JP3295336B2 - Microwave plasma processing apparatus and plasma processing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a microwave plasma processing apparatus and a plasma processing method. More specifically, the present invention relates to a microwave plasma processing apparatus and a plasma processing method capable of performing high-quality high-speed processing of a large-area substrate at a low temperature and generating uniform plasma with a high density and a large area.

[0002]

2. Description of the Related Art A plasma processing apparatus using a microwave as an excitation source for generating plasma includes a CVD apparatus,
An etching device, an ashing device, and the like are known.

[0003] Such a so-called microwave plasma CV
The film formation using the D apparatus is performed, for example, as follows.
That is, a gas is introduced into a plasma generation chamber and a film formation chamber (processing chamber) of a microwave plasma CVD apparatus, and simultaneously, microwave energy is supplied to generate plasma in the plasma generation chamber, thereby exciting and decomposing the gas. Then, a deposited film is formed on a substrate disposed in a film forming chamber (processing chamber).

[0004] Etching of a substrate to be processed using a so-called microwave plasma etching apparatus is performed, for example, as follows. That is, an etchant gas is guided into the processing chamber of the apparatus, and at the same time, microwave energy is emitted to excite and decompose the etchant gas to generate plasma in the processing chamber, thereby distributing the plasma in the processing chamber. The surface of the substrate to be processed is etched.

[0005] In the microwave plasma processing apparatus,
Since a microwave is used as a gas excitation source, electrons can be accelerated by an electric field having a high frequency, and gas molecules can be efficiently ionized and excited. Therefore, the microwave plasma processing apparatus has the advantages of high gas ionization efficiency, excitation efficiency and decomposition efficiency, relatively easy formation of high-density plasma, and the advantage of high-speed high-quality processing at low temperatures. Have. In addition, since the microwave has a property of transmitting through the dielectric, the plasma processing apparatus can be configured as an electrodeless discharge type, and therefore, there is an advantage that highly clean plasma processing can be performed.

In order to further increase the speed of such a microwave plasma processing apparatus, an electron cyclotron resonance (EC)
R) has been put into practical use. In the case of ECR, when the magnetic flux density is 87.5 mT, the electron cyclotron frequency at which electrons rotate around the lines of magnetic force coincides with the general microwave frequency of 2.45 GHz, and the electrons resonately absorb the microwaves and accelerate. This is a phenomenon in which high-density plasma is generated. In such an ECR plasma processing apparatus, the following four configurations are known as typical configurations of the microwave introduction unit and the magnetic field generation unit.

That is, (i) a microwave propagated through a waveguide is introduced into a cylindrical plasma generation chamber from a facing surface of a substrate to be processed through a transmission window, and is coaxial with a central axis of the plasma generation chamber. (Ii) a microwave transmitted from a waveguide is transmitted from a facing surface of a substrate to be processed into a bell-shaped plasma generating chamber by introducing a diverging magnetic field through an electromagnetic coil provided around the plasma generating chamber. And a magnetic field coaxial with the central axis of the plasma generation chamber is introduced through an electromagnetic coil provided around the plasma generation chamber, and (iii) through a Risitano coil which is a kind of cylindrical slot antenna. A configuration in which microwaves are introduced into the plasma generation chamber from the periphery, and a magnetic field coaxial with the central axis of the plasma generation chamber is introduced through an electromagnetic coil provided around the plasma generation chamber. (Iv) Through the waveguide Transmitted Microwave is introduced from the opposing surface of the substrate to be processed into a cylindrical plasma generation chamber through a flat slot antenna, and a loop-shaped magnetic field parallel to the antenna plane is passed through a permanent magnet provided on the back surface of the flat antenna. There is known a configuration for introducing the same.

As an example of a microwave plasma processing apparatus,
In recent years, a device using an annular waveguide having a plurality of slots formed on an inner surface thereof has been proposed as a uniform and efficient device for introducing microwaves (US Pat. No. 5,487,875). FIG. 1 shows an example of the microwave plasma processing apparatus, and FIG. 2 shows a schematic cross-sectional view of the plasma generation mechanism. 501 is a plasma generation chamber, 502 is a dielectric separating the plasma generation chamber (501) from the atmosphere side, 503 is a slotted endless annular waveguide for introducing microwaves into the plasma generation chamber (501), 504 is Gas introduction means for plasma generation, 5
11 is a processing chamber connected to the plasma generation chamber (501);
12 is a substrate to be processed, 513 is a support of the substrate to be processed (512), 514 is a heater for heating the substrate to be processed (512), 515 is a processing gas introducing means, 516 is an exhaust port,
21 is a block for distributing microwaves to the left and right, 522 is a slot, 523 is a microwave introduced into the annular waveguide (503), 524 is a microwave propagating in the annular waveguide (503), and 525 is a microwave. The microwave leakage wave 526 introduced into the plasma generation chamber (501) through the slot (522) and the dielectric (502) is inserted into the slot (52).
Microwave surface wave 527 propagating through dielectric (502) through 2), plasma 527 generated by leaky wave, 52
Reference numeral 8 denotes a plasma generated by the surface wave.

The generation and processing of plasma are performed as follows. The inside of the plasma generation chamber (501) and the inside of the processing chamber (511) are evacuated via an exhaust system (not shown). Subsequently, the plasma generating gas is supplied to the gas introducing means (50).
The gas is introduced into the plasma generation chamber (501) at a predetermined flow rate via 4). Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted to maintain the inside of the plasma generation chamber (501) at a predetermined pressure. A desired power is supplied from a microwave power supply (not shown) into the plasma generation chamber (501) via the annular waveguide (503). On this occasion,
The microwave (52) introduced into the annular waveguide (503)
3) is divided right and left by a distribution block (521),
It propagates with a longer guide wavelength than free space.又 は or 1 of the guide wavelength of the propagating microwave (524)
/ 4 to the dielectric (5)
The leaked wave (525) introduced into the plasma generation chamber (501) through the (02) generates a plasma (527) near the slot (522). Microwaves incident at an angle equal to or greater than the Brewster angle with respect to a straight line perpendicular to the surface of the dielectric (502) are totally reflected on the surface of the first dielectric (502) and pass through the inside of the dielectric (502). It propagates as a surface wave (526). Plasma (528) is also generated by the electric field exuding from the surface wave (526). At this time, the processing gas is supplied to the processing chamber (51) through the processing gas introduction pipe (515).
When introduced into 1), the processing gas is excited by the generated high-density plasma, and the substrate to be processed (512) placed on the support (513) by the excited gas
Surface is treated. At this time, a processing gas may be introduced from the plasma generating gas introduction means (504) depending on the application.

FIGS. 3 and 4 schematically show the relationship between the annular waveguide 503 and the plasma generation chamber 501. FIG. 3 and 4, the same parts as those in FIGS. 1 and 2 are denoted by the same reference numerals. FIG. 3 is a schematic perspective view, and FIG. 4 is a schematic sectional view. 3 and 4 show only the main parts.

By using such a microwave plasma processing apparatus, the electron temperature 3e can be uniformly applied to a large-diameter space having a diameter of 300 mm or more with a microwave power of 1 kW or more.
V or less, low-temperature high-density plasma with an electron density of 10 ¹² / cm ³ or more can be generated, and the gas can react sufficiently and be supplied to the substrate in an active state, enabling high-quality and high-speed processing even at low temperatures. Become.

[0012]

However, when processing is performed at a low temperature using a microwave plasma processing apparatus that generates a low-temperature and high-density plasma as shown in FIGS. In addition, there is a demand for an apparatus and a method capable of generating higher-density plasma and performing higher-quality processing at lower temperature, for example, film formation, etching or ashing at higher speed.

SUMMARY OF THE INVENTION An object of the present invention is to provide a microwave plasma processing apparatus and a microwave plasma processing apparatus capable of generating a large-area, uniform and high-density plasma with low power and capable of performing high-quality processing at high speed even at a low temperature. Is to provide a way.

[0014]

[0015]

According to the present invention, there is provided a plasma generation chamber having an interior separated from the atmosphere side, and a plurality of slots disposed outside a cylindrical dielectric material constituting the plasma generation chamber. Microwave introducing means having a cylindrical endless annular waveguide, supporting means for a substrate to be processed, gas introducing means for introducing gas into the plasma generation chamber, and exhaust means for exhausting the plasma generation chamber. comprising a, in the microwave plasma processing apparatus that generates plasma by introducing microwaves into the plasma generation chamber through said cylindrical dielectric from said plurality of slots, the cylindrical endless annular waveguide Radius (R _g ), the wavelength of the microwave in the endless annular waveguide (λ _g ), the radius of the cylindrical dielectric (R _s ), and the wavelength of the surface wave propagating in the dielectric (λ _s ) is R _s / λ _s = (2n + 1) The present invention relates to a microwave plasma processing apparatus that substantially satisfies a relationship represented by R _g / λ _g (n is 0 or a natural number).

According to the present invention, there is provided a plasma generation chamber having an interior separated from the atmosphere side, and a first chamber constituting the plasma generation chamber .
Of dielectric and microwave introduction means that having a endless annular waveguide having a disposed are a plurality of slots on the outside of gas to be introduced and the support means of the processed substrate, a gas into the plasma generation chamber < a plasma introduction chamber, and exhaust means for exhausting the plasma generation chamber, wherein the plurality of slots are provided through the first dielectric.
To introduce a microwave into the plasma generation chamber
In the microwave plasma processing apparatus that generates, same or different from the first dielectric in the interior of the annular waveguide
About microwave plasma processing apparatus second dielectric made of a material is characterized in that it is filled.

[0017]

In addition, the present invention provides a plasma generation chamber having an interior separated from the atmosphere side, and a cylindrical chamber having a plurality of slots disposed outside a cylindrical dielectric constituting the plasma generation chamber. Microwave introduction means having an endless annular waveguide, support means for the substrate to be processed, gas introduction means for introducing gas into the plasma generation chamber, and exhaust means for exhausting the plasma generation chamber, the circle from the plurality of slots
Cylindrical with the dielectric using a microwave plasma processing apparatus that generates plasma by introducing microwaves into the plasma generation chamber, the radius of the cylindrical endless annular waveguide (R
_g ), the wavelength of the microwave in the endless annular waveguide (λ _g ), the radius of the cylindrical dielectric (R _s ), and the wavelength of the surface wave propagating in the dielectric (λ _s ) are R _The present invention relates to a microwave plasma processing method for performing plasma processing on a substrate to be processed so as to substantially satisfy a relationship represented by _s / λ _s = (2n + 1) R _g / λ _g (n is 0 or a natural number).

[0019] The present invention comprises a plasma generation chamber inside is isolated from the atmosphere side, constitute the plasma generating chamber
Introducing a microwave introduction means that having a endless annular waveguide having a first dielectric plurality of slots disposed on the outside of that, the supporting means of the processed substrate, a gas into the plasma generation chamber
To the gas introduction means, said plasma generation chamber comprises an exhaust means for exhausting the dielectric of the first from the plurality of slots
A microwave is introduced into the plasma generation chamber through the
A microwave plasma processing apparatus that generates plasma, wherein the inside of the annular waveguide is filled with a second dielectric made of the same or different material as the first dielectric, The present invention relates to a microwave plasma processing method in which the substrate to be processed is mounted and plasma processing is performed.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the drawings.

FIG. 5 shows an example of the microwave plasma processing apparatus of the present invention, and FIG. 6 shows a plasma generation mechanism thereof. 10
1 is a plasma generation chamber, 102 is a plasma generation chamber (10
1) a dielectric which separates from the atmosphere side, 103 is an endless annular waveguide with slots for introducing microwaves into the plasma generation chamber (101), 104 is a plasma generating gas introducing means, and 111 is a plasma generation chamber. Processing chamber connected to 11
2 is a substrate to be processed, 113 is a support for the substrate to be processed (112), 114 is a heater for heating the substrate to be processed (112),
Reference numeral 115 denotes a processing gas introduction unit, and reference numeral 116 denotes an exhaust port.
121 is a block for distributing microwaves to the left and right, 122
Is a slot, 123 is a microwave introduced into the annular waveguide (103), 124 is a microwave propagating in the annular waveguide (103), and 125 is a slot passing through the slot (122) and passing through the dielectric (102). The leakage wave of the microwave introduced into the plasma generation chamber (101) through the through-hole 126 is a slot (1).
22) a microwave surface wave propagating through the dielectric (102) through the dielectric (102);
28 is a plasma generated by the surface wave.

The generation and processing of plasma are performed as follows. The inside of the plasma generation chamber (101) and the inside of the processing chamber (111) are evacuated via an exhaust system (not shown). Subsequently, the plasma generating gas is supplied to the gas introducing means (10
4) and is introduced into the plasma generation chamber (101) at a predetermined flow rate. Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted to maintain the inside of the plasma generation chamber (101) and the inside of the processing chamber (111) at a predetermined pressure. A desired power from a microwave power supply (not shown) is supplied to the plasma generation chamber (1) through the annular waveguide (103).
01) to generate plasma in the plasma generation chamber (101). At this time, the microwave (123) introduced into the annular waveguide (103) is distributed to the distribution block (1).
At 21), the light is split right and left and propagates through the annular waveguide (103). A slot (12) provided for every 1/2 or 1/4 of the guide wavelength of this propagating microwave (124).
2) through the dielectric (102) through the plasma generation chamber (1).
01) is introduced into the slot (1).
22) Generate a nearby plasma (127). Further, the microwave incident on the straight line perpendicular to the surface of the dielectric (102) at an angle equal to or more than the Brewster's angle
2) It is totally reflected on the surface and propagates inside the dielectric (102) as a surface wave (126). Plasma (128) is also generated by the electric field exuding from the surface wave (126).

In the case of the apparatus shown in FIGS. 1 and 2, since the surface wave (526) is not excited during propagation, the generated plasma (528) is thinner than the plasma (527) due to the leaky wave (525). . However, in the case of the device of the present invention shown in FIGS. 5 and 6, the annular waveguide (103) is aligned so that the slot (122) is aligned every half of the wavelength of the surface wave (126). The in-tube wavelength and perimeter are optimized. As a result, the surface wave (126) interferes with the leaky wave (125) from another slot during propagation and is amplified, and the generated plasma (128) becomes denser and more uniform than in the case of the aforementioned device. . At this time, when the processing gas is introduced into the processing chamber (111) through the processing gas introduction pipe (115), the processing gas is excited by the generated high-density plasma, and is supported by the excited gas. The surface of the substrate (112) placed on the body (113) is treated. At this time, a processing gas may be introduced from the plasma generating gas introduction means (104) depending on the application.

In the microwave plasma processing apparatus of the present invention described above, the circumference (L) of the annular waveguide (103) is set.
_g ), the wavelength (λ _g ) of the microwave (124) in the annular waveguide, the perimeter (L _s ) of the dielectric (102), and the wavelength (λ) of the surface wave (126) propagating in the dielectric. _s ) substantially satisfies the relationship represented by L _s / λ _s = (2n + 1) L _g / λ _g (n is 0 or a natural number), so that the microwave surface wave propagating in the dielectric material periodically Excited, more strongly and efficiently propagated, with lower power,
A large area, uniform and high density plasma can be generated. It is preferable that the relationship of the above expression be satisfied within a range of ± 10%.

When the annular waveguide (103) is cylindrical, the center radius (R _g ) of the annular waveguide, the wavelength of the microwave in the annular waveguide (λ _g ), the dielectric Radius (R _s ) and the wavelength (λ _s ) of the surface wave propagating in the dielectric
Substantially satisfies the relationship expressed by R _s / λ _s = (2n + 1) R _g / λ _g (n is 0 or a natural number), whereby the microwave surface wave propagating in the dielectric is periodically excited, Propagating stronger and more efficiently, with lower power,
A large area, uniform and high density plasma can be generated. It is preferable that the relationship of the above expression be satisfied within a range of ± 10%.

FIG. 7 shows another preferred example of the microwave plasma processing apparatus of the present invention, and FIG.
Shown in In FIGS. 7 and 8, the same members as those shown in FIGS. 5 and 6 indicate the same members, and therefore description thereof will be omitted.

In the device shown in FIGS. 7 and 8,
A different point from the above-described device is that an annular waveguide 103 is filled with a second dielectric, separately from a dielectric (first dielectric) 102 that separates the plasma generation chamber 101 from the atmosphere side. .

In the case of the device shown in FIG.
Is not excited during propagation, and the generated plasma 52
8 is thinner than the plasma 527 due to the leaky wave 525, but in the case of the apparatus shown in FIG. 7, the position of the slot 122 is adjusted every half of the wavelength of the surface wave 126.
By optimizing the dielectric constant of the second dielectric 704,
The surface wave 126 is a leakage wave 1 from another slot during propagation.
The plasma 128 which is amplified by interfering with the plasma 25 becomes darker and more uniform than in the case of FIG. At this time, if the processing gas is introduced into the processing gas processing chamber 111 via the processing gas introducing means 115, the processing gas is excited by the generated high-density plasma, and the substrate 112 to be processed placed on the support 113. Treat the surface. In this case as well, a processing gas may be introduced into the plasma generating gas inlet 105 depending on the application.

A desired power from a microwave power supply (not shown) is passed through the first dielectric 102 through the annular waveguide 103 filled with the second dielectric 704 to generate plasma. By supplying the gas into the chamber 101, plasma is generated in the plasma generation chamber 101. At this time, the microwave 123 introduced into the annular waveguide 203 is split right and left by the distribution block 121 and propagates in the second dielectric 704 with a wavelength shorter than free space. Leakage waves 125 introduced into the plasma generation chamber 101 through the first dielectric 102 from the slots 122 provided for every ま た は or の of the guide wavelength pass through the first dielectric 102 from the slots 122. The leaked waves 125 introduced into the plasma generation chamber 101 through the
Generate Further, microwaves incident at an angle equal to or more than the Brewster angle with respect to a straight line perpendicular to the surface of the first dielectric 102 are totally reflected on the surface of the first dielectric 102 and pass through the inside of the first dielectric 102. It propagates as a surface wave 126. The plasma 128 is also generated by the electric field exuding from the surface wave 126.

As described above, inside the annular waveguide,
The first dielectric that separates the plasma generation chamber from the atmosphere is filled with a second dielectric that is the same as or different from the first dielectric. By making it equal to the reciprocal of the square of the ratio of the circumference of the two dielectrics,
Since the microwave surface wave propagating in the first dielectric material is periodically excited, the microwave propagates more strongly and efficiently, and can generate plasma with lower power, larger area, and higher density.

The microwave frequency used in the microwave plasma processing apparatus and the processing method of the present invention is set to 0.
It can be appropriately selected from the range of 8 GHz to 20 GHz.

The shape of the waveguide used in the microwave plasma processing apparatus of the present invention may be cylindrical or other shapes such as a disk or polygon depending on the shape of the plasma generation chamber.

As the dielectric used in the microwave plasma processing apparatus, the processing apparatus and the processing method of the present invention, SiO ₂ -based quartz, various glasses, Si ₃ N ₄ , Na
Cl, LiF, CaF ₂ , BaF ₂ , Al ₂ O ₃ , Al
Films and sheets of inorganic substances such as N and MgO, and organic substances such as polyethylene, polyester, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, and polyimide can be applied.

In the microwave plasma processing apparatus and the processing method of the present invention, a magnetic field generating means may be used for processing at a lower pressure. As a magnetic field used in the microwave plasma processing apparatus and the processing method of the present invention, a mirror magnetic field or the like can be applied. The magnetic flux density of the magnetic field near the slot having lines of magnetic force almost perpendicular to the body is optimally a cusp magnetic field larger than the magnetic flux density of the magnetic field near the substrate. As the magnetic field generating means, a coil, a permanent magnet, or the like can be used. When a coil is used, a cooling means such as a water cooling mechanism or air cooling may be used to prevent overheating. By such a magnetic field generating means, the magnetic field in the vicinity of the slot is set to approximately 3.57 × 1 of the frequency of the microwave.
It is preferable to control the magnetic flux density to 0 ⁻¹¹ (T / Hz) times. It is desirable that the value of this magnification be within ± 10%.

In order to improve the quality of the treatment, the surface of the substrate to be treated may be irradiated with light energy such as ultraviolet light. As a light source, any light source that emits light absorbed by a substrate to be processed or a gas attached to the substrate can be used, and an excimer laser, an excimer lamp, a rare gas resonance line lamp, a low-pressure mercury lamp, and the like are suitable. .

In the microwave plasma processing method of the present invention, the pressure in the plasma generation chamber and the pressure in the processing chamber are usually
From the range of 0.0002 to 10 Torr, especially 1 mTorr to 100 mTorr for film formation and 0.2 mTorr for etching.
r ~ 100mTorr, 100mTorr ~ 1 for ashing
It is preferable to select from the range of 0 Torr.

The formation of a deposited film by the microwave plasma processing method of the present invention can be performed by appropriately selecting a gas to be used, thereby obtaining Si ₃ N ₄ , SiO ₂ , Ta ₂ O ₅ , TiO ₂ , Ti
Insulating film of N, Al ₂ O ₃ , AlN, MgF _2, etc., a-S
i, semiconductor film of poly-Si, SiC, GaAs, etc., A
Various deposited films such as metal films of 1, W, MO, Ti, Ta and the like can be efficiently formed.

The substrate to be processed by the plasma processing method of the present invention may be a semiconductor, a conductive substrate, or an electrically insulating substrate. Further, the present invention can be applied to plastics having low heat resistance.

As the conductive substrate, Fe, Ni, Cr,
Al, MO, Au, Nb, Ta, V, Ti, Pt, Pb
And alloys thereof, such as brass and stainless steel.

Examples of the insulating substrate include SiO ₂ -based quartz and various kinds of glass, Si ₃ N ₄ , NaCl, KCl, LiF, C
inorganic substances such as aF ₂ , BaF ₂ , Al ₂ O ₃ , AlN, MgO, polyethylene, polyester, polycarbonate,
Cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide,
Examples include films and sheets of organic substances such as polyimide.

As the thin film forming gas (processing gas),
Generally known gases can be used. The gas which is easily decomposed by the action of the plasma and can be deposited alone can be provided with a processing gas introducing means in the film forming chamber (processing chamber) in order to achieve a stoichiometric composition and to prevent film deposition in the plasma generating chamber. It is desirable to introduce it into the film forming chamber (processing chamber) through the interface. Further, it is desirable that a gas that is not easily decomposed by the action of the plasma and that is difficult to deposit alone is introduced into the plasma generation chamber via the plasma generation gas conducting means in the plasma generation chamber.

When forming a Si-based semiconductor thin film such as a-Si, poly-Si, SiC, etc., a raw material containing Si atoms introduced through a processing gas introducing means is SiH.
_4, Si ₂ H inorganic silanes such as _6, tetraethyl silane (TES), tetramethylsilane (TMS), organic silanes such as dimethylsilane _{(DMS), SiF 4, Si} 2 F
₆ , SiHF ₃ , SiH ₂ F ₂ , SiCl ₄ , Si ₂ Cl ₆ ,
SiHCl ₃ , SiH ₂ Cl ₂ , SiH ₃ Cl, SiCl ₂
Examples include halosilanes such as F _{2 and the} like, which are in a gaseous state at normal temperature and normal pressure, or those which can be easily gasified. Also,
In this case, the plasma generating gas introduced through the plasma generating gas introducing means includes H ₂ , He, Ne, and A.
r, Kr, Xe, Rn and the like.

When a thin film of a Si compound such as Si ₃ N ₄ or SiO ₂ is formed, the raw material containing Si atoms introduced through a processing gas introducing means may be SiH ₄ , Si ₂ H
Inorganic silanes such as ₆ , tetraethoxysilane (TEO)
S), organic silanes such as tetramethoxysilane (TMOS), octamethylcyclotetrasilane (OMCTS), SiF ₄ , Si ₂ F ₆ , SiHF ₃ , SiH ₂ F ₂ , Si
Cl ₄ , Si ₂ Cl ₆ , SiHCl ₃ , SiH ₂ Cl ₂ , Si
H ₃ Cl, etc. halosilanes such as SiCl ₂ F _2, include those which may be intended or easily gasified gas state at normal temperature and pressure. In this case, the raw materials introduced through the plasma generating gas introducing means include N ₂ , NH ₃ , N ₂
H ₄ , hexamethyldisilazane (HMDS), O ₂ ,
O ₃ , H ₂ O, NO, N ₂ O, NO _{2 and the} like can be mentioned.

In the case of forming a metal thin film of Al, W, Mo, Ti, Ta, etc., as a raw material containing a metal atom to be introduced through a processing gas introduction means, trimethyl aluminum (TMAl), triethyl aluminum ( TEA
l), triisobutylaluminum (TIBAl), dimethylaluminum hydride (DMAIH), tungsten carbonyl (W (CO) ₆ ), molybdenum carbonyl (Mo (CO) ₆ ), trimethylgallium (TM)
Ga), organic metals such as triethylgallium (TEGa), and halogenated metals such as AlCl ₃ , WF ₆ , TiCl ₃ , and TaCl ₅ . In this case, the plasma generating gas introduced through the plasma generating gas introducing means includes H ₂ , He, Ne, Ar, Kr, Xe,
Rn and the like.

Al ₂ O ₃ , AlN, Ta ₂ O ₅ , TiO ₂ ,
When forming a thin film of a metal compound such as TiN or WO ₃ ,
As a raw material containing a metal atom to be introduced via a processing gas introducing means, trimethyl aluminum (TMA
1), triethylaluminum (TEAl), triisobutylaluminum (TIBAl), dimethylaluminum hydride (DMAIH), tungsten carbonyl (W (CO) ₆ ), molybdenum carbonyl (Mo)
(CO) ₆ ), organic metals such as trimethylgallium (TMGa) and triethylgallium (TEGa), AlC
metal halides such as l ₃ , WF ₆ , TiCl ₃ , and TaCl ₅ . In this case, the source gas introduced through the plasma generating gas introduction means includes O ₂ ,
O ₃ , H ₂ O, NO, N ₂ O, NO ₂ , N ₂ , NH ₃ , N
₂ H ₄ and hexamethyldisilazane (HMDS).

When the microwave plasma processing apparatus and the processing method of the present invention are also applied to surface modification, by appropriately selecting a gas to be used, for example, Si, Al, Ti, Using Zn, Ta, or the like, oxidation or nitridation of these substrates or surface layers, and doping of B, As, P, or the like can be performed.

Further, the film forming technique employed in the present invention can be applied to a cleaning method. In this case, it can be used for cleaning oxides, organic substances, heavy metals, and the like.

When the substrate to be treated is subjected to oxidizing surface treatment, the oxidizing gas introduced through the plasma generating gas introducing means may be O ₂ , O ₃ , H ₂ O, NO, N ₂ O, NO _2, etc. Is mentioned. When the substrate is subjected to nitriding surface treatment, N ₂ , NH ₃ , N ₂ H ₄ , hexamethyldisilazane (HMDS) and the like can be mentioned as the nitriding gas introduced through the plasma generating gas introducing means. . In this case, since the film is not formed, the processing gas is not introduced through the processing gas introduction unit, or the same gas as the gas introduced through the plasma generation gas introduction unit is supplied through the processing gas introduction unit. To introduce.

When cleaning the organic substance on the surface of the substrate to be treated, O ₂ , O ₃ , H ₂ O, NO,
N ₂ O, NO _{2 and the} like can be mentioned. Further, when cleaning the inorganic substance on the surface of the substrate to be treated, the cleaning gas introduced from the plasma generating gas introducing means may be F.
₂ , CF ₄ , CH ₂ F ₂ , C ₂ F ₆ , CF ₂ Cl ₂ , SF ₆ , N
F _3, and the like. Also in this case, since the film is not formed, the source gas is not introduced through the film introducing gas introducing means, or the same gas as the gas introduced through the plasma generating gas introducing means is supplied to the film forming gas introducing means. Introduce through.

Hereinafter, the present invention will be described with reference to more specific embodiments. However, the present invention is not limited to these, and can be appropriately modified and combined within the scope of the present invention.

Embodiment 1 A microwave plasma processing apparatus shown in FIGS. 5 and 6, which is an example of the present invention, will be described as an example.

The dielectric (102) is made of quartz having a dielectric constant of 3.8 and has a center diameter of 299 mm. Annular waveguide (10
3), the dimension of the inner wall cross section is s = 27 m in FIG.
m, t = 75 mm, and the center diameter was 335 mm. The material of the annular waveguide (103) is made of stainless steel to maintain mechanical strength, and its inner wall surface is coated with copper to suppress microwave propagation loss, and further coated with silver. Two-layer plating is applied. The annular waveguide (103) has a slot (122) for introducing microwaves into the plasma generation chamber (101). The shape of the slot is a rectangle having a length of 53 mm and a width of 3 mm, and is formed at intervals of 1/4 of the wavelength of the microwave (124) in the annular waveguide (103).
The wavelength (λ _g ) in this annular waveguide depends on the frequency of the microwave used and the dimensions of the cross section of the waveguide, but the microwave having a frequency of 2.45 GHz and the annular waveguide having the above dimensions are used. When used, it is about 210 mm. At this time,
The wavelength (λ _s ) of the surface wave propagating in the dielectric is 63 mm. In the annular waveguide (103) used in this embodiment, 20 slots are formed at intervals of about 52.5 mm. A 4E tuner, a directional coupler, an isolator, and a microwave power supply (not shown) having a frequency of 2.45 GHz are sequentially connected to the annular waveguide (103).

The generation and processing of plasma using the apparatus of this embodiment are performed as follows. The interior of the plasma generation chamber (101) and the processing chamber (11) are evacuated via an exhaust system (not shown).
1) The inside is evacuated. Subsequently, a plasma generation gas is introduced into the plasma generation chamber (101) at a predetermined flow rate via the gas introduction means (104). Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted so as to adjust the inside of the plasma generation chamber (101) and the processing chamber (11).
1) The inside is maintained at a predetermined pressure. Next, a desired power from a microwave power supply (not shown) is passed through the dielectric (102) through the annular waveguide (103), and the plasma generation chamber (10).
1) to generate plasma in the plasma generation chamber (101). At this time, the processing gas introduction means (11
If the processing gas is introduced into the processing chamber (111) through 5), the processing gas is excited by the generated high-density plasma, and the excited gas causes the support (113) to be excited.
The surface of the substrate to be processed (112) placed thereon is processed. At that time, a processing gas may be introduced from the plasma generating gas introduction means (104) depending on the application.

Using the microwave plasma processing apparatus of this embodiment shown in FIG. 5 and FIG.
cm, pressure: 10 mTorr, microwave power: 3.0 kW
Plasma was generated under the following conditions, and the obtained plasma was measured. The plasma was measured by the single probe method as follows. The voltage applied to the probe is
The current flowing through the probe was measured with an IV measuring instrument while changing the voltage in the range of 50 to +50 V, and the electron density, electron temperature, and plasma potential were calculated from the obtained IV curve by the method of Langmuir et al. As a result, the electron density is 3.3 ×
It was 10 ¹² / cm ³ ± 4.1% (within φ200 plane), and it was confirmed that high-density and uniform plasma was formed.

Embodiment 2 Embodiment 1 is the same as Embodiment 1 except that the distance between the center of the plasma generation chamber and the substrate is 100 mm apart from the apparatus of Embodiment 1.
A plasma processing apparatus similar to that described above was manufactured. The apparatus (isolated plasma processing apparatus) of the present embodiment is provided with a substrate supporting means so that the substrate to be processed is arranged at a position separated from the plasma generation region. Here, the “position isolated from the plasma generation region” means a position where the plasma density is preferably 1/10 or less of the densest part. The generation and processing of plasma in the apparatus of the present embodiment can be performed in the same manner as in the first embodiment.

Embodiment 3 FIG. 9 shows an optically assisted microwave plasma processing apparatus as an example of the present invention. 301 is a plasma generation chamber, 302 is a quartz tube (dielectric) that separates the plasma generation chamber (301) from the atmosphere side, and 303 is a microwave generation chamber (3).
01) a slotted endless annular waveguide for introduction into
304 is a gas introduction means for plasma generation, 310 is a porous transparent diffusion plate, 311 is a processing chamber connected to the plasma generation chamber,
Reference numeral 312 denotes a substrate to be processed, 313 denotes a support for the substrate to be processed (312), 314 denotes a heater for heating the substrate (312) to be processed, 315 denotes a processing gas introducing means, 316 denotes an exhaust port,
Reference numeral 17 denotes illumination means for irradiating at least ultraviolet light to the surface of the substrate to be processed (312), and 318 denotes illumination means (31
This is a light introduction window for introducing the visible ultraviolet light from 7) through the plasma generation chamber (301) into the processing chamber (311).

The generation and processing of plasma are performed as follows. The inside of the plasma generation chamber (301) and the inside of the processing chamber (311) are evacuated via an exhaust system (not shown). Subsequently, the surface of the substrate (312) is irradiated with visible ultraviolet light from the illumination means (317) through the light introduction window (318), and the substrate (312) is maintained at a desired temperature. Further, a gas for plasma generation is supplied at a predetermined flow rate through the gas introduction means (304) to the plasma generation chamber (3).
01). Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted to maintain the inside of the plasma generation chamber (301) at a predetermined pressure. Next, a desired power is supplied from a microwave power supply (not shown) into the plasma generation chamber (301) via the annular waveguide (303) to generate plasma in the plasma generation chamber (301). At this time, if the processing gas is introduced into the processing chamber (311) via the processing gas introducing means (315),
The processing gas is excited by the generated high-density plasma,
The surface of the substrate to be processed (312) placed on the support (313) is treated by the excited gas. At this time, the surface of the base is activated by the ultraviolet light, so that a higher quality treatment can be performed. At this time, a processing gas may be introduced from the plasma generating gas introducing means (304) depending on the application.

As a light source of the illumination means (317), a low-pressure mercury lamp, a xenon-mercury lamp, a deuterium lamp, A
For a gas or a precursor adhering to a substrate surface or a substrate surface such as an r resonance line lamp, a Kr resonance line lamp, a Xe resonance line lamp, an excimer lamp, an excimer laser, an Ar ⁺ laser harmonic, an N ₂ laser, and a YAG laser harmonic. Any light source having a wavelength that can be absorbed can be used.

Embodiment 4 FIG. 10 shows a bias plasma processing apparatus as an example of the present invention.
Shown in Reference numeral 401 denotes a plasma generation chamber; 402, a dielectric separating the plasma generation chamber (401) from the atmosphere side; 403, a slotted endless annular waveguide for introducing microwaves into the plasma generation chamber (401); Plasma generating gas introducing means 411 is a processing chamber connected to the plasma generating chamber, 412 is a substrate to be processed, and 413 is a substrate to be processed (41
2) The support, 414 is a heater for heating the substrate to be processed (412), 415 is a processing gas introducing means, 416 is an exhaust port, and 419 is a high frequency supply means for applying a bias to the support (413).

The generation and processing of plasma are performed as follows. The inside of the plasma generation chamber (401) and the inside of the processing chamber (411) are evacuated via an exhaust system (not shown). Subsequently, the substrate to be processed (41) is heated by the heater (414).
2) is heated and maintained at a desired temperature. Further, a gas for plasma generation is introduced into the plasma generation chamber (401) at a predetermined flow rate through the gas introduction means (404). Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted to maintain the inside of the plasma generation chamber (401) and the inside of the processing chamber (411) at a predetermined pressure. Next, a desired power is supplied from a microwave power supply (not shown) into the plasma generation chamber (401) via the annular waveguide (403) to generate plasma in the plasma generation chamber (401). Further, by applying a high frequency to the support (413) by the high frequency supply means (419), a self-bias is generated on the surface of the substrate to be processed. At this time, the processing gas is supplied to the processing chamber (41) via the processing gas introduction pipe (415).
When introduced into 1), the processing gas is excited by the generated high-density plasma, and the generated ions are accelerated by a self-bias, and are placed on the support (413) by the accelerated ions. The surface of the substrate to be processed (412) is processed. At this time, a processing gas may be introduced from the plasma generating gas introducing means (404) depending on the application.

The frequency of the high-frequency supply means (419) is 100 kHz to 20 kHz in terms of discharge stability and self-bias.
MHz is preferable, and 1 to 5 MHz is more preferable.

Embodiment 5 FIG. 7 shows a microwave plasma processing apparatus as an example of the present invention.
Shown in As described above, 101 is a plasma generation chamber, 1
02 is a first dielectric separating the plasma generation chamber 101 from the atmosphere side, and 103 is a microwave
Endless annular waveguide with slot for introduction into
Are the second dielectric filled in the annular waveguide 103, 10
4 is a plasma generating gas introducing means, 111 is a processing chamber connected to the plasma generating chamber, 112 is a substrate to be processed, 113 is a support for the substrate 112, 114 is a heater for heating the substrate 112, and 115 is a processing gas introducing means. , 116 are exhaust gas.

The annular waveguide 103 has an inner wall cross-sectional dimension of W
27 mm x 96 mm, the same as the RT-2 standard waveguide, and the center diameter was 354 mm. The material of the annular waveguide 103 is
It is made of stainless steel to maintain mechanical strength,
The inner wall is coated with copper and further coated with silver to suppress the propagation loss of microwaves. The inside of the annular waveguide 103 is filled with quartz as a second dielectric 704. The annular waveguide 103 has a slot for introducing a microwave into the plasma generation chamber 101. The shape of the slot is a rectangle having a length of 21 mm and a width of 2 mm, and is formed at intervals of 1/4 of the guide wavelength. The guide wavelength depends on the frequency of the microwave to be used, the permittivity of the second dielectric, and the dimensions of the cross section of the waveguide. However, the microwave having a frequency of 2.45 GHz, quartz, Is about 80 mm when the above waveguide is used. The annular waveguide 103 used
In the figure, 56 slots are formed at intervals of about 20 mm. To the annular waveguide 103, a 4E tuner, a directional coupler, an isolator, and a microwave power supply (not shown) having a frequency of 2.45 GHz are sequentially connected.

The generation and processing of plasma are performed as follows. Plasma generation 10 via an exhaust system (not shown)
1 and the processing chamber 111 are evacuated. Subsequently, a plasma generation gas is introduced into the plasma generation chamber 101 at a predetermined flow rate through the plasma generation gas introduction means 104. Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted to maintain the inside of the plasma generation chamber 101 and the inside of the processing chamber 111 at a predetermined pressure. A desired power is supplied from a microwave power supply (not shown) to the second dielectric 70.
The plasma is supplied into the plasma generation chamber 101 through the first dielectric 102 through the annular waveguide 103 filled with 4, whereby plasma is generated in the plasma generation chamber 101. At this time, if the processing gas is introduced into the processing chamber 111 through the processing gas introducing means 115, the processing gas is excited by the generated high-density plasma, and
The surface of the substrate to be processed 112 placed thereon is processed. At this time, depending on the application, the plasma generating gas introducing means 104 is used.
A processing gas may be introduced into the air.

Using the microwave plasma processing apparatus shown in FIG. 7, an Ar flow rate of 500 sccm and a pressure of 10 mTo
Plasma was generated under the conditions of rr and microwave power of 3.0 kW, and the obtained plasma was measured. The plasma measurement was performed by the single probe method as follows. The voltage applied to the probe was changed in the range of -50 to +50 V, the current flowing through the probe was measured by an IV measuring instrument, and the electron density, electron temperature and plasma were obtained from the obtained IV curve by the method of Langmuir et al. The potential was calculated. As a result, the electron density was 3.2 × 10 ¹² / cm ³ ±
4.3% (within φ200 plane), and it was confirmed that high-density and uniform plasma was formed.

Embodiment 6 FIG. 11 shows an isolated plasma processing apparatus as an example of the present invention. 201 is a plasma generation chamber, 202 is a first dielectric separating the plasma generation chamber 201 from the atmosphere side, 203 is an annular waveguide with a slot for introducing microwaves into the plasma generation chamber 201, and 1101 is an annular waveguide. A second dielectric 204 filled in the tube 203; 204, a gas introduction means for plasma generation; 211, a processing chamber connected to the plasma generation chamber;
12 is a substrate to be processed, 213 is a support for the substrate 212, 21
4 is a heater for heating the substrate 212, 215 is a processing gas introducing means, and 216 is an exhaust port. The distance between the plasma and the substrate was 100 mm as compared with the apparatus example 1.

The generation and processing of plasma are performed as follows. Plasma generation chamber 2 via exhaust system (not shown)
The inside of the chamber 01 and the inside of the processing chamber 211 are evacuated. Subsequently, the gas for plasma generation is introduced into the gas introduction means 204 for plasma generation.
And into the plasma generation chamber 201 at a predetermined flow rate. Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted to maintain the inside of the plasma generation chamber 201 at a predetermined pressure. A desired power is supplied from a microwave power supply (not shown) to the second dielectric 1 in the plasma generation chamber 201.
By supplying via the annular waveguide 203 filled with 101, high-density plasma is further generated in the plasma generation chamber 201. At this time, if the processing gas is introduced into the processing chamber 211 through the processing gas introducing means 215, the processing gas reacts with the plasma generation gas excited by the generated high-density plasma, and The surface of the coated substrate 212 placed on top is treated. At this time, a processing gas may be introduced into the plasma generating gas introduction means 204 depending on the application.

Embodiment 7 FIG. 1 shows an optically assisted plasma processing apparatus as an example of the present invention.
It is shown in FIG. 301 is a plasma generation chamber, 302 is a quartz tube for separating the plasma generation chamber 301 from the atmosphere side, 303 is an annular waveguide for introducing microwave into the plasma generation chamber 301, and 1201 is filled in the annular waveguide. The second dielectric, 304 is a gas introduction means for plasma generation, 301 is a porous transparent diffusion plate, 311 is a plasma generation chamber connected to the plasma generation chamber, 312 is a substrate to be processed, 313 is a substrate 31
2, a heater for heating the base 312,
15 is a processing gas introducing means, 316 is exhaust, 317 is an illumination system for irradiating the surface of the substrate 312 with ultraviolet light, 31
Reference numeral 8 denotes a plasma generation chamber 3 which emits visible ultraviolet light from the illumination system 317.
Reference numeral 01 denotes a light introduction window for introducing the light into the processing chamber 311.

The generation and processing of plasma are performed as follows. Plasma generation chamber 3 via an exhaust system (not shown)
The inside of the chamber 01 and the inside of the processing chamber 311 are evacuated. Subsequently, the surface of the base 312 is irradiated with visible ultraviolet light from the illumination system 317 through the light introduction window 318, and the base 312 is maintained at a desired temperature. Further, a plasma generation gas is introduced into the plasma generation chamber 301 at a predetermined flow rate through the plasma generation gas introduction means 304. Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted to maintain the inside of the plasma generation chamber 301 at a predetermined pressure. A desired power is supplied from the microwave power supply (not shown) into the plasma generation chamber 301 through the annular waveguide 303 filled with the second dielectric 1201 to thereby generate the plasma generation chamber 30.
A plasma is generated in 1. At this time, if the processing gas is introduced into the generation chamber 311 via the processing gas introduction means 315, the processing gas is excited by the generated high-density plasma, and the substrate to be processed placed on the support 313 312
Treat the surface. At this time, since the surface is activated by the ultraviolet light, higher quality processing can be performed. At this time, a processing gas may be introduced into the plasma generating gas introduction means 304 depending on the application.

The light source of the illumination system 317 includes a low-pressure mercury lamp, a xenon-mercury lamp, a deuterium lamp, an Ar resonance line lamp, a Kr resonance line lamp, a Xe resonance line lamp, an excimer lamp, an excimer laser, an Ar + laser harmonic, N
Any light source having a wavelength that can be absorbed by the substrate surface or a gas attached to the substrate surface or a precursor, such as a ₂ laser or a YAG laser harmonic, can be used.

Embodiment 8 FIG. 13 shows a bias plasma processing apparatus as an example of the present invention.
Shown in Reference numeral 401 denotes a plasma generation chamber; 402, a first dielectric constituting the plasma generation chamber 401; 403, an annular waveguide for introducing microwaves into the plasma generation chamber 401; The second dielectric 404 is a gas introduction means for plasma generation 411
Is a plasma generation chamber connected to the plasma generation chamber, 412 is a substrate to be processed, 413 is a support for the substrate 412, 414 is a heater for heating the substrate 412, 415 is a processing gas introducing means, 416 is exhaust, and 419 is a substrate support. A high-frequency supply unit that applies a bias to the body 413.

The generation and processing of plasma are performed as follows. Plasma generation chamber 4 via an exhaust system (not shown)
The inside of the chamber 01 and the inside of the processing chamber 411 are evacuated. Subsequently, the base 412 is heated and maintained at a desired temperature via the heater 414. Further, a plasma generation gas is introduced into the plasma generation chamber 401 at a predetermined flow rate through the plasma generation gas introduction means 404. Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted to maintain the inside of the plasma generation chamber 401 at a predetermined pressure. Annular waveguide 403 filled with second dielectric 1301 in plasma generating chamber 401 with desired power from a microwave power supply (not shown)
, A plasma is generated in the plasma generation chamber 401. Further, a self-bias is generated on the surface of the base by applying a high frequency to the base support 413 via the high-frequency supply means 419. At this time, if the processing gas is introduced into the generation chamber 411 via the processing gas introduction means 415, the processing gas is excited by the generated high-density plasma, and the generated ions are accelerated by a self-bias. The surface of the target substrate 412 placed on the substrate 413 is processed. At this time, a processing gas may be introduced into the plasma generating gas introduction means 404 depending on the application.

The frequency of the high frequency supply means 419 is 100
kHz to 20 MHz, particularly 1 MHz to 5 MHz, are optimal in terms of discharge stability and self-bias.

[0074]

BRIEF DESCRIPTION OF THE DRAWINGS FIG.
Various examples of film formation using the VD apparatus will be described. of course,
The present invention is not limited to the following specific examples.

Example 1 A microwave plasma processing apparatus shown in FIG. 5 (Embodiment 1)
Was used to form a silicon nitride film for a magneto-optical disk.

The substrate to be processed (112) has a thickness of 1.2 μm.
Polycarbonate (PC) substrate with m-width groove (φ
3.5 inches). First, the PC board (112)
After installing on the support (113), the exhaust system (not shown)
Through the plasma generation chamber (101) and the processing chamber (11).
The inside of 1) was evacuated and the pressure was reduced to 10 ^-6 Torr. Subsequently, nitrogen gas was introduced into the plasma generation chamber (101) at a flow rate of 100 sccm and argon gas at a flow rate of 600 sccm via the plasma generating gas introducing means (104). At the same time, monosilane gas was introduced into the processing chamber (111) at a flow rate of 200 sccm via the processing gas introducing means (115). Next, the conductance valve (not shown) provided in the exhaust system (not shown) was adjusted, and the inside of the processing chamber (111) was adjusted to 20 mT.
orr. Next, power of 3.0 kW is supplied from a microwave power supply (not shown) of 2.45 GHz to the annular waveguide (10).
It was supplied into the plasma generation chamber (101) via 3).
Thus, plasma was generated in the plasma generation chamber (101). At this time, the nitrogen gas introduced via the plasma generating gas introducing means (104) is excited and decomposed in the plasma generating chamber (101) to become active species, and is transported in the direction of the silicon substrate (112). By reacting with the monosilane gas introduced through the processing gas introduction means (115), a silicon nitride film was formed on the silicon substrate (112) with a thickness of 100 nm in 12 seconds.

After the film formation, the film quality was evaluated. The film formation rate of the obtained silicon nitride film was extremely high at 500 nm / min, and the film quality was confirmed to be a very good quality film having a refractive index of 2.2 and good adhesion and durability. . Further, the density was 2.9 g / cm ³ , and a denser film was formed than when the parameters such as the in-tube wavelength were not optimized.

Example 2 A microwave plasma processing apparatus shown in FIG. 5 (Embodiment 1)
Was used to form a silicon oxide film and a silicon nitride film for preventing reflection of plastic lenses.

The substrate to be treated (112) has a diameter of 50
mm plastic convex lenses were used. Lens (11
After installing 2) on the support (113), the exhaust system (not shown)
Shown), the plasma generation chamber (101) and the processing chamber (1).
11) The inside is evacuated, and 10 ^-6The pressure was reduced to Torr. Continued
And nitrogen through the plasma generating gas introduction means (104).
Plasma generation chamber (101) at a flow rate of 150 sccm of elementary gas
Introduced within. At the same time, processing gas introducing means (115)
Through the processing chamber at a flow rate of 100 sccm of monosilane gas.
(111). Next, the exhaust system (not shown)
Adjust the provided conductance valve (not shown),
The inside of the processing chamber (111) was kept at 5 mTorr. Next, 2.
3.0 kW from a 45 GHz microwave power supply (not shown)
Power from the plasma generation chamber through the annular waveguide (103)
(101). In this way, the plasma
Plasma was generated in the living room (101). At this time,
Introduced via the plasma generating means for plasma generation (104)
The excited nitrogen gas is excited and separated in the plasma generation chamber (101).
It is dissolved and becomes active species such as nitrogen atom, and the lens (11
It is transported in the direction of 2), and the processing gas introduction means (115)
Reacts with the monosilane gas introduced through the
A cone film is formed on the lens (112) with a thickness of 21 nm.
Was.

Next, the plasma generating gas introducing means (10
Oxygen gas was introduced into the plasma generation chamber (101) via 4) at a flow rate of 200 sccm. At the same time, monosilane gas was introduced into the processing chamber (111) at a flow rate of 100 sccm via the processing gas introducing means (115). Next, a conductance valve (not shown) provided in an exhaust system (not shown) was adjusted to maintain the inside of the processing chamber (111) at 1 mTorr. Next, a microwave power supply of 2.45 GHz (not shown)
From 2.0 kW was supplied into the plasma generation chamber (101) through the annular waveguide (103) filled with quartz. Thus, plasma was generated in the plasma generation chamber (101). At this time, the oxygen gas introduced through the plasma generating gas introducing means (104) is excited and decomposed in the plasma generating chamber (101) to become active species such as oxygen atoms, and is directed toward the lens (112). The silicon oxide film is transported and reacts with the monosilane gas introduced through the processing gas introduction means (115), and the silicon oxide film is converted into the lens (1).
12) It was formed on top with a thickness of 86 nm.

After the film formation, the film formation speed and the reflection characteristics were evaluated. The deposition rates of the obtained silicon nitride film and silicon oxide film were 300 nm / min and 360 n, respectively.
m / min, which is a very good optical characteristic with a reflectivity of about 0.3% at around 500 nm.

Example 3 A microwave plasma processing apparatus shown in FIG. 5 (Embodiment 1)
Was used to form a silicon nitride film for protecting semiconductor elements.

As the substrate to be processed (112), a P-type single-piece silicon substrate with an interlayer SiO ₂ film on which an Al wiring pattern (line and space 0.5 μm) was formed (plane orientation <100>, resistivity 10 Ωcm) It was used. First, after setting the silicon substrate (112) on the support (113), the plasma generating chamber (10) is evacuated through an exhaust system (not shown).
1) and the inside of the processing chamber (111) are evacuated to 10 ^-6 Torr
The pressure was reduced to Subsequently, the heater (114) is energized to heat the silicon substrate (112) to 300 ° C., and the substrate is maintained at this temperature.
04) was introduced into the plasma generation chamber (101) at a flow rate of 500 sccm. At the same time, the monosilane gas was supplied at a rate of 100 sccm through the processing gas introducing means (115).
Into the processing chamber (111). Next, a conductance valve (not shown) provided in an exhaust system (not shown) was adjusted to maintain the inside of the processing chamber (111) at 20 mTorr. Next, power of 3.0 kW was supplied from a microwave power supply (not shown) of 2.45 GHz into the plasma generation chamber (101) through the annular waveguide (103) filled with quartz. Thus, plasma was generated in the plasma generation chamber (101). At this time, the nitrogen gas introduced via the plasma generating gas introducing means (104) is excited and decomposed into active species in the plasma generating chamber (101), and is transported in the direction of the silicon substrate (112) to be processed. Reacts with the monosilane gas introduced through the introduction gas introduction means (115) to form the silicon nitride film on the silicon substrate (11).
2) It was formed on top with a thickness of 1.0 μm.

After film formation, film quality such as film formation speed and stress was evaluated. The deposition rate of the obtained silicon nitride film was 4
Very large as 60 nm / min, even stress ^{1.1 × 10 9 dyn / cm 2} ( compression) for film quality, the leakage current 1.
It was confirmed that the film was a very good film having 2 × 10 ⁻¹⁰ A / cm ² and a withstand voltage of 9 MV / cm. The stress was determined by measuring the change in the amount of warpage of the substrate before and after film formation using a laser interferometer Zygo (trade name).

Embodiment 4 A microwave plasma processing apparatus shown in FIG. 5 (Embodiment 1)
The semiconductor element BPSG film was etched by using a device provided with a magnetic field generating means (coil).

The substrate to be processed (112) is a P-type single-crystal silicon substrate (plane orientation <100>, resistivity 10 Ωcm) having a 1 μm thick BPSG film formed on a polysilicon pattern (line and space 0.5 μm). )It was used. First, a silicon substrate (112) is placed on a support (113).
After being installed above, the inside of the plasma generation chamber (101) and the processing chamber (111) are evacuated via an exhaust system (not shown),
The pressure was reduced to 10 ^-6 Torr. Subsequently, CF ₄ was introduced into the plasma generation chamber (101) at a flow rate of 300 sccm through the plasma generation gas introducing means (104). Next, the conductance valve (not shown) provided in the exhaust system (not shown) was adjusted to adjust the inside of the plasma generation chamber (101) by 0.5 mm.
It was kept at mTorr. Next, electric power is supplied from a DC power supply (not shown) to the coil (not shown) and the plasma generation chamber (101) is supplied.
1. After generating a magnetic field with a maximum magnetic flux density of 90 mT in
1.5 kW of power from a 45 GHz microwave power supply through the annular waveguide (103) to the plasma generation chamber (101)
Supplied within. Thus, the plasma generation chamber (10
Plasma was generated in 1). The CF ₄ gas introduced through the plasma generating gas introducing means (105) is excited and decomposed in the plasma generating chamber (101) to become active species, and is transported in the direction of the silicon substrate (112), and is subjected to BPS.
The G film was etched.

After etching, etching rate, selectivity,
And the etching shape was evaluated. The etched shape was evaluated by observing the cross section of the etched silicon oxide film with a scanning electron microscope (SEM). It was confirmed that the etching rate was 300 nm / min, the selectivity to polysilicon was 30 and good, the etching shape was almost vertical, and the microloading effect was small.

Example 5 A silicon oxide film for semiconductor device gate insulation was formed using the isolated plasma processing apparatus (Embodiment 2) shown in FIG.

As the substrate to be processed (112), a P-type single-crystal silicon substrate (plane orientation <100>, resistivity 10 Ωcm)
It was used. This silicon substrate (112) is used as a support (1).
13) After being installed above, the inside of the plasma generation chamber (101) and the processing chamber (111) were evacuated via an exhaust system (not shown) to reduce the pressure to 10 ^-6 Torr. Then, the heater (11
4), the silicon substrate (112) was heated to 300 ° C., and the silicon substrate (112) was kept at this temperature.
Oxygen gas was introduced into the plasma generation chamber (101) at a flow rate of 200 sccm via the plasma generation gas introduction means (104). At the same time, the processing chamber (11) was supplied with monosilane gas at a flow rate of 50 sccm via the film forming gas introducing means (115).
Introduced in 1). Next, the conductance valve (not shown) provided in the exhaust system (not shown) was adjusted, and the inside of the plasma generation chamber (101) and the processing chamber (111) was adjusted to 20 mTorr.
kept at r. Next, 1.5 kW of power is supplied from a microwave power supply (not shown) of 2.45 GHz to the annular waveguide (10).
It was supplied into the plasma generation chamber (101) via 3).
Thus, plasma was generated in the plasma generation chamber (101). At this time, the oxygen gas introduced via the plasma generating gas introducing means (104) is excited and decomposed in the plasma generating chamber (101) to become active species such as oxygen atoms, and is directed toward the silicon substrate (112). And reacted with the monosilane gas introduced through the processing gas introduction means (115) to form a silicon oxide film with a thickness of 0.1 μm on the silicon substrate (112).

After the film formation, the film formation rate, uniformity, leak current,
The breakdown voltage and the interface state density were evaluated. The deposition rate of the obtained silicon oxide film was 120 nm / min, the uniformity was good with ± 2.2%, and the film quality was 5 × 10 ⁻¹¹ A / cm ² , the withstand voltage was 10 MV / cm,
The interface state density was 5 × 10 ¹⁰ cm ⁻² , and it was confirmed that the film was an extremely good quality film. The interface state density was obtained from a CV curve obtained by applying a high frequency of 1 MHz obtained by a capacitance measuring device.

Example 6 An optically assisted microwave plasma processing apparatus (Embodiment 3) shown in FIG. 9 was used to form a silicon oxide film for interlayer insulation of semiconductor elements.

As the substrate to be treated (312), a P-type single crystal silicon substrate (plane orientation <100>, resistivity 10 Ωcm) having an Al pattern (line and space 0.5 μm) formed on the uppermost portion was used. First, a silicon substrate (3
After placing 12) on the support (313), the inside of the plasma generation chamber (301) and the processing chamber (311) were evacuated via an exhaust system (not shown), and the pressure was reduced to 10 ^-6 Torr.
Subsequently, the KrCl ^* excimer lamp of the lighting means (317) was turned on to irradiate the surface of the silicon substrate (312) with light so that the light illuminance on the surface of the silicon substrate (312) became 20 mW / cm ² . Next, the heater (31)
4), the silicon substrate (312) was heated to 300 ° C., and the substrate was kept at this temperature. Oxygen gas was introduced into the plasma generation chamber (301) at a flow rate of 500 sccm via the plasma generation gas introduction means (304). At the same time, tetraethoxysilane (TEOS) gas was introduced into the processing chamber (311) at a flow rate of 200 sccm from the processing gas introducing means (315). Next, the conductance valve (not shown) provided in the exhaust system (not shown) is adjusted,
0.1 Torr inside the plasma generation chamber (301)
11) was kept at 0.05 Torr. Next, 2.45G
An electric power of 1.5 kW was supplied from a microwave power supply (not shown) of 1 Hz into the plasma generation chamber (301) through an annular waveguide (303) filled with quartz. In this way,
Plasma was generated in the plasma generation chamber (301).
The oxygen gas introduced via the plasma generating gas introducing means (304) is excited and decomposed into active species in the plasma generating chamber (301), and is transported in the direction of the silicon substrate (312) to form a film forming gas. By reacting with the tetraethoxysilane gas introduced through the introduction means (315), a silicon oxide film was formed with a thickness of 0.8 μm on the silicon substrate (312).

After the film formation, the film formation speed, uniformity, dielectric strength, and step coverage were evaluated. The deposition rate of the obtained silicon oxide film was 190 nm / min, and the uniformity was ± 2.5.
%, And the dielectric strength of the film quality is 9.5.
The MV / cm and the cover factor were 0.9, and it was confirmed that the film was a good quality film. The cover factor (step coverage) is obtained by observing the cross section of the silicon oxide film formed on the Al wiring pattern with a scanning electron microscope (SEM) and determining the ratio of the film thickness on the step sidewall to the film thickness on the step. It is.

Example 7 The polysilicon film between the gate electrodes of the semiconductor element was etched using the bias microwave plasma processing apparatus (Embodiment 4) shown in FIG.

As the substrate to be processed (412), a P-type single crystal silicon substrate (plane orientation <100>, resistivity 10 Ωcm) having a polysilicon film formed on the uppermost portion was used. First, after the silicon substrate (412) is set on the support (413), the inside of the plasma generation chamber (401) and the processing chamber (411) are evacuated via an exhaust system (not shown), and
^The pressure was reduced to ^-6 Torr. Gas generating means for plasma generation (4
04), 300 sccm of CF4 gas and 20 sc of oxygen
It was introduced into the plasma generation chamber (401) at a flow rate of cm. Next, the conductance valve (not shown) provided in the exhaust system (not shown) was adjusted to maintain the inside of the plasma generation chamber (401) at 0.5 mTorr. Next, the high frequency applying means (4
19) The high frequency of 400 kHz is applied to the support (413).
And a power of 1.5 kW from a microwave power supply of 2.45 GHz was supplied into the plasma generation chamber (401) through the annular waveguide (403). Thus, plasma was generated in the plasma generation chamber (401). The CF ₄ gas and oxygen introduced via the plasma generating gas introducing means (404) are supplied to the plasma generating chamber (40).
Excited and decomposed in 1) to become active species, transported in the direction of the silicon substrate (412), and the polysilicon film was etched by ions accelerated by the self-bias.

After etching, etching rate, selectivity,
And the etching shape was evaluated. The etching rate was 600 nm / min, the selectivity to SiO ₂ was good together with 30, and it was confirmed that the etching shape was vertical and the microloading effect was smaller than when no high frequency was applied. The etched shape is obtained by scanning a cross section of the etched polysilicon film with a scanning electron microscope (SE).
M) was observed and evaluated.

Example 8 A silicon nitride film for a magneto-optical disk was formed using the microwave plasma processing apparatus shown in FIG.

As the substrate 112, a polycarbonate (PC) substrate (φ3.5 inches) with a 1.2 μm width group was used. First, the PC board 112 is attached to the base support 1.
After being set on the plasma generator 13, the inside of the plasma generation chamber 101 and the film formation chamber 111 is evacuated via an exhaust system (not shown),
^-6 Torr. Nitrogen gas and argon gas were introduced into the plasma generation chamber 101 at a flow rate of 100 sccm and a flow rate of 600 sccm via the plasma generation gas introducing means 104. At the same time, a monosilane gas is supplied at a flow rate of 200 sccm through the film forming gas introducing means 115 to the film forming chamber 111.
Introduced within. Then, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted, and the film forming chamber 11 is adjusted.
1 was kept at 20 mTorr. Plasma generation chamber 10
Within 1.3.0k from 2.45GHz microwave power supply
W power was supplied via the annular waveguide 103 filled with quartz 704. Thus, plasma was generated in the plasma generation chamber 101. At this time, the nitrogen gas introduced via the plasma generating gas introducing means 104 is excited and decomposed in the plasma generating chamber 101 to become active species, transported in the direction of the silicon substrate 112, and
15 reacts with the monosilane gas introduced through the silicon substrate 15 and a silicon nitride film is formed on the silicon substrate 112 for 10 seconds.
It was formed with a thickness of 0 nm. After the film formation, the film quality such as the refractive index was evaluated.

The film formation rate of the obtained silicon nitride film is 5
It is extremely large at 00 nm / min, and the film quality is 2.
2. It was confirmed that the film was a very good film having good adhesion and durability. The density was 2.9 g / cm ³ , and a denser film was formed than when the second dielectric 704 was not filled.

Example 9 Using a microwave plasma processing apparatus shown in FIG. 7, a silicon oxide film and a silicon nitride film for preventing plastic lens reflection were formed.

As the base 112, a plastic convex lens having a diameter of 50 mm was used. After the lens 112 is set on the base 113, the inside of the plasma generation chamber 101 and the film formation chamber 111 is evacuated via an exhaust system (not shown), and
The pressure was reduced to a value of 0 ^-6 Torr. Nitrogen gas was introduced into the plasma generation chamber 201 at a flow rate of 150 sccm via the plasma generation gas introduction means 104. At the same time, 100 silane gas is supplied through the film-forming gas introducing means 115.
It was introduced into the film forming chamber 111 at a flow rate of sccm. Then
A conductance valve (not shown) provided in an exhaust system (not shown) was adjusted, and the inside of the film forming chamber 111 was maintained at 5 mTorr. Next, power of 3.0 kW was supplied from a microwave power supply (not shown) of 2.45 GHz into the plasma generation chamber 101 through the annular waveguide 103 filled with quartz 704. Thus, plasma was generated in the plasma generation chamber 101. At this time, the nitrogen gas introduced through the plasma generating gas introducing means 104 is excited and decomposed in the plasma generating chamber 101 to become active species such as nitrogen atoms, and is transported in the direction of the lens 112 to be formed. By reacting with the monosilane gas introduced through the gas introduction means 115, a silicon nitride film was formed on the lens 112 with a thickness of 21 nm.

Next, oxygen gas was introduced into the plasma generation chamber 101 through the plasma generation gas inlet 104 at a flow rate of 200 sccm. At the same time, the film forming gas introducing means 1
A monosilane gas was introduced into the film forming chamber 111 at a flow rate of 100 sccm through the line 15. Next, an exhaust system (not shown)
The conductance valve (not shown) provided in the chamber was adjusted, and the inside of the film forming chamber 111 was maintained at 1 mTorr. Next, a power of 2.0 kW was supplied from a microwave power supply (not shown) of 2.45 GHz into the plasma generation chamber 101 through the annular waveguide 103 filled with quartz 704. Thus, plasma was generated in the plasma generation chamber 101. At this time, the oxygen gas introduced through the plasma generation gas inlet 104 is excited and decomposed in the plasma generation chamber 101 to become active species such as oxygen atoms, and is transported in the direction of the glass substrate 112 to form a film. Gas introduction means 115
The silicon oxide film was formed on the glass substrate 112 with a thickness of 86 nm by reacting with the monosilane gas introduced through the substrate. After the film formation, the film formation speed and reflection characteristics were evaluated.

The deposition rates of the obtained silicon nitride film and silicon oxide film were 300 nm / min and 360 n, respectively.
m / min, and the film quality was confirmed to be very good optical characteristics with a reflectance of about 0.3% near 500 nm.

Example 10 A silicon nitride film for protecting semiconductor elements was formed using the microwave plasma processing apparatus shown in FIG.

As the base 112, a P-type single crystal silicon substrate with an interlayer SiO ₂ film on which an Al wiring pattern (line and space 0.5 μm) was formed (plane orientation <10
0>, resistivity 10 Ωcm). First, after the silicon substrate 112 is set on the base support 113, the plasma generation chamber 101 and the film formation chamber 1 are connected via an exhaust system (not shown).
The inside of the chamber 11 was evacuated and the pressure was reduced to a value of 10 ^-6 Torr. Subsequently, a heater (not shown) is energized and the silicon substrate 1
12 was heated to 300 ° C. and the substrate was kept at this temperature. Nitrogen gas was introduced into the plasma generating chamber 101 at a flow rate of 500 sccm through the plasma generating gas introducing means 104. At the same time, the monosilane gas is supplied at a flow rate of 100 sccm through the film-forming gas introduction means 115 and the monosilane gas is supplied at a flow rate of 100 sccm through the film-forming gas introduction means 115.
At a flow rate of? Next, a conductance valve (not shown) provided in an exhaust system (not shown) was adjusted, and the inside of the film forming chamber 111 was maintained at 20 mTorr. Next, power of 3.0 kW was supplied from a 2.45 GHz microwave power supply (not shown) through the annular waveguide 103 filled with quartz 704. Thus, plasma was generated in the plasma generation chamber 101. At this time, the nitrogen gas introduced via the plasma generating gas introducing means 104 is excited and decomposed in the plasma generating chamber 101 to become an active species, transported in the direction of the silicon substrate 112, and formed into the film forming gas introducing means 115. Reacts with the monosilane gas introduced through the silicon substrate 112 to form a silicon nitride film with a thickness of 1.0 μm on the silicon substrate 112. After the film formation, film quality such as film formation speed and stress was evaluated. The stress was determined by measuring the change in the amount of warpage of the substrate before and after film formation using a laser interferometer Zygo (trade name).

The film formation rate of the obtained silicon nitride film is 4
Extremely large at 60 nm / min, and film quality is 1.1 × stress.
10 ⁹ dyn / cm ² (compression), leak current 1.2 × 1
^{0 -1} 0 A / cm ^2, it was confirmed that an extremely high-quality film of dielectric strength 9 MV / cm.

Example 11 The semiconductor device BPSG film was etched using the microwave plasma processing apparatus shown in FIG.

As the base 112, a P-type single crystal silicon substrate (plane orientation <100>, resistivity 10 Ωcm) having a 1 μm thick BPSG film formed on a polysilicon pattern (line and space 0.5 μm) was used. . First,
After placing the silicon substrate 112 on the substrate support 113, the inside of the plasma generation chamber 101 and the etching chamber 111 is evacuated via an exhaust system (not shown), and 10 ^-6 Torr
The pressure was reduced to the value of. Gas inlet 104 for plasma generation
Through was introduced into the plasma generation chamber 111 to CF ₄ at 300sccm flow rate. Next, a conductance valve (not shown) provided in an exhaust system (not shown) was adjusted to maintain the inside of the plasma generation chamber 101 at 0.5 mTorr.
Then, power is supplied from a DC power supply (not shown) to the coil 106 to generate a magnetic field having a maximum magnetic flux density of 90 mT in the plasma generation chamber 101, and then 1.5 kW of power is annularly guided from a 2.45 GHz microwave power supply. The gas was supplied into the plasma generation chamber 101 through the tube 103. Thus, plasma was generated in the plasma generation chamber 101. The CF ₄ gas introduced through the plasma generating gas introducing means 104 was excited and decomposed in the plasma generating chamber 101 to become active species, was transported in the direction of the silicon substrate 112, and the BPSG film was etched. After etching, etching rate,
The selectivity and the etched shape were evaluated. The etched shape was evaluated by observing the cross section of the etched silicon oxide film with a scanning electron microscope (SEM).

It was confirmed that the etching rate and the selectivity ratio with respect to polysilicon were as good as 300 and 300 nm / min, the etching shape was almost vertical, and the microloading effect was small.

Example 12 Using the isolated plasma processing apparatus shown in FIG. 11, a silicon oxide film for semiconductor device gate insulation was formed.

A P-type single crystal silicon substrate (plane orientation <100>, resistivity 10 Ωcm) was used as the base 212.
After the silicon substrate 212 was set on the base support 213, the inside of the plasma generation chamber 201 and the film formation chamber 211 was evacuated via an exhaust system (not shown) to reduce the pressure to a value of 10 ^-6 Torr. Subsequently, a heater (not shown) is energized to heat the silicon substrate 212 to 300 ° C.
2 was kept at this temperature. Oxygen gas was introduced into the plasma generation chamber 201 through the plasma generation gas introducing means 204 at a flow rate of 200 sccm. At the same time, a monosilane gas was introduced into the film forming chamber 211 at a flow rate of 50 sccm through the film forming gas introducing means 215. Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted so that the inside of the plasma generation chamber 201 and the film formation chamber 211 is closed by two.
It was kept at 0 mTorr. Next, 1.5 kW of power from a microwave power supply of 2.45 GHz is applied to the plasma generation chamber 20 through the annular waveguide 203 filled with quartz 1101.
1. Thus, plasma was generated in the plasma generation chamber 201. At this time, the oxygen gas introduced via the plasma generating gas introducing means 204 is excited and decomposed in the plasma generating chamber 201 to become active species such as oxygen atoms, and is transported in the direction of the silicon substrate 212 to form a film. Reacts with the monosilane gas introduced through the use gas introduction means 215 to form a silicon oxide film on the silicon substrate 212 with a thickness of 0.1 μm. After the film formation, the film formation speed, uniformity, leak current, dielectric strength, and interface state density were evaluated. The interface state density was determined from a CV curve obtained by applying a high frequency of 1 MHz obtained by a capacitance measuring device.

The film formation rate and uniformity of the obtained silicon oxide film were as good as 110 nm / min ± 2.3%.
Leakage current 4 × 10 ^-11 A / cm ² , withstand voltage ¹¹ MV
/ Cm and an interface state density of 6 × 10 ¹⁰ cm ⁻² , and it was confirmed that the film was an extremely good film.

Embodiment 13 Using the optically assisted microwave plasma processing apparatus shown in FIG. 12, a silicon oxide film for insulating a semiconductor element layer was formed.

As the base 312, a P on which an Al pattern (line and space 0.5 μm) was formed on the uppermost portion was used.
Type single crystal silicon substrate (plane orientation <100>, resistivity 10
Ωcm). First, after the silicon substrate 312 is placed on the substrate support 313, the inside of the plasma generation chamber 301 and the film formation chamber 311 is evacuated via an exhaust system (not shown), and the pressure is reduced to a value of 10 ^-6 Torr. . Subsequently, the KrCI ^* excimer lamp of the illumination system 317 was turned on to irradiate the surface of the silicon substrate 312 with light so that the light illuminance on the surface of the silicon substrate 312 became 20 mW / cm ² . Subsequently, a heater (not shown) was energized to heat the silicon substrate 312 to 300 ° C., and the substrate was kept at this temperature. Oxygen gas is supplied through plasma generating gas introduction means 304 to 50
It was introduced into the plasma generation chamber 311 at a flow rate of 0 sccm. At the same time, tetraethoxysilane (TEOS) gas was introduced into the deposition chamber 311 from the deposition gas introduction means 315 at a flow rate of 200 sccm. Next, an exhaust system (not shown)
Of the plasma generation chamber 301 was maintained at 0.1 Torr, and the inside of the film formation chamber 311 was maintained at 0.05 Torr. Then, 2.
1.5 kW of power was supplied from a 45 GHz microwave power supply into the plasma generation chamber 301 through an annular waveguide 303 filled with quartz 1201. Thus, plasma was generated in the plasma generation chamber 301. The oxygen gas introduced through the plasma generating gas introducing means 304 is excited and decomposed in the plasma generating chamber 301 to become active species,
The silicon oxide film was transported in the direction of the silicon substrate 312 and reacted with the tetraethoxysilane gas introduced through the film-forming gas introduction means 315 to form a silicon oxide film with a thickness of 0.8 μm on the silicon substrate 312. After the film formation, the film formation rate, uniformity, dielectric strength, and step coverage were evaluated. The step coverage is determined by observing the cross section of the silicon oxide film formed on the Al wiring pattern with a scanning electron microscope (SEM), and calculating the ratio (cover factor) of the film thickness on the step sidewall to the film thickness on the step. evaluated.

The film formation rate and uniformity of the obtained silicon oxide film were as good as 180 nm / min ± 2.7%. Was confirmed.

Example 14 The polysilicon film between the gate electrodes of the semiconductor element was etched using the bias plasma processing apparatus shown in FIG.

As the base 412, a P-type single crystal silicon substrate having a polysilicon film formed on the uppermost portion (plane orientation <1)
00>, resistivity 10 Ωcm). First, after the silicon substrate 412 was placed on the base support 413, the inside of the plasma generation chamber 401 and the etching chamber 411 were evacuated via an exhaust system (not shown) to reduce the pressure to a value of 10 ^-6 Torr. CF ₄ gas was introduced into the plasma generation chamber 411 at a flow rate of 300 sccm and oxygen at a flow rate of 20 sccm via the plasma generation gas introducing means 404. Next, a conductance valve (not shown) provided in an exhaust system (not shown) was adjusted to make the inside of the plasma generation chamber 401 0.5 mT.
orr. Then, a high frequency of 400 kHz is applied to the substrate support 413 via the high frequency applying means 419, and a high frequency power of 2.45 GHz is applied to the substrate support 413.
An annular waveguide 4 filled with quartz 1301 with a power of 5 kW
03, and supplied into the plasma generation chamber 401. Thus, plasma was generated in the plasma generation chamber 401. The CF ₄ gas and oxygen introduced via the plasma generating gas introducing means 404 are excited and decomposed into active species in the plasma generating chamber 401, are transported in the direction of the silicon substrate 412, and are accelerated by self-bias. As a result, the polysilicon film was etched. After the etching, the etching rate, the selectivity, and the etching shape were evaluated. The etched shape was evaluated by observing the cross section of the etched polysilicon film with a scanning electron microscope (SEM). The etching rate and the selectivity ratio to SiO ₂ were as good as 600 nm / min and 30, respectively, and it was confirmed that the etching shape was vertical and the micro-rotating effect was smaller than when no high frequency was applied.

[0118]

As is apparent from the above description, according to the present invention, a microwave surface wave propagating in a dielectric material is periodically excited and propagates more strongly and efficiently. It is possible to provide a plasma processing apparatus and a plasma processing method capable of generating a large-area, uniform and high-density plasma and performing high-quality processing at high speed even at a low temperature.

Further, inside the annular waveguide, the same as the first dielectric for separating the plasma generation chamber from the atmosphere, or
By filling a different second dielectric, in particular, the ratio of the dielectric constant of the first and second dielectrics is substantially approximately equal to the reciprocal of the square of the ratio of the perimeters of the first and second dielectrics. By doing so, it is possible to provide a plasma processing apparatus and a plasma processing method that can generate plasma with a lower power, a larger area, and a higher density, and perform higher quality processing at a lower temperature at a higher speed.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view for explaining an example of a plasma processing apparatus.

FIG. 2 is a schematic sectional view for explaining an example of a plasma generation mechanism.

FIG. 3 is a schematic perspective view for explaining an example of a wave tube.

FIG. 4 is a schematic plan view for explaining an example of a wave tube.

FIG. 5 is a schematic cross-sectional view for explaining an example of the plasma processing apparatus of the present invention.

FIG. 6 is a schematic cross-sectional view for explaining an example of a plasma generation mechanism of the present invention.

FIG. 7 is a schematic sectional view for explaining an example of the plasma processing apparatus of the present invention.

FIG. 8 is a schematic cross-sectional view for explaining an example of the plasma generation mechanism of the present invention.

FIG. 9 is a schematic sectional view for explaining an example of the plasma processing apparatus of the present invention.

FIG. 10 is a schematic sectional view for explaining an example of the plasma processing apparatus of the present invention.

FIG. 11 is a schematic sectional view for explaining an example of the plasma processing apparatus of the present invention.

FIG. 12 is a schematic sectional view for explaining an example of the plasma processing apparatus of the present invention.

FIG. 13 is a schematic sectional view for explaining an example of the plasma processing apparatus of the present invention.

[Explanation of symbols]

101, 201, 301, 401, 501 Plasma generation chamber 102, 202, 302, 402, 502 Dielectric (first dielectric) 103, 203, 303, 403, 503 Non-terminal annular waveguide with slot 104, 204 , 304, 404, 504 Plasma generating gas introduction means 111, 211, 311, 411, 511 Processing chambers 112, 212, 312, 412, 512 Substrates 113, 213, 313, 413, 513, Supports 114, 214, 314, 414, 514 Heater 115, 215, 315, 415, 515 Processing gas introduction means 116, 216, 316, 416, 516 Exhaust port 121, 521 Block 122, 522 Slot 123, 523 annular for distributing microwaves to left and right Microwave 124 52 introduced into waveguide Microwave 125, 525 Leakage wave 126, 526 Surface wave 127, 527 Plasma generated by leaky wave 128, 528 Plasma generated by surface wave 310 Perforated transparent diffuser plate 317 Lighting means 318 Light introduction window 419 High frequency supply means 704, 1101, 1201, 1301 Second dielectric

────────────────────────────────────────────────── ─── front page continued (51) Int.Cl. ⁷ identifications FI H05H 1/46 H01L 21/302 B (56 ) references Patent Rights 5-345982 (JP, a) Patent Rights 7-130494 ( JP, A) JP-A-8-111297 (JP, A) JP-A-8-241797 (JP, A) JP-A-3-122271 (JP, A) JP-A-7-90591 (JP, A) JP Hei 7-263186 (JP, A) JP-A-63-103088 (JP, A) WO 96/25834 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) H01L 21/31 C23C 16/50 C23F 4/00 H01L 21/205 H01L 21/3065 H05H 1/46

Claims (37)

(57) [Claims] 1. A cylindrical endless annular conductor having a plurality of slots disposed outside a cylindrical dielectric that forms a part of the plasma generation chamber, the interior being separated from the atmosphere side. A plurality of slots provided with microwave introduction means having a wave tube, support means for a substrate to be processed, gas introduction means for introducing gas into the plasma generation chamber, and exhaust means for exhausting the plasma generation chamber. in a more microwave plasma processing apparatus that generates plasma by introducing microwaves into the plasma generation chamber through the cylindrical dielectric, the radius of the cylindrical endless annular waveguide (R _g), the Microwave wavelength (λ _g ) in an endless annular waveguide, the cylinder
The radius (R _s ) of the dielectric in the form of a circle and the wavelength (λ _s ) of a surface wave propagating in the dielectric are represented by R _s / λ _s = (2n + 1) R _g / λ _g (n is 0 or a natural number). A microwave plasma processing apparatus, which substantially satisfies the relationship. 2. A further microwave plasma processing apparatus according to claim 1 having a magnetic field generating means. 3. The method according to claim 1, wherein the magnetic field generating means reduces the magnetic field near the slot to approximately 3.57 × 10 ^-11 of the microwave frequency.
3. The microwave plasma processing apparatus according to claim 2 , wherein the magnetic flux density is controlled to (T / Hz) times. 4. A microwave plasma processing apparatus according to claim 1 for supporting the substrate to be processed at a position distant from the plasma generation region. 5. A microwave plasma processing apparatus according to claim 1 comprising means for irradiating the light energy to a target substrate. 6. The light energy includes ultraviolet light.
5 microwave plasma processing apparatus according. 7. The microwave plasma processing apparatus according to claim 1 having a high-frequency supply means connected to said support means. 8. A microwave plasma processing apparatus according to claim 1, wherein another dielectric is filled with the dielectric in the waveguide. 9. Another microwave plasma processing apparatus according to claim 1, wherein the dielectric is filled made of a material different from that of the dielectric in the waveguide. 10. A non-terminal annular waveguide having a plurality of slots disposed outside a first dielectric constituting the plasma generation chamber, the plasma generation chamber having an interior separated from the atmosphere side. A microwave introduction means, a support means for the substrate to be processed, a gas introduction means for introducing a gas into the plasma generation chamber, and an exhaust means for exhausting the plasma generation chamber. In a microwave plasma processing apparatus for generating a plasma by introducing a microwave into the plasma generation chamber through one dielectric, a first material made of the same or different material as the first dielectric is provided inside the annular waveguide. A microwave plasma processing apparatus characterized by being filled with a second dielectric. 11. The method of claim 1, further comprising a magnetic field generating means
0. The microwave plasma processing apparatus according to item 0 . 12. The magnetic field generating means changes the magnetic field near the slot to approximately 3.57 × 10
The microwave plasma processing apparatus according to claim 11 , wherein the magnetic flux density is controlled to be ^-11 (T / Hz) times. 13. The microwave plasma processing apparatus according to claim 10 , wherein the substrate to be processed is supported at a position distant from a plasma generation region. 14. The microwave plasma processing apparatus according to claim 10, further comprising means for irradiating the substrate to be processed with light energy. 15. The microwave plasma processing apparatus according to claim 10, further comprising a high-frequency supply unit connected to said substrate supporting unit. 16. A plasma generating chamber whose inside is separated from the atmosphere side, and a cylindrical shape provided with a plurality of slots and arranged outside a cylindrical dielectric body forming the plasma generating chamber. Microwave introduction means having an endless annular waveguide, support means for a substrate to be processed, gas introduction means for introducing gas into the plasma generation chamber, and exhaust means for exhausting the plasma generation chamber. , using a microwave plasma processing apparatus for introducing microwaves into the plasma generation chamber through said cylindrical dielectric from said plurality of slots generates plasma, the radius of the cylindrical endless annular waveguide (R _g ), the wavelength of the microwave in the endless annular waveguide (λ _g ), the cylinder
The radius (R _s ) of the dielectric in the form of a circle and the wavelength (λ _s ) of the surface wave propagating in the dielectric are represented by R _s / λ _s = (2n + 1) R _g / λ _g (n is 0 or a natural number). A microwave plasma processing method for performing a plasma process on a substrate to be processed so as to substantially satisfy the relationship described above. 17. The microwave plasma processing method according to claim 16 , wherein the plasma processing is performed in a state where a magnetic field is applied. 18. The magnetic field according to claim 1, wherein the magnetic field near the slot is approximately 3.57 × 10 ⁻¹¹ (T / H) of the microwave frequency.
18. The microwave plasma processing method according to claim 17 , wherein the magnetic flux density is doubled. 19. The microwave plasma processing method according to claim 16, further comprising the step of arranging the substrate to be processed on the substrate supporting means at a position distant from the plasma generation region. 20. The microwave plasma processing method according to claim 16, wherein the plasma processing is performed while irradiating the substrate to be processed with light energy. 21. The microwave plasma processing method according to claim 20, wherein the light energy includes ultraviolet light. 22. The microwave plasma processing method according to claim 16, wherein the plasma processing is performed while supplying a high frequency to the support means. 23. The microwave plasma processing method according to claim 16, wherein the waveguide is filled with a dielectric different from the dielectric. 24. The microwave plasma processing method according to claim 16 , wherein another dielectric made of a material different from the dielectric is filled in the waveguide. 25. An unterminated annular waveguide having a plurality of slots disposed outside a first dielectric constituting the plasma generation chamber, the plasma generation chamber having an interior separated from the atmosphere side. A microwave introduction means, a support means for the substrate to be processed, a gas introduction means for introducing a gas into the plasma generation chamber, and an exhaust means for exhausting the plasma generation chamber. A microwave plasma processing apparatus for generating plasma by introducing microwaves into the plasma generation chamber through one dielectric, wherein the annular waveguide is made of the same or different material as the first dielectric. A microwave plasma processing method, comprising placing the substrate to be processed in a microwave plasma processing apparatus filled with a second dielectric material and performing plasma processing. 26. The microwave plasma processing method according to claim 25 , wherein the plasma processing is performed in a state where a magnetic field is applied. 27. The magnetic field, wherein the magnetic field near the slot is approximately 3.57 × 10 ⁻¹¹ (T / H) of the microwave frequency.
27. The microwave plasma processing method according to claim 26 , wherein the magnetic flux density is doubled. 28. The microwave plasma processing method according to claim 25, further comprising the step of arranging the gas to be processed on the substrate supporting means at a position distant from the plasma generation region. 29. The microwave plasma processing method according to claim 25, wherein the plasma processing is performed while irradiating the target substrate with light energy. 30. The microwave plasma processing method according to claim 29, wherein the light energy includes ultraviolet light. 31. The microwave plasma processing method according to claim 25, wherein the plasma processing is performed while supplying a high frequency to the supporting means. 32. The plasma processing is film formation.
17. The microwave plasma processing method according to 16 . 33. The microwave plasma processing method according to claim 16 , wherein the plasma processing is etching. 34. The microwave plasma processing method according to claim 16 , wherein the plasma processing is ashing. 35. The plasma processing is film formation.
26. The microwave plasma processing method according to item 25 . 36. The microwave plasma processing method according to claim 25 , wherein the plasma processing is etching. 37. The microwave plasma processing method according to claim 26 , wherein the plasma processing is ashing.