JP4660226B2 - Plasma processing equipment - Google Patents

Description

  The present invention relates to a plasma processing apparatus, and more particularly, to a plasma processing apparatus including a first electrode and a second electrode arranged to face each other.

  2. Description of the Related Art Conventionally, a parallel plate type plasma processing apparatus including a first electrode capable of holding a substrate and a second electrode arranged to face the first electrode is known.

  FIG. 15 is a schematic view showing a conventional parallel plate type plasma processing apparatus. Referring to FIG. 15, in a conventional parallel plate type plasma processing apparatus 301, an upper electrode (first electrode) 303 and a lower electrode (second electrode) 304 are installed in a vacuum chamber 302 so as to face each other. Has been. Further, the upper electrode 303 is configured to be able to hold the substrate 310 on the side facing the lower electrode 304. A plurality of gas supply ports 304 a for supplying a source gas are provided on the side of the lower electrode 304 facing the upper electrode 303. In addition, an exhaust port 302 a is provided on one side surface of the vacuum chamber 302, and the exhaust port 302 a is connected to a vacuum exhaust facility 306 via an exhaust flow rate adjustment valve 305. The vacuum evacuation equipment 306 includes a turbo molecular pump (TMP) 306a and an oil rotary pump (RP) 306b. The gas supply port 304 a of the lower electrode 304 is connected to the source gas supply source 307.

  In the conventional parallel plate type plasma processing apparatus 301 described above, a region 301 a between the upper electrode 303 and the lower electrode 304 becomes a region where plasma is generated, and a region 301 a between the upper electrode 303 and the lower electrode 304. The source gas is decomposed by the plasma generated in Further, in the configuration of the conventional parallel plate type plasma processing apparatus 301 described above, unreacted gas (raw material gas), negative ions, malignant radicals and flakes (negative ion polymerization) generated when the raw material gas is decomposed. The fine particles generated by the reaction are discharged through an exhaust port 302 a provided on one side surface of the vacuum chamber 302.

  However, in the conventional parallel plate type plasma processing apparatus 301 shown in FIG. 15, discharge of unreacted gas (source gas), negative ions, malignant radicals, flakes, and the like is provided on one side surface of the vacuum chamber 302. Since the process is performed only by the exhaust port 302a, the region on the exhaust port 302a side of the substrate 310 and the exhaust port 302a of the substrate 310 are used when a film having a large area is formed by depositing a film formation species on the substrate 310. The variation in the discharge amount of unreacted gas (raw material gas), negative ions, malignant radicals and flakes in the opposite region increases. For this reason, there arises a disadvantage that it is difficult to make the film thickness and film quality of the film formed on the substrate 310 uniform.

  Therefore, conventionally, in order to suppress variation in the discharge amount of unreacted gas (source gas), negative ions, malignant radicals and flakes depending on the region, unreacted gas (source gas) is provided on one of the two electrodes facing each other. ), A parallel plate type plasma processing apparatus provided with an exhaust port for discharging negative ions, malignant radicals and flakes has been proposed (see, for example, Patent Documents 1 and 2).

  Patent Document 1 discloses a plasma processing apparatus including an upper electrode having a plurality of gas supply ports and one exhaust port. Further, Patent Document 2 discloses a plasma processing apparatus including an upper electrode having a plurality of gas supply ports and a plurality of exhaust ports smaller than the number of gas supply ports. In Patent Documents 1 and 2, the substrate is fixed to the lower electrode.

  In the plasma processing apparatuses disclosed in Patent Documents 1 and 2, the conventional plasma processing apparatus 301 is provided with the exhaust port 302a only on one side surface of the vacuum chamber 302 by providing the upper electrode with the exhaust port. Compared with (refer to FIG. 15), it is suppressed that the discharge | emission amount of an unreacted gas (raw material gas), a negative ion, a malignant radical, and flakes changes with areas. For this reason, in the plasma processing apparatuses disclosed in Patent Documents 1 and 2, the film thickness and film quality of the film formed on the substrate are not uniform compared to the conventional plasma processing apparatus 301 shown in FIG. Can be suppressed.

Japanese Patent Laid-Open No. 9-223865 Japanese Patent Laid-Open No. 11-144891

  However, in the plasma processing apparatuses disclosed in Patent Documents 1 and 2, since the number of exhaust ports provided in the upper electrode is smaller than the number of gas supply ports, unreacted gas (source gas), negative ions, malignant When radicals and flakes are discharged from the exhaust port of the upper electrode, the discharge amount is reduced in a predetermined region near the exhaust port of the upper electrode and in a region far from the exhaust port of the upper electrode than the predetermined region. There is an inconvenience of variation. As a result, Patent Documents 1 and 2 have a problem in that it is difficult to further suppress variations in film thickness and film quality of the film formed on the substrate.

  The present invention has been made to solve the above-described problems, and one object of the present invention is to provide a plasma processing apparatus capable of suppressing variations in film thickness and film quality over a wide area. It is to be.

Means for Solving the Problems and Effects of the Invention

  In order to achieve the above object, a plasma processing apparatus according to one aspect of the present invention is installed in a plasma processing chamber and is capable of holding a substrate, and faces the first electrode in the plasma processing chamber. A plurality of first nozzles for performing one of gas supply and discharge, and the other of the gas supply and discharge and disposed inside each of the plurality of first nozzles. And a second electrode including a second nozzle.

  In the plasma processing apparatus according to the one aspect, as described above, a plurality of first nozzles for performing one of gas supply and discharge, and the other of gas supply and discharge, Since one first nozzle is provided for one second nozzle by configuring the second electrode to include a second nozzle disposed inside each of the first nozzles, for example, When the gas is supplied by the second nozzle provided inside the first nozzle while the gas is discharged by the first nozzle, the amount of the gas discharged by the first nozzle is prevented from varying depending on the region. Can do. As a result, the amount of unreacted gas (source gas), negative ions, malignant radicals and flakes discharged by the first nozzle can be prevented from varying within the region where the plasma is generated, so that the source gas is decomposed. Thus, it is possible to suppress the occurrence of inconvenience that the generation amount of the film forming species generated varies. As a result, it is possible to suppress variation in the thickness of the film formed by depositing the film-forming species on the substrate. Moreover, since it can suppress that the quantity of the unreacted gas (raw material gas) mixed with the film | membrane formed on a board | substrate, a malignant radical, and a flake can be suppressed, it can also suppress that a film quality varies.

  In the plasma processing apparatus according to the above aspect, the first nozzle and the second nozzle are preferably connected to the main part of the first gas flow path and the main part of the second gas flow path, respectively. The cross-sectional area of at least one of the main part of the flow path and the main part of the second gas flow path is larger than the cross-sectional area of at least one of the corresponding first nozzle and second nozzle. If comprised in this way, the conductance (ease of gas flow) of at least one of the main part of the first gas flow path and the main part of the second gas flow path is determined from the conductance of the corresponding first nozzle or second nozzle. Can also be increased. In this case, even if the length of the gas flow path of the main part of the first gas flow path (the main part of the second gas flow path) is increased, the first position located in a predetermined region close to the gas supply source or the vacuum exhaust equipment. The synthetic conductance between one nozzle and the main part of the first gas flow path (second nozzle and the main part of the second gas flow path) and the distance from the gas supply source or the vacuum exhaust equipment is farther than the predetermined area. It is possible to suppress variation in the combined conductance between the first nozzle located and the main part of the first gas flow path (the second nozzle and the main part of the second gas flow path). As a result, when the length of the gas flow path of the main part of the first gas flow path (main part of the second gas flow path) is increased, the first position located in a predetermined region close to the gas supply source or the vacuum exhaust equipment. The amount of gas supplied or discharged by one nozzle (second nozzle) and supplied by a first nozzle (second nozzle) located in a region farther than a predetermined region from the gas supply source or the vacuum exhaust equipment or Variations in the amount of gas discharged can be suppressed.

  In the configuration in which the first nozzle and the second nozzle are connected to the main part of the first gas flow path and the main part of the second gas flow path, respectively, preferably, the second electrode includes a plurality of first nozzles. A first plate having a second plate having a plurality of second nozzles disposed on one surface side of the first plate, and a third plate disposed on a surface side opposite to the first plate of the second plate The main part of the first gas flow path is provided between the first plate and the second plate, and the main part of the second gas flow path is between the second plate and the third plate. It is provided in between. If comprised in this way, while being able to connect a 1st nozzle to the principal part of the 1st gas flow path between a 1st plate and a 2nd plate easily, a 2nd nozzle can be connected to a 2nd plate. To the main part of the second gas flow path between the first plate and the third plate.

  In the configuration in which the second electrode includes the first plate, the second plate, and the third plate, the intermediate plate that is preferably disposed in at least one of the first gas channel and the second gas channel and has a plurality of openings. The opening of the intermediate plate is arranged for each of at least one of the first nozzle and the second nozzle, and the main part of the first gas flow path and the main part of the second gas flow path The cross-sectional area of at least one of the parts is larger than the cross-sectional area of the opening of the intermediate plate. If comprised in this way, the conductance of at least one of the main part of a 1st gas flow path and the main part of a 2nd gas flow path can be made larger than the conductance of the opening part of an intermediate | middle plate. In this case, even if the length of the gas flow path of the main part of the first gas flow path (the main part of the second gas flow path) is increased, the intermediate position located in a predetermined region near the gas supply source or the vacuum exhaust equipment The synthetic conductance between the opening of the plate and the main part of the first gas flow path (the opening of the intermediate plate and the main part of the second gas flow path) and the distance from the gas supply source or the vacuum exhaust equipment are determined from a predetermined region. Further, it is possible to suppress variation in the combined conductance between the opening of the intermediate plate located in the far region and the main part of the first gas flow path (the opening of the intermediate plate and the main part of the second gas flow path). . Thereby, when the length of the gas flow path of the main part of the first gas flow path (the main part of the second gas flow path) is increased, the intermediate position located in a predetermined region near the gas supply source or the vacuum exhaust equipment The amount of gas supplied or exhausted through the opening of the plate and supplied or exhausted through the opening of the intermediate plate located in a region farther than the predetermined region from the gas supply source or vacuum exhaust equipment It is possible to suppress variation in the amount of gas to be generated. As a result, the amount of gas supplied or discharged by the first nozzle (second nozzle) corresponding to the opening of the intermediate plate located in a predetermined region near the gas supply source or the vacuum exhaust equipment, and the gas supply source or vacuum Further suppressing variation in the amount of gas supplied or discharged by the first nozzle (second nozzle) corresponding to the opening of the intermediate plate located in a region far from the predetermined region from the exhaust facility. Can do.

  In the plasma processing apparatus according to the above aspect, the first electrode is preferably configured to be swingable in a direction parallel to the surface of the second electrode. According to this structure, the substrate held by the first electrode can be swung by swinging the first electrode. Therefore, the second gas constituting the source gas supply unit can be swung by swinging the substrate. The first nozzle or the second nozzle of the electrode can be distributed on the surface of the substrate on average during film formation. Thereby, the thickness of the film formed by depositing the film-forming species generated by the decomposition of the source gas on the substrate can be made uniform.

  In this case, it is preferable that the plurality of first nozzles and the plurality of second nozzles have a predetermined interval in a row so as to be inclined at a predetermined angle with respect to a direction in which the first electrode swings in a plan view. They are spaced apart. According to this structure, the substrate held by the first electrode is swung, so that the gas is evenly distributed even in the region corresponding to the row between the plurality of first nozzles (second nozzles) arranged in a row. In the film formed on the substrate, regions corresponding to the plurality of first nozzles (second nozzles) arranged in a row and the plurality of first arranged in a row are provided. It is possible to suppress variations in film thickness and film quality between the regions corresponding to the rows of nozzles (second nozzles).

  In the plasma processing apparatus according to the above aspect, the gas is preferably supplied by one of the first nozzle and the second nozzle, and the inner surface of one of the first nozzle and the second nozzle to which the gas is supplied is provided. A spiral groove is formed. If comprised in this way, the source gas supplied from the 1st nozzle or 2nd nozzle in which the spiral groove part was formed in the inner surface compared with the case where vortex is not produced | generated by the spiral produced | generated spirally. Since the mixing is further promoted, the source gas can be uniformly dispersed in the region where the plasma is generated. Thereby, in the area | region where a plasma generate | occur | produces, the source gas supplied from a 1st nozzle or a 2nd nozzle can be decomposed | disassembled uniformly. In addition, since the source gas supplied from the first nozzle or the second nozzle is accelerated by the spiral generated vortex as compared with the case where no vortex is generated, the source gas in the region where the plasma is generated is increased. Residence time can be lengthened. As a result, the amount of film formation species generated by decomposition of the source gas increases, so that the film formation speed can be increased.

  In the plasma processing apparatus according to the above aspect, the gas is preferably supplied by one of the first nozzle and the second nozzle, and the gas is supplied on the inner surface side of one of the first nozzle and the second nozzle. The tip is formed in a sharp shape that is not rounded. If comprised in this way, the source gas supplied from the 1st nozzle or the 2nd nozzle formed in the sharp shape where the front-end | tip part of the inner surface side is not rounded will be formed in the sharp shape which is not round. The vortex generated in the vicinity of the tip portion further promotes the mixing as compared with the case where no vortex is generated, so that the source gas can be uniformly dispersed in the region where the plasma is generated. Thereby, in the area | region where a plasma generate | occur | produces, the source gas supplied from a 1st nozzle or a 2nd nozzle can be decomposed | disassembled uniformly. Further, the source gas supplied from the first nozzle or the second nozzle is further promoted to be mixed as compared with the case where no vortex is generated due to the vortex generated in the vicinity of the tip formed in a sharp shape that is not rounded. Therefore, the residence time of the source gas in the region where plasma is generated can be increased. As a result, the amount of film formation species generated by decomposition of the source gas increases, so that the film formation speed can be increased.

  In the plasma processing apparatus according to the above aspect, the first nozzle and the second nozzle are preferably arranged coaxially so that the center of the first nozzle and the center of the second nozzle substantially coincide with each other. If comprised in this way, gas can be easily discharged or supplied by a 2nd nozzle, supplying or discharging gas by a 1st nozzle.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

(First embodiment)
FIG. 1 is a schematic view showing a plasma processing apparatus according to a first embodiment of the present invention, and FIG. 2 is a plan view showing a lower electrode of the plasma processing apparatus according to the first embodiment shown in FIG. . 3 and 4 are cross-sectional views taken along lines 100-100 and 200-200 in FIG. 2, respectively. First, with reference to FIGS. 1-4, the structure of the plasma processing apparatus 1 by 1st Embodiment is demonstrated.

  As shown in FIG. 1, the plasma processing apparatus 1 according to the first embodiment has a parallel plate structure in which an upper electrode 3 and a lower electrode 4 are installed in a vacuum chamber 2 so as to face each other. In such a parallel plate type plasma processing apparatus 1, a region 1 a between the upper electrode 3 and the lower electrode 4 is a region where plasma is generated. In the region 1 a between the upper electrode 3 and the lower electrode 4, plasma is generated substantially uniformly. The upper electrode 3 and the lower electrode 4 each have a size of about 600 mm square. The vacuum chamber 2 is an example of the “plasma processing chamber” in the present invention. The upper electrode 3 and the lower electrode 4 are examples of the “first electrode” and the “second electrode” in the present invention, respectively.

  Here, in the first embodiment, the upper electrode 3 is configured to be swingable in a direction (direction A) parallel to the surface of the lower electrode 4. Specifically, the upper electrode 3 is attached to a swing mechanism unit 5 installed in the vacuum chamber 2 and is swung in the A direction by the swing mechanism unit 5. Further, the upper electrode 3 has a holding portion 3 a for holding the substrate 10. The distance between the substrate 10 held by the holding portion 3a of the upper electrode 3 and the lower electrode 4 is set to about 15 mm. The upper electrode 3 includes a heating / cooling mechanism (not shown) for maintaining the substrate 10 at a predetermined temperature.

  Further, in the first embodiment, the lower electrode 4 is configured so that the source gas is supplied into the vacuum chamber 2 while the unreacted gas (source gas) or negative ions or malignant radicals generated by decomposition of the source gas are decomposed. And flakes (fine particles generated by the polymerization reaction of negative ions) and the like can be discharged. Specifically, as shown in FIGS. 3 and 4, the lower electrode 4 includes a gas discharge plate 14, a gas supply plate 24, and a lower plate 34. The gas discharge plate 14, the gas supply plate 24, and the lower plate 34 are examples of the “first plate”, “second plate”, and “third plate” of the present invention, respectively.

  In the first embodiment, the gas discharge plate 14 has a plurality of circular gas discharge openings 14a having an inner diameter D1 of about 3 mm. The gas discharge opening 14a is an example of the “first nozzle” in the present invention. The plurality of gas discharge openings 14a are arranged in a matrix (matrix) at a pitch (center distance) P1 of about 10 mm, as shown in FIG. Further, as shown in FIGS. 3 and 4, the gas discharge plate 14 is the side (uppermost part) closest to the upper electrode 3 (see FIG. 1) among the three plates (14, 24 and 34) described above. Is arranged.

  Further, in the first embodiment, the gas supply plate 24 is separated from the gas discharge plate 14 by an interval L1 of about 20 mm on the surface side opposite to the upper electrode 3 (see FIG. 1) of the gas discharge plate 14. Are arranged. A space region between the gas supply plate 24 and the gas discharge plate 14 is a main portion 14b of the exhaust gas flow path through which the exhaust gas discharged through the plurality of gas discharge openings 14a flows. The main portion 14b of the exhaust gas passage is an example of the “main portion of the first gas passage” in the present invention.

In the first embodiment, the gas supply plate 24 has a plurality of gas supply nozzles 24a each having a circular pipe shape extending toward the gas discharge plate 14. The gas supply nozzle 24a is an example of the “second nozzle” in the present invention. The pipe-shaped gas supply nozzle 24a has an outer diameter D2 (about 1 mm) smaller than the inner diameter D1 (about 3 mm) of the circular gas discharge opening 14a. The gas supply nozzle 24a has an inner diameter D3 of about 0.8 mm. The cross-sectional area of the gas flowing portion of the gas supply nozzle 24a is πr ² = π × (D3 / 2) ² = about 0.5 mm ² . Further, as shown in FIG. 2, the gas supply nozzle 24a has a coaxial shape in which the center of the gas supply nozzle 24a and the center of the gas discharge opening 14a coincide with each other in plan view. It arrange | positions inside each of the some opening part 14a for gas discharge. Further, as shown in FIG. 3, the gas supply nozzle 24 a is arranged so that the position of the upper surface of the tip of the gas supply nozzle 24 a coincides with the position of the upper surface of the gas discharge plate 14. Thereby, the cross-sectional area of the gas flowing through the gas discharge opening 14a is changed from the cross-sectional area of the gas discharge opening 14a (about 7 mm ² ) to the cross-sectional area of the entire gas supply nozzle 24a (πr ² = π × ( D2 / 2) ² = about 0.8 mm ² ) is subtracted (about 6.2 mm ² ). That is, in the first embodiment in which the space region between the gas supply plate 24 and the gas discharge plate 14 arranged at an interval of about 20 mm is the main portion 14b of the exhaust gas flow channel, the exhaust gas flow channel The conductance of the main portion 14b is larger than the conductance of the gas discharge opening portion 14a having a cross-sectional area of a portion through which a gas of about 6.2 mm ² flows.

In the first embodiment, the lower plate 34 is disposed on the surface side of the gas supply plate 24 opposite to the gas discharge plate 14. Further, as shown in FIGS. 2 and 3, the lower plate 34 has a plurality of grooves 34a extending in the swinging direction (A direction) of the upper electrode 3 (see FIG. 1). The plurality of grooves 34a of the lower plate 34 are arranged at a pitch P1 of about 10 mm so as to correspond to the gas supply nozzle 24a. Further, the depth L2 (see FIG. 3) of the groove 34a of the lower plate 34 is about 7 mm, and the width W1 (see FIG. 2) of the groove 34a is about 7 mm. The main portion 24b of the supply gas flow path having a square cross section through which the supply gas supplied from the plurality of gas supply nozzles 24a flows is formed by the groove 34a of the lower plate 34 and the lower surface of the gas supply plate 24. Is configured. That is, the cross-sectional area of the main portion 24b of the supply gas flow path having a square cross section is about 7 mm × about 7 mm = about 49 mm ² . Therefore, in the first embodiment, the conductance (ease of gas flow) of the main portion 24b of the supply gas flow path is larger than the conductance of the gas supply nozzle 24a having a cross-sectional area of about 0.5 mm ² . The main part 24b of the supply gas flow path is an example of the “main part of the second gas flow path” in the present invention.

  As shown in FIG. 1, the vacuum chamber 2 has an exhaust port 2a, and the exhaust port 2a is connected to a high vacuum exhaust system 7 through a valve 6a. The valve 6a is closed during film formation. The high vacuum evacuation facility 7 includes a turbo molecular pump (TMP) 7a and an oil rotary pump (RP) 7b. The main part 24 b (see FIG. 3) of the supply gas flow path of the lower electrode 4 is connected to the source gas supply source 8. The main portion 14b (see FIG. 3) of the exhaust gas flow path of the lower electrode 4 is connected to the vacuum exhaust equipment 9 via the exhaust flow rate adjustment valve 6b. The evacuation equipment 9 is composed of a mechanical booster pump (MBP) 9a and an oil rotary pump (RP) 9b.

  In the first embodiment, as described above, the lower electrode 4 includes the plurality of gas discharge openings 14a and the gas supply nozzles 24a disposed inside each of the plurality of gas discharge openings 14a. Since one gas discharge opening 14a is provided for one gas supply nozzle 24a, unreacted gas (raw material gas), negative ions, malignancy are formed by the gas discharge opening 14a. An unreacted gas (raw material) discharged from the gas discharge opening 14a when supplying the raw material gas by the gas supply nozzle 24a provided inside the gas discharge opening 14a while discharging radicals and flakes. Gas), negative ions, malignant radicals, and flakes can be prevented from varying from one region to another. As a result, the amount of unreacted gas (raw material gas), negative ions, malignant radicals and flakes discharged through the gas discharge opening 14a can be suppressed from varying in the region 1a where the plasma is generated. Generation | occurrence | production of the problem that the production amount of the film-forming seed | species produced | generated by decomposition | disassembly of source gas varies can be suppressed. As a result, it is possible to suppress variation in the thickness of the film formed by depositing the film-forming species on the substrate 10. Moreover, since it can suppress that the quantity of the unreacted gas (raw material gas) mixed with the film | membrane formed on the board | substrate 10 and a malignant radical and flakes can vary, it can also suppress that film quality varies.

  In the first embodiment, the conductance of the main portion 14b of the exhaust gas flow path is made larger than the conductance of the gas discharge opening 14a, so that the length of the gas flow path of the main portion 14b of the exhaust gas flow path is increased. Is increased, the combined conductance of the gas exhaust opening 14a located in a predetermined area close to the vacuum exhaust equipment 9 and the main portion 14b of the exhaust gas flow path and the distance from the vacuum exhaust equipment 9 are within the predetermined area. It is possible to suppress variation in the combined conductance between the gas discharge opening 14a located in a farther region and the main portion 14b of the exhaust gas flow path. As a result, when the length of the gas flow path of the main portion 14b of the exhaust gas flow path is increased, the amount of gas discharged by the gas discharge opening 14a located in a predetermined area close to the vacuum exhaust equipment 9 Further, it is possible to suppress variation in the amount of gas discharged by the gas discharge opening 14a located in a region far from the vacuum exhaust facility 9 than the predetermined region.

  Also, when the conductance of the main part 24b of the supply gas flow path is made larger than the conductance of the gas supply nozzle 24a, the length of the gas flow path of the main part 24b of the supply gas flow path is increased. The combined conductance of the gas supply nozzle 24a located in a predetermined area close to the source gas supply source 8 and the main part 24b of the supply gas flow path and the distance from the source gas supply source 8 are farther than the predetermined area. It is possible to suppress variation in the combined conductance between the gas supply nozzle 24a located and the main portion 24b of the supply gas flow path. Thereby, even when the length of the gas flow path of the main portion 24b of the supply gas flow path is increased, the amount of gas supplied by the gas supply nozzle 24a located in a predetermined region close to the source gas supply source 8 And the amount of gas supplied by the gas supply nozzle 24a located in a region far from the predetermined region from the source gas supply source 8 can be suppressed.

  Here, with reference to FIG. 5, the effect regarding the conductance of the first embodiment will be described in detail. FIG. 5 shows a pipe structure in which a pipe 201 having a gas flow path having a diameter D11 and a pipe 202 having a gas flow path having a diameter D12 larger than the diameter D11 are connected. In the structure of the first embodiment, the pipe 201 corresponds to the gas discharge opening 14a (gas supply nozzle 24a), and the pipe 202 corresponds to the main portion 14b of the exhaust gas flow path (main of the supply gas flow path). It is assumed that it corresponds to the part 24b).

First, when the temperature of the air is 20 ° C., the conductance C (m ³ / s) of the viscous flow when a large pressure gradient is not generated in the pipe is obtained by the following equation (1). Here, the magnitude of the pressure gradient in the pipe decreases as the cross-sectional area of the pipe increases, but it can be said that it is proportional to the amount of gas flowing in the pipe, so it is determined appropriately from the required gas flow rate. To do.

C = 1349 × (D ⁴ / L) × P (1)
In the above formula (1), D: diameter of pipe (m), L: length of pipe (m), and P: average pressure (Pa).

In the pipe 201 shown in FIG. 5, when the diameter D11 and the length L11 of the gas flow path are 0.001 m and 0.005 m, respectively, and the average pressure is 200 Pa, the conductance C1 of the pipe 201 is From the formula (1), C1 = 1349 × (0.001 ⁴ /0.005)×200=5.39×10 ⁻⁵ m ³ / s.

Next, in the pipe 202 shown in FIG. 5, when the diameter D12 and length L12 of the gas flow path are 0.03 m and 0.01 m, respectively, and the average pressure is 200 Pa, the conductance C2 of the pipe 202 is From the above equation (1), C2 = 1349 × (0.03 ⁴ /0.01)×200=21.8 m ³ / s. In the pipe 202 shown in FIG. 5, when the diameter D12 and the length L12 of the gas flow path are 0.03 m and 0.1 m, respectively, and the average pressure is 200 Pa, the conductance C2 of the pipe 202 is as described above. From the formula (1), C2 = 1349 × (0.03 ⁴ /0.1)×200=2.18 m ³ / s. That is, in the pipe 202, when the diameter D12 (0.03 m) of the gas flow path is the same and the length L12 of the gas flow path is increased from 0.01 m to 0.1 m, the conductance C2 is 21.8 m ³ / It becomes small from 2.s to 2.18 m ³ / s, and it becomes difficult to flow.

  And when length L12 of the gas flow path of the piping 202 is 0.01 m, the synthetic conductance C3 of the piping 201 and the piping 202 is calculated | required by following Formula (2).

C3 = 1 / ((1 / C1) + (1 / C2)) (2)
Therefore, according to the above equation (2), the combined conductance C3 between the pipe 201 and the pipe 202 when the length L12 of the gas flow path of the pipe 202 is 0.01 m is C3 = 1 / (0.185 × 10 ⁵ +0 .458 × 10 ⁻¹ ). Here, 0.458 × 10 ⁻¹ (the term of C2 in the above formula (2)) is a very small value with respect to 0.185 × 10 ⁵ (the term of C1 in the above formula (2)). Can be ignored. Therefore, when the gas flow path length L12 of the pipe 202 is 0.01 m, the combined conductance C3 between the pipe 201 and the pipe 202 is C3≈5.4 × 10 ⁻³ m ³ / s.

Further, the combined conductance C3 of the pipe 201 and the pipe 202 when the length L12 of the gas flow path of the pipe 202 is 0.1 m is C3 = 1 / (0.185 × 10 ⁵ +0 by the above equation (2). .458). Also in this case, as in the case where the length L12 of the gas flow path of the pipe 202 is 0.01 m, 0.458 (the term of C2 in the above formula (2)) is 0.185 × 10 ⁵ (the above formula). Since it is a very small value with respect to the term (C1 in (2)), it can be ignored. Therefore, the combined conductance C3 between the pipe 201 and the pipe 202 when the length L12 of the gas flow path of the pipe 202 is 0.1 m is a pipe when the length L12 of the gas flow path of the pipe 202 is 0.01 m. Similar to the combined conductance C3 of 201 and the pipe 202, C3≈5.4 × 10 ⁻³ m ³ / s.

  From the calculation result of the synthetic conductance described above, in the pipe structure in which the pipe 201 and the pipe 202 are connected, by making the conductance of the pipe 202 larger than the conductance of the pipe 201, the length L12 of the gas flow path of the pipe 202 is obtained. Even if it is increased, it can be said that the combined conductance C3 of the pipe 201 and the pipe 202 has substantially the same value. This is because, even when the length L12 of the gas flow path of the pipe 202 is increased, for example, the pipe 201 located near one end of the gas flow path of the pipe 202 and the one end of the gas flow path of the pipe 202 are far from each other. It means that the ease of gas flow is substantially the same with the pipe 201 at the position.

  Therefore, in the first embodiment in which the conductances of the main part 14b of the exhaust gas flow path and the main part 24b of the supply gas flow path are larger than the conductances of the gas discharge opening 14a and the gas supply nozzle 24a, respectively, When the length of the gas flow path of the main part 14b of the gas flow path (main part 24b of the supply gas flow path) is increased, the gas located in a predetermined region close to the vacuum exhaust equipment 9 (source gas supply source 8) Gas located in a region where the amount of gas discharged (supplied) by the discharge opening 14a (gas supply nozzle 24a) and the distance from the vacuum exhaust equipment 9 (raw material gas supply source 8) is farther than a predetermined region It can be said that variation in the amount of gas discharged (supplied) by the discharge opening 14a (gas supply nozzle 24a) can be suppressed.

  In the first embodiment, the lower electrode 4 includes a gas discharge plate 14 having a plurality of gas discharge openings 14a, a gas supply plate 24 having a plurality of gas supply nozzles 24a, and a lower plate 34. The gas exhaust plate 14 and the gas supply plate 24 constitute the main part 14b of the exhaust gas flow path, and the gas supply plate 24 and the lower plate 34 supply gas. By configuring the main portion 24b of the flow path, the gas exhaust opening 14b can be easily connected to the main portion 14b of the exhaust gas flow path, and the gas supply nozzle 24b is connected to the supply gas flow path. Can be connected to the main part 24b.

  In the first embodiment, the upper electrode 3 is configured to be swingable in a direction (direction A) parallel to the surface of the lower electrode 4 by the swing mechanism 5. Since the substrate 10 held by the upper electrode 3 can be swung by swinging the electrode 3, the nozzle for gas supply of the lower electrode 4 constituting the source gas supply unit is swung by the swing of the substrate 10. 24a can be averagely distributed with respect to the surface of the substrate 10 during film formation. Thereby, the thickness of the film formed by depositing the film-forming species generated by the decomposition of the source gas on the substrate 10 can be made uniform.

  In the first embodiment, the gas supply nozzle 24a and the center of the gas discharge opening 14a are arranged coaxially so that the center substantially coincides with the gas discharge opening 14a. The gas can be supplied by the gas supply nozzle 24a while discharging the gas.

  Next, a plasma processing method for forming a predetermined film on the substrate 10 by the plasma processing apparatus 1 according to the first embodiment will be described with reference to FIGS.

  First, as shown in FIG. 1, after fixing the substrate 10 to the upper electrode 3 of the plasma processing apparatus 1, the inside of the vacuum chamber 2 is evacuated by the high vacuum evacuation equipment 7 connected to the exhaust port 2 a of the vacuum chamber 2. .

  Next, a source gas is supplied to a region 1 a between the upper electrode 3 and the lower electrode 4 from a plurality of gas supply nozzles 24 a of the lower electrode 4 connected to the source gas supply source 8. At this time, in the first embodiment, as shown in FIG. 3, the source gas is supplied to the gas supply nozzle 24a via the main portion 24b of the supply gas flow path having a conductance larger than the conductance of the gas supply nozzle 24a. Supplied.

  Then, as shown in FIG. 1, plasma is generated in a region 1 a between the upper electrode 3 and the lower electrode 4 by supplying high-frequency power to the lower electrode 4. As a result, the source gas is decomposed by the plasma, and a film formation seed is generated. At this time, in the region 1a between the upper electrode 3 and the lower electrode 4, an unreacted gas (raw material gas) that is not decomposed by plasma and a negative gas generated by the decomposition of the raw material gas by the plasma, in addition to the film formation species There are ions and malignant radicals. There are also fine particles (flakes) produced by the polymerization reaction.

  At this time, in the first embodiment, in the lower electrode 4, while supplying the raw material gas from the gas supply nozzle 24a, the plurality of gas discharge openings 14a allows unreacted gas (raw material gas), negative ions, malignant radicals. And aspirate flakes. At this time, in the first embodiment, since the gas supply nozzle 24a is disposed inside each of the plurality of gas discharge openings 14a, unreacted gas (raw material gas) discharged by the gas discharge openings 14a. ), The amount of negative ions, malignant radicals, and flakes can be suppressed from varying depending on the region. Further, as shown in FIG. 3, unreacted gas (raw material gas), negative ions, malignant radicals and flakes sucked by the gas discharge opening 14a have conductance larger than the conductance of the gas discharge opening 14a. It is discharged through the main part 14b of the exhaust gas flow path.

  As shown in FIG. 1, unreacted gas (raw material gas), negative ions, malignant radicals and flakes are also discharged through the exhaust port 2 a of the vacuum chamber 2.

  Thereafter, a film formation species generated by the decomposition of the source gas by plasma is deposited on the substrate 10, whereby a predetermined film (not shown) is formed on the substrate 10.

  At this time, in the first embodiment, the upper electrode 3 (substrate 10) is swung in the direction parallel to the surface of the lower electrode 4 (direction A) (see FIGS. 1 and 2) by the swing mechanism 5. However, a film-forming species may be deposited on the substrate 10.

  Next, a description will be given of an experiment conducted to confirm the effect relating to the variation in film thickness and film quality of the first embodiment. In this confirmation experiment, a microcrystalline Si film is formed on a substrate 10 using the plasma processing apparatus 1 according to the first embodiment shown in FIG. 1, and each of the thickness and quality of the microcrystalline Si film is formed. Variation was measured. In this confirmation experiment, the ratio (Ic / Ia) between the Raman spectrum intensity of the amorphous component (Ia) of the microcrystalline Si film and the Raman spectrum intensity of the crystalline component (Ic) is used as the film quality of the microcrystalline Si film. It was measured.

Example 1
When forming the microcrystalline Si film according to Example 1, the plasma processing apparatus 1 shown in FIG. 1 was used and the lower electrode 4 similar to the lower electrode 4 shown in FIGS. 2 and 3 was used. . That is, in forming the microcrystalline Si film according to Example 1, the lower electrode 4 in which the gas supply nozzle 24a is disposed inside each of the plurality of gas discharge openings 14a is used.

And the magnitude | size of the upper electrode 3 and the lower electrode 4 was set to 600 mm square, respectively, and the distance between the board | substrate 10 hold | maintained at the upper electrode 3 and the lower electrode 4 was set to 15 mm. Further, the cross-sectional area of the gas flowing through the gas discharge opening 14a was set to 6.2 mm ² , and the cross-sectional area of the gas flowing through the gas supply nozzle 24a was set to 0.5 mm ² . The distance L1 between the gas supply plate 24 and the gas discharge plate 14 is set to 20 mm so that the conductance of the main portion 14b of the exhaust gas flow path is larger than the conductance of the gas discharge opening 14a. . Further, the cross-sectional area of the main portion 24b of the supply gas flow path was set to about 49 mm ² so that the conductance of the main portion 24b of the supply gas flow path is larger than the conductance of the gas supply nozzle 24a. Further, the gas discharge openings 14a (gas supply nozzles 24a) were arranged in a matrix at a pitch P1 of 10 mm. In addition, the number of gas discharge openings 14a (gas supply nozzles 24a) was set to 3721 (61 × 61).

  Then, two types of glass substrates of 100 mm square and 500 mm square are prepared as the substrate 10, and a microcrystalline Si film is formed on the surface of each of the two types of glass substrates under the formation conditions shown in Table 1 below. did.

上記表１を参照して、実施例１による微結晶系Ｓｉ膜を形成する際には、周波数、投入電力、圧力、基板温度および形成時間を、それぞれ、４０ＭＨｚ、５００Ｗ、６６５Ｐａ、２３０℃および３０分に設定した。また、実施例１による微結晶系Ｓｉ膜を形成する際の原料ガス流量を、ＳｉＨ_４ガス：６５ｓｃｃｍおよびＨ_２ガス：３０００ｓｃｃｍに設定した。

Referring to Table 1 above, when forming the microcrystalline Si film according to Example 1, the frequency, input power, pressure, substrate temperature, and formation time were set to 40 MHz, 500 W, 665 Pa, 230 ° C., and 30 respectively. Set to minutes. The raw material gas flow rates when forming the microcrystalline Si film according to Example 1 were set to SiH ₄ gas: 65 sccm and H ₂ gas: 3000 sccm.

  In forming the microcrystalline Si film according to Example 1, the film was formed without swinging the upper electrode 3 (substrate 10).

(Example 2)
When forming the microcrystalline Si film according to the second embodiment, unlike the first embodiment, the upper electrode 3 (substrate 10) is parallel to the surface of the lower electrode 4 (direction A) (FIG. 1). Further, the film was formed while being swung in the manner shown in FIG. At this time, the rocking width was set to 100 mm and the rocking speed was set to 5 mm / sec. Further, when forming the microcrystalline Si film according to Example 2, the same lower electrode 4 as that used when forming the microcrystalline Si film according to Example 1 was used.

  Then, two types of glass substrates of 100 mm square and 500 mm square are prepared as the substrate 10, and a microcrystalline Si film is formed on the surface of each of the two types of glass substrates under the formation conditions shown in Table 1 above. did.

(Comparative Example 1)
Next, as a comparative example for Examples 1 and 2 described above, a microcrystalline Si film according to Comparative Example 1 was formed using the plasma processing apparatus 301 shown in FIG. Further, when forming the microcrystalline Si film according to Comparative Example 1, the lower electrode 304 as shown in FIGS. 6 and 7 was used. Specifically, the lower electrode 304 used for forming the microcrystalline Si film according to Comparative Example 1 is a gas supply plate having a plurality of gas supply openings 314a (diameter: D21) as shown in FIG. 314 and a lower plate 324. Further, the gas supply plate 314 and the lower plate 324 are arranged at a predetermined interval. A space region between the gas supply plate 314 and the lower plate 324 is a main portion 314b of the supply gas flow path through which the supply gas supplied by the plurality of gas supply openings 314a flows. As shown in FIG. 6, the plurality of gas supply openings 314a are arranged in a matrix at a predetermined pitch P21.

  In Comparative Example 1, the diameter D21 of the gas supply opening 314a was set to 1.2 mm. The pitch P21 of the plurality of gas supply openings 314a arranged in a matrix was set to 10 mm. The number of gas supply nozzles 314a was set to 3721 (61 × 61). Further, the distance between the substrate 310 and the lower electrode 304 was set to 15 mm. The size of each of the upper electrode 303 and the lower electrode 304 was set to 600 mm square.

  Then, two types of glass substrates of 100 mm square and 500 mm square are prepared as the substrate 310, and a microcrystalline Si film is formed on the surface of each of the two types of glass substrates under the formation conditions shown in Table 1 above. did.

(Common to Examples 1 and 2 and Comparative Example 1)
Next, for the microcrystalline Si films according to Examples 1 and 2 and Comparative Example 1 formed as described above, the thickness and quality variations of the microcrystalline Si film were measured. Specifically, for a microcrystalline Si film formed on a 100 mm square glass substrate, the thickness of nine points A1 to I1 and the Raman spectrum intensity ratio of nine points A1 to I1 shown in FIG. (Ic / Ia) was measured, and the average value and standard deviation of the thickness and Raman spectrum intensity ratio at nine points A1 to I1 were calculated. E1 in FIG. 8 is the center of a 100 mm square glass substrate, and L31 in FIG. 8 is 30 mm. For the microcrystalline Si film formed on the 500 mm square glass substrate, the thickness of nine points A2 to I2 shown in FIG. 9 and the Raman spectral intensity ratio (Ic / Ia) was measured, and the average value and standard deviation of the thickness and Raman spectrum intensity ratio at nine points A2 to I2 were calculated. In addition, E2 in FIG. 9 is the center of a 500 mm square glass substrate, and L32 in FIG. 9 is 200 mm. The thicknesses and Raman spectrum intensity ratios of the microcrystalline Si films according to Examples 1 and 2 and Comparative Example 1 are shown in Tables 2 to 7 below.

上記表２、表３、表６および表７を参照して、実施例１と比較例１とを比較した場合、複数のガス排出用開口部１４ａと、複数のガス排出用開口部１４ａの各々の内側に配置されたガス供給用ノズル２４ａとを含む下部電極４を用いた実施例１は、複数のガス供給用開口部３１４ａのみを含む下部電極３０４を用いた比較例１よりも、微結晶系Ｓｉ膜の厚みおよびラマンスペクトル強度比の各々のばらつき（標準偏差）が小さくなることが判明した。具体的には、上記表２に示すように、実施例１による微結晶系Ｓｉ膜（１００ｍｍ角）において、図８に示した９つのポイント（Ａ１〜Ｉ１）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、１４．８および０．７１であった。また、上記表３に示すように、実施例１による微結晶系Ｓｉ膜（５００ｍｍ角）において、図９に示した９つのポイント（Ａ２〜Ｉ２）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、１０．５および０．６６であった。その一方、上記表６に示すように、比較例１による微結晶系Ｓｉ膜（１００ｍｍ角）において、図８に示した９つのポイント（Ａ１〜Ｉ１）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、２２．４および０．９０であった。また、上記表７に示すように、比較例１による微結晶系Ｓｉ膜（５００ｍｍ角）において、図９に示した９つのポイント（Ａ２〜Ｉ２）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、１７．４および０．９０であった。

When comparing Example 1 and Comparative Example 1 with reference to Table 2, Table 3, Table 6, and Table 7, each of the plurality of gas discharge openings 14a and the plurality of gas discharge openings 14a The first embodiment using the lower electrode 4 including the gas supply nozzle 24a disposed inside the microcrystal is more crystalline than the comparative example 1 using the lower electrode 304 including only the plurality of gas supply openings 314a. It has been found that each variation (standard deviation) of the thickness of the Si-based film and the Raman spectrum intensity ratio becomes small. Specifically, as shown in Table 2 above, in the microcrystalline Si film (100 mm square) according to Example 1, the thickness and Raman spectral intensity ratio standard at the nine points (A1 to I1) shown in FIG. The deviations were 14.8 and 0.71, respectively. Further, as shown in Table 3 above, in the microcrystalline Si film (500 mm square) according to Example 1, the standard deviation of the thickness and the Raman spectrum intensity ratio at the nine points (A2 to I2) shown in FIG. They were 10.5 and 0.66, respectively. On the other hand, as shown in Table 6 above, in the microcrystalline Si film (100 mm square) according to Comparative Example 1, the standard deviation of the thickness and the Raman spectrum intensity ratio at the nine points (A1 to I1) shown in FIG. , 22.4 and 0.90, respectively. Further, as shown in Table 7 above, in the microcrystalline Si film (500 mm square) according to Comparative Example 1, the standard deviation of the thickness and the Raman spectrum intensity ratio at the nine points (A2 to I2) shown in FIG. They were 17.4 and 0.90, respectively.

  From this result, in Example 1 using the lower electrode 4 including the plurality of gas discharge openings 14a and the gas supply nozzle 24a disposed inside each of the plurality of gas discharge openings 14a, the gas It is considered that the amount of unreacted gas (raw material gas), negative ions, malignant radicals and flakes discharged through the discharge opening 14a can be suppressed from varying depending on the region. For this reason, in Example 1, since it was possible to suppress the inconvenience that the generation amount of the film forming species generated by the decomposition of the raw material gas was varied, the film forming species was deposited on the glass substrate. It is considered that variation in the thickness of the microcrystalline Si film formed can be suppressed. In addition, since the amount of unreacted gas (raw material gas), malignant radicals and flakes mixed in the microcrystalline Si film formed on the glass substrate could be suppressed, the Raman spectrum intensity ratio (film quality) ) Is considered to have been able to be suppressed.

  As shown in Table 2, the thicknesses of the nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 1 are A1: 692 nm, B1: 703 nm, C1: 674 nm, D1 respectively. : 672 nm, E1: 665 nm, F1: 687 nm, G1: 672 nm, H1: 708 nm and I1: 685 nm. Further, the average value of the thicknesses at the nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 1 was 684.2 nm. In addition, the Raman spectral intensity ratios of nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 1 are A1: 5.7, B1: 5.2, C1: 5.7, D1: 6.2, E1: 7.4, F1: 6.6, G1: 7.1, H1: 6.6 and I1: 6.1. In addition, the average value of the Raman spectrum intensity ratio at the nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 1 was 6.3.

  Further, as shown in Table 3 above, the thicknesses of the nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 1 are A2: 711 nm, B2: 699 nm, C2: 712 nm, D2 respectively. : 698 nm, E2: 682 nm, F2: 706 nm, G2: 709 nm, H2: 697 nm and I2: 716 nm. In addition, the average value of the thickness at the nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 1 was 703.3 nm. In addition, the Raman spectral intensity ratios of nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 1 are A2: 5.6, B2: 5.1, C2: 5.5, respectively. D2: 6.3, E2: 7.1, F2: 6.5, G2: 6.9, H2: 6.4 and I2: 6.2. Further, the average value of the Raman spectrum intensity ratios at the nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 1 was 6.2.

  Further, as shown in Table 6 above, the thicknesses of the nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Comparative Example 1 are A1: 685 nm, B 1: 711 nm, C 1: 682 nm, and D 1, respectively. : 661 nm, E1: 667 nm, F1: 701 nm, G1: 651 nm, H1: 717 nm and I1: 687 nm. Moreover, the average value of the thickness at nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Comparative Example 1 was 684.7 nm. The Raman spectrum intensity ratios of nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Comparative Example 1 are A1: 5.6, B1: 4.9, C1: 5.8, D1: 6.3, E1: 7.5, F1: 6.1, G1: 7.1, H1: 4.8 and I1: 5.7. Further, the average value of the Raman spectrum intensity ratios at the nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Comparative Example 1 was 6.0.

  Further, as shown in Table 7 above, the thicknesses of the nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Comparative Example 1 are A2: 734 nm, B2: 720 nm, C2: 730 nm, D2 respectively. : 708 nm, E2: 682 nm, F2: 709 nm, G2: 733 nm, H2: 702 nm and I2: 728 nm. The average value of the thickness at the nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Comparative Example 1 was 716.2 nm. In addition, the Raman spectrum intensity ratios of nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Comparative Example 1 are A2: 5.2, B2: 4.8, C2: 5.3, respectively. D2: 6.2, E2: 7.1, F2: 6.8, G2: 6.8, H2: 4.8 and I2: 5.6. Moreover, the average value of the Raman spectrum intensity ratio at 9 points A2 to I2 of the microcrystalline Si film (500 mm square) according to Comparative Example 1 was 5.8.

  Next, referring to Table 2, Table 3, Table 4, and Table 5, when Example 1 and Example 2 are compared, the upper electrode 3 (glass substrate) of the plasma processing apparatus 1 is swung. The second embodiment in which the microcrystalline Si film is formed is more microcrystalline Si film than the first embodiment in which the microcrystalline Si film is formed without swinging the upper electrode 3 (glass substrate) of the plasma processing apparatus 1. It was found that the variation (standard deviation) of the thickness and Raman spectrum intensity ratio of each of the samples became small. Specifically, as shown in Table 4 above, in the microcrystalline Si film (100 mm square) according to Example 2, the thickness and Raman spectrum intensity ratio standard at the nine points (A1 to I1) shown in FIG. The deviations were 10.3 and 0.59, respectively. Further, as shown in Table 5 above, in the microcrystalline Si film (500 mm square) according to Example 2, the standard deviation of the thickness and the Raman spectrum intensity ratio at the nine points (A2 to I2) shown in FIG. They were 9.9 and 0.59, respectively. On the other hand, as shown in Table 2 above, in the microcrystalline Si film (100 mm square) according to Example 1, the standard deviation of the thickness and Raman spectrum intensity ratio at the nine points (A1 to I1) shown in FIG. Were 14.8 and 0.71, respectively. Further, as shown in Table 3 above, in the microcrystalline Si film (500 mm square) according to Example 1, the standard deviation of the thickness and the Raman spectrum intensity ratio at the nine points (A2 to I2) shown in FIG. Were 10.5 and 0.66, respectively.

  From these results, in Example 2 in which the microcrystalline Si film was formed while the upper electrode 3 of the plasma processing apparatus 1 was swung, the glass substrate on which the film-forming species was deposited was swung. It can be considered that the deposition amount of the film-forming species in the sample was more uniform than in Example 1.

  As shown in Table 4, the thicknesses of the nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 2 are A1: 688 nm, B1: 697 nm, C1: 676 nm, and D1 respectively. : 678 nm, E1: 672 nm, F1: 672 nm, G1: 678 nm, H1: 698 nm and I1: 691 nm. Moreover, the average value of the thickness at nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 2 was 683.3 nm. In addition, the Raman spectrum intensity ratios of nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 2 are respectively A1: 5.6, B1: 5.3, C1: 5.6, D1: 6.1, E1: 6.9, F1: 6.5, G1: 6.9, H1: 6.5 and I1: 6.5. The average value of the Raman spectrum intensity ratios at the nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 2 was 6.2.

  Further, as shown in Table 5 above, the thicknesses of the nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 2 are A2: 712 nm, B2: 701 nm, C2: 705 nm, D2 respectively. : 696 nm, E2: 682 nm, F2: 705 nm, G2: 706 nm, H2: 695 nm and I2: 715 nm. The average value of the thickness at the nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 2 was 701.9 nm. In addition, the Raman spectrum intensity ratios of nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 2 are A2: 5.6, B2: 5.3, C2: 5.6, respectively. D2: 6.1, E2: 6.9, F2: 6.5, G2: 6.9, H2: 6.5 and I2: 6.5. In addition, the average value of the Raman spectrum intensity ratios at the nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 2 was 6.2.

(Second Embodiment)
FIG. 10 is a plan view showing a lower electrode of the plasma processing apparatus according to the second embodiment of the present invention. Referring to FIGS. 1 and 10, in the second embodiment, unlike the first embodiment, a plurality of gas discharge openings (gas supply nozzles) are seen in a plan view, and the upper electrode swings. A case will be described in which a predetermined interval is arranged in a row so as to be inclined at a predetermined angle with respect to the moving direction. The configuration other than the lower electrode of the plasma processing apparatus according to the second embodiment is the same as that of the plasma processing apparatus 1 according to the first embodiment shown in FIG.

  In the second embodiment, as shown in FIG. 10, the lower electrode 44 is configured to decompose the unreacted gas (raw material gas) and the raw material gas while supplying the raw material gas into the vacuum chamber 2 (see FIG. 1). The negative ions, malignant radicals, flakes and the like generated by this can be discharged. Similarly to the lower electrode 4 of the first embodiment, the lower electrode 44 includes a gas discharge plate 54, a gas supply plate (not shown), and a lower plate (not shown). . The lower electrode 44 is an example of the “second electrode” in the present invention, and the gas discharge plate 54 is an example of the “first plate” in the present invention.

  In the second embodiment, the gas discharge plate 54 has a plurality of gas discharge openings 54a. The gas discharge opening 54a is an example of the “first nozzle” in the present invention. The plurality of gas discharge openings 54a are inclined by a predetermined angle θ (tan θ = about 0.1) with respect to the swinging direction (A direction) of the upper electrode 3 (see FIG. 1) in plan view. In this way, they are arranged in a row at a pitch P1 of about 10 mm.

  In the second embodiment, the gas supply plate (not shown) has a plurality of gas supply nozzles 64a. The gas supply nozzle 64a is an example of the “second nozzle” in the present invention. The gas supply nozzle 64a has an inner side of each of the plurality of gas discharge openings 54a so that the center of the gas supply nozzle 64a and the center of the gas discharge opening 54a coincide with each other in plan view. Are arranged.

  Further, in the second embodiment, the lower plate (not shown) has a predetermined angle θ (tan θ = tan θ) with respect to the swinging direction (A direction) of the upper electrode 3 (see FIG. 1) in plan view. A plurality of grooves 74a extending in a direction inclined by about 0.1). The plurality of grooves 74a of the lower plate are arranged at a pitch P1 of about 10 mm so as to correspond to the gas supply nozzle 64a.

  In addition, the other structure of the lower electrode 44 of 2nd Embodiment is the same as that of the lower electrode 4 of the said 1st Embodiment. That is, the distance (not shown) between the gas discharge plate 54 and the gas supply plate (not shown) is about 20 mm. The gas discharge opening 54a has an inner diameter D1 of about 3 mm. The gas supply nozzle 64a has an outer diameter D2 (about 1 mm) smaller than an inner diameter D1 (about 3 mm) of the gas discharge opening 54a and an inner diameter D3 of about 0.8 mm. The groove 74a of the lower plate has a depth (not shown) of about 7 mm and a width W1 of about 7 mm.

  Therefore, in the second embodiment, the conductance of the main part (not shown) of the exhaust gas flow path is larger than the conductance of the gas discharge opening 54a, as in the first embodiment. Further, the conductance of the main portion (not shown) of the supply gas flow path is larger than the conductance of the gas supply nozzle 64a.

  In the second embodiment, as described above, the lower electrode 44 includes the plurality of gas discharge openings 54a and the gas supply nozzles 64a disposed inside each of the plurality of gas discharge openings 54a. Since the amount of unreacted gas (raw material gas) discharged from the gas discharge opening 54a can be suppressed from varying depending on the region, the raw material gas is decomposed as in the first embodiment. Thus, it is possible to suppress the occurrence of inconvenience that the generation amount of the film forming species generated varies. As a result, as in the first embodiment, it is possible to suppress variation in the thickness of the film formed by depositing the film-forming species on the substrate 10.

  Further, in the second embodiment, the plurality of gas discharge openings 54a (gas supply nozzles 64a) are viewed in a plan view by a predetermined angle θ with respect to the swinging direction (A direction) of the upper electrode 3. A plurality of gas discharge openings 54a (gas supply) arranged in a row are formed by swinging the substrate 10 held by the upper electrode 3 by arranging in a row at a predetermined pitch P1 so as to be inclined. Since gas is supplied and discharged also in a region corresponding to the space between the nozzles 64a), a plurality of gas discharge openings 54a (gas supply) arranged in rows in the film formed on the substrate 10. The film thickness and the film quality are prevented from varying between the region corresponding to the nozzles 64a) and the region corresponding to the rows of the plurality of gas discharge openings 54a (gas supply nozzles 64a) arranged in a row. can do

  The remaining effects of the second embodiment are similar to those of the aforementioned first embodiment.

  Next, the plasma processing method of the second embodiment is the same as the plasma processing method of the first embodiment. However, in the second embodiment, the upper electrode 3 (substrate 10) is swung in a direction parallel to the surface of the lower electrode 44 (direction A) (see FIGS. 1 and 10) by the swing mechanism 5. However, a film-forming species is deposited on the substrate 10.

  Next, a description will be given of an experiment conducted for confirming the effects related to the variation in film thickness and film quality of the second embodiment. In this confirmation experiment, as in the confirmation experiments in Examples 1 and 2 and Comparative Example 1 described above, a microcrystalline Si film was actually formed, and the thickness of the microcrystalline Si film and the Raman spectrum intensity ratio ( Each variation in film quality was measured.

(Example 3)
When forming the microcrystalline Si film according to the third embodiment, in the plasma processing apparatus 1 shown in FIG. 1, a lower electrode 44 similar to the lower electrode 44 shown in FIG. Using. That is, in forming the microcrystalline Si film according to the third embodiment, the gas supply nozzle 64a is disposed inside each of the plurality of gas discharge openings 54a, and the plurality of gas supply nozzles 64a (gas The lower electrodes 44 arranged in rows at predetermined intervals so that the discharge openings 54a) are inclined at a predetermined angle with respect to the swinging direction (A direction) of the upper electrode 3 in plan view. Was used.

  The inclination angle θ of the plurality of gas supply nozzles 64a (gas discharge openings 54a) arranged in a row with respect to the swinging direction (direction A) of the upper electrode 3 is tan θ = 0.1. Set. Further, the gas supply nozzles 64a (gas discharge openings 54a) were arranged at a pitch P1 of 10 mm. The other structure of the lower electrode 44 used when forming the microcrystalline Si film according to Example 3 is the same as that of the lower electrode 4 used when forming the microcrystalline Si film according to Example 1. It produced so that it might become.

  Then, two types of glass substrates of 100 mm square and 500 mm square are prepared as the substrate 10, and a microcrystalline Si film is formed on the surface of each of the two types of glass substrates under the formation conditions shown in Table 1 above. did.

  When forming the microcrystalline Si film according to Example 3, the upper electrode 3 (substrate 10) is in a direction parallel to the surface of the lower electrode 44 (direction A) (see FIGS. 1 and 10). Film formation was performed while rocking. At this time, the rocking width was set to 100 mm and the rocking speed was set to 5 mm / sec.

  Next, for the microcrystalline Si film formed in Example 3 as described above, the thickness of the microcrystalline Si film and the variations in the Raman spectrum intensity ratio (film quality) were measured. The measurement points of the microcrystalline Si film formed on the 100 mm square glass substrate are A1 to I1 shown in FIG. 8 as in Examples 1 and 2 and Comparative Example 1 described above. Further, the measurement points of the microcrystalline Si film formed on the 500 mm square glass substrate are A2 to I2 shown in FIG. 9 as in Examples 1 and 2 and Comparative Example 1 described above. The thickness and Raman spectrum intensity ratio of the microcrystalline Si film according to Example 3 are shown in Table 8 and Table 9 below.

上記表４、表５、表８および表９を参照して、上部電極３（ガラス基板）を揺動させながら微結晶系Ｓｉ膜を形成した実施例２と実施例３とを比較した場合、列状に配置された複数のガス供給用ノズル６４ａ（ガス排出用開口部５４ａ）を上部電極３の揺動方向（Ａ方向）に対して角度θだけ傾斜させた下部電極４４を用いた実施例３は、列状に配置された複数のガス供給用ノズル２４ａ（ガス排出用開口部１４ａ）を上部電極３の揺動方向（Ａ方向）に対して傾斜させていない下部電極４を用いた実施例２よりも、微結晶系Ｓｉ膜の厚みおよびラマンスペクトル強度比の各々のばらつき（標準偏差）が小さくなることが判明した。具体的には、上記表８に示すように、実施例３による微結晶系Ｓｉ膜（１００ｍｍ角）において、図８に示した９つのポイント（Ａ１〜Ｉ１）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、９．７および０．５２であった。また、上記表９に示すように、実施例３による微結晶系Ｓｉ膜（５００ｍｍ角）において、図９に示した９つのポイント（Ａ２〜Ｉ２）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、９．８および０．４９であった。その一方、上記表４に示したように、実施例２による微結晶系Ｓｉ膜（１００ｍｍ角）において、図８に示した９つのポイント（Ａ１〜Ｉ１）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、１０．３および０．５９であった。また、上記表５に示したように、実施例２による微結晶系Ｓｉ膜（５００ｍｍ角）において、図９に示した９つのポイント（Ａ２〜Ｉ２）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、９．９および０．５９であった。

Referring to Table 4, Table 5, Table 8, and Table 9 above, when Example 2 and Example 3 in which a microcrystalline Si film was formed while swinging the upper electrode 3 (glass substrate) were compared, Example using a lower electrode 44 in which a plurality of gas supply nozzles 64a (gas discharge openings 54a) arranged in a row are inclined by an angle θ with respect to the swinging direction (A direction) of the upper electrode 3 3 is an implementation using a lower electrode 4 in which a plurality of gas supply nozzles 24a (gas discharge openings 14a) arranged in a row are not inclined with respect to the swinging direction (A direction) of the upper electrode 3. It was found that the variation (standard deviation) of the thickness of the microcrystalline Si film and the Raman spectral intensity ratio (standard deviation) was smaller than in Example 2. Specifically, as shown in Table 8 above, in the microcrystalline Si film (100 mm square) according to Example 3, the thickness and Raman spectrum intensity ratio standard at the nine points (A1 to I1) shown in FIG. The deviations were 9.7 and 0.52, respectively. Further, as shown in Table 9 above, in the microcrystalline Si film (500 mm square) according to Example 3, the standard deviation of the thickness and Raman spectrum intensity ratio at the nine points (A2 to I2) shown in FIG. They were 9.8 and 0.49, respectively. On the other hand, as shown in Table 4 above, in the microcrystalline Si film (100 mm square) according to Example 2, the standard deviation of the thickness and Raman spectral intensity ratio at the nine points (A1 to I1) shown in FIG. Were 10.3 and 0.59, respectively. Further, as shown in Table 5 above, in the microcrystalline Si film (500 mm square) according to Example 2, the standard deviation of the thickness and the Raman spectrum intensity ratio at the nine points (A2 to I2) shown in FIG. , 9.9 and 0.59, respectively.

  From this result, the lower electrode 44 in which a plurality of gas supply nozzles 64a (gas discharge openings 54a) arranged in a row are inclined by an angle θ with respect to the swinging direction (A direction) of the upper electrode 3 is obtained. In Example 3 used, it is considered that gas was supplied and discharged also in a region corresponding to the space between the plurality of gas supply nozzles 64a (gas discharge openings 54a) arranged in a row. For this reason, in Example 3, in the microcrystalline Si film formed on the glass substrate, a region corresponding to the plurality of gas supply nozzles 64a (gas discharge openings 54a) arranged in a row, and the row The variation in film thickness and Raman spectral intensity ratio (film quality) in the region corresponding to the row of the plurality of gas supply nozzles 64a (gas discharge openings 54a) arranged in a shape is suppressed more than in the second embodiment. It is thought that it was possible.

  As shown in Table 8 above, the thicknesses of the nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 3 are respectively A1: 688 nm, B1: 696 nm, C1: 676 nm, and D1. : 678 nm, E1: 665 nm, F1: 688 nm, G1: 674 nm, H1: 691 nm and I1: 684 nm. The average value of the thickness at the nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 3 was 682.2 nm. In addition, the Raman spectral intensity ratios of nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 3 are A1: 5.7, B1: 5.5, C1: 5.2, D1: 5.9, E1: 6.4, F1: 6.5, G1: 6.5, H1: 6.7 and I1: 6.1. Further, the average value of the Raman spectrum intensity ratios at the nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 3 was 6.1.

  Further, as shown in Table 9 above, the thicknesses of the nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 3 are respectively A2: 709 nm, B2: 703 nm, C2: 711 nm, D2 : 695 nm, E2: 682 nm, F2: 708 nm, G2: 702 nm, H2: 695 nm and I2: 712 nm. The average value of the thickness at the nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 3 was 701.9 nm. In addition, the Raman spectrum intensity ratios of nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 3 are A2: 5.6, B2: 5.5, C2: 5.3, respectively. D2: 5.8, E2: 6.3, F2: 6.6, G2: 6.4, H2: 6.6 and I2: 6.1. In addition, the average value of the Raman spectrum intensity ratios at the nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 3 was 6.0.

(Third embodiment)
FIG. 11 is a cross-sectional view illustrating a lower electrode of a plasma processing apparatus according to a third embodiment of the present invention. Referring to FIGS. 1 and 11, in the third embodiment, unlike the first and second embodiments, an intermediate plate having a plurality of openings is provided in each of the supply gas passage and the exhaust gas passage. The case where it arrange | positions is demonstrated. The configuration other than the lower electrode of the plasma processing apparatus according to the third embodiment is the same as that of the plasma processing apparatus 1 according to the first embodiment shown in FIG.

  In the third embodiment, as shown in FIG. 11, the lower electrode 84 is configured to decompose the unreacted gas (raw material gas) and the raw material gas while supplying the raw material gas into the vacuum chamber 2 (see FIG. 1). The negative ions, malignant radicals, flakes and the like generated by this can be discharged. The lower electrode 84 is an example of the “second electrode” in the present invention. The lower electrode 84 includes a gas discharge plate 94, a gas supply plate 104, and a lower plate 114. The gas discharge plate 94, the gas supply plate 104, and the lower plate 114 are examples of the “first plate”, “second plate”, and “third plate” of the present invention, respectively. In the third embodiment, the lower electrode 84 further includes intermediate plates 121 and 122 in addition to the gas discharge plate 94, the gas supply plate 104, and the lower plate 114 described above.

  In the third embodiment, the gas discharge plate 94 has a plurality of circular gas discharge openings 94a having an inner diameter D1 of about 3 mm. The gas supply opening 94a is an example of the “first nozzle” in the present invention. The plurality of gas discharge openings 94a are arranged in a matrix at a pitch P1 of about 10 mm, like the gas discharge openings 14a of the first embodiment shown in FIG. The gas discharge plate 94 is disposed on the side (uppermost portion) closest to the upper electrode 3 (see FIG. 1) among the three plates (94, 104, and 114) described above.

  Further, in the third embodiment, as shown in FIG. 11, the gas supply plate 104 is formed on the surface side opposite to the upper electrode 3 (see FIG. 1) of the gas discharge plate 94 from the gas discharge plate 94. They are arranged at a predetermined interval. The intermediate plate 121 is disposed between the gas supply plate 104 and the gas discharge plate 94 with a distance L3 of about 20 mm from the gas supply plate 104. A space region between the intermediate plate 121 and the gas supply plate 104 is a main portion 94b of the exhaust gas flow path through which the exhaust gas discharged through the plurality of gas discharge openings 94a flows. The main part 94b of the exhaust gas flow path is an example of the “main part of the first gas flow path” in the present invention.

In the third embodiment, the gas supply plate 104 has a plurality of gas supply nozzles 104a each having a circular pipe shape extending toward the gas discharge plate 94. The gas supply nozzle 104a is an example of the “second nozzle” in the present invention. The pipe-shaped gas supply nozzle 104a has an outer diameter D2 (about 1 mm) smaller than the inner diameter D1 (about 3 mm) of the circular gas discharge opening 94a. The gas supply nozzle 104a has an inner diameter D3 of about 0.8 mm. The cross-sectional area of the gas flowing portion of the gas supply nozzle 104a is πr ² = π × (D3 / 2) ² = about 0.5 mm ² . Further, the gas supply nozzle 104a is arranged inside each of the plurality of gas discharge openings 94a so that the center of the gas supply nozzle 104a and the center of the gas discharge opening 94a are coaxial. Has been placed. Further, the gas supply nozzle 104a is disposed so that the position of the upper surface of the tip of the gas supply nozzle 104a and the position of the upper surface of the gas discharge plate 94 coincide. As a result, the cross-sectional area of the portion of the gas discharge opening 94a through which the gas flows is changed from the cross-sectional area of the gas discharge opening 94a (approximately 7 mm ² ) to the cross-sectional area of the entire gas supply nozzle 104a (πr ² = π × ( D2 / 2) ² = about 0.8 mm ² ) is subtracted (about 6.2 mm ² ). That is, in the third embodiment in which the space region between the gas supply plate 104 and the intermediate plate 121 arranged at an interval of about 20 mm is the main part 94b of the exhaust gas flow path, The conductance of the portion 94b is larger than the conductance of the gas discharge opening 94a having a cross-sectional area of a portion through which a gas of about 6.2 mm ² flows.

In the third embodiment, the intermediate plate 121 has a plurality of openings 121a. The plurality of openings 121a of the intermediate plate 121 are arranged one by one with respect to the four gas discharge openings 94a. The opening 121a of the intermediate plate 121 has a diameter D4 of about 6 mm. The cross-sectional area of the opening 121a of the intermediate plate 121 is πr ² = π × (D4 / 2) ² approximately 28 mm ² . Therefore, in the third embodiment in which the space region between the gas supply plate 104 and the intermediate plate 121 arranged at an interval of about 20 mm is the main part 94b of the exhaust gas flow path, the main part of the exhaust gas flow path The conductance of the portion 94b is larger than the conductance of the opening 121a of the intermediate plate 121.

In the third embodiment, the lower plate 114 is arranged on the surface side of the gas supply plate 104 opposite to the gas discharge plate 94. The intermediate plate 122 is disposed between the lower plate 114 and the gas supply plate 104. Further, the lower plate 114 has a plurality of grooves 114a extending in the swing direction (A direction) of the upper electrode 3 (see FIG. 1). The plurality of grooves 114a of the lower plate 114 are arranged at a pitch P1 of about 10 mm so as to correspond to the gas supply nozzle 104a, like the grooves 34a of the lower plate 34 of the first embodiment shown in FIG. Has been. The depth L2 of the groove 114a of the lower plate 114 is about 7 mm, and the width (not shown) of the groove 34a is about 7 mm. The groove 114a of the lower plate 114 and the lower surface of the intermediate plate 122 constitute the main portion 104b of the supply gas flow path having a square cross section through which the supply gas supplied from the plurality of gas supply nozzles 104a flows. Has been. That is, the cross-sectional area of the main portion 104b of the supply gas flow path having a square cross section is about 7 mm × about 7 mm = about 49 mm ² . Therefore, in the third embodiment, the conductance of the main portion 104b of the supply gas flow path is larger than the conductance of the gas supply nozzle 104a having a cross-sectional area of a portion through which a gas of about 0.5 mm ² flows. The main part 104b of the supply gas channel is an example of the “main part of the second gas channel” in the present invention.

In the third embodiment, the intermediate plate 122 has a plurality of openings 122a. The plurality of openings 122a of the intermediate plate 122 are arranged one by one with respect to the four gas supply nozzles 104a. The opening 122a of the intermediate plate 122 has a diameter D5 of about 3 mm. The cross-sectional area of the opening 122a of the intermediate plate 122 is πr ² = π × (D5 / 2) ² = about 7 mm ² . Therefore, in the third embodiment, the conductance of the main portion 104 b of the supply gas flow path having a cross-sectional area of about 49 mm ² is larger than the conductance of the opening 122 a of the intermediate plate 122.

  In the third embodiment, as described above, the lower electrode 84 includes the plurality of gas discharge openings 94a and the gas supply nozzle 104a disposed inside each of the plurality of gas discharge openings 94a. As in the first embodiment described above, the amount of unreacted gas (raw gas), negative ions, malignant radicals, and flakes discharged from the gas discharge opening 94a is suppressed from varying depending on the region. Therefore, it is possible to suppress the occurrence of inconvenience that the generation amount of the film forming species generated by the decomposition of the source gas varies. As a result, as in the first embodiment, it is possible to suppress variation in the thickness of the film formed by depositing the film-forming species on the substrate 10.

  In the third embodiment, the intermediate plate 121 having a plurality of openings 121a is arranged in the exhaust gas flow path, and the conductance of the main portion 94b of the exhaust gas flow path is set to be the conductance of the opening 121a of the intermediate plate 121. Even if the length of the gas flow path of the main portion 94b of the exhaust gas flow path is increased by increasing the size of the exhaust gas flow path, the opening 121a of the intermediate plate 121 located in a predetermined area close to the vacuum exhaust equipment 9 and the exhaust gas The combined conductance between the main portion 94b of the flow path and the combined conductance between the opening portion 121a of the intermediate plate 121 and the main portion 94b of the exhaust gas flow path located in a region far from the predetermined region from the vacuum exhaust equipment 9. It is possible to suppress the variation. Thereby, when the length of the gas flow path of the main part 94b of the exhaust gas flow path is increased, the gas discharged through the opening 121a of the intermediate plate 121 located in a predetermined region near the vacuum exhaust equipment 9 And the amount of gas exhausted through the opening 121a of the intermediate plate 121 located in a region far from the predetermined region can be suppressed. As a result, the amount of gas discharged by the gas discharge opening 94a corresponding to the opening 121a of the intermediate plate 121 located in a predetermined region close to the vacuum exhaust equipment 9 and the distance from the vacuum exhaust equipment 9 are predetermined. It is possible to suppress the variation in the amount of gas discharged by the gas discharge opening 94a corresponding to the opening 121a of the intermediate plate 121 located in a region farther from the region than in the first embodiment.

  In the third embodiment, the intermediate plate 122 having a plurality of openings 122a is arranged in the supply gas flow path, and the conductance of the main part 104b of the supply gas flow path is set to be the conductance of the opening 122a of the intermediate plate 122. Even if the length of the gas flow path of the main part 104b of the supply gas flow path is increased, the supply with the opening 122a of the intermediate plate 122 located in a predetermined region near the source gas supply source 8 is performed. The synthetic conductance with the main part 104b of the gas flow path, and the opening 122a of the intermediate plate 122 and the main part 104b of the supply gas flow path located in a region far from the predetermined region from the source gas supply source 8. It is possible to suppress variation in the synthetic conductance. Thereby, when the length of the gas flow path of the main part 104b of the supply gas flow path is increased, the gas is supplied through the opening 122a of the intermediate plate 122 located in a predetermined region near the source gas supply source 8. Variations in the amount of gas and the amount of gas supplied through the opening 122a of the intermediate plate 122 located in a region far from the predetermined region from the source gas supply source 8 can be suppressed. . As a result, the amount of gas supplied by the gas supply nozzle 104a corresponding to the opening 122a of the intermediate plate 122 located in a predetermined region near the source gas supply source 8 and the distance from the source gas supply source 8 are predetermined. It is possible to further suppress the variation in the amount of gas supplied by the gas supply nozzle 104a corresponding to the opening 122a of the intermediate plate 122 located in a region farther from the region than in the first embodiment.

  Other effects of the third embodiment are the same as those of the first embodiment.

  Next, the plasma processing method of the third embodiment is the same as the plasma processing method of the first embodiment. However, in the plasma processing method of the third embodiment, when the source gas is supplied from the gas supply nozzle 104a, the opening 122a of the intermediate plate 122 having a conductance smaller than the conductance of the main part 104b of the supply gas flow path. Then, the source gas is supplied from the main part 104b of the supply gas flow path to the gas supply nozzle 104a. In the plasma processing method of the third embodiment, the exhaust gas sucked by the gas discharge opening 94a passes through the opening 121a of the intermediate plate 121 having a conductance smaller than the conductance of the main portion 94b of the exhaust gas flow path. To reach the main portion 94b of the exhaust gas flow path.

  Next, a description will be given of an experiment conducted for confirming the effects relating to the variations in film thickness and film quality of the third embodiment. In this confirmation experiment, as in the confirmation experiments in Examples 1 and 2 and Comparative Example 1 described above, a microcrystalline Si film was actually formed, and the thickness of the microcrystalline Si film and the Raman spectrum intensity ratio ( Each variation in film quality was measured.

Example 4
When forming the microcrystalline Si film according to the fourth embodiment, in the plasma processing apparatus 1 shown in FIG. 1, a lower electrode 84 similar to the lower electrode 84 shown in FIG. Using. That is, in forming the microcrystalline Si film according to the fourth embodiment, the gas supply nozzle 104a is disposed inside each of the plurality of gas discharge openings 94a, and the supply gas flow path and the exhaust gas flow path are provided. In addition, the lower electrode 84 in which the intermediate plates 122 and 121 are disposed is used.

And the magnitude | size of the upper electrode 3 and the lower electrode 84 was set to 600 mm square, respectively, and the distance between the board | substrate 10 hold | maintained at the upper electrode 3 and the lower electrode 44 was set to 15 mm. In addition, the cross-sectional area of the gas flowing through the gas discharge opening 94a was set to 6.2 mm ² , and the cross-sectional area of the gas flowing through the gas supply nozzle 104a was set to 0.5 mm ² . Further, the distance L3 between the gas supply plate 104 and the intermediate plate 121 was set to 20 mm so that the conductance of the main portion 94b of the exhaust gas flow path is larger than the conductance of the gas discharge opening 94a. Further, the cross-sectional area of the main portion 104b of the supply gas flow path was set to 49 mm ² so that the conductance of the main portion 104b of the supply gas flow path was larger than the conductance of the gas supply nozzle 104a. Further, the gas discharge openings 94a (gas supply nozzles 104a) were arranged in a matrix at a pitch P1 of 10 mm. The number of gas discharge openings 94a (gas supply nozzles 104a) was set to 3721 (61 × 61).

Further, the intermediate plate 121 is configured such that one opening 121a is arranged for each of the four gas discharge openings 94a, and one opening 122a is provided for the four gas supply nozzles 104a. The intermediate plate 122 was configured to be arranged one by one. Further, the cross-sectional area of the opening 121a of the intermediate plate 121 was set to 28 mm ² so that the conductance of the main portion 94b of the exhaust gas flow path was larger than the conductance of the opening 121a of the intermediate plate 121. Further, the cross-sectional area of the opening 122a of the intermediate plate 122 was set to 7 mm ² so that the conductance of the main portion 104b of the supply gas flow path was larger than the conductance of the opening 122a of the intermediate plate 122.

  Then, two types of glass substrates of 100 mm square and 500 mm square are prepared as the substrate 10, and a microcrystalline Si film is formed on the surface of each of the two types of glass substrates under the formation conditions shown in Table 1 above. did.

  When forming the microcrystalline Si film according to Example 4, the upper electrode 3 (substrate 10) is swung in a direction parallel to the surface of the lower electrode 84 (direction A) (see FIG. 1). The film formation was performed. At this time, the rocking width was set to 100 mm and the rocking speed was set to 5 mm / sec.

  Next, for the microcrystalline Si film according to Example 4 formed as described above, the thickness of the microcrystalline Si film and the variation in the Raman spectrum intensity ratio (film quality) were measured. The measurement points of the microcrystalline Si film formed on the 100 mm square glass substrate are A1 to I1 shown in FIG. 8 as in Examples 1 and 2 and Comparative Example 1 described above. Further, the measurement points of the microcrystalline Si film formed on the 500 mm square glass substrate are A2 to I2 shown in FIG. 9 as in Examples 1 and 2 and Comparative Example 1 described above. Table 10 and Table 11 below show the thickness and Raman spectrum intensity ratio of the microcrystalline Si film according to Example 4.

上記表４、表５、表１０および表１１を参照して、上部電極３（ガラス基板）を揺動させながら微結晶系Ｓｉ膜を形成した実施例２と実施例４とを比較した場合、供給ガス流路および排出ガス流路に、それぞれ、中間プレート１２２および１２１を配置した下部電極８４を用いた実施例４は、中間プレートを配置していない下部電極４を用いた実施例２よりも、微結晶系Ｓｉ膜の厚みおよびラマンスペクトル強度比の各々のばらつき（標準偏差）が小さくなることが判明した。具体的には、上記表１０に示すように、実施例４による微結晶系Ｓｉ膜（１００ｍｍ角）において、図８に示した９つのポイント（Ａ１〜Ｉ１）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、９．６および０．５２であった。また、上記表１１に示すように、実施例４による微結晶系Ｓｉ膜（５００ｍｍ角）において、図９に示した９つのポイント（Ａ２〜Ｉ２）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、９．０および０．４０であった。その一方、上記表４に示したように、実施例２による微結晶系Ｓｉ膜（１００ｍｍ角）において、図８に示した９つのポイント（Ａ１〜Ｉ１）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、１０．３および０．５９であった。また、上記表５に示したように、実施例２による微結晶系Ｓｉ膜（５００ｍｍ角）において、図９に示した９つのポイント（Ａ２〜Ｉ２）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、９．９および０．５９であった。

Referring to Table 4, Table 5, Table 10, and Table 11, when comparing Example 2 and Example 4 in which the microcrystalline Si film was formed while swinging the upper electrode 3 (glass substrate), The fourth embodiment using the lower electrode 84 in which the intermediate plates 122 and 121 are disposed in the supply gas flow path and the exhaust gas flow path, respectively, is more than the second embodiment in which the lower electrode 4 in which the intermediate plate is not disposed. It has been found that each variation (standard deviation) in the thickness of the microcrystalline Si film and the Raman spectrum intensity ratio becomes small. Specifically, as shown in Table 10 above, in the microcrystalline Si film (100 mm square) according to Example 4, the thickness and Raman spectrum intensity ratio standard at the nine points (A1 to I1) shown in FIG. The deviations were 9.6 and 0.52, respectively. Further, as shown in Table 11 above, in the microcrystalline Si film (500 mm square) according to Example 4, the standard deviation of the thickness and Raman spectrum intensity ratio at the nine points (A2 to I2) shown in FIG. They were 9.0 and 0.40, respectively. On the other hand, as shown in Table 4 above, in the microcrystalline Si film (100 mm square) according to Example 2, the standard deviation of the thickness and Raman spectral intensity ratio at the nine points (A1 to I1) shown in FIG. Were 10.3 and 0.59, respectively. Further, as shown in Table 5 above, in the microcrystalline Si film (500 mm square) according to Example 2, the standard deviation of the thickness and the Raman spectrum intensity ratio at the nine points (A2 to I2) shown in FIG. , 9.9 and 0.59, respectively.

  From this result, in Example 4 using the lower electrode 84 in which the intermediate plates 122 and 121 are arranged in the supply gas passage and the exhaust gas passage, respectively, the intermediate plate located in a predetermined region close to the vacuum exhaust equipment 9 Corresponding to the opening 121a of the intermediate plate 121 located in a region where the amount of gas discharged by the gas discharge opening 94a corresponding to the opening 121a of 121 and the distance from the vacuum evacuation equipment 9 is far from the predetermined region It is considered that the variation in the amount of gas discharged through the gas discharge opening 94a to be performed could be suppressed more than in Example 2. Furthermore, the amount of gas supplied by the gas supply nozzle 104a corresponding to the opening 122a of the intermediate plate 122 located in a predetermined region near the source gas supply source 8 and the distance from the source gas supply source 8 are predetermined. It is considered that variation in the amount of gas supplied by the gas supply nozzle 104a corresponding to the opening 122a of the intermediate plate 122 located in a region farther than the region can be suppressed more than in the second embodiment.

  As shown in Table 10, the thicknesses of the nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 4 are A1: 688 nm, B1: 689 nm, C1: 676 nm, and D1 respectively. : 671 nm, E1: 665 nm, F1: 688 nm, G1: 674 nm, H1: 688 nm and I1: 691 nm. Moreover, the average value of the thickness at the nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 4 was 681.1 nm. In addition, the Raman spectral intensity ratios of nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 4 are A1: 5.7, B1: 5.5, C1: 5.2, respectively. D1: 5.9, E1: 6.4, F1: 6.5, G1: 6.5, H1: 6.7 and I1: 6.1. Further, the average value of the Raman spectrum intensity ratios at the nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 4 was 6.1.

  As shown in Table 11, the thicknesses of the nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 4 are A2: 702 nm, B2: 696 nm, C2: 701 nm, and D2, respectively. : 699 nm, E2: 674 nm, F2: 698 nm, G2: 702 nm, H2: 698 nm and I2: 704 nm. In addition, the average value of the thickness at nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 4 was 697.1 nm. In addition, the Raman spectrum intensity ratios of nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 4 are respectively A2: 5.9, B2: 5.6, C2: 5.3, D2: 5.8, E2: 6.2, F2: 6.2, G2: 6.3, H2: 6.6, and I2: 6.2. In addition, the average value of the Raman spectrum intensity ratio at the nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 4 was 6.0.

(Fourth embodiment)
FIG. 12 is an enlarged cross-sectional view of the periphery of the gas supply nozzle and the gas discharge opening of the lower electrode of the plasma processing apparatus according to the fourth embodiment of the present invention. Referring to FIG. 12, in the fourth embodiment, unlike the first to third embodiments, the tip portion on the inner surface 144 b side of the gas supply nozzle 144 a of the gas supply plate 144 constituting the lower electrode 124. However, it is formed in a sharp shape that is not rounded. Further, the gas supply nozzle 144 a is disposed inside the gas discharge opening 134 a of the gas discharge plate 134 constituting the lower electrode 124. The lower electrode 124 is an example of the “second electrode” in the present invention. The gas discharge plate 134 is an example of the “first plate” in the present invention, and the gas supply plate 144 is an example of the “second plate” in the present invention. The gas discharge opening 134a is an example of the “first nozzle” in the present invention, and the gas supply nozzle 144a is an example of the “second nozzle” in the present invention.

  In addition, the other structure of the lower electrode 124 of 4th Embodiment is the same as that of the lower electrode 4 of the said 1st Embodiment. The configuration of the plasma processing apparatus according to the fourth embodiment other than the lower electrode 124 is the same as that of the plasma processing apparatus 1 according to the first embodiment shown in FIG.

  In the fourth embodiment, as described above, the tip on the inner surface 144b side of the gas supply nozzle 144a is formed in a sharp shape that is not rounded, so that the tip on the inner surface 144b is not rounded. The source gas supplied from the gas supply nozzle 144a formed in a sharp shape is compared with the case where no vortex is generated due to the vortex generated in the vicinity of the tip portion formed in the sharp shape that is not rounded. Since the mixing is further promoted, the source gas can be uniformly dispersed in the region 1a where the plasma is generated. Thereby, the source gas supplied from the gas supply nozzle 144a can be uniformly decomposed in the region 1a where the plasma is generated. In addition, the raw material gas supplied from the gas supply nozzle 144a is further promoted to be mixed by the vortex generated in the vicinity of the tip portion formed in a non-rounded sharp shape as compared with the case where no vortex is generated. Therefore, the residence time of the source gas in the region 1a where plasma is generated can be increased. As a result, the amount of film formation species generated by decomposition of the source gas increases, so that the film formation speed can be increased.

  The remaining effects of the fourth embodiment are similar to those of the aforementioned first embodiment.

  Next, a description will be given of an experiment conducted for confirming the effects related to variations in film thickness and film quality of the fourth embodiment. In this confirmation experiment, as in the confirmation experiments in Examples 1 and 2 and Comparative Example 1 described above, a microcrystalline Si film was actually formed, and the thickness of the microcrystalline Si film and the Raman spectrum intensity ratio ( Each variation in film quality was measured.

(Example 5)
When forming the microcrystalline Si film according to the fifth embodiment, in the plasma processing apparatus 1 shown in FIG. 1, a lower electrode 124 similar to the lower electrode 124 shown in FIG. Using. That is, in the formation of the microcrystalline Si film according to the fifth embodiment, the gas supply nozzle 144a is disposed inside each of the plurality of gas discharge openings 134a, and the inner side surface 144b of the gas supply nozzle 144a. The lower electrode 124 in which the tip on the side was formed in a sharp shape not rounded was used. The other structure of the lower electrode 124 used when forming the microcrystalline Si film according to Example 5 is the same as that of the lower electrode 4 used when forming the microcrystalline Si film according to Example 1. It produced so that it might become.

  Then, two types of glass substrates of 100 mm square and 500 mm square are prepared as the substrate 10, and a microcrystalline Si film is formed on the surface of each of the two types of glass substrates under the formation conditions shown in Table 1 above. did.

  When the microcrystalline Si film according to the fifth embodiment is formed, the upper electrode 3 (substrate 10) is swung in a direction parallel to the surface of the lower electrode 124 (direction A) (see FIG. 1). The film formation was performed. At this time, the rocking width was set to 100 mm and the rocking speed was set to 5 mm / sec.

  Next, for the microcrystalline Si film formed in Example 5 as described above, the thickness of the microcrystalline Si film and the variations in the Raman spectrum intensity ratio (film quality) were measured. The measurement points of the microcrystalline Si film formed on the 100 mm square glass substrate are A1 to I1 shown in FIG. 8 as in Examples 1 and 2 and Comparative Example 1 described above. Further, the measurement points of the microcrystalline Si film formed on the 500 mm square glass substrate are A2 to I2 shown in FIG. 9 as in Examples 1 and 2 and Comparative Example 1 described above. The thickness and Raman spectrum intensity ratio of the microcrystalline Si film according to Example 5 are shown in Table 12 and Table 13 below.

上記表４、表５、表１２および表１３を参照して、上部電極３（ガラス基板）を揺動させながら微結晶系Ｓｉ膜を形成した実施例２と実施例５とを比較した場合、ガス供給用ノズル１４４ａの内側面１４４ｂ側の先端部が、丸みを帯びない尖った形状に形成された下部電極１２４を用いた実施例５は、ガス供給用ノズル２４ａの先端部が、平坦な形状になるように形成された下部電極４を用いた実施例２よりも、微結晶系Ｓｉ膜の厚みおよびラマンスペクトル強度比の各々のばらつき（標準偏差）が小さくなることが判明した。具体的には、上記表１２に示すように、実施例５による微結晶系Ｓｉ膜（１００ｍｍ角）において、図８に示した９つのポイント（Ａ１〜Ｉ１）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、１０．２および０．５５であった。また、上記表１３に示すように、実施例５による微結晶系Ｓｉ膜（５００ｍｍ角）において、図９に示した９つのポイント（Ａ２〜Ｉ２）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、９．７および０．５１であった。その一方、上記表４に示したように、実施例２による微結晶系Ｓｉ膜（１００ｍｍ角）において、図８に示した９つのポイント（Ａ１〜Ｉ１）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、１０．３および０．５９であった。また、上記表５に示したように、実施例２による微結晶系Ｓｉ膜（５００ｍｍ角）において、図９に示した９つのポイント（Ａ２〜Ｉ２）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、９．９および０．５９であった。

When comparing Example 2 and Example 5 in which the microcrystalline Si film was formed while the upper electrode 3 (glass substrate) was swung with reference to Table 4, Table 5, Table 12, and Table 13, In Example 5 using the lower electrode 124 in which the tip on the inner surface 144b side of the gas supply nozzle 144a is formed in a sharp shape not rounded, the tip of the gas supply nozzle 24a has a flat shape. It was found that each variation (standard deviation) in the thickness of the microcrystalline Si film and the Raman spectrum intensity ratio was smaller than in Example 2 using the lower electrode 4 formed so as to be. Specifically, as shown in Table 12 above, in the microcrystalline Si film (100 mm square) according to Example 5, the thickness and Raman spectrum intensity ratio standard at the nine points (A1 to I1) shown in FIG. Deviations were 10.2 and 0.55, respectively. Further, as shown in Table 13, in the microcrystalline Si film (500 mm square) according to Example 5, the standard deviation of the thickness and the Raman spectrum intensity ratio at the nine points (A2 to I2) shown in FIG. They were 9.7 and 0.51, respectively. On the other hand, as shown in Table 4 above, in the microcrystalline Si film (100 mm square) according to Example 2, the standard deviation of the thickness and Raman spectral intensity ratio at the nine points (A1 to I1) shown in FIG. Were 10.3 and 0.59, respectively. Further, as shown in Table 5 above, in the microcrystalline Si film (500 mm square) according to Example 2, the standard deviation of the thickness and the Raman spectrum intensity ratio at the nine points (A2 to I2) shown in FIG. 9.9 and 0.59, respectively.

  From this result, the gas supply nozzle 144a is supplied from the gas supply nozzle 144a in the fifth embodiment in which the tip of the inner surface 144b side of the gas supply nozzle 144a is formed in a sharp shape that is not rounded. Plasma is generated because the raw material gas is promoted to be mixed as compared with the case where the vortex is not generated (Example 2) by the vortex generated in the vicinity of the tip portion formed in the sharp shape not rounded. It is considered that the source gas was uniformly decomposed in the region 1a.

  Further, when comparing Example 2 and Comparative Example 5 in which the microcrystalline Si film was formed while swinging the upper electrode 3 (glass substrate), the tip on the inner side surface 144b side of the gas supply nozzle 144a was The fifth embodiment using the lower electrode 124 formed in a sharp shape not rounded is an embodiment using the lower electrode 4 formed so that the tip of the gas supply nozzle 24a has a flat shape. It was found that the film formation rate (average thickness) was higher than 2. Specifically, as shown in Table 12 above, in the microcrystalline Si film (100 mm square) of Example 5, the average value of the thickness at the nine points (A1 to I1) shown in FIG. It was 6 nm. Further, as shown in Table 13 above, in the microcrystalline Si film (500 mm square) according to Example 5, the average value of the thickness at the nine points (A2 to I2) shown in FIG. 9 was 703.6 nm. It was. On the other hand, as shown in Table 4 above, in the microcrystalline Si film (100 mm square) according to Example 2, the average value of the thickness at the nine points (A1 to I1) shown in FIG. 8 is 683.3 nm. Met. Further, as shown in Table 5 above, in the microcrystalline Si film (500 mm square) according to Example 2, the average value of the thickness at the nine points (A2 to I2) shown in FIG. 9 is 701.9 nm. there were.

  From this result, the gas supply nozzle 144a is supplied from the gas supply nozzle 144a in the fifth embodiment in which the tip of the inner surface 144b side of the gas supply nozzle 144a is formed in a sharp shape that is not rounded. The source gas in the region 1a where the plasma is generated because the source gas is promoted to be mixed by the vortex generated in the vicinity of the tip portion formed in the sharp shape not rounded as compared with the case where the vortex is not generated. It can be considered that the residence time of can be increased. For this reason, in Example 5, since the quantity of the film-forming seed | species produced | generated by decomposition | disassembly of source gas increased, it is thought that the film-forming speed | rate could be enlarged.

  As shown in Table 12, the thicknesses of the nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 5 are A1: 701 nm, B1: 698 nm, C1: 687 nm, and D1. : 686 nm, E1: 671 nm, F1: 697 nm, G1: 678 nm, H1: 698 nm and I1: 690 nm. In addition, the Raman spectral intensity ratios of nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 5 are A1: 5.8, B1: 5.4, C1: 4.8, D1: 5.7, E1: 6.1, F1: 6.1, G1: 6.7, H1: 5.9 and I1: 6.3. Further, the average value of the Raman spectrum intensity ratios at the nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 5 was 5.9.

  As shown in Table 13, the thicknesses of the nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 5 are A2: 711 nm, B2: 699 nm, C2: 712 nm, D2 respectively. : 701 nm, E2: 681 nm, F2: 703 nm, G2: 709 nm, H2: 705 nm and I2: 711 nm. In addition, the Raman spectrum intensity ratios of nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 5 are A2: 5.9, B2: 5.5, C2: 5.1, respectively. D2: 5.6, E2: 6.0, F2: 5.9, G2: 6.8, H2: 6.1 and I2: 6.5. Further, the average value of the Raman spectrum intensity ratios at the nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 5 was 5.9.

(Fifth embodiment)
FIG. 13 is an enlarged cross-sectional view of the periphery of the gas supply nozzle and the gas discharge opening of the lower electrode of the plasma processing apparatus according to the fifth embodiment of the present invention. Referring to FIG. 13, in the fifth embodiment, unlike the first to fourth embodiments, the inner surface 174b of the gas supply nozzle 174a of the gas supply plate 174 constituting the lower electrode 154 has a spiral shape. The groove portion 174c is formed. Further, the gas supply nozzle 174 a is disposed inside the gas discharge opening 164 a of the gas discharge plate 164 constituting the lower electrode 154. The lower electrode 154 is an example of the “second electrode” in the present invention. The gas discharge plate 164 is an example of the “first plate” in the present invention, and the gas supply plate 174 is an example of the “second plate” in the present invention. The gas discharge opening 164a is an example of the “first nozzle” in the present invention, and the gas supply nozzle 174a is an example of the “second nozzle” in the present invention.

  In addition, the other structure of the lower electrode 154 of 5th Embodiment is the same as that of the lower electrode 4 of the said 1st Embodiment. The configuration of the plasma processing apparatus according to the fifth embodiment other than the lower electrode 154 is the same as that of the plasma processing apparatus 1 according to the first embodiment shown in FIG.

  In the fifth embodiment, as described above, the gas supply nozzle in which the spiral groove 174c is formed on the inner surface 174b by forming the spiral groove 174c on the inner surface 174b of the gas supply nozzle 174a. The source gas supplied from 174a is further mixed and promoted by spiral generated vortex compared to the case where vortex is not generated, so that the source gas can be uniformly dispersed in the region 1a where plasma is generated. it can. Thereby, the source gas supplied from the gas supply nozzle 174a can be uniformly decomposed in the region 1a where the plasma is generated. Further, since the raw material gas supplied from the gas supply nozzle 174a is further promoted by the spiral generated spiral as compared with the case where the spiral is not generated, the retention of the raw material gas in the region 1a where the plasma is generated The time can be lengthened. As a result, the amount of film formation species generated by decomposition of the source gas increases, so that the film formation speed can be increased.

  The remaining effects of the fifth embodiment are similar to those of the aforementioned first embodiment.

  Next, an experiment conducted for confirming the effects relating to the film thickness and film quality variations of the fifth embodiment will be described. In this confirmation experiment, as in the confirmation experiments in Examples 1 and 2 and Comparative Example 1 described above, a microcrystalline Si film was actually formed, and the thickness of the microcrystalline Si film and the Raman spectrum intensity ratio ( Each variation in film quality was measured.

(Example 6)
When the microcrystalline Si film according to the sixth embodiment is formed, the lower electrode 154 similar to the lower electrode 154 shown in FIG. 13 is used instead of the lower electrode 4 in the plasma processing apparatus 1 shown in FIG. Using. That is, in the formation of the microcrystalline Si film according to the sixth embodiment, the gas supply nozzle 174a is disposed inside each of the plurality of gas discharge openings 164a, and the inner side surface 174b of the gas supply nozzle 174a. In addition, the lower electrode 154 in which the spiral groove 174c was formed was used. The other structure of the lower electrode 154 used when forming the microcrystalline Si film according to Example 6 is the same as that of the lower electrode 4 used when forming the microcrystalline Si film according to Example 1. It produced so that it might become.

  Then, two types of glass substrates of 100 mm square and 500 mm square are prepared as the substrate 10, and a microcrystalline Si film is formed on the surface of each of the two types of glass substrates under the formation conditions shown in Table 1 above. did.

  When the microcrystalline Si film according to Example 6 is formed, the upper electrode 3 (substrate 10) is swung in a direction parallel to the surface of the lower electrode 154 (direction A) (see FIG. 1). The film formation was performed. At this time, the rocking width was set to 100 mm and the rocking speed was set to 5 mm / sec.

  Next, with respect to the microcrystalline Si film according to Example 6 formed as described above, variations in the thickness of the microcrystalline Si film and the Raman spectrum intensity ratio (film quality) were measured. The measurement points of the microcrystalline Si film formed on the 100 mm square glass substrate are A1 to I1 shown in FIG. 8 as in Examples 1 and 2 and Comparative Example 1 described above. Further, the measurement points of the microcrystalline Si film formed on the 500 mm square glass substrate are A2 to I2 shown in FIG. 9 as in Examples 1 and 2 and Comparative Example 1 described above. The thickness and Raman spectrum intensity ratio of the microcrystalline Si film according to Example 6 are shown in Table 14 and Table 15 below.

上記表４、表５、表１４および表１５を参照して、上部電極３（ガラス基板）を揺動させながら微結晶系Ｓｉ膜を形成した実施例２と実施例６とを比較した場合、ガス供給用ノズル１７４ａの内側面１７４ｂに、螺旋状の溝部１７４ｃが形成された下部電極１５４を用いた実施例６は、ガス供給用ノズル２４ａの内側面に、螺旋状の溝部が形成されていない下部電極４を用いた実施例２よりも、微結晶系Ｓｉ膜の厚みおよびラマンスペクトル強度比の各々のばらつき（標準偏差）が小さくなることが判明した。ただし、ガラス基板のサイズ（５００ｍｍ角）が大きい場合には、微結晶系Ｓｉ膜のラマンスペクトル強度比のばらつき（標準偏差）が同じであった。具体的には、上記表１４に示すように、実施例６による微結晶系Ｓｉ膜（１００ｍｍ角）において、図８に示した９つのポイント（Ａ１〜Ｉ１）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、９．９および０．５９であった。また、上記表１５に示すように、実施例６による微結晶系Ｓｉ膜（５００ｍｍ角）において、図９に示した９つのポイント（Ａ２〜Ｉ２）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、９．７および０．５３であった。その一方、上記表４に示したように、実施例２による微結晶系Ｓｉ膜（１００ｍｍ角）において、図８に示した９つのポイント（Ａ１〜Ｉ１）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、１０．３および０．５９であった。また、上記表５に示したように、実施例２による微結晶系Ｓｉ膜（５００ｍｍ角）において、図９に示した９つのポイント（Ａ２〜Ｉ２）における厚みおよびラマンスペクトル強度比の標準偏差は、それぞれ、９．９および０．５９であった。

When comparing Example 2 and Example 6 in which the microcrystalline Si film was formed while swinging the upper electrode 3 (glass substrate) with reference to Table 4, Table 5, Table 14, and Table 15, In Example 6 using the lower electrode 154 in which the spiral groove 174c is formed on the inner surface 174b of the gas supply nozzle 174a, the spiral groove is not formed on the inner surface of the gas supply nozzle 24a. It was found that the variation (standard deviation) of the thickness of the microcrystalline Si film and the Raman spectrum intensity ratio (standard deviation) was smaller than in Example 2 using the lower electrode 4. However, when the size of the glass substrate (500 mm square) was large, the variation (standard deviation) in the Raman spectrum intensity ratio of the microcrystalline Si film was the same. Specifically, as shown in Table 14 above, in the microcrystalline Si film (100 mm square) according to Example 6, the thickness and Raman spectral intensity ratio standard at the nine points (A1 to I1) shown in FIG. The deviations were 9.9 and 0.59, respectively. Further, as shown in Table 15 above, in the microcrystalline Si film (500 mm square) according to Example 6, the standard deviation of the thickness and Raman spectrum intensity ratio at the nine points (A2 to I2) shown in FIG. They were 9.7 and 0.53, respectively. On the other hand, as shown in Table 4 above, in the microcrystalline Si film (100 mm square) according to Example 2, the standard deviation of the thickness and Raman spectral intensity ratio at the nine points (A1 to I1) shown in FIG. Were 10.3 and 0.59, respectively. Further, as shown in Table 5 above, in the microcrystalline Si film (500 mm square) according to Example 2, the standard deviation of the thickness and the Raman spectrum intensity ratio at the nine points (A2 to I2) shown in FIG. , 9.9 and 0.59, respectively.

  From this result, in Example 6 using the lower electrode 154 in which the spiral groove 174c is formed on the inner surface 174b of the gas supply nozzle 174a, the source gas supplied from the gas supply nozzle 174a is spiral. It is considered that the source gas was uniformly decomposed in the region 1a where the plasma was generated because the mixing was promoted more by the vortex generated in the case of no vortex being generated (Example 2).

  Further, when Example 2 in which a microcrystalline Si film was formed while swinging the upper electrode 3 (glass substrate) was compared with Comparative Example 6, a spiral groove portion was formed on the inner surface 174b of the gas supply nozzle 174a. In Example 6 using the lower electrode 154 in which 174c is formed, the film formation rate is higher than in Example 2 using the lower electrode 4 in which the spiral groove is not formed on the inner surface of the gas supply nozzle 24a. It has been found that (average thickness) increases. Specifically, as shown in Table 14 above, in the microcrystalline Si film (100 mm square) according to Example 6, the average value of the thickness at the nine points (A1 to I1) shown in FIG. It was 2 nm. Further, as shown in Table 15 above, in the microcrystalline Si film (500 mm square) according to Example 6, the average value of the thickness at the nine points (A2 to I2) shown in FIG. 9 was 704.6 nm. It was. On the other hand, as shown in Table 4 above, in the microcrystalline Si film (100 mm square) according to Example 2, the average value of the thickness at the nine points (A1 to I1) shown in FIG. 8 is 683.3 nm. Met. Further, as shown in Table 5 above, in the microcrystalline Si film (500 mm square) according to Example 2, the average value of the thickness at the nine points (A2 to I2) shown in FIG. 9 is 701.9 nm. there were.

  From this result, in Example 6 using the lower electrode 154 in which the spiral groove 174c is formed on the inner surface 174b of the gas supply nozzle 174a, the source gas supplied from the gas supply nozzle 174a is spiral. It is considered that the residence time of the source gas in the region 1a where the plasma is generated can be increased because the mixing is further promoted by the generated vortex compared to the case where the vortex is not generated (Example 2). For this reason, in Example 6, since the quantity of the film-forming seed | species produced | generated by decomposition | disassembly of source gas increased, it is thought that the film-forming speed | velocity could be enlarged.

  As shown in Table 14, the thicknesses of the nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 6 are respectively A1: 695 nm, B1: 692 nm, C1: 705 nm, and D1. : 697 nm, E1: 674 nm, F1: 706 nm, G1: 685 nm, H1: 689 nm and I1: 696 nm. In addition, the Raman spectrum intensity ratios of nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 6 are A1: 5.7, B1: 5.4, C1: 4.7, respectively. D1: 5.5, E1: 6.2, F1: 5.9, G1: 6.8, H1: 5.8 and I1: 6.2. The average value of the Raman spectrum intensity ratios at the nine points A1 to I1 of the microcrystalline Si film (100 mm square) according to Example 6 was 5.7.

  As shown in Table 15, the thicknesses of the nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 6 are A2: 712 nm, B2: 705 nm, C2: 708 nm, and D2, respectively. : 703 nm, E2: 680 nm, F2: 705 nm, G2: 710 nm, H2: 706 nm and I2: 712 nm. In addition, the Raman spectrum intensity ratios of nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 6 are A2: 5.6, B2: 5.5, C2: 5.1, respectively. D2: 5.6, E2: 6.3, F2: 6.1, G2: 6.9, H2: 5.9 and I2: 6.1. Further, the average value of the Raman spectrum intensity ratios at the nine points A2 to I2 of the microcrystalline Si film (500 mm square) according to Example 6 was 5.7.

  The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is shown not by the above description of the embodiments but by the scope of claims for patent, and further includes all modifications within the meaning and scope equivalent to the scope of claims for patent.

  For example, in the first to fifth embodiments, the first nozzle of the present invention is used as a gas discharge nozzle and the second nozzle of the present invention is used as a gas supply nozzle. The first nozzle may be used as a gas supply nozzle, and the second nozzle may be used as a gas discharge nozzle.

  Moreover, in the said 1st-5th embodiment, although comprised so that the position of the upper surface of the front-end | tip part of the nozzle for gas supply might correspond with the position of the upper surface of a gas discharge plate, this invention is not limited to this. The tip of the gas supply nozzle may protrude from the upper surface of the gas discharge plate. For example, as shown in FIG. 14, in the configuration of the first embodiment shown in FIG. 3, the tip of the gas supply nozzle 24 c may protrude from the upper surface of the gas discharge plate 14. With this configuration, plasma can be generated in the vicinity of the protruding tip of the gas supply nozzle 24c, so that the plasma density can be increased. Thereby, since source gas can be decomposed | disassembled efficiently by high-density plasma, more film-forming seed | species can be produced | generated. As a result, the film formation rate can be further increased.

1 is a schematic diagram illustrating a plasma processing apparatus according to a first embodiment of the present invention. It is the top view which showed the lower electrode of the plasma processing apparatus by 1st Embodiment shown in FIG. FIG. 3 is a cross-sectional view taken along line 100-100 in FIG. 2. FIG. 3 is a cross-sectional view taken along line 200-200 in FIG. 2. It is the schematic which showed the piping structure for demonstrating the effect regarding the conductance of 1st Embodiment. 6 is a plan view showing a lower electrode used when forming a microcrystalline Si film according to Comparative Example 1. FIG. It is sectional drawing along the 300-300 line of FIG. It is the top view which showed the measurement point of the thickness of the microcrystal type Si film | membrane formed in confirmation experiment, and a Raman spectrum intensity ratio. It is the top view which showed the measurement point of the thickness of the microcrystal type Si film | membrane formed in confirmation experiment, and a Raman spectrum intensity ratio. It is the top view which showed the lower electrode of the plasma processing apparatus by 2nd Embodiment of this invention. It is sectional drawing which showed the lower electrode of the plasma processing apparatus by 3rd Embodiment of this invention. It is an expanded sectional view of the periphery of the gas supply nozzle and gas discharge opening of the lower electrode of the plasma processing apparatus according to the fourth embodiment of the present invention. It is an expanded sectional view of the periphery of the gas supply nozzle and gas discharge opening of the lower electrode of the plasma processing apparatus according to the fifth embodiment of the present invention. It is sectional drawing which showed the lower electrode of the plasma processing apparatus by the modification of 1st Embodiment. It is the schematic which showed the conventional parallel plate type plasma processing apparatus.

Explanation of symbols

2 Vacuum chamber (plasma processing room)
3 Upper electrode (first electrode)
4, 44, 84, 124, 154 Lower electrode (second electrode)
14, 54, 94, 134, 164 Gas discharge plate (first plate)
14a, 54a, 94a, 134a, 164a Gas discharge opening (first nozzle)
14b, 94b Main part of exhaust gas flow path (main part of first gas flow path)
24, 104, 144, 174 Gas supply plate (second plate)
24a, 64a, 104a, 144a, 174a Gas supply nozzle (second nozzle)
24b, 104b Main part of supply gas flow path (main part of second gas flow path)
34, 114 Lower plate (third plate)
121, 122 Intermediate plate 121a, 122a Opening portion 144b, 174b Inner surface 174c Groove portion

Claims (7)

A first electrode installed in the plasma processing chamber and capable of holding a substrate;
Wherein disposed so as to face the first electrode in a plasma processing chamber, and a second electrode including a second nozzle disposed inside each of the previous SL plurality of first nozzles,
When the first nozzle discharges the gas and the second nozzle supplies the gas, the first nozzle supplies the main portion of the first gas flow path serving as an exhaust gas flow path, and the second nozzle supplies Connected to the main part of the second gas flow path, which is the gas flow path,
When the first nozzle supplies gas and the second nozzle discharges gas, the first nozzle discharges to the main part of the second gas flow path that becomes a supply gas flow path, and the second nozzle discharges. It is connected to the main part of the first gas flow path that becomes the gas flow path,
The cross-sectional area of at least one of the main part of the first gas flow path and the main part of the second gas flow path is larger than the cross-sectional area of at least one of the corresponding first nozzle and second nozzle,
The second electrode includes a first plate having the plurality of first nozzles, a second plate having the plurality of second nozzles disposed on one surface side of the first plate, and the second plate. A third plate disposed on the surface side opposite to the first plate,
The main part of the first gas flow path is provided between the first plate and the second plate, and the main part of the second gas flow path is the second plate and the third plate. Between
A first intermediate plate disposed in the first gas flow path and having a plurality of openings; and a second intermediate plate disposed in the second gas flow path and having a plurality of openings;
The opening of the intermediate plate is arranged one by one for each of at least one of the first nozzle and the second nozzle,
The plasma processing apparatus, wherein a cross-sectional area of a main part of the first gas flow path is larger than a cross-sectional area of an opening of the first intermediate plate.   2. The plasma processing apparatus according to claim 1, wherein a cross-sectional area of a main part of the second gas flow path is larger than a cross-sectional area of an opening of the second intermediate plate.   The plasma processing apparatus according to claim 1, wherein the first electrode is configured to be swingable in a direction parallel to a surface of the second electrode.   The plurality of first nozzles and the plurality of second nozzles are arranged at predetermined intervals in a row so as to be inclined at a predetermined angle with respect to a direction in which the first electrode swings in a plan view. The plasma processing apparatus according to claim 3. Wherein it is a case where I Riga scan supply is Ru performed first Nozzle, an inner surface of the first nozzle supplying the gas is carried out,
Said even if the supply of gas is performed by the second nozzle, the inner surface of the front Stories second Nozzle supply gas Ru performed,
The plasma processing apparatus according to claim 1, wherein a spiral groove is formed. Wherein it is a case where I Riga scan supply is Ru performed first Nozzle tip portion of the inner surface side of the first nozzle supplying the gas is carried out,
Said even if the supply of gas is performed by the second nozzle, the tip portion of the inner surface side of the front Stories second Nozzle supply gas Ru performed,
The plasma processing apparatus according to claim 1, wherein the plasma processing apparatus is formed in a sharp shape that is not rounded.   The said 1st nozzle and the said 2nd nozzle are arrange | positioned coaxially so that the center of the said 1st nozzle and the center of the said 2nd nozzle may correspond substantially, The any one of Claims 1-6. The plasma processing apparatus as described.

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