JPH11193466A - Plasma treating device and plasma treating method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a treating device capable of uniformly executing microwave plasma treatment for a substrate of a large area with >=300 mm diameter at a high speed. SOLUTION: This plasma treating device is composed of a plasma treating chamber 101, a means 103 of supporting the substrate 102 to be treated set in the plasma treating chamber, a means 105 of introducing a gas for treatment into the plasma treating chamber, a means 106 of exhausting the inside of the plasma treating chamber and a means composed of an endless circular waveguide 108 having a plurality of slots and introducing microwaves into the plasma treating chamber, the slots are covered wish dielectric sheets 109 having conductance of >0 to 0.1 l/s, and a gas for treatment is introduced into the plasma treating chamber 101 through the dielectric sheets.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a plasma processing apparatus and a plasma processing method. More specifically, the present invention relates to a microwave plasma processing apparatus and method capable of generating high-density plasma having a large diameter and uniformity in order to perform high-quality processing of a large-area substrate uniformly and at high speed.

[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. CVD using such a so-called microwave plasma CVD apparatus is performed, for example, as follows. That is, a gas is introduced into a plasma generation chamber and a film formation chamber of a microwave plasma CVD apparatus, and simultaneously, microwave energy is supplied to generate plasma in the plasma generation chamber, and the gas is excited and decomposed to form a gas in the film formation chamber. A deposited film is formed on the arranged substrate.

[0003] An etching process for 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 introduced into the processing chamber of the apparatus, and simultaneously, microwave energy is applied to excite and decompose the etchant gas to generate plasma in the processing chamber. The surface of the processing substrate is etched.

An ashing process for a substrate to be processed using a so-called microwave plasma ashing apparatus is performed, for example, as follows. In other words, an ashing gas is introduced into the processing chamber of the apparatus, and simultaneously, microwave energy is applied to excite and decompose the ashing gas to generate plasma in the processing chamber, thereby forming a plasma disposed in the processing chamber. Ashing the surface of the processing substrate.

In a 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, for microwave plasma processing equipment, gas ionization efficiency,
It has the advantages of high excitation efficiency and decomposition efficiency, relatively easy formation of high-density plasma, and high-speed processing at low temperature and high speed. 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 a 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 also been put to practical use. The ECR is such that when the magnetic flux density is 87.5 mT, the electron cyclotron frequency at which electrons rotate around the lines of magnetic force is:
Coincides with the general microwave frequency of 2.45 GHz,
This is a phenomenon in which electrons are resonantly absorbed by microwaves, accelerated, and 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. (NTT type) in which the divergent magnetic field of (i) is introduced through an electromagnetic coil provided around the plasma generation chamber;
i) A microwave transmitted through the waveguide is introduced into the bell-shaped plasma generation chamber from the opposite surface of the substrate to be processed, and a magnetic field coaxial with the center axis of the plasma generation chamber is provided around the plasma generation chamber. (Hitachi method); (iii) microwaves are introduced into the plasma generation chamber from the periphery through a Rigitano coil, which is a kind of cylindrical slot antenna, and the center axis of the plasma generation chamber and A configuration in which a coaxial magnetic field is introduced through an electromagnetic coil provided around a plasma generation chamber (Rigitano method); (iv) microwaves transmitted through a waveguide are flattened from the opposing surface of a substrate to be processed. A configuration in which a loop-shaped magnetic field parallel to the antenna plane is introduced through a permanent magnet provided on the back surface of the planar antenna (plane It is a Ttoantena method).

As an example of a microwave plasma processing apparatus,
In recent years, a device using an endless annular waveguide in which a plurality of slots are formed on the inner surface has been proposed as a uniform and efficient microwave introduction device (Japanese Patent Laid-Open Publication No. Hei 5-345).
No. 982).

[0009]

However, using the microwave plasma processing apparatus as described above,
When processing large-area substrates of 0 mm or more, it is necessary to increase the thickness of the dielectric window to 20 mm or more in order to cope with an increase in the diameter, and the microwave electric field generated in the plasma processing chamber becomes weak and the plasma density becomes low. There is a problem that the processing speed is reduced and the processing speed is hardly improved.

A main object of the present invention is to solve the above-mentioned problems in the conventional microwave plasma processing apparatus,
Provided is a plasma processing apparatus and a plasma processing method capable of generating a large-diameter uniform high-density plasma so that processing can be performed uniformly and at high speed even when processing a large-area substrate of 300 mm or more. It is in.

[0011]

SUMMARY OF THE INVENTION The present inventor has solved the above-mentioned problems in the conventional microwave plasma processing apparatus and has made intensive efforts to achieve the above object. In a plasma processing apparatus using an annular waveguide as microwave introduction means, a slot is covered with a dielectric plate having a low but non-zero conductance, and a processing gas is introduced into the endless annular waveguide, and plasma is passed through the dielectric plate. By supplying to the processing chamber, φ
It has been found that high-density plasma can be uniformly generated in a large-diameter space of 400 mm or more, and a large-area substrate having a diameter of 300 mm or more can be uniformly and rapidly processed.

That is, the present invention is as follows. 1. A plasma processing chamber, support means for supporting a substrate to be processed installed in the plasma processing chamber, processing gas introducing means for introducing a processing gas into the plasma processing chamber,
A plasma processing apparatus comprising: an exhaust unit that exhausts the plasma processing chamber; and a microwave supply unit that has an endless annular waveguide having a plurality of slots and supplies a microwave to the plasma processing chamber. And the slot is 0.1
1 / s or less and covered with a dielectric plate having a non-zero conductance, the processing gas introducing means is provided in the endless annular waveguide, and the processing gas is passed through the dielectric plate. A microwave plasma processing apparatus, which is introduced into a plasma processing chamber. 2. 2. The plasma processing apparatus according to the above item 1, wherein the conductance of the dielectric plate is not 0 at 0.01 l / s or less. 3. 3. The plasma processing apparatus according to any one of the above items 1 to 2, wherein through holes are formed in the dielectric plate. 4. The plasma processing apparatus according to any one of the above items 1 to 3, wherein the dielectric plate is a porous body. 5. In a plasma processing apparatus for processing a substrate to be processed disposed in a processing chamber using plasma, a microwave is supplied into the processing chamber through a plurality of slots provided in a waveguide, and the plurality of slits are provided. A plasma processing apparatus, wherein a processing gas is supplied into the processing chamber from a derivative gas outlet provided between the processing chamber and the substrate. 6. 6. The plasma processing apparatus according to the above 5, wherein the waveguide is an endless annular waveguide. 7. 7. The plasma processing apparatus according to the above item 5 or 6, wherein the waveguide has a rectangular cross section, and the slot is provided on a surface including a long side thereof. 8. The above-mentioned 5 or 6 wherein the slot is provided in a surface of the waveguide which is arranged substantially in parallel with the surface to be processed of the substrate to be processed.
3. The plasma processing apparatus according to 1. 9. 7. The plasma processing apparatus according to the above item 5 or 6, wherein the waveguide has the slot in the H plane, and the H plane is arranged so as to face the surface of the substrate to be processed. 10. 7. The plasma processing apparatus according to the above item 5 or 6, wherein the processing gas released from the slot is released into a plasma generation region from a gas discharge port provided in the dielectric. 11. The plasma processing apparatus according to the above item 10, wherein the gas discharge port is a hole of a porous body constituting the derivative. 12. The waveguide is provided with a gas inlet which communicates with a gas supply system and introduces a processing gas into the waveguide.
Or the plasma processing apparatus according to 6. 13. A plasma processing chamber, support means for supporting a substrate to be processed installed in the plasma processing chamber, processing gas introducing means for introducing a processing gas into the plasma processing chamber, and exhausting the plasma processing chamber Surface of the substrate to be processed in a plasma processing apparatus, comprising: an exhaust unit for supplying a microwave to the plasma processing chamber, comprising: an endless annular waveguide having a plurality of slots; The slot is provided on the surface of the endless annular waveguide so as to face the substrate, and a processing gas is discharged to a dielectric provided between the surface provided with the slot and the object to be processed. A plasma processing apparatus having an emission port. 14． A plasma processing method using any one of the plasma processing apparatuses described in 1 to 4 above. 15. A plasma processing method for performing a surface treatment on a substrate to be processed using the plasma processing apparatus according to the above 5 or 13.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A microwave plasma processing apparatus according to the present invention will be described with reference to FIG. 101 is a plasma processing chamber, 102 is a substrate to be processed, 103 is a support for the substrate 102, 104 is a substrate temperature adjusting means (heater or cooler), 105 is a processing gas introducing means, 106 is an exhaust port,
Reference numeral 108 denotes a slotted endless annular waveguide for supplying microwaves to the plasma processing chamber 101, and reference numeral 109 denotes a dielectric plate that covers the slots.

The plasma processing is performed as follows.
The inside of the plasma processing chamber 101 is evacuated through an exhaust system including an exhaust pump VP and a valve CV. Subsequently, the processing gas is supplied from the gas cylinder GB, the opening / closing valve OV, and the mass flow controller MFC to the endless annular waveguide 108 at a predetermined flow rate through the introduction port 105 as the processing gas supply means.
The gas is supplied into the plasma processing chamber 101 through the inside and the slot, and further through the gas discharge port of the dielectric plate 109. Next, the conductance valve CV provided in the exhaust system is adjusted to maintain the inside of the plasma processing chamber 101 at a predetermined pressure. By supplying desired power from the microwave power supply MWP into the plasma processing chamber 101 via the endless annular waveguide 108 and the slot, the plasma processing chamber 101
Plasma is generated inside. The processing gas is excited by the generated high-density plasma, and processes the processing surface of the processing target 102 placed on the support 103.

FIG. 4A shows a plasma generation mechanism of the microwave plasma processing apparatus. Reference numeral 109 denotes a dielectric window that separates the plasma processing chamber 101 from the atmosphere, 108 denotes a slotted endless annular waveguide for introducing microwaves into the plasma processing chamber 901 through the dielectric window 907, and 911 denotes a microwave-free waveguide. A block distributed to the left and right of the terminal waveguide,
912 is a slot for emitting microwaves, 913 is a microwave propagating in the endless annular waveguide 108, 91
4 is a leakage wave of the microwave introduced into the plasma processing chamber 901 through the slot 912 and the dielectric window 907;
Reference numeral 15 denotes a microwave surface wave propagating in the dielectric window 907 through the slot 912, reference numeral 916 denotes plasma generated by leaky waves, and reference numeral 917 denotes plasma generated by surface waves.

At this time, the microwave 913 introduced into the endless annular waveguide 108 is split right and left by the distribution block 911 and propagates with a longer guide wavelength than the free air. Leakage waves 914 introduced into the plasma processing chamber 101 through the dielectric window 109 from the slots 912 installed at every 1/2 or 1/4 of the guide wavelength
A plasma 916 in the vicinity of 12 is generated. 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 window 109 are totally reflected at the surface of the dielectric window 109 and propagate as surface waves 915 on the surface of the dielectric window 109. . Plasma 917 is also generated by the electric field exuding from the surface wave 915. The processing gas is excited by the generated high-density plasma, and processes the surface of the substrate to be processed 902 mounted on the support 903.

By using such a microwave plasma processing apparatus, an electron density of 10 ¹² cm ^-3 or more, with a microwave power of 1 kW or more, uniformity within ± 3% for a large-diameter space having a diameter of about 300 mm, and Since high-density low-potential plasma having an electron temperature of 3 eV or less and a plasma potential of 20 V or less can be generated, the gas can be sufficiently reacted and supplied to the substrate in an active state, and substrate surface damage due to incident ions is reduced. High quality, uniform and high-speed processing becomes possible.

Relatively high pressure (1 T) such as ashing
In the case where the processing is performed near (orr), the diffusion of plasma is suppressed, so that the processing speed near the center of the base decreases. Therefore, in the present invention, E which constitutes the short side of the rectangular cross section of the waveguide is
The surface 111 is a curved surface, and H is the long side of the rectangular cross section of the waveguide.
A flat endless annular waveguide (PMA: Plane M) in which slots formed in the surface 110 are radially arranged on the same plane.
multi-SlotAntenna) was used (FIG. 4B).

The material of the dielectric plate 109 used in the microwave plasma processing apparatus of the present invention is applicable as long as the material has a small dielectric loss so that the mechanical strength is sufficient and the microwave transmittance is sufficiently high. For example, quartz, alumina (sapphire), aluminum nitride, and the like are optimal. The conductance of one dielectric plate with gas outlets 109 used in the microwave plasma processing apparatus of the present invention is C = Q / (P · n) (1) [C: conductance, Q: minimum flow rate, P: discharge Starting pressure, n: number of slots]. Specifically, 0.1
It is preferable to stabilize the generation of plasma by setting it to 1 / s or less.
As a means for adding low conductance for forming a gas discharge port of the dielectric plate 109 used in the microwave plasma processing apparatus of the present invention, a porous material may be used as a dielectric, and a communicating hole thereof may be used. Alternatively, a through hole may be formed in the dielectric plate. The material constituting the wall of the slotted endless annular waveguide 108 used in the microwave plasma processing apparatus of the present invention can be used as long as it is a conductor.
In order to minimize the propagation loss of microwaves, Al, Cu, Ag / Cu-plated SUS, etc. having high conductivity are optimal. The direction of the introduction port of the slotted endless annular waveguide 108 used in the present invention is described as an example in which the distribution direction is divided into two in the direction perpendicular to the H-plane 110 and in the left and right direction of the propagation space. As long as microwaves can be efficiently introduced into the microwave propagation space having a rectangular cross section in the endless annular waveguide 108, the microwaves may be introduced from the tangential direction of the propagation space parallel to the H plane 110. The shape of the slot of the slotted endless annular waveguide 108 used in the present invention is as follows.
As long as the length in the direction perpendicular to the microwave propagation direction is 1/4 or more of the guide wavelength, it may be rectangular, elliptical, or array. The slot spacing of the slotted endless annular waveguide 108 used in the present invention is optimally ま た は or の of the guide wavelength so that the electric field crossing the slot is enhanced by interference.

At least one gas outlet per slot or one gas outlet per slot.
It is good to arrange so that it may correspond to pieces.

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

In the microwave plasma processing apparatus and processing method of the present invention, a magnetic field generating means may be used for processing at a lower pressure. As the magnetic field used in the plasma processing apparatus and the processing method of the present invention, a mirror magnetic field or the like can be applied, but a loop magnetic field is generated on a curve connecting the centers of a plurality of slots of the endless annular waveguide with slots 108. The magnetic flux density of the magnetic field near the slot is optimally a magnetron magnetic field larger than the magnetic flux density of the magnetic field near the substrate. As the magnetic field generating means, a permanent magnet other than a coil can be used. When using a coil, other cooling means such as a water cooling mechanism or air cooling may be used to prevent overheating.

In order to improve the quality of the treatment, the surface of the substrate may be irradiated with ultraviolet light. Any light source can be used as long as it emits light that is absorbed by the substrate to be processed or the gas attached to the substrate. Excimer lasers, excimer lamps,
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 processing chamber is from 0.1 mTorr to 1 mTorr.
0 Torr range, more preferably 1 m of CVD
Torr to 100 mTorr;
5m Torr to 50m Torr, Ashing Fried 1
It can be selected from the range of 00 mTorr to 10 Torr.

In the formation of a deposited film by the microwave plasma processing method of the present invention, Si ₃ N ₄ , SiO ₂ , SiOF, Ta ₂ O ₅ , Ti
Insulating films such as O ₂ , TiN, Al ₂ O ₃ , AlN, and MgF ₂ , amorphous Si (a-Si), polycrystalline Si (poly-
Semiconductor films such as Si), SiC, GaAs, Al, W,
Various deposited films such as metal films of MO, Ti, Ta and the like can be efficiently formed.

The substrate 102 to be processed by the plasma processing method of the present invention may be a semiconductor, a conductive material, or an electrically insulating material.

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 glasses, Si ₃ N ₄ , NaCl, KCl, LiF, C
inorganic materials such as aF ₂ , BaF ₂ , Al ₂ O ₃ , AlN, and 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 a gas used for forming a thin film on a substrate by the CVD method, generally known gases can be used.

When a Si-based semiconductor thin film such as a-Si, poly-Si or SiC is formed, the source gas containing Si atoms introduced into the plasma processing chamber 101 through the processing gas introducing means 105 is SiH ₄ , inorganic silanes such as Si ₂ H ₆ , tetraethylsilane (TES), tetramethylsilane (TMS), dimethylsilane (DM
S), organic silanes such as dimethyldifluorosilane (DMDFS), dimethyldichlorosilane (DMDCS), SiF ₄ , Si ₂ F ₆ , Si ₃ F ₈ , SiHF ₃ , SiH
₂ F ₂ , SiCl ₄ , Si ₂ Cl ₆ , SiHCl ₃ , SiH ₂
Examples thereof include halogenated silanes such as Cl ₂ , SiH ₃ Cl, and SiCl ₂ F ₂ , which are in a gaseous state at normal temperature and pressure or those which can be easily gasified. In this case, Si
H ₂ , He, Ne, Ar, Kr, X
e and Rn.

Si_ThreeN_Four, SiO_TwoSi compound thin
Via the processing gas introducing means 105 for forming the membrane
As a raw material containing Si atoms to be introduced, SiH_Four,
Si_TwoH₆Inorganic silanes such as tetraethoxysilane
(TEOS), tetramethoxysilane (TMOS),
Kutamethylcyclotetrasilane (OMCTS), Dimethi
Rudifluorosilane (DMDFS), dimethyldichloro
Organic silanes such as silane (DMDCS), SiF_Four,
Si_TwoF₆, Si_ThreeF₈, SiHF_Three, SiH_TwoF_Two, SiC
l_Four, Si_TwoCl₆, SiHCl_Three, SiH_TwoCl_Two, SiH
_ThreeCl, SiCl_TwoF _TwoSuch as halogenated silanes
It can be gasified or easily gasified at normal temperature and temperature
Things. In this case, the simultaneous introduction
As the raw material gas or the oxygen raw material gas, N_Two, NH_Three,
N_TwoH_Four, Hexamethyldisilazane (HMDS), O_Two,
O_Three, H_TwoO, NO, N_TwoO, NO_TwoAnd the like.

When a metal thin film of Al, W, Mo, Ti, Ta or the like is formed, as a raw material containing a metal atom to be introduced through the processing gas introducing means 105, trimethyl aluminum (TMA1), triethyl aluminum ( TEA1), triisobutylaluminum (TIBA)
1), dimethyl aluminum hydride (DMA1
H), organic metals such as tungsten carbonyl (W (CO) ₆ ), molybdenum carbonyl (Mo (CO) ₆ ), trimethylgallium (TMGa) and triethylgallium (TEGa), AlCl ₃ , WF ₆ , TiCl ₃ , TaC
metal halide or the like such as l ₅ and the like. In this case, the additive gas or carrier gas which may be introduced as a mixture with the Si source gas is H ₂ , He, Ne, or A 2.
r, Kr, Xe, and Rn.

Al ₂ O ₃ , AlN, Ta ₂ O ₅ , TiO ₂ ,
When a metal compound thin film such as TiN or WO ₃ is formed, trimethyl aluminum (TM
A1), triethylaluminum (TEA1), triisobutylaluminum (TIBA1), dimethylaluminum hydride (DMA1H), tungsten carbonyl (W (CO) 6), molybdenum carbonyl (Mo)
(CO) ₆ ), organic metals such as trimethylgallium (TMGa) and triethylgallium (TEGa), AlCl
₃ , metal halides such as WF ₆ , TiCl ₃ , and TaCl ₅ . O ₂ , O ₃ , H ₂
O, NO, N ₂ O, NO ₂ , N ₂ , NH ₃ , N ₂ H ₄ , hexamethyldisilazane (HMDS) and the like.

As the etching gas introduced from the processing gas inlet 105 for etching the substrate surface, F ₂ , CF ₄ , CH ₂ F ₂ , C ₂ F ₆ , C ₃ F ₈ , C ₄ F _{8 are used.} ,
CF ₂ Cl ₂ , SF ₆ , NF ₃ , Cl ₂ , CCl ₄ , CH ₂ C
l ₂ , C ₂ Cl _{6 and the} like.

The ashing gas introduced from the processing gas inlet 115 for ashing for removing organic components such as a photoresist on the substrate surface by ashing is O ₂ , O ₃ , H _2.
O, NO, N ₂ O, NO ₂ , H _{2 and the} like can be mentioned.

When the microwave plasma processing apparatus and the plasma processing method of the present invention are applied to surface modification, by appropriately selecting a gas to be used, for example, Si, Al, Ti, Zn, Using 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. It can also be used for cleaning oxides, organic substances and heavy metals.

The oxidizing gas introduced through the processing gas inlet 105 when the substrate is subjected to oxidizing surface treatment is O 2
₂ , O ₃ , H ₂ O, NO, N ₂ O, NO _{2 and the} like. In addition, as the nitriding gas introduced through the processing gas inlet 115 when performing a nitriding surface treatment on the substrate,
N ₂ , NH ₃ , N ₂ H ₄ , hexamethyldisilazane (HMD
S) and the like.

The cleaning / ashing gas introduced from the gas inlet 105 for cleaning organic substances on the substrate surface or for ashing removal of organic components such as photoresist on the substrate surface is O ₂ ,
O ₃ , H ₂ O, NO, N ₂ O, NO ₂ , H _{2 and the} like can be mentioned. The cleaning gas introduced from the gas inlet for plasma generation for cleaning the inorganic substance on the substrate surface includes F ₂ , CF ₄ , CH ₂ F ₂ , C ₂ F ₆ , C _2
4 F ₈ , CF ₂ Cl ₂ , SF ₆ , NF _{3 and the} like.

[0039]

EXAMPLES Hereinafter, the microwave plasma processing apparatus and the plasma processing method of the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Embodiment 1 Apparatus Example 1 An example using a slotted endless annular waveguide covered with a dielectric plate having through holes in a microwave plasma processing apparatus of the present invention will be described with reference to FIG. 101 is a plasma processing chamber, 102 is a substrate to be processed, 103 is a support for the substrate 102, 104 is a substrate temperature adjusting means (heater or cooler), 105 is a processing gas introducing means, 106 is an exhaust gas,
Reference numeral 08 denotes an endless annular waveguide with a flat plate-like slot for introducing microwaves into the plasma processing chamber 101, and reference numeral 109 denotes a dielectric plate covering a slot in which a through-hole is formed.

The plasma processing is performed as follows.
The inside of the plasma processing chamber 101 is evacuated via the exhaust systems CV and VP. Subsequently, the processing gas is supplied from the inside of the slotted flat endless annular waveguide 108 at a predetermined flow rate through the gas introduction port 105 of the processing gas introducing means to the plasma through the slots and the through-holes of the dielectric plate 109. Processing chamber 101
Introduce within. Next, the conductance valves CV provided in the exhaust systems CV and VP are adjusted, and the plasma processing chamber 10 is adjusted.
1 is maintained at a predetermined pressure. A desired power from the microwave power supply MWP is supplied to the slotted endless annular waveguide 108.
The plasma is generated in the plasma processing chamber 101 by being supplied into the plasma processing chamber 101 via the. The processing gas is excited by the generated high-density plasma, and processes the surface of the substrate to be processed 102 placed on the support 103.

The dielectric plate 109 is made of synthetic quartz and has through holes. At least 1 mm in diameter
Individually formed. Endless annular waveguide with slot 108
Is that the inner wall cross-sectional dimension is 27 mm x 96 mm and the center diameter of the waveguide is 202 mm (perimeter 4λg: λg is wavelength)
It is. The material of the slotted endless annular waveguide 108 is
In order to suppress the propagation loss of microwaves, all use Al. H-plane 11 of slotted endless annular waveguide 108
A slot for introducing microwaves into the plasma processing chamber 101 is formed at 0. The shape of the slot is a rectangle having a length of 45 mm and a width of 4 mm.
It is formed radially at intervals. The guide wavelength depends on the frequency of the microwave used and the cross-sectional dimensions of the waveguide. However, the combination using the microwave having the frequency of 2.45 GHz and the waveguide having the above-mentioned size is approximately required. 159 mm. In the used endless annular waveguide with slots 108, 32 slots are formed at intervals of about 39.8 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 slotted endless annular waveguide 108.

Using the microwave plasma processing apparatus shown in FIG. 1, an Ar flow rate of 500 sccm and a pressure of 10 mTo
Plasma was generated under the conditions of rr, 1 Torr, and microwave power of 1.5 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 +100 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 is 10 mT
1.1 × 10 ¹² cm ^-3 ± 2.7% (φ30
5.7 × 10 ¹¹ cm ⁻³ ± 1 at 1 Torr
It was 4.2% (within φ300 plane), and it was confirmed that high-density and uniform plasma was formed in the large-diameter space.

Embodiment 2 Apparatus Example 2 An example using a slotted endless annular waveguide covered with a porous dielectric plate in a microwave plasma processing apparatus of the present invention will be described with reference to FIG. 201 is a plasma processing chamber, 2
02 is the substrate to be treated, 203 is the support of the substrate 202, 20
4 is a substrate temperature adjusting means (heater or cooler), 205
Is a processing gas introducing means, 206 is an exhaust, 208 is an endless annular waveguide with slots for introducing microwaves into the plasma processing chamber 201, and 209 is a porous dielectric plate covering the slots.

The plasma processing is performed as follows.
The inside of the plasma processing chamber 201 is evacuated via an exhaust system (not shown). Subsequently, a processing gas is introduced into the plasma processing chamber 201 from the inside of the slotted endless annular waveguide 208 through the dielectric plate 209 at a predetermined flow rate through the processing gas introduction means 205. Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted to maintain the inside of the plasma processing chamber 201 at a predetermined pressure. By supplying a desired power from a microwave power supply (not shown) to the plasma processing chamber 201 through the slotted endless annular waveguide 208, plasma is generated in the plasma processing chamber 201. The processing gas is excited by the generated high-density plasma, and processes the surface of the target substrate 202 placed on the support 203.

The dielectric plate 209 is made of porous alumina. The slotted endless annular waveguide 208 is
The dimensions of the inner wall cross section are 27 mm × 96 mm, and the center diameter of the waveguide is 202 mm (peripheral length 4λg). The material of the slotted endless annular waveguide 208 is all Al in order to suppress microwave propagation loss. Slots for introducing microwaves into the plasma processing chamber 201 are formed on the H surface 210 of the slotted endless annular waveguide 208. The shape of the slot is 45mm in length and 4 in width
mm, and are formed radially at intervals of 1/4 of the guide wavelength. The guide wavelength depends on the frequency of the microwave used and the cross-sectional dimensions of the waveguide.
When a microwave of 45 GHz and a waveguide having the above dimensions are used, the distance is about 159 mm. In the slotted endless annular waveguide 208 used, the slot is approximately 39.8 m.
32 are formed at m intervals. 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 slotted endless annular waveguide 208.

Using the microwave plasma processing apparatus shown in FIG. 2, an Ar flow rate of 500 sccm and a pressure of 10 mTo
Plasma was generated under the conditions of rr, 1 Torr, and microwave power of 2.0 kW, and the obtained plasma was measured. As a result, the electron density was 10 mTOrr.
4 × 10 ¹² cm ^-3 ± 2.9% (φ300 plane), 1To
The rr was 7.4 × 10 ¹¹ cm ⁻³ 3.6% (within φ300 plane), confirming that high-density and uniform plasma was formed in the large-diameter space.

Embodiment 3 Apparatus Example 3 An example using the RF bias application mechanism of the microwave plasma processing apparatus of the present invention will be described with reference to FIG. 301 is a plasma processing chamber, 302 is a substrate to be processed, 303 is a substrate 3
Reference numeral 02 denotes an RF electrode serving also as a support, reference numeral 304 denotes a substrate temperature adjusting unit (heater or cooler), reference numeral 305 denotes a processing gas introducing unit, reference numeral 306 denotes exhaust, and reference numeral 308 denotes a slot for introducing microwaves into the plasma processing chamber 301. An endless annular waveguide, 309 is a dielectric plate covering the slot in which the through hole is formed, and 310 is a high frequency power source for substrate bias.

The plasma processing is performed as follows.
The inside of the plasma processing chamber 301 is evacuated via an exhaust system (not shown). Subsequently, a processing gas is introduced into the plasma processing chamber 301 from the inside of the slotted endless annular waveguide 308 through the dielectric plate 309 at a predetermined flow rate through the processing gas introduction means 305. Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted to maintain the inside of the plasma processing chamber 301 at a predetermined pressure. RF electrode 303 serving also as a support with desired power from RF power supply 310
And a desired power from a microwave power supply (not shown) is supplied to the plasma processing chamber 301 through the slotted endless annular waveguide 308 to generate plasma in the plasma processing chamber 301. I do. The processing gas is excited by the generated high-density plasma, and the substrate 302 to be processed placed on the RF electrode 303 also serving as a support.
Treat the surface.

The dielectric plate 309 is made of sapphire and has one through hole with a diameter of 1 mm. The endless annular waveguide 308 with a slot has an inner wall cross-sectional dimension of 27 mm.
× 96 mm, and the center diameter of the waveguide is 202 mm (peripheral length 4λg). Endless annular waveguide with slot 308
Are all made of Al to suppress microwave propagation loss. Endless annular waveguide with slot 308
Microwave is applied to the plasma processing chamber 301
A slot is formed for introduction into the housing. The shape of the slot is a rectangle having a length of 45 mm and a width of 4 mm, and is formed radially at intervals of 1/4 of the guide wavelength. The guide wavelength depends on the frequency of the microwave used and the cross-sectional dimensions of the waveguide. However, the combination using the microwave having the frequency of 2.45 GHz and the waveguide having the above-mentioned size is approximately required. 159m
m. Used slotted endless annular waveguide 308
In this example, 32 slots are formed at intervals of about 39.8 mm. The endless annular waveguide with slot 308 has 4E
Tuner, directional coupler, isolator, 2.45GH
A microwave power supply (not shown) having a frequency of z is connected in order.

Using the microwave plasma processing apparatus shown in FIG. 3, an Ar flow rate of 500 sccm and a pressure of 10 mTo
Plasma was generated under the conditions of rr, 1 Torr, and microwave power of 3 kW, and the obtained plasma was measured.
As a result, the electron density is 1.6 × 10 mTorr.
10 ¹² cm ^-3 ± 2.5% (in φ300 plane), 1 Torr
In this case, the density was 8.0 × 10 ¹¹ cm ⁻³ ± 4.7% (within φ300 plane), and it was confirmed that high-density and uniform plasma was formed in the large-diameter space.

Example 4 Ashing of a photoresist was performed using the microwave plasma processing apparatus shown in FIG.

As the base 102, silicon (S) immediately after the interlayer SiO ₂ film was etched and via holes were formed.
i) A substrate (φ12 inch) was used. First, after setting the Si substrate 102 on the base support 103, the heater 10
4 was heated to 200 ° C. was used to evacuate the plasma processing chamber 101 through an exhaust system (not shown), 10 ^@ 4 the To
The pressure was reduced to rr. Gas inlet 105 for plasma processing
Oxygen gas at a flow rate of 2 slm through the plasma processing chamber 1
01. Next, a conductance valve (not shown) provided in an exhaust system (not shown) was adjusted to maintain the inside of the processing chamber 101 at 1 Torr. Plasma processing chamber 10
Within 2.0k from 2.45GHz microwave power supply
W power was supplied through the slotted endless annular waveguide 108. Thus, plasma was generated in the plasma processing chamber 101. At this time, the plasma processing gas inlet 1
Oxygen gas introduced through the plasma processing chamber 10
Excited, decomposed and reacted in 1 to form ozone, transported in the direction of the silicon substrate 102, oxidized the photoresist on the substrate 102, and vaporized and removed. After the ashing, the ashing speed and the substrate surface charge density were evaluated.

The obtained ashing speed was 8.5 μm /
min ± 6.2%, and the surface charge density is also 1.
This was a sufficiently low value of 4 × 10 ¹¹ cm ⁻² .

Example 5 Photoresist ashing was performed using the microwave plasma processing apparatus shown in FIG.

As the base 202, silicon (S) immediately after the interlayer SiO ₂ film was etched and via holes were formed.
i) A substrate (φ12 inch) was used. First, after placing the Si substrate 202 on the base support 203, the heater 20
4 and heated to 200 ° C., and the inside of the plasma processing chamber 201 was evacuated via an exhaust system (not shown) to 10 ^-5 To.
The pressure was reduced to rr. Gas inlet 205 for plasma processing
Oxygen gas at a flow rate of 2 slm through the plasma processing chamber 2
01. Next, a conductance valve (not shown) provided in an exhaust system (not shown) was adjusted to maintain the inside of the processing chamber 201 at 2 Torr. Plasma processing chamber 20
Within 2.0k from 2.45GHz microwave power supply
W power was supplied via slotted endless annular waveguide 208. Thus, plasma was generated in the plasma processing chamber 201. At this time, the plasma processing gas inlet 2
Oxygen gas introduced through the plasma processing chamber 20
Excited, decomposed and reacted in 1 to form ozone, transported in the direction of the silicon substrate 202, oxidized the photoresist on the substrate 202, and vaporized and removed. After the ashing, the ashing speed and the substrate surface charge density were evaluated.

The obtained ashing speed was 8.6 μm /
min ± 7.8%, and the surface charge density is also 1.
This was a sufficiently low value of 2 × 10 ¹¹ cm ⁻² .

Example 6 Using the microwave plasma processing apparatus shown in FIG. 1, a silicon nitride film for protecting a semiconductor element was formed.

As the base 102, a φ300 mm P-type single crystal silicon substrate (plane orientation <100>, resistivity 10 Ωcm) with an interlayer SiO ₂ film on which an Al wiring pattern (line and space 0.5 μm) was formed was used.
First, after the silicon substrate 102 is set on the base support 103, the plasma processing chamber 10 is set via an exhaust system (not shown).
The 1 was evacuated, it was reduced to 10 ^@ 7 Torr. Subsequently, a current is supplied to the heater 104 so that the silicon substrate 102
Heated to 0 ° C. and kept the substrate at this temperature. 600 sc of nitrogen gas through the plasma processing gas inlet 105
cm and a flow rate of monosilane gas of 200 sccm
Into the processing chamber 101 at a flow rate of Next, a conductance valve (not shown) provided in an exhaust system (not shown) was adjusted to maintain the inside of the processing chamber 101 at 20 mTorr. Then, 3.0 kW of power was supplied from a 2.45 GHz microwave power supply (not shown) via the slotted endless annular waveguide 108. Thus, plasma was generated in the plasma processing chamber 101. At this time, the nitrogen gas introduced through the plasma processing gas inlet 105 is excited and decomposed into active species in the plasma processing chamber 101, is transported in the direction of the silicon substrate 102, reacts with the monosilane gas, and reacts with the silicon nitride. A film was formed on the silicon substrate 102 with a thickness of 1.0 μm. 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 deposition rate of the obtained silicon nitride film is 5
Extremely large at 80 nm / min and the film quality is 1.1 ×
10 ⁹ dyne · cm ^-2 (compression), leak current 1.2 ×
^{10 -} 10 A · cm ^-2, it was confirmed that an extremely high-quality film of dielectric strength 10.3MV / cm.

Example 7 The microwave plasma processing apparatus shown in FIG. 2 was used to form a silicon oxide film and a silicon nitride film for preventing plastic lens reflection.

As the substrate 202, a plastic convex lens having a diameter of 50 mm was used. After the lens 202 was set on the substrate support 203, the inside of the plasma processing chamber 201 was evacuated via an exhaust system (not shown) to reduce the pressure to 10 ^-7 Torr. Nitrogen gas was introduced into the processing chamber 201 at a flow rate of 150 sccm, and monosilane gas was introduced at a flow rate of 100 sccm through the plasma processing gas inlet 205. Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted so that the inside of the processing chamber 201 is 5 m.
Torr. Next, a power of 3.0 kW from a microwave power supply (not shown) of 2.45 GHz is supplied to the plasma processing chamber 201 through the slotted endless annular waveguide 203.
Supplied within. Thus, plasma was generated in the plasma processing chamber 201. At this time, the nitrogen gas introduced through the plasma processing gas inlet 205 is excited and decomposed in the plasma processing chamber 201 to become active species such as nitrogen atoms, is transported in the direction of the lens 202, and reacts with the monosilane gas. Then, a silicon nitride film is formed on the lens 202 by 20 nm.
It was formed with the thickness of.

Next, oxygen gas and monosilane gas were introduced into the processing chamber 201 through the plasma processing gas inlet 205 at a flow rate of 200 sccm and at a flow rate of 100 sccm. Next, a conductance valve (not shown) provided in an exhaust system (not shown) was adjusted to maintain the inside of the processing chamber 201 at 1 mTorr. Then, 2.0 kW of power was supplied from a 2.45 GHz microwave power supply (not shown) into the plasma generation chamber 201 via the slotted endless annular waveguide 208. Thus, the plasma processing chamber 201
A plasma was generated inside. At this time, the oxygen gas introduced through the plasma processing gas inlet 205 is excited and decomposed in the plasma processing chamber 201 to become active species such as oxygen atoms, is transported in the direction of the glass substrate 202, and is converted into a monosilane gas. The silicon oxide film reacts and the glass substrate 20
2 was formed with a thickness of 85 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 350 nm / min and 390 n, respectively.
m / min, and the film quality was confirmed to be very good, with a reflectance around 500 nm of 0.23%.

Example 8 Using the microwave plasma processing apparatus shown in FIG. 3, a silicon oxide film for interlayer insulation of a semiconductor element was formed.

As the substrate 302, a φ having an Al pattern (line and space 0.5 μm) formed on the uppermost portion was formed.
300 mm P-type single crystal silicon substrate (plane orientation <10
0>, resistivity 10 Ωcm). First, a silicon substrate 302 was set on a base support 303. The inside of the plasma processing chamber 301 was evacuated through an exhaust system (not shown) to reduce the pressure to 10 ^-7 Torr. Subsequently, the heater 30
4 to heat the silicon substrate 302 to 300 ° C.
The substrate was kept at this temperature. Oxygen gas is supplied at a flow rate of 500 sccm through the gas inlet 305 for plasma processing.
Further, a monosilane gas was introduced into the processing chamber 301 at a flow rate of 200 sccm. Next, a conductance valve (not shown) provided in an exhaust system (not shown) was adjusted to maintain the inside of the plasma processing chamber 301 at 30 mTorr. Then, through the high frequency applying means 310 of 400 kHz, 30
While applying 0 W power to the substrate support 302,
A power of 2.0 kW was supplied from a microwave power supply of 2.45 GHz into the plasma processing chamber 301 via the slotted endless annular waveguide 303. Thus, plasma was generated in the plasma processing chamber 301. The oxygen gas introduced through the plasma processing gas inlet 305 is excited and decomposed in the plasma processing chamber 301 to become active species, is transported in the direction of the silicon substrate 302, reacts with the monosilane gas, and reacts with the silicon oxide film to form a silicon oxide film. 0.8μ on the substrate 302
m. At this time, the ion species is accelerated by the RF bias and is incident on the substrate to cut the film on the pattern to improve the flatness. After the treatment, the film forming speed, uniformity, dielectric strength, and step coverage were evaluated. The step coverage was evaluated by observing a cross section of the silicon oxide film formed on the Al wiring pattern with a scanning electron microscope (SEM) and observing voids.

The obtained silicon oxide film has a good film formation rate and uniformity of 290 nm / min ± 2.5%, a film quality of 9.1 MV / cm, a void-free film and good quality. Was confirmed.

Example 9 Using the microwave plasma processing apparatus shown in FIG. 3, the etching of the SiO ₂ film between semiconductor elements was performed.

As the substrate 302, a 1 μm thick interlayer S was formed on an Al pattern (line and space 0.35 μm).
A φ300 mm P-type single crystal silicon substrate (plane orientation <100>, resistivity 10 Ωcm) on which an iO ₂ film was formed was used. First, after the silicon substrate 302 is set on the base support 303, the etching chamber 3 is set via an exhaust system (not shown).
01 was evacuated to a vacuum of 10 ^-7 Torr.
30 CF ₄ was introduced through the plasma processing gas inlet 305.
It was introduced into the plasma processing chamber 301 at a flow rate of 0 sccm. Next, a conductance valve (not shown) provided in an exhaust system (not shown) is adjusted, and the plasma processing chamber 301 is adjusted.
The inside was maintained at a pressure of 5 mTorr. Then 400k
While applying 300 W of electric power to the substrate support 302 through the high frequency applying means 310 of 2.45 GHz.
Was supplied into the plasma processing chamber 301 through the slotted endless annular waveguide 303 from the microwave power source of No.3. Thus, plasma was generated in the plasma processing chamber 301. The CF ₄ gas introduced through the plasma processing gas inlet 305 is excited and decomposed in the plasma processing chamber 301 to become an active species, and the silicon substrate 302
, And the interlayer SiO ₂ film was etched by the ions accelerated by the self-bias. The cooler 307 increased the substrate temperature only up to 90 ° C. 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 silicon oxide film with a scanning electron microscope (SEM).

It was confirmed that the etching rate and the selectivity to polysilicon were as good as 720 nm / min and 20, respectively, and that the etching shape was almost vertical and the microloading effect was small.

Embodiment 10 The microwave plasma processing apparatus shown in FIG. 3 was used to etch a polysilicon film between gate electrodes of a semiconductor device.

As the substrate 302, a φ300 mm P-type single crystal silicon substrate (plane orientation <100>, resistivity 10 Ωcm) having a polysilicon film formed on the top was used.
First, after the silicon substrate 302 is set on the base support 303, the plasma processing chamber 30 is set via an exhaust system (not shown).
The inside of 1 was evacuated and the pressure was reduced to 10 ^-7 Torr. CF ₄ gas is supplied through the plasma processing gas inlet 305.
Oxygen was introduced into the plasma processing chamber 301 at a flow rate of 00 sccm and 20 sccm. Next, the conductance valve (not shown) provided in the exhaust system (not shown) is adjusted,
The inside of the plasma processing chamber 301 was maintained at a pressure of 2 mTorr. Next, 300 W of high-frequency power from a 400-kHz high-frequency power supply (not shown) is applied to the substrate support 303, and 2.0-kHz from a 2.45-GHz microwave power supply.
W power was supplied into the plasma processing chamber 301 via the slotted endless annular waveguide 303. Thus, plasma was generated in the plasma processing chamber 301. The CF ₄ gas and oxygen introduced through the plasma processing gas inlet 305 are excited and decomposed into active species in the plasma processing chamber 301, transported toward the silicon substrate 302, and accelerated by self-bias. As a result, the polysilicon film was etched. Due to the cooler 304, the substrate temperature rose only to 80 ° C. 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 to SiO ₂ were as good as 850 nm / min and 24, respectively, and it was confirmed that the etching shape was vertical and the microloading effect was small.

[0074]

As described above, the plasma processing chamber, the means for supporting the substrate to be processed installed in the plasma processing chamber, the means for introducing a processing gas into the plasma processing chamber, the plasma processing chamber, A plasma processing apparatus comprising: means for exhausting the chamber; and means for introducing a microwave into the plasma processing chamber, the plasma processing apparatus comprising an endless annular waveguide having a plurality of slots, wherein the slot has a gas discharge port. By introducing the processing gas into the plasma processing chamber through the dielectric plate,
Even when processing large area substrates of φ300 mm or more,
A plasma processing apparatus and a plasma processing method capable of generating a large-diameter uniform high-density plasma so that uniform and high-speed processing can be performed can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic view showing one example of a microwave plasma processing apparatus of the present invention.

FIG. 2 is a schematic view showing another example of the microwave plasma processing apparatus of the present invention.

FIG. 3 is a schematic diagram of a bias microwave plasma processing apparatus as an example of the present invention.

FIG. 4 is a schematic view showing a conventional microwave plasma processing apparatus (FIG. 4A) and a plasma generation mechanism (FIG. 4B).

[Explanation of symbols]

101, 201, 301 Plasma processing chambers 102, 202, 302 Substrates to be processed 103, 203, 303 Supports 104, 204, 304 Substrate temperature adjusting means (heater or cooler) 105, 205, 305 Processing gas introducing means 106, 206 , 306 Exhaust (port) 108, 208, 308 Slotted endless annular waveguide 109, 209, 309 Dielectric plate 310 High-frequency power supply for substrate bias 901 Plasma processing chamber 902 Substrate to be processed 903 Support 904 Substrate temperature adjusting means 905 Processing gas introducing means 906 Exhaust 907 Dielectric window 908 Slotted endless annular waveguide 911 Dual distribution block 912 Slot 913 Microwave introduced into endless annular waveguide 914 Leakage wave 915 Surface wave 916 Generated by leaky wave Plasma 917 Table Plasma generated by wave

Claims (15)

[Claims] A plasma processing chamber; supporting means for supporting a substrate to be processed installed in the plasma processing chamber; processing gas introducing means for introducing a processing gas into the plasma processing chamber; Exhaust means for exhausting the processing chamber;
A plasma processing apparatus comprising: an endless annular waveguide having a plurality of slots; and a microwave supply means for supplying a microwave to the plasma processing chamber, wherein the slot is 0.1 l / s or less. The processing gas introduction means is provided in the endless annular waveguide, and the processing gas is supplied to the plasma processing chamber through the dielectric plate. A microwave plasma processing apparatus to be introduced. 2. The conductance of said dielectric plate is 0.0
2. The plasma processing apparatus according to claim 1, wherein the value is not 0 at 1 l / s or less. 3. The plasma processing apparatus according to claim 1, wherein through holes are formed in the dielectric plate. 4. The plasma processing apparatus according to claim 1, wherein said dielectric plate is a porous body. 5. A plasma processing apparatus for processing a substrate to be processed disposed in a processing chamber using plasma, wherein microwaves are supplied into the processing chamber through a plurality of slots provided in a waveguide, and A plasma processing apparatus, wherein a processing gas is supplied into the processing chamber from a derivative gas outlet provided between the plurality of slots and the substrate to be processed. 6. The plasma processing apparatus according to claim 5, wherein said waveguide is an endless annular waveguide. 7. The waveguide according to claim 5, wherein the waveguide has a rectangular cross section, and the slot is provided on a surface including a long side thereof.
3. The plasma processing apparatus according to 1. 8. The plasma processing apparatus according to claim 5, wherein said slot is provided on a surface of said waveguide which is disposed substantially parallel to a surface to be processed of said substrate to be processed. 9. The plasma according to claim 5, wherein the waveguide has the slot in the H plane, and the H plane is arranged so as to face the processing surface of the substrate to be processed. Processing equipment. 10. The plasma processing apparatus according to claim 5, wherein the processing gas released from the slot is released to a plasma generation region from a gas discharge port provided in the dielectric. 11. The plasma processing apparatus according to claim 10, wherein the gas outlet is a hole of a porous body constituting the derivative. 12. The waveguide communicates with a gas supply system,
7. The plasma processing apparatus according to claim 5, further comprising a gas inlet for introducing a processing gas into the waveguide. 13. A plasma processing chamber, and support means for supporting a substrate to be processed installed in the plasma processing chamber;
A processing gas introducing means for introducing a processing gas into the plasma processing chamber, an exhaust means for exhausting the plasma processing chamber, and an endless annular waveguide having a plurality of slots; A microwave supply unit for supplying a wave, wherein the slot is provided on the surface of the endless annular waveguide so as to face a surface to be processed of the substrate to be processed, A plasma processing apparatus, characterized in that a discharge port for discharging a processing gas is provided in a dielectric provided between the surface provided and the object to be processed. 14. A plasma processing method using any one of the plasma processing apparatuses according to claim 1. 15. A plasma processing method for performing a surface treatment of a substrate to be processed using the plasma processing apparatus according to claim 5.