjusted . The positions for supplying the high-frequency power are four positions on the electrode that are spaced apart from each other, and the relative positions of the pulse modulation of the high-frequency power that are respectively supplied to two positions of the four positions that are opposed to the left and right or up and down. 18. The plasma processing method according to claim 13 , wherein the relative phase difference of the pulse modulation of the high frequency power is adjusted so that the phase difference becomes 180 ° . The plasma processing method according to any one of claims 13 to 19, wherein a frequency of the pulse modulation is adjusted in a range of 1 kHz to 500 kHz . In the vacuum chamber, a substrate holder for placing a large-area substrate and an electrode larger than the outer dimension of the substrate placed on the substrate holder facing the substrate holder are provided, and a film forming gas is introduced into the vacuum chamber. Supplying a plurality of pulse-modulated high-frequency powers to positions spaced apart from the electrodes, and propagating a plurality of pulse-modulated high-frequency powers to the spaced positions on the electrodes as a whole on the electrode surface. A plasma CVD method comprising: generating and processing the large area substrate . The plasma CVD method according to claim 21 , wherein the film quality of the thin film deposited on the large-area substrate is controlled by adjusting the frequency of the pulse modulation .

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