JPH07153595A - Existent magnetic field inductive coupling plasma treating device - Google Patents

Abstract

PURPOSE:To provide a plasma treating device having large throughput by which formation of an accumulating film or etching treatment on a uniform and large areal board can be performed at high speed by generating plasma over a wide range with high density in a vacuum vessel. CONSTITUTION:After the inside of a plasma generating chamber 101 is evacuated, plasma generating gas is introduced, and is held under constant pressure. Prescribed electric power is supplied to a coil 106 from DC electric power supply, and a mirror magnetic field is generated in the plasma generating chamber 101. Desired electric power is supplied in the plasma generating chamber 101 from high frequency electric power supply 103 through an antenna 104. An electron having heat speed close to phase velocity of a circularly polarized wave generated in the plasma generating chamber 101 is resonantly accelerated, and high density plasma is generated in the plasma generating chamber 101. Since a central shaft of a high frequency introducing means by the antenna 104 is arranged so that the magnetic field directions by a coil 106 coincide with each other and become respectively parallel with a treating surface of a board 112 to be treated, a helicon wave is generated in a large range, so that a plasma generating area is uniformized.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasma processing apparatus employed for film forming processing for forming various deposited films such as nitride films and oxide films on substrates such as synthetic resins and semiconductors, or etching processing for sample surfaces. .

[0002]

2. Description of the Related Art Conventionally, an inductively coupled plasma processing apparatus has been used for a CVD apparatus, an etching apparatus and the like. In an inductively coupled plasma CVD apparatus, a raw material gas for film formation is introduced into the film formation chamber, and at the same time, high frequency energy is introduced into the vacuum container to excite and decompose the raw material gas to generate plasma, and the plasma is generated on the substrate. Form a deposited film.

In the inductively coupled plasma etching apparatus, an etchant gas is introduced into the processing chamber and, at the same time, high frequency is applied to input energy to generate plasma and etch the surface of the substrate to be processed.

In order to increase the processing speed of such an inductively coupled plasma processing apparatus, a so-called magnetic field inductively coupled plasma processing apparatus equipped with a magnetic field generator has been proposed. And among these, there is one that uses helicon waves. The helicon wave is an electromagnetic wave generated when the central axis of the high-frequency introducing means by inductive coupling such as a loop antenna and the direction of the magnetic field generated by the stationary magnetic field generating means such as a coil coincide with each other and the following condition is satisfied. That is, the magnetic flux density of the stationary magnetic field is equal to or larger than the magnitude that causes electron cyclotron resonance (when the high frequency f is 13.56 MHz, the magnetic flux density B is
About 0.48 mT or more;

[0005]

[Outer 1] ), And the Larmor frequency of the electrons traveling around the magnetic field lines is equal to or higher than the collision frequency of the electrons. The helicon wave has a wavelength determined by the frequency of the high frequency, the magnetic flux density, the inner diameter of the tubular tube, and the like, and becomes a clockwise circularly polarized electromagnetic wave (circularly polarized wave). When the phase velocity of circularly polarized wave is close to the thermal velocity of electrons, random attenuation occurs in which the energy of the helicon wave is resonantly absorbed by the electrons. Therefore, the electrons are accelerated and high density plasma is generated. So far
It has been reported that a helicon wave is used to generate a plasma having a higher density than that of electron cyclotron resonance (ECR) plasma which is a typical high density plasma.

A typical configuration of such a magnetic field inductively coupled plasma processing apparatus is Plasma Mater.
It is known that an MORI source manufactured by ials Technology (PMT) is used as a plasma source. MORI
FIG. 4 shows the configuration of a helicon wave plasma etching apparatus (Apex 7000 manufactured by Alcan Tech) using a source. In FIG. 4, 1101 is a plasma generation chamber, 11
Reference numeral 02 denotes an etching gas introduction pipe for introducing the etching gas into the plasma generation chamber 1101, 1103 a high frequency power supply, 1104 for a helical antenna for introducing a high frequency into the plasma generation chamber 1101, 1105 for the plasma generation chamber 11
Quartz tube constituting 01, 1106 is plasma generation chamber 11
A coil for generating a stationary magnetic field in 01, an etching chamber 1111 connected to a plasma generation chamber, 1112 a substrate to be etched, 1113 a support for mounting the substrate 1112, 1115 gas exhaust, 1116 an electron wall. It is a magnet that generates a multicusp magnetic field that suppresses recombination.
The high frequency generated by the high frequency power supply 1103 propagates inside the helical antenna 1105, and thus the plasma generation chamber 1
An induction electric field is generated in 101 to accelerate electrons and generate plasma. At this time, the condition that the magnetic flux density of the stationary magnetic field generated via the coil 1106 is set to be equal to or higher than the magnetic flux density at which electron cyclotron resonance occurs and that the Larmor frequency of the electrons around the magnetic field lines is equal to or higher than the collision frequency of the electrons is satisfied. Right-handed circularly polarized wave is effectively generated, electrons having a thermal velocity close to the phase velocity of circularly polarized wave are resonantly accelerated, and high-density plasma is generated in the plasma generation chamber 1101.
The etching gas introduced into the etching chamber 1111 through the etching gas introduction pipe 1102 is excited by the generated high density plasma, and etches the surface of the substrate 1112 to be etched placed on the support 1113.

However, in the magnetic field inductively coupled plasma processing apparatus shown in FIG. 4, the diameter of the plasma generating chamber is limited because there is only one set of high frequency introducing means and magnetic field generating means, and plasma is generated in the high density region. Since it is strongly localized in the center of the chamber, it is not enough to spread the plasma by diffusion, and it is difficult to uniformly process a large-diameter substrate. Therefore,
It is also not suitable for through-type plasma processing that can achieve high throughput.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a plasma processing apparatus which solves the above-mentioned problems in the conventional magnetic field inductively coupled plasma processing apparatus.

That is, the diameter of the plasma generating chamber is limited,
Moreover, since the high-density region is strongly localized in the center of the plasma generation chamber, it is not enough to spread the plasma by diffusion, and it is difficult to uniformly process a large-diameter substrate. is there.

Another object of the present invention is to generate a uniform high density plasma over a wide range, particularly in the longitudinal direction, even when the through method is employed in which plasma processing is carried out while transporting the substrate. An object of the present invention is to provide a plasma processing apparatus capable of forming an insulating film, a semiconductor film or the like having a uniform film quality with a large throughput. That is, it is to provide a plasma processing apparatus which has a large number of wafers to be processed per unit time and has a large mass production capability.

[0011]

The present inventor has earnestly studied to solve the above-mentioned problems in the conventional magnetic field inductively coupled plasma processing apparatus, and as a result, the center of high frequency introducing means such as a loop antenna and a helical antenna. The axis is aligned with the direction of the magnetic field generated by the magnetic field generating means such as a coil, and the central axis and the magnetic field direction are arranged parallel to the processing surface of the substrate to be processed. We contemplate a magnetic field inductively coupled plasma processing system in which a plurality of magnetic fields are arranged. As a result, under the above-mentioned conditions, if the magnitude of the magnetic field, the frequency of the high frequency, etc. are adjusted, the helicon wave can be generated in a large range, and the plasma generation region in the vacuum container is uniformly and greatly expanded. Therefore, even when the through method is adopted in which plasma processing is performed while the substrate is being transported, a uniform high-density plasma can be generated over a wide range, particularly in the longitudinal direction, and an insulator film or semiconductor with uniform film quality can be generated. It has been found that a plasma processing apparatus capable of forming a film with a large throughput can be provided.

The plasma processing apparatus of the present invention made on the basis of such knowledge is a vacuum container, a means for introducing a high frequency wave into the vacuum container by inductive coupling, a means for generating a magnetic field in the vacuum container and the inside of the vacuum container. In the magnetic field coupled plasma processing apparatus having means for transferring the substrate to be processed, a plurality of the high frequency introducing means and the plurality of magnetic field generating means are respectively arranged.

The present invention also includes the following requirements.
That is, the central axes of the plurality of high-frequency introducing means, the central axes of the plurality of magnetic field generating means, and the surface to be processed of the substrate to be processed are arranged substantially in parallel, and the central axis is the object to be processed. Substantially in the transport direction of the substrate.

The high frequency introducing means is an antenna.

The antenna is a helical antenna.

The antenna is a loop antenna.

Substrate transfer means is arranged at a position separated from the plasma generation region in the vacuum container.

A differential pressure generating means such as a perforated quartz plate is arranged between the plasma generating region in the vacuum container and the substrate support.

A means is provided for irradiating the surface of the substrate to be treated with visible ultraviolet light.

By using the above magnetic field inductively coupled plasma processing apparatus, the helicon wave spreads in a wide range in the vacuum container, and the helicon wave causes plasma in a wide range. Therefore, it is possible to solve the problem that the high-density region of plasma, which has been a problem in the past, is strongly localized in the center of the plasma generation chamber. This is because the size of the treated area of the plasma processing apparatus mainly depends on whether or not the high-density plasma spreads greatly. Further, the higher the density, the faster the substrate can be processed. Therefore, it is possible to provide a magnetic field inductively coupled plasma processing apparatus capable of performing etching and forming a deposited film at a high speed over a wide area even on a large-area substrate and capable of performing a uniform and efficient processing.

By using the above-mentioned magnetic field inductively coupled plasma processing apparatus, the substrate to be processed transferred into the plasma generation chamber of the magnetic field inductively coupled plasma processing apparatus is made uniform and subjected to plasma processing with high throughput.

An example of the magnetic field inductively coupled plasma processing apparatus of the present invention is shown in FIG. 101 is a plasma generation chamber, 102
Is a gas generating means for plasma generation, 103 is a high frequency power source,
104 is an antenna for introducing a high frequency into the plasma generation chamber 101, 105 is a quartz window formed in a part of the plasma generation chamber 101, and 106 is a magnetic field parallel to the central axis of the antenna 104 in the plasma generation chamber 101. Magnetic field generating means such as a coil, 111 a plasma processing chamber connected to the plasma generating chamber, 112 a substrate to be processed, 113 a substrate 1
12 is a transfer means, 114 is a processing gas introduction means, 115
Is exhaust.

The generation and processing of plasma are performed as follows. Plasma generation chamber 1 via an exhaust system (not shown)
The inside of 01 is evacuated. Then, a gas for plasma generation is introduced into the plasma generation chamber 101 through the gas inlet 102 at a predetermined flow rate. Next, a conductance valve (not shown) provided in the exhaust system (not shown) is adjusted to maintain the inside of the plasma generation chamber 101 at a predetermined pressure. Then, a magnetic field is generated in the plasma generation chamber 101 using the magnetic field generation means 106, and then desired power is supplied from the high frequency power supply (not shown) into the plasma generation chamber 101 via the antenna 104. Electrons having a thermal velocity close to the phase velocity of circularly polarized waves generated in the plasma generation chamber 101 are resonantly accelerated, and high-density 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 introduction pipe 114, the processing gas is excited by the generated high density plasma and the substrate to be processed placed on the transfer means 113. The surface of 112 is plasma treated. At this time, the plasma processing gas may be introduced into the plasma generation gas inlet 102 depending on the application.

In the use of the magnetic field inductively coupled plasma processing apparatus of the present invention, the high frequency used is 1
Other than 3.56MHz, 100kHz to 300MH
It can be appropriately selected from the range of z.

The shape of the antenna used in the present invention may be a coil shape, a loop shape or another shape as long as it can generate a high frequency electric field by inductive coupling in the plasma generation chamber. As for the constituent material of the antenna, even if Ni is coated on copper, Cu, Al, F
e, Ni and other metals and alloys, various glasses, quartz, silicon nitride, alumina, acrylic, polycarbonate, polyvinyl chloride, polyimide and other insulators, Al, Ni,
Any material that has sufficient mechanical strength and is covered with a conductive layer with a thickness greater than the permeation thickness of high frequencies, such as those coated with metal thin films of W, Mo, Ti, Ta, Cu, Ag, etc. It is possible.

As the magnetic field generating means, other than a coil, a permanent magnet can be used as long as it can generate a magnetic field parallel to the central axis of the antenna. Other cooling means such as a water cooling mechanism or air cooling may be used to prevent overheating of the coil.

[0027]

[Example of Apparatus] The present invention will be described below with reference to specific examples of the plasma processing apparatus of the present invention.

(Apparatus Example 1) A 10-pole type magnetic field inductively coupled plasma processing apparatus which is an example of the present invention will be described with reference to FIG. Reference numeral 101 is a plasma generating chamber, 102 is a plasma generating gas introducing means, 103 is a high frequency power source, 104 is a loop antenna for introducing a high frequency into the plasma generating chamber 101, and 105 is quartz formed in a part of the plasma generating chamber 101. A window, 106 is a coil for generating a magnetic field parallel to the central axis of the loop antenna 104 in the plasma generation chamber 101,
111 is a plasma processing chamber connected to the plasma generating chamber, 1
12 is a substrate to be processed, 113 is a means for transferring the substrate 112, 1
Reference numeral 14 is a processing gas introducing means, and 115 is an exhaust.

The material of the loop antenna 104 is 6 m in diameter.
A copper pipe of m having a Ni coating was used. Further, in order to prevent oxidation of the antenna due to overheating, cooling water can flow inside the antenna. 10
Two loop antennas were coaxially installed on the opposite side with a quartz window sandwiched therebetween, and high frequencies were introduced so that the high frequency propagation directions were in the same rotation direction. For convenience, the five pairs of antennas were installed such that the central axes of adjacent pairs of antennas were 100 mm apart from each other, and high frequencies were introduced so that the high frequencies propagated in the same rotation direction.

The coil 106, which is a magnetic field generating means, has an inner diameter of 2
Ten pieces of a water-cooled stainless steel cylindrical bobbin having a length of 4 mm and a length of 60 mm wound with a coated copper wire having a diameter of 1.5 mm 240 times and hardened with wax were used. The ten coils were arranged such that the central axes thereof coincide with the central axes of the ten loop antennas to form a mirror magnetic field.

The generation and processing of plasma are performed as follows. Plasma generation chamber 1 via an exhaust system (not shown)
The inside of 01 is evacuated. Then, a gas for plasma generation is introduced into the plasma generation chamber 101 through the gas inlet 102 at a predetermined flow rate. Next, a conductance valve (not shown) provided in the exhaust system (not shown) is adjusted to maintain the inside of the plasma generation chamber 101 at a predetermined pressure. Then, after a desired power is supplied to the coil 106 from a DC power supply (not shown) to generate a mirror magnetic field in the plasma generation chamber 101, the desired power is supplied from the high frequency power supply 103 into the plasma generation chamber 101 via the antenna 104. Supply. Electrons having a thermal velocity close to the phase velocity of circularly polarized waves generated in the plasma generation chamber 101 are resonantly accelerated, and high-density plasma is generated in the plasma generation chamber 101. At this time, the processing gas introduction pipe 1
When the processing gas is introduced into the processing chamber 111 via 14, the processing gas is excited by the generated high-density plasma, and the surface of the substrate 112 to be processed placed on the transfer means 113 is plasma-processed. . At this time, the plasma processing gas may be introduced into the plasma generation gas inlet 102 depending on the application.

Using this apparatus, N2 flow rate 100 sccm,
The uniformity of the electron density of the plasma obtained under the conditions of a pressure of 3 mTorr, a central magnetic flux density of 70 mT, and an rf power of 1.5 kW was evaluated. The uniformity of the electron density was evaluated by the 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 device, and the obtained I−
The electron density was calculated from the V curve by the method of Langmuir et al. Measure the electron density at equal intervals in the plasma generation chamber.
The evaluation was carried out at 4 points, and the uniformity was evaluated by the variation of the maximum value / minimum value. As a result, the electron density is 500 mm x 200 m
It was 6.4 × 10 ¹² / cm ³ ± 9.6% in the m-plane, and it was confirmed that a high-density and almost uniform plasma was formed.

(Device Example 2) FIG. 2 schematically shows the structure of a magnetic field inductively coupled isolation plasma CVD device which is an example of the present invention. In the present apparatus example, the apparatus shown in the apparatus example 1 is provided with a porous separation plate for separating the plasma generation chamber and the plasma processing chamber, and the other configurations are the same as the apparatus example 1. 201 is a plasma generating chamber, 202 is a plasma generating gas introducing means,
Reference numeral 203 is a high frequency power supply, 204 is a loop antenna for introducing a high frequency into the plasma generation chamber 201, 205 is a quartz window formed in a part of the plasma generation chamber 201, and 206 is a coil for generating a magnetic field in the plasma generation chamber 201. Two
11 is a plasma processing chamber connected to the plasma generating chamber, 21
Reference numeral 2 denotes a substrate to be processed, 213 means for transferring the substrate 212, and 21
Reference numeral 4 is a processing gas introducing means, 215 is an exhaust gas, and 216 is a porous separation plate for separating the plasma generation chamber 201 and the plasma processing chamber 211.

The generation and processing of plasma are performed as follows. Plasma generation chamber 2 via an exhaust system (not shown)
The inside of 01 is evacuated. Then, a plasma generating gas is introduced into the plasma generating chamber 201 at a predetermined flow rate through the gas inlet 202. Next, a conductance valve (not shown) provided in the exhaust system (not shown) is adjusted to maintain the inside of the plasma generation chamber 201 at a predetermined pressure. Then, after a desired power is supplied from a DC power supply (not shown) to the coil 206 to generate a magnetic field in the plasma generation chamber 201, a desired power is supplied from the high frequency power supply 203 into the plasma generation chamber 201 via the antenna 204. To do. Plasma generation chamber 201
Electrons having a thermal velocity close to the phase velocity of the circularly polarized wave generated in the inside are resonantly accelerated, and the substrate 21 enters the plasma generation chamber 201.
A high density plasma isolated from 2 is generated. At this time, the processing gas is processed through the processing gas introduction pipe 214. At this time, if the processing gas is introduced into the processing chamber 211 through the processing gas introduction pipe 214, the processing gas is generated and high density plasma is generated. The surface of the substrate 212 to be processed placed on the transfer means 213 is plasma-processed. At this time, since the surface of the substrate is not in contact with plasma, it is possible to perform the treatment with less ion damage. At this time, the plasma processing gas may be introduced into the plasma generation gas introduction port 202 depending on the application.

(Device Example 3) FIG. 3 schematically shows the structure of an optically assisted magnetic field inductively coupled plasma CVD device which is an example of the present invention. In this device example, the device shown in device example 2 is provided with a light irradiation means for irradiating the surface of the substrate with visible ultraviolet light, and the other configurations are the same as in device example 2. 301 is a plasma generating chamber, 302 is a plasma generating gas introducing means, 30
3 is a high frequency power source, 304 is a high frequency plasma generating chamber 30
1, 305 is a quartz tube formed in a part of the plasma generation chamber 301, 306 is a coil for generating a magnetic field in the plasma generation chamber 301, 311
Is a plasma processing chamber connected to the plasma generation chamber, 312 is a substrate to be processed, 313 is means for transferring the substrate 312, 314 is processing gas introducing means, 315 is exhaust gas, and 321 is the substrate 31.
Illumination system for irradiating the surface of 2 with visible ultraviolet light, 325
Is a plasma generation chamber 30 which emits visible ultraviolet light from the illumination system 321.
It is a light introduction window which is introduced into the processing chamber 311 through 1. Here, the illumination system 321 includes a light source 322 and a reflect mirror 323 that reflects the light from the light source 322.

The generation and processing of plasma are performed as follows. Plasma generation chamber 3 via an exhaust system (not shown)
The inside of 01 is evacuated. Subsequently, visible ultraviolet light from the illumination system 321 is applied to the surface of the base 312 through the light introduction window 325. Further, a gas for generating plasma is introduced into the gas inlet 302
It is introduced into the plasma generating chamber 301 at a predetermined flow rate via the. Next, a conductance valve (not shown) provided in the exhaust system (not shown) is adjusted to maintain the inside of the plasma generation chamber 301 at a predetermined pressure. Then, after a desired power is supplied to the coil 306 from a DC power supply (not shown) to generate a magnetic field, the desired power is supplied from the high frequency power supply (not shown) to the antenna 3
It is supplied into the plasma generation chamber 301 via 04. Electrons having a heat velocity close to the phase velocity of the circularly polarized wave generated in the plasma generation chamber 301 are resonantly accelerated, and the plasma generation chamber 3
High-density plasma is generated within 01. At this time, if the processing gas is introduced into the processing chamber 311 through the processing gas introducing pipe 314, the processing gas is excited by the generated high density plasma and the substrate to be processed placed on the transfer means 313. The surface of 312 is plasma treated. At this time, since the surface is activated by visible ultraviolet light, higher quality treatment is possible. At this time, a plasma processing gas may be introduced into the plasma generation gas inlet 302 depending on the application.

As the light source 322 of the illumination system 321, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon-mercury lamp, a xenon lamp, a deuterium lamp, A
r resonance line lamp, Kr resonance line lamp, Xe resonance line lamp, excimer laser, Ar ⁺ laser 2nd harmonic, N ₂ laser, YAG laser 3rd harmonic, etc. Any light source can be used.

The plasma processing apparatus of the present invention includes the apparatus of the above-mentioned apparatus examples 1 to 3 which is appropriately improved or a combination thereof.

In the magnetic field inductively coupled plasma processing apparatus of the present invention, the pressure in the plasma processing chamber or the plasma generation chamber and the processing chamber is preferably 0.1 mTorr to 1.
It can be selected from the range of 00 mTorr.

The formation of the deposited film by the magnetic field inductively coupled plasma processing apparatus of the present invention is performed by appropriately selecting the gas to be used. 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., aS
i, poly-Si, SiC, GaAs and other semiconductor films, A
It is possible to efficiently form various deposited films such as metal films of l, W, Mo, Ti, Ta and the like.

The magnetic field inductively coupled plasma processing apparatus of the present invention can also be applied to surface modification. In that case, by appropriately selecting the gas to be used, for example, Si, Al, Ti, Zn, Ta or the like is used as the substrate or the surface layer, and the oxidation treatment or the nitriding treatment of the substrate or the surface layer is further performed. It is possible to do the doping process. Further, the plasma processing technique adopted in the present invention can be applied to a cleaning method. In that case, it can also be used for cleaning oxides, organic substances, heavy metals and the like.

The substrate on which the functional deposited film is formed by the magnetic field inductively coupled plasma processing apparatus of the present invention may be a semiconductor, a conductive one, or an electrically insulating one. . In addition, these substrates are dense,
-500 to improve performance such as adhesion and step coverage
DC bias from V to + 200V or frequency 40H
An AC bias of z to 300 MHz may be applied.

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

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

As the deposited film forming gas, a generally known gas can be used.

The gas which is easily decomposed by the action of plasma and can be deposited even by itself is used for achieving a stoichiometric composition and for preventing film deposition in the plasma generation chamber through a processing gas introduction means in the processing chamber. It is desirable to introduce Further, it is desirable that a gas that is not easily decomposed by the action of plasma and that is difficult to deposit by itself is introduced into the plasma generation chamber through the plasma generation gas introduction port in the plasma generation chamber.

Si such as a-Si, poly-Si and SiC
As a raw material containing Si atoms to be introduced through the processing gas introduction means in the case of forming a system-based semiconductor thin film, SiH
₄ , inorganic silanes such as Si ₂ H ₆ , tetraethylsilane (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 C
l ₆ , SiHCl ₃ , SiH ₂ Cl ₂ , SiH ₃ Cl, Si
Examples thereof include halosilanes such as Cl ₂ F ₂ and the like, which are in a gas state at normal temperature and pressure or which can be easily gasified.
Further, in this case, as the plasma generating gas introduced through the plasma generating gas inlet, H2, He, N
Examples include e, Ar, Kr, Xe, and Rn.

As the raw material containing Si atoms introduced through the processing gas introduction means for forming a Si compound type thin film such as Si ₃ N ₄ or SiO ₂ , SiH 4 or Si _{2 is used.}
Inorganic silanes such as H ₆ , tetraethoxysilane (TE
OS), tetramethoxysilane (TMOS), organic silanes such as octamethylcyclotetrasilane (OMCTS), SiF ₄ , Si ₂ F ₆ , SiHF ₃ , SiH ₂ F ₂ , S
iCl ₄ , Si ₂ Cl ₆ , SiHCl ₃ , SiH ₂ Cl ₂ , S
Examples thereof include halosilanes such as iH ₃ Cl and SiCl ₂ F ₂ which are in a gas state at normal temperature and pressure or which can be easily gasified. Further, in this case, as the raw material introduced through the plasma generating gas introduction port, 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.

As the raw material containing metal atoms introduced through the processing gas introduction means when forming a metal thin film of Al, W, Mo, Ti, Ta or the like, trimethylaluminum (TMAl) and triethylaluminum (TEA) are used.
l), triisobutylaluminum (TIBAl), dimethylaluminum hydride (DMAlH), tungsten carbonyl (W (CO) ₆ ), molybdenum carbonyl (Mo (CO) ₆ ), trimethylgallium (TMG)
a), organic metals such as triethylgallium (TEGa), and halogenated metals such as AlCl ₃ , WF ₆ , TiCl ₃ and TaCl ₅ . Further, as the plasma generating gas introduced through the plasma generating gas introducing port in this case, H2, He, Ne, Ar, Kr, Xe and R are used.
n is mentioned.

Al ₂ O ₃ , AlN, Ta ₂ O ₅ , TiO ₂ ,
Trimethyl aluminum (TMA) is used as a raw material containing metal atoms, which is introduced through a processing gas introducing means when a metal compound thin film such as TiN or WO ₃ is formed.
l), triethyl aluminum (TEAl), triisobutyl aluminum (TIBAl), dimethyl aluminum hydride (DMAlH), tungsten carbonyl (W (CO) ₆ ), molybdenum carbonyl (Mo (C
O) ₆ ), trimethylgallium (TMGa), triethylgallium (TEGa) and other organic metals, AlCl ₃ ,
Examples thereof include metal halides such as WF ₆ , TiCl ₃ and TaCl ₅ . Further, in this case, as the raw material gas introduced through the plasma generating gas introduction port, O ₂ , O ₃ , H
_{2 O, NO, N 2 O} , NO 2, N 2, NH 3, N 2 H 4, etc. hexamethyldisilazane (HMDS) may be cited.

The oxidizing gas introduced through the plasma generating gas introduction port when the substrate is subjected to the oxidation surface treatment is as follows:
O ₂ , O ₃ , H ₂ O, NO, N ₂ O, NO _{2 and the} like can be mentioned. Further, as the nitriding gas introduced through the plasma-generating gas introduction port when the substrate is subjected to the nitriding surface treatment, N
₂ , NH ₃ , N ₂ H ₄ , hexamethyldisilazane (HMD
S) and the like. In this case, since the film is not formed, the raw material gas is not introduced through the processing gas introduction means, or the same gas as the gas introduced through the plasma generation gas introduction port is introduced.

The cleaning gas introduced through the plasma generating gas introduction port for cleaning the organic substance on the surface of the substrate is O ₂ , O ₃ , H ₂ O, NO, N ₂ O or NO.
₂ etc. Further, as the cleaning gas introduced from the plasma generating gas introduction port when cleaning the inorganic substance on the substrate surface, F ₂ , CF ₄ , CH
₂ F ₂ , C ₂ F ₆ , CF ₂ Cl ₂ , SF ₆ , NF _{3 and the} like can be mentioned. In this case, since the film is not formed, the raw material gas is not introduced through the processing gas introduction means, or the same gas as the gas introduced through the plasma generation gas introduction port is introduced.

[0053]

EXAMPLES The magnetic field inductively coupled plasma processing apparatus of the present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples of use.

Example 1 The plasma processing apparatus shown in FIG. 1 was used as a magnetic field inductively coupled plasma CVD apparatus,
A silicon nitride film for protecting a semiconductor element was formed.

As the base 112, a P-type single crystal silicon substrate (plane direction [100], resistivity 10 Ωcm) was used. First, the silicon substrate 112 is attached to the substrate transfer belt 113.
After installation on the top, the inside of the plasma generation chamber 101 and the processing chamber 111 is evacuated through an exhaust system (not shown), and 10 ^-6 T
The pressure was reduced to the value of orr. Nitrogen gas was introduced into the plasma generation chamber 101 at a flow rate of 500 sccm through the plasma generation gas introduction port 102. At the same time, 100 sccm of monosilane gas is passed through the processing gas introducing means 114.
Was introduced into the processing chamber 111 at a flow rate of. Then, a conductance valve (not shown) provided in the exhaust system (not shown) was adjusted to maintain the inside of the processing chamber 111 at 3 mTorr. Electric power of 500 W was supplied from the 13.56 MHz high frequency power source into the plasma generation chamber 101 through the antenna 104. Thus, plasma was generated in the plasma generation chamber 101. At this time, the plasma generation gas inlet 10
The nitrogen gas introduced through the plasma generator chamber 101
The silicon substrate 11 is excited and decomposed inside to become active species.
The silicon nitride film was transported in the direction 2 and reacted with the monosilane gas introduced through the processing gas introduction means 114 to form a silicon nitride film on the silicon substrate 112 with a thickness of 1.0 μm. After film formation, film quality such as film formation rate 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 with a laser interferometer Zygo (trade name).

The obtained throughput of the silicon nitride film formation was extremely large at 86 sheets / hour and the film quality was 1 stress.
× 10 ⁹ dyn / cm ² , leakage current 1 × 10 ^-10 A / c
It was confirmed that the film had a very high quality of m ² and a withstand voltage of 8 MV / cm.

(Embodiment 2) Using the plasma processing apparatus shown in FIG. 1 as a magnetic field inductively coupled plasma CVD apparatus,
A silicon nitride film for protecting the magneto-optical disk was formed.

As the base 112, a polycarbonate (PC) substrate (φ3.5 inch) was used. First, P
After placing the C substrate 112 on the substrate transfer belt 113,
The inside of the plasma generation chamber 101 and the processing chamber 111 was evacuated through an exhaust system (not shown) to reduce the pressure to 10 ⁻⁶ Torr. Nitrogen gas is supplied through the plasma generating gas inlet 102 at a flow rate of 200 sccm in the plasma generating chamber 101.
Introduced in. At the same time, the monosilane gas is supplied through the processing gas introducing means 114 at a flow rate of 200 sccm to the processing chamber 1.
Introduced in 11. Then, a conductance valve (not shown) provided in the exhaust system (not shown) was adjusted to maintain the inside of the processing chamber 111 at 5 mTorr. 13.56MHz
1 kW of electric power was supplied from the high-frequency power source to the inside of the plasma generation chamber 101 via the antenna 104. Thus, plasma was generated in the plasma generation chamber 101. On this occasion,
The nitrogen gas introduced through the plasma generation gas introduction port 102 is excited and decomposed in the plasma generation chamber 101 to become active species, which is transported toward the silicon substrate 112 and introduced through the processing gas introduction means 114. A silicon nitride film was formed on the silicon substrate 112 to a thickness of 100 nm by reacting with the generated monosilane gas. After film formation, film quality such as film formation rate and refractive index was evaluated.

The throughput of the obtained silicon nitride film formation is extremely high at 1800 sheets / hour, and the film quality is also an extremely high quality film having a refractive index of 2.2 and a stress of 1.8 × 10 ⁹ dyn / cm ^2. confirmed.

Example 3 Using the plasma processing apparatus shown in FIG. 2 as a surface reforming apparatus, the surface of a silicon substrate was oxidized to form a silicon oxide film for semiconductor element gate insulation.

As the base 212, a P-type single crystal silicon substrate (plane direction [100], resistivity 10 Ωcm) was used. After the silicon substrate 212 is placed on the substrate transfer belt 213, the inside of the plasma generation chamber 201 and the processing chamber 211 is evacuated through an exhaust system (not shown) to 10 ⁻⁶ Torr.
The pressure was reduced to the value of r. Gas inlet 20 for plasma generation
Oxygen gas was introduced into the plasma generation chamber 201 at a flow rate of 500 sccm. Next, a conductance valve (not shown) provided in the exhaust system (not shown) was adjusted to maintain the inside of the processing chamber 211 at 1 mTorr. Then 13.
Electric power of 1000 W was supplied from the high frequency power source of 56 MHz into the plasma generation chamber 201 through the antenna 204.
Thus, plasma was generated in the plasma generation chamber 201. At this time, the oxygen gas introduced through the plasma generation gas introduction port 202 is excited and decomposed in the plasma generation chamber 201 to become active species such as oxygen atoms, which are transported in the direction of the silicon substrate 212 and transferred to the surface of the silicon substrate 212. Reacts with the silicon substrate 2 to form a 50 nm thick silicon oxide film.
Formed on 12. After oxidation, oxidation rate, leak current,
And the withstand voltage were evaluated. The leak current was obtained by forming an Al electrode on the deposited film, applying a DC voltage between the Al electrode and the Si substrate to apply an electric field of 5 MV / cm to the deposited film, and measuring the current flowing in this state. . The withstand voltage was evaluated by the electric field when a leak current of 1 × 10 ⁻⁶ A / cm ² or more flows.

The obtained throughput of the silicon oxide film formation was as good as 19 sheets / hour and the film quality was 2 × leak current.
10 ^-11 A / cm ² , withstand voltage ¹¹ MV / cm,
It was confirmed that the film was extremely good quality.

Example 4 The plasma processing apparatus shown in FIG. 3 was used as an optically assisted inductively coupled plasma CVD apparatus to form a silicon oxide film for semiconductor element interlayer insulation.

As the substrate 312, a P-type single crystal silicon substrate (plane direction [100], resistivity 10 Ωcm) was used. First, the silicon substrate 312 is transferred to the substrate transfer belt 313.
After being installed on the upper side, the inside of the plasma generation chamber 301 and the processing chamber 311 is evacuated through an exhaust system (not shown) to 10 ⁻⁶ T
The pressure was reduced to the value of orr. Then, the ultra-high pressure mercury lamp of the illumination system 321 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 was 0.6 W / cm ² . Oxygen gas was introduced into the plasma generation chamber 311 at a flow rate of 1000 sccm through the plasma generation gas inlet 302. At the same time, tetraethoxysilane (TEO
S) gas was introduced into the processing chamber 311 at a flow rate of 200 sccm. Then, a conductance valve (not shown) provided in the exhaust system (not shown) is adjusted to make the plasma generation chamber 3
01 inside 0.1 Torr, processing chamber 311 inside 0.03T
Hold at orr. Electric power of 1500 W was supplied from the 13.56 MHz high frequency power source into the plasma generation chamber 301 through the antenna 304. Thus, the plasma generation chamber 3
Plasma was generated within 01. The oxygen gas introduced through the plasma generation gas introduction port 302 is excited and decomposed in the plasma generation chamber 301 to become active species, which is transported toward the silicon substrate 312, and is then introduced into the processing gas introduction means 31.
Reacts with the tetraethoxysilane gas introduced through the silicon oxide film, and the silicon oxide film is 1.0 μm on the silicon substrate 312.
It was formed with a thickness of m. After the film formation, the film formation rate, uniformity, withstand voltage, and step coverage were evaluated. The step coverage is determined by observing the cross section of the silicon oxide film formed on the Al step formed in the line and space 0.5 μm line pattern with a scanning electron microscope (SEM), and comparing the step sidewall with the film thickness on the step. The film thickness ratio (cover factor) above was obtained and evaluated.

The obtained throughput of silicon oxide film formation was as good as 48 wafers / hour, and the film quality was 9 MV.
It was confirmed that the film was a good quality film having a / cm and a cover factor of 0.9.

[0066]

As described above, according to the magnetic field inductively coupled plasma processing apparatus of the present invention, plasma is generated in a vacuum container in a high density and in a wide range. It is possible to obtain a plasma processing apparatus with high throughput, which can perform processing such as deposition film formation and etching.

[Brief description of drawings]

FIG. 1 is a schematic view of a 10-pole type magnetic field inductively coupled plasma processing apparatus of the present invention. (A) is a cross-sectional view taken along a line perpendicular to the transport direction, and (b) is a view of the cross-section taken along AA 'in (a) as seen from above.

FIG. 2 is a schematic diagram of a magnetic field inductively coupled isolation plasma processing apparatus of the present invention. (A) is a cross-sectional view taken along a line perpendicular to the transport direction, and (b) is a view of the cross-section taken along AA 'in (a) as seen from above. Here, the porous separation plate 216 is not drawn.

FIG. 3 is a schematic view of an optically assisted magnetic field inductively coupled plasma processing apparatus of the present invention. (A) is a cross-sectional view taken along a line perpendicular to the transport direction, and (b) is a view of the cross-section taken along AA 'in (a) as seen from above.

FIG. 4 is a schematic diagram of a conventional helicon wave plasma processing apparatus.

[Explanation of symbols]

 101, 201, 301, 1101 Plasma generation chamber 102, 202, 302 Plasma generation gas introduction means 103, 203, 303, 1103 High frequency power source 104, 204, 304 Loop antenna 1104 Helical antenna 105, 205, 305, 1105 Quartz tube 106 , 206, 306, 1106 Coil 111, 211, 311, 1111 Plasma processing chamber 112, 212, 312, 1122 Substrate 113, 213, 313 Transfer means 114, 214, 314 Processing gas introducing means 115, 215, 315, 1115 exhaust

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location H01L 21/205 21/3065

Claims (8)

[Claims] 1. A magnetic field coupling comprising a vacuum container, means for introducing a high frequency wave into the vacuum container by inductive coupling, means for generating a magnetic field in the vacuum container, and means for transferring a substrate to be processed into the vacuum container. In the plasma processing apparatus, a plurality of magnetic field inducing means and a plurality of magnetic field generating means are arranged, respectively. 2. The center axes of the plurality of high-frequency introducing means, the center axes of the plurality of magnetic field generating means, and the surface to be processed of the substrate to be processed are arranged substantially in parallel, and the central axes are The magnetic field inductively coupled plasma processing apparatus according to claim 1, wherein the magnetic field inductively coupled plasma processing apparatus is positioned substantially in a transfer direction of the substrate to be processed. 3. The magnetic field inductively coupled plasma processing apparatus according to claim 1, wherein the high frequency introducing unit is an antenna. 4. The magnetic field inductively coupled plasma processing apparatus according to claim 1, wherein the antenna is a helical antenna. 5. The magnetic field inductively coupled plasma processing apparatus according to claim 1, wherein the antenna is a loop antenna. 6. The substrate transfer means is arranged at a position separated from the plasma generation region in the vacuum container.
A magnetic field inductively coupled plasma processing apparatus according to claim 1. 7. The magnetic field inductively coupled plasma processing apparatus according to claim 1, wherein a differential pressure generating means such as a perforated quartz plate is arranged between the plasma generating region in the vacuum container and the substrate support. 8. The magnetic field inductively coupled plasma processing apparatus according to claim 1, further comprising means for irradiating the surface of the substrate to be processed with visible ultraviolet light.