JPH11256327A - Forming method of metallic compound thin film and film forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a metallic compd. thin film stable in characteristics at a low substrate temp. at a high speed by preventing a damage from being provided to the thin film. SOLUTION: This method for forming a metallic compd. thin film is the one in which a stage for forming a metallic ultrathin film composed of metal or the incomplete reactant of the metal on a substrate in a vacuum tank 11 and a stage in which this metallic ultrathin film is brought to contact with the active seed of an electrically neutral reactive gas and the metallic ultrathin film is made to react with the active seed of the reactive gas to convert it into the metallic compd. ultrathin film are successively repeated and the plural layers of the metallic compd. ultrathin film are formed and deposited by which the metallic compd. thin film having the objective film thickness is formed on the substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a metal compound thin film stably and at a high speed on a substrate by a magnetron sputtering method or a vacuum evaporation method, and a film forming apparatus used for the method.

[0002]

2. Description of the Related Art It is widely practiced to form a thin film of a metal or a metal compound such as an oxide, nitride or fluoride by sputtering. There are the following representative methods for forming a thin film of a metal compound such as an oxide, a nitride or a fluoride as compared with the case of forming a metal thin film. A method in which a reactive gas (for example, oxygen, nitrogen, or fluorine gas) is introduced into a metal compound target (insulating) or a metal target (conductive) using a radio frequency (RF) power supply to form a thin film by reactive sputtering. A method of forming a thin film by DC reactive magnetron sputtering in which a reactive gas is introduced into a metal target using a direct current (DC) power supply to form a film.

However, both methods have the following problems. The deposition rate of the thin film is slow (particularly, RF sputtering is remarkable). The plasma raises the temperature of the substrate, and it is difficult to perform the deposition at 100 ° C. or less. (In particular, RF sputtering is remarkable.) In the case of DC reactive magnetron sputtering, the target material, particularly the non-erosion portion, is scattered on the substrate by the arc discharge, and this scatter may cause defects to occur in the thin film being formed. Conceivable. In the case of RF magnetron sputtering, electric charges are accumulated in a device component or the like at a ground potential, or in an insulating thin film formed on a substrate, a substrate holding jig, or the like, which causes abnormal discharge and causes arcing. It is considered that the material that caused the discharge scatters on the substrate, or an arc mark remains on the substrate, which causes a defect in the thin film being formed. This phenomenon increases as the size of the substrate increases.

[0004] Compound thin films obtained by sputtering or the like are deficient in the constituent elements oxygen, nitrogen and fluorine, and are liable to produce incomplete metal compounds. For example, when a SiO ₂ thin film, which is a representative of an oxide thin film and is used for an optical film, an insulating film, a protective film, and the like, is formed, in general, the SiO ₂
A target (insulating) is formed by forming an SiO ₂ thin film by RF magnetron sputtering using a high-frequency power source, and a Si target (conductive) is formed using a DC power source.
An SiO ₂ thin film is formed by C magnetron sputtering. At this time, the operating gas A for sputtering is used.
If oxygen, which is a reactive gas introduced simultaneously with r, is insufficient, the composition of the formed thin film will be SiOx (X <2). In order to prevent this phenomenon, oxygen deficiency can be prevented by introducing a sufficient amount of oxygen into the sputtering atmosphere to react, but the deposition rate of the thin film in this case is compared with the deposition rate of the metal thin film. At 1/5 to 1/1
It drops to zero.

The reactive gas introduced at this time reacts on the surface of the target to form SiO ₂ . This SiO ₂
Then, the electric charge of the argon plus ion and the oxygen plus ion of the plasma is accumulated. When a large amount of this positively charged electric charge is accumulated and exceeds the insulation limit of the SiO ₂ film, dielectric breakdown occurs. Alternatively, an arc discharge is caused to the conductive part of the target, the earth shield (anode),
The stored charge escapes. This is the process and the cause of the abnormal discharge of the target. This arc discharge causes the following problems. The target material is scattered on the substrate, causing defects in the thin film being formed. Arc traces remain on the target surface, and the accumulation of SiO ₂ , which is an insulating portion, progresses around the arc traces, causing further abnormal discharge.

[0006] Also in the vacuum deposition method, a method of repeatedly forming an ultrathin metal film and converting it to a metal oxide is effective. In this case, the evaporation source, particularly the cathode portion of the electron beam source, causes abnormal discharge due to the anticorrosive organism (insulator). In terms of film formation rate, generally, film formation by sputtering can achieve only a film formation rate of about 1/2 to 1/10 compared to vacuum deposition of an ion beam heating method or a resistance heating method. There is a problem in producing. In general, since sputtering forms a film using plasma, collisions of charged particles (ions, electrons) cause heating of components of the apparatus, a substrate holder, a substrate, and the like. It is difficult to form a film on a material having poor properties. This is especially true for R using a high frequency power supply.
This is remarkable in F magnetron sputtering.
The above points cause problems and are a major obstacle in forming a compound thin film by sputtering.

The present applicant has previously made the following proposal. A step of depositing an ultrathin film made of a metal such as titanium on a substrate by sputtering, and a step of irradiating the ultrathin film with an ion beam of a reactive gas such as oxygen to convert it into an ultrathin film of a metal compound such as titanium oxide. Is repeated to form a desired metal compound thin film. (Japanese Patent Publication 8-1951
No. 8) A step of depositing an ultrathin film made of metal on a substrate by sputtering, and a step of irradiating the ultrathin film with plasma of a reactive gas generated by an inductive plasma source to convert it into an ultrathin metal compound film Is repeated to form a desired metal compound thin film. (JP-A-8-176821
No.)

However, regarding the above method,
Ion guns require replacement of filaments due to wear, and also require a large number of filaments, screen electrodes, suppressor electrodes, and components, and with these, power supply current capacity due to contamination of the vacuum chamber and increase in screen electrode current. It was found that there were problems such as a temperature rise due to the neutralizer. Another method irradiates the substrate with charged particles (Ar ions, reactive gas ions, and electrons) as plasma, so that the charged particles may damage the substrate and the thin film being formed on the substrate, or may increase the temperature of the substrate. It turned out to be.

[0009]

SUMMARY OF THE INVENTION According to the present invention, when a thin film having a predetermined thickness is formed while performing reactions such as oxidation, nitridation and fluorination on an ultra-thin metal film, damage to the thin film is prevented, It is an object to stably produce a metal compound thin film having a stable temperature at a low temperature.

[0010]

SUMMARY OF THE INVENTION According to the present invention, there is provided a method for forming a metal compound thin film, comprising the steps of forming an ultrathin metal film comprising a metal or an incomplete reactant of a metal on a substrate in a vacuum chamber; Contacting the thin film with an active species of an electrically neutral reactive gas, reacting the ultra-thin metal film with the active species of the reactive gas and converting it into a metal compound ultra-thin film. Are formed and deposited to form a metal compound thin film having a desired film thickness on a substrate.

The formation of the metal ultra-thin film can be performed by a magnetron sputtering method, a vacuum evaporation method, or the like.
It is particularly suitable for a method of forming an ultrathin metal film using a metal target by a magnetron sputtering method, especially a DC magnetron sputtering method. In the process of converting an ultrathin metal film made of a metal or an incomplete compound of a metal into an ultrathin metal compound by reacting with a reactive gas, the neutral neutralization of radicals, excited radicals, atoms, molecules, etc. Use of active species is effective.

The film forming apparatus of the present invention is an apparatus for forming a metal compound thin film in a magnetron sputtering apparatus; a metal ultra-thin film made of a metal or an incomplete reactant of a metal on a substrate by a magnetron sputtering method. A film forming process zone for performing a step of forming a film;
A reaction process zone in which an active species of an electrically neutral reactive gas is brought into contact with the ultrathin metal film, and the ultrathin metal film reacts with the active species of the reactive gas to convert it into a metal compound ultrathin film. Transport means for transporting the substrate between the film formation process zone and the reaction process zone; and a reactive gas mixed into the film formation process zone by spatially and pressure separating the film formation process zone and the reaction process zone Shielding means for preventing transfer of the substrate; transporting and processing the substrate repeatedly a plurality of times between the stable film forming process zone and the reaction process zone to form a plurality of metal compound ultra-thin layers;
It is characterized in that a metal compound thin film having a target film thickness is formed on a substrate by depositing. Further, the present invention can be applied to a vacuum evaporation apparatus instead of the magnetron sputtering apparatus. That is, the formation of the ultrathin metal film on the substrate can be performed by a vacuum evaporation method.

[0013]

1 and 2 are explanatory views showing a method and an apparatus for forming a thin film according to the present invention. FIG. 1 is a top view (partially sectioned for easy understanding), and FIG. FIG. 2 is a side view taken along the line ABC of FIG. 1. Around the substantially cylindrical substrate holder 13 in the vacuum chamber 11, sputtering electrodes 21, 41, an active species generator 61 and a grid 81 are arranged. Sputtering electrode 2
The front surfaces of 1, 41 are film forming process zones 20, 4 respectively.
0. In FIG. 1, the sputtering electrode 2 is assumed on the assumption that two different types of substances are sputtered.
The case where two 1, 41 are provided is shown. On the other hand, the front surface of the active species generator 61 and the grid 81 constitute a reaction process zone 60.

On the substrate (not shown) mounted on the substrate holder 13, a metal ultra-thin film of Si or the like is formed in front of the film forming process zone with the rotation of the substrate holder 13 by the motor 17, and the reaction process zone is formed. Is converted into SiO ₂ or the like on the front surface of the substrate to form an ultrathin metal oxide film. By repeating this operation, the metal oxide ultra-thin film
It is deposited to form a thin film of SiO ₂ or the like having a final target film thickness. The ultra-thin film according to the present invention is a term used to prevent confusion with the final thin film because the ultra-thin film is deposited a plurality of times to form a final thin film.
This means that it is much thinner than the final thin film. The thickness of the ultrathin film is arbitrary, but is preferably about 0.1 to 20 Å, or about 0.5 to 10 Å.

[0015] metal such as Si, can be formed at high speed by DC magnetron sputtering, by converting it into a metal compound such as SiO ₂ by the reaction process zone, SiO ₂ at a high speed by DC magnetron sputtering, A thin film of a metal compound such as TiO ₂ can be obtained. The film forming process zone 20 (similarly for 40) includes a sputter electrode 21, a sputter power source 23, a target 29, a sputter gas cylinder 27, a mass flow controller 25, and a shielding plate (shielding means) 12.
Argon gas for sputtering is introduced into the shielding plate 12 of the vacuum chamber 11 whose degree of vacuum is adjusted by the vacuum pump 15, and the vacuum gas atmosphere in the film forming process zone 20 is adjusted to perform DC magnetron sputtering. .

As the target 29, Al, Ti, Z
r, Sn, Cr, Ta, Si, Te, Ni-Cr, In
Metal target such as -Sn are used, the active species exposure of the reactive _{gases, Al 2 O 3, TiO 2} , ZrO 2,
Optical films or insulating films such as Ta ₂ O ₅ and SiO ₂ , conductive films such as ITO, magnetic films such as Fe ₂ O ₃ , TiN, CrN, T
It is a superhard film such as iC. TiO ₂ , ZrO ₂ , Si
Insulating metal compounds such as O ₂ are metals (Ti, Z
The method of the present invention is particularly useful because the sputtering rate is extremely slow and productivity is low as compared with (r, Si).

The present invention can also be implemented by performing high-frequency magnetron sputtering using SiO ₂ or the like as the target 29. This is because oxygen deficiency may be observed as in SiOx (x <2) due to sputtering of SiO ₂ . Such an ultra-thin SiOx thin film is converted into a stable ultra-thin SiO ₂ thin film in the subsequent reaction process zone 60. That is, the metal ultra-thin film according to the present invention refers to an ultra-thin metal film and an SiOx (x
As described in <2), an ultrathin film made of an incompletely reacted metal is also included. Next, the ultra-thin metal film is converted into an ultra-thin metal oxide film such as SiO ₂ in the reaction process zone 60.

The reaction process zone mainly comprises an active species generator 61, a grid 81, and a shielding plate (shielding means) 14. The plasma generated by the discharge in the reactive gas plasma generation chamber 63 of the active species generator 61 includes plasma ions, electrons, radicals, radicals in excited state, atoms, molecules, and the like as constituent elements. In the present invention, by the grid 81,
Radicals as active species in the reaction gas plasma, radicals in excited state, atoms, molecules, and the like are selectively guided to the reaction process zone 60, while electrons and ions as charged particles cannot pass through the grid 81 and react with the reaction process zone 60. It does not leak into the zone 60. Therefore, in the reaction process zone 60, the metal ultra-thin film is exposed to (contacts) only the active species of the electrically neutral reactive gas without reacting with the charged particles, and reacts with the metal such as Si. From SiO
It is converted to a metal compound such as ₂ . The radical is
A radical is an atom or molecule that has one or more unpaired electrons. In addition, the excited state (ex
The term “citate state” refers to a state having higher energy than a stable ground state having the lowest energy.

In a reactive film forming process for obtaining a metal compound from a metal or an incomplete compound of a metal, the active species such as radicals and excited species are more chemically active than charged particles such as ions and electrons, and Electrically neutral particles play a critical role in chemical reactions. In addition, it does not damage the thin film like charged particles, suppresses the rise of the substrate temperature, and controls chemical, optical, mechanical, and electrical properties of the thin film in a combined manner. By clearly separating the reaction process from the film formation process and using only the particles that most contribute to the chemical reaction, a thin film having the desired characteristics can be easily obtained.

The active species generator 61 is also called a radical source, and comprises a reactive gas plasma generating section having a reactive gas plasma generating chamber 63, an electrode 65 for generating plasma, a high frequency power supply 69, and a grit 81. ing. A reactive gas such as oxygen gas is supplied from a reaction gas cylinder 73 via a mass flow controller 71 to a reaction gas plasma generation chamber 63, and a high frequency power from a high frequency power supply 69 is supplied through a matching box 67 to a reactive gas comprising a quartz tube. When applied to the coiled electrode 65 wound on the outer peripheral surface of the gas plasma chamber 63, a plasma of a reactive gas is generated in the reactive gas plasma chamber 63.

As the reactive gas, an oxidizing gas such as oxygen and ozone, a nitriding gas such as nitrogen, a carbonizing gas such as methane, and a fluorinating gas such as CF ₄ are used. As the reactive gas plasma part, an inductively coupled plasma source having electrodes provided outside or inside the reactive gas plasma generation chamber, a capacitively coupled plasma source, a mixedly coupled inductively coupled and capacitively coupled plasma source, or the like can be used. The following are specific examples of these.

(1) Plasma source shown in FIGS. 1 and 2:
A coil-shaped electrode 65 is provided on the peripheral surface of the reactive gas plasma gas generation chamber 63 made of a dielectric material such as a cylindrical quartz glass.
Is arranged, and 100 KHz to 40 MH is applied to this coiled electrode.
An inductively-coupled plasma generation source for generating plasma by applying high frequency power of z. (2) Plasma source shown in FIG. 3: A spiral (mosquito coil) coil electrode 91 is arranged on the atmosphere side of a reactive gas plasma generation chamber 63 made of a dielectric substance such as a disk-shaped quartz glass. 100 KHz to 40 for coil electrode 91
An inductively coupled plasma generation source that generates plasma by applying high-frequency power of MHz. FIG. 2B is a plan view of the spiral coil electrode 91. (3) Plasma source shown in FIG. 4: A plate-like electrode 93 is arranged inside the reactive gas plasma generation chamber 63, and plasma is generated by applying high-frequency power of 100 KHz to 40 MHz to the plate-like electrode 93. Capacitively coupled plasma source. (4) Plasma source shown in FIG. 5: reactive gas generation chamber 63
And a coil generating electrode in which inductively coupled plasma and capacitively coupled plasma coexist by applying a high-frequency power of 100 KHz to 40 MHz to these electrodes.

Further, by adjusting the shape of the coil and the like, a helical wave plasma source can be used to increase the generation efficiency of active species in the plasma. Further, FIG.
As shown in FIG. 2, by arranging the external magnet 71 and / or the internal magnet 73 and forming a magnetic field of 20 to 300 Gauss in the plasma generating section, high-density plasma can be obtained, and the generation efficiency of active species can be increased. Can be. In the plasma in the reactive gas plasma generation chamber 63, there are reactive gas ions / electrons as charged particles and radicals / atoms / molecules in active state of electrically neutral reactive gas, radicals / excited states. However, in the present invention, only the latter electrically neutral particles are selectively guided to the reaction process zone 60, and the conversion reaction from the ultrathin metal film to the ultrathin metal oxide film (for example, Si → SiO _{2) is performed.} ).

Therefore, a grid is provided between the reactive gas plasma generating chamber 63 and the reaction process zone 60 to selectively allow only electrically neutral active species particles to pass, while not allowing charged particles to pass. Charge exchange is performed between ions and electrons in the plasma on the surface of the grid to be neutralized. Examples of such grids include a multi-aperture grid and a multi-slit grid. FIG. 6 shows a multi-aperture grid 101.
FIG. Multi-aperture grid 1
01 is a flat plate made of metal or insulator and has a diameter of 0.1
Innumerable holes 103 of ３3 mm are drilled.

FIG. 7 is a plan view showing a multi-slit grid. Multi slit grid 111
Is a flat plate made of metal or insulating material with a width of 0.1 to 1 m
An infinite number of m slits are provided. Grid 10
Desirably, 1,111 is cooled by cooling pipes 105, 115, etc., such as water cooling. Grid 101, 111
Exchanges ions and electrons in the plasma on the surface thereof, and guides an electrically neutral, reactive active species having no charge to the reaction process zone.

Next, the shielding means (shielding plate) will be described. As shown in FIGS. 1 and 2, each of the film forming process zones 20 and 40 and the reaction process zone 60
2, 14, 16 (shielding means), and separate spaces can be formed in the vacuum chamber 11 in a vacuum atmosphere. That is, the ones that are not completely partitioned in the large vacuum chamber 11 are almost independent and can be controlled independently in two vacuum chambers, that is, a film forming process zone (2).
0,40) and a reaction process zone 60. As a result, each zone (chamber) can have a vacuum atmosphere in which the influence from other zones is individually suppressed, and optimal conditions can be set for each zone. For example, a discharge by sputtering and a discharge by generation of reactive species of a reactive gas can be controlled individually and do not affect each other, so that a stable discharge can be performed and reliability can be improved without causing an accident. Is high. Especially film formation process zone 2
Desirably, the pressure at 0,40 is higher than the reaction process zone 60. Thereby, the reaction process zone 6
The reactive gas introduced into the film forming process zone 2
0, 40 is prevented, and abnormal discharge due to the formation of a metal compound on the target surfaces of the film forming process zones 20, 40 can be prevented.

Providing a shielding plate is particularly suitable when a plurality of targets are provided adjacent to each other. The pressure (degree of vacuum) of the film formation pros zones 20 and 40 is 0.8 to
10 × 10 ⁻³ Torr is preferred. The pressure (degree of vacuum) in the reaction process zone 60 is 0.5 to 8 × 10 ⁻³ Torr.
r is preferred. Typical operating conditions are shown below.

(1) Sputtering conditions (Si) Input power: 3.6 kW Substrate temperature: room temperature Pressure in film forming process zone: 2.0 × 10 ⁻³ Torr Number of rotations of substrate holder: 100 rpm Thickness of supermetal thin film: 2 ６6 Å (2) Sputtering conditions (Zr) Input power: 1.9 kW Substrate temperature: room temperature Pressure in the film formation process zone: 5.0 × 10 ⁻³ Torr Number of rotations of substrate holder: 100 rpm Thickness of supermetal thin film: 1 (3) Driving conditions of active species generator Apparatus: Inductively-coupled plasma generator shown in FIGS. 1 and 2 Input power: 1.9 kW Pressure: 1.4 × 10 ^-3 Torr

At this time, in order to positively prevent abnormal discharge on the surface of the target, +5 at intervals of 1 to 200 kHz.
By inverting the potential of the target to 0 to +200 V to neutralize the positively charged charges accumulated in the compound formed in the non-erosion portion of the target with the electrons in the plasma, the film formation process is performed stably. Very effective on the above. At this time, the components constituting the film forming process zone by the plasma generated by the sputtering process, such as a shield plate and a target shield surrounding the film forming process zone, are water-cooled to prevent the temperature of the substrate from rising. It is desirable to provide a cooling means such as.

One example of the case of forming a multilayer anti-reflection film using the apparatus shown in FIG. 1 is as follows. A metal target whose oxide such as Si has a low refractive index is fixed to the target 29, while Ti, Zr
Such oxides fix a metal target having a high refractive index. The target 29 is sputtered to form an ultra-thin Si film, which is converted into an ultra-thin SiO ₂ film in the reaction process zone 60. The substrate holder 13 is rotated to form a SiO ₂ thin film having a desired thickness. Next, the target 49 is sputtered to form a Ti or Zr ultra-thin film.
The conversion of the iO ₂ or ZrO ₂ ultra-thin film is repeated to form a TiO ₂ or ZrO ₂ thin film having a desired film thickness. By repeating the above operation, a low refractive index layer (SiO ₂ )
/ A multilayer antireflection film composed of alternately laminated films of high refractive index layers (TiO ₂ , ZrO ₂ ) is obtained.

FIG. 8 is a plan view showing another embodiment of the present invention. The apparatus configuration includes a film forming chamber 121, a substrate loading chamber 123 before and after the film forming chamber 121, and a substrate unloading chamber 125 as a whole. Each chamber has its own exhaust system,
P indicates a rotary pump, and TMP indicates a turbomolecular pump. The chambers are connected via gate valves 131 and 133. The substrate loading chamber 123 can be opened to the atmosphere by a gate valve 135 or an opening / closing door, and the substrate unloading chamber 125 can be opened to the atmosphere by a gate valve 137 or an opening / closing door. That is, each chamber is pressure-isolated and has its own exhaust system,
Further, the substrate holder 143 can be transferred through the gate valves 131 and 133.

The substrate holder 143 on which the substrate 141 is mounted
The substrate is loaded into the substrate load chamber 123 via the gate valve 135, and the substrate load chamber 123 is evacuated by the RP to undergo necessary pretreatment such as heating. After this processing is completed, the substrate holder 143 is transferred to the film forming chamber 121. That is, the substrate loading chamber 123 has a function of attaching / detaching / evacuating the substrate holder and performing a pretreatment as needed. In the film forming chamber 121, a thin film is formed on the substrate 141. In order to avoid complication, only the substrate holder 143 is shown by a dashed line in the drawing, and the illustration of the substrate 141 is omitted.

The substrate holder 143 on which the film forming process has been completed is conveyed to the substrate unloading chamber 125, subjected to post-processing if necessary, and taken out through the gate valve 137. That is, the substrate unloading chamber 125 has a function of attaching / detaching / evacuating the substrate holder and performing post-processing when necessary. The film forming process in the film forming chamber 121 is basically the same as the embodiment shown in FIGS. 1 and 2 except that the substrate holder has a horizontal plate shape. That is, the shielding plate 15
1, 161 formed film formation process zone
Targets 155 and 165 are arranged at 3,163 and D
An ultrathin metal film is formed by a C magnetron sputtering method. MFC indicates a mass flow controller. Due to the rotation of the substrate holder 143, the metal ultra-thin film becomes, for example, S
It is converted into a metal oxide ultra-thin film like i → SiO ₂ .
This is performed by the reaction process zone 173 surrounded by the shielding plate 171, and by the exposure of the active species generator 175 to active species such as electrically neutral radicals.

[0034]

According to the present invention, a metal compound thin film having stable characteristics is prevented from being damaged,
It can be formed at a high speed at a low substrate temperature.

[Brief description of the drawings]

FIG. 1 is an explanatory top view showing an embodiment of an apparatus used in the present invention.

FIG. 2 shows an embodiment of the apparatus used in the present invention, FIG.
FIG. 5 is a cross-sectional view taken along line ABC of FIG.

FIG. 3 is an explanatory diagram showing a configuration example of a plasma source.

FIG. 4 is an explanatory diagram showing a configuration example of a plasma source.

FIG. 5 is an explanatory diagram showing a configuration example of a plasma source.

FIG. 6 is a plan view showing a multi-aperture grid.

FIG. 7 is a plan view showing a multi-slit grid.

FIG. 8 is an explanatory plan view showing an embodiment of an apparatus used in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 Vacuum tank 12, 14, 16 Shielding plate 13 Substrate holder 15 Vacuum pump 17 Motor 20, 40 Deposition process zone 21, 41 Sputtering electrode 23, 43 Sputter power supply 25, 45 Mass flow controller 27, 47 Sputter gas cylinder 29, 49 Target 60 Reaction process zone 61 Active species generator 63 Reactive gas plasma generation chamber 65 Electrode 67 Matching box 69 High frequency power supply 71 External coil 73 Internal coil 77 Mass flow controller 79 Reactive gas cylinder 81 Grid 91 Spiral electrode 93 Flat plate electrode 95 Coiled electrode 101 Multi-aperture grid 103 Hole 105 Cooling pipe 111 Multi-slit grid 113 Slit 115 Cooling pipe 121 Deposition chamber 123 Substrate loading chamber 125 Substrate unloading Load chamber 131, 133, 135, 137 Gate valve 141 Substrate 143 Substrate holder 151, 161, 171 Shielding plate 153, 163 Film formation process zone 155, 165 Target 173 Reaction process zone 175 Active species generator

Claims (19)

[Claims] 1. A step of forming an ultrathin metal film made of a metal or an incomplete reactant of a metal on a substrate in a vacuum chamber, and contacting the ultrathin metal film with an active species of an electrically neutral reactive gas. The step of reacting the ultra-thin metal film with the active species of the reactive gas to convert it into a ultra-thin metal compound film is sequentially repeated, and by forming and depositing a plurality of ultra-thin metal compound films, the desired film thickness is obtained. A method for forming a metal compound thin film, comprising forming a metal compound thin film on a substrate. 2. The method according to claim 1, wherein the ultrathin metal film is formed by a magnetron sputtering method. 3. The method for forming a metal compound thin film according to claim 1, wherein the formation of the ultrathin metal film is performed by a vacuum deposition method. 4. The method for forming a metal compound thin film according to claim 1, wherein the active species of the reactive gas is a radical or an excited radical, atom or molecule. 5. A reactive gas plasma comprising reactive gas ions, electrons, and electrically neutral active species is reacted by introducing a reactive gas, applying high frequency power, and discharging. Generated in a reactive gas plasma generation chamber; the reactive gas plasma selectively traps electrons and ions as charged particles, while using a grid to selectively allow electrically neutral active species to pass through. A neutral active species is taken out of the reactive gas plasma generation chamber into a vacuum chamber and brought into contact with an ultrathin metal film to react.
5. The method for forming a metal compound thin film according to any one of 4. 6. The method according to claim 5, wherein the grid is a multi-apatcher grid or a multi-slit grid. 7. A magnetron sputtering apparatus; a film forming process zone for performing a step of forming a metal ultra-thin film made of a metal or an incomplete reactant of a metal on a substrate by a magnetron sputtering method; Contact active species of neutral reactive gas
A reaction process zone for performing a step of reacting the ultra-thin metal film with an active species of a reactive gas to convert it into a metal compound ultra-thin film; a transfer means for transferring a substrate between the film formation process zone and the reaction process zone; Shielding means for spatially and pressure-separating the film forming process zone from the reaction process zone to prevent the reactive gas from entering the film forming process zone; a stable film forming process zone and a reaction process zone The substrate is transported repeatedly multiple times between
A film forming apparatus, wherein a metal compound thin film having a desired film thickness is formed on a substrate by processing and forming and depositing a plurality of metal compound ultra-thin films. 8. A vacuum deposition apparatus; a film forming process zone for performing a step of forming a metal ultra-thin film made of a metal or an incomplete reactant of a metal on a substrate by a vacuum vapor deposition method; Reacting the active species of a neutral reactive gas with the active species and reacting the ultra-thin metal film with the reactive species of the reactive gas to convert it into a metal compound ultra-thin film; Transport means for transporting the substrate between the processing zone; shielding means for spatially and pressure-separating the film forming process zone and the reaction process zone to prevent the reactive gas from entering the film forming process zone; By repeatedly transporting and processing the substrate a plurality of times between the stable film formation process zone and the reaction process zone to form and deposit a plurality of ultrathin metal compound thin films. And a metal compound thin film having a desired thickness on a substrate. 9. The film forming apparatus according to claim 7, wherein the active species of the reactive gas is a radical or an excited radical, atom or molecule. 10. An active species generating device for generating active species, wherein reactive gas is introduced and high frequency power is applied to form reactive gas ions, electrons and electrically neutral active species. A reactive gas plasma generating section for generating a reactive gas plasma, and selectively trap electrons and ions as charged particles from the reactive gas plasma, while selectively trapping electrically neutral active species. The film forming apparatus according to any one of claims 7 to 9, further comprising: a grid that allows the active neutral species to be supplied to the reaction process zone. 11. The film forming apparatus according to claim 10, wherein the grid is a multi-apatcher grid or a multi-slit grid. 12. A coil-shaped electrode is disposed as a reactive gas plasma generating section of the active species generating device on the atmosphere-side peripheral surface of a cylindrical dielectric, and the coil-shaped electrode is provided at 100 KHz.
The film forming apparatus according to claim 10, wherein an inductively coupled plasma generation source that generates plasma by applying a high-frequency power of 〜40 MHz is used. 13. A spiral coil electrode is disposed on the atmospheric side of a disk-shaped dielectric as a reactive gas plasma generator of the active species generator.
The film forming apparatus according to claim 10, wherein an inductively coupled plasma generation source that generates plasma by applying a high frequency power of 0 KHz to 40 MHz is used. 14. A reactive gas plasma generating section of the active species generating apparatus, wherein a flat electrode is disposed inside the reactive gas plasma generating section, and the flat electrode has a frequency of 100 kHz to 4 kHz.
The film forming apparatus according to claim 10, wherein a capacitively coupled plasma generation source that generates plasma by applying a high-frequency power of 0 MHz is used. 15. A coil-shaped electrode or a spiral coil electrode is disposed inside the reaction gas generator as a reactive gas plasma generator of the active species generator, and high frequency power of 100 KHz to 40 MHz is applied to these electrodes. The film forming apparatus according to claim 10, wherein a plasma generation source in which inductively coupled plasma and capacitively coupled plasma coexist is used. 16. The film forming apparatus according to claim 10, wherein a helicon wave plasma is generated by a reactive gas plasma generating unit in order to increase the generation efficiency of the active species of the active species generator. . 17. A reactive gas plasma generating unit, comprising:
The film forming apparatus according to any one of claims 10 to 16, further comprising an external coil or an internal coil that forms a magnetic field of -300 gauss. 18. The film forming apparatus according to claim 7, wherein a substrate holder supporting the substrate is electrically insulated from a device potential in order to prevent abnormal discharge in the substrate. 19. The film forming apparatus according to claim 7, wherein a substrate holder is further provided before and after a film forming chamber having a film forming process zone and a reaction process zone.
It has two chambers: a substrate loading chamber where pre-processing can be performed as required, and a substrate unloading chamber where desorption / exhaust of the substrate holder and evacuation / subsequent post-processing can be performed. Wherein the substrate is transferred between a substrate loading chamber, a film forming chamber, and a substrate unloading chamber, thereby performing a sequential process of forming a thin film.