JP4401952B2 - Thin film production apparatus and thin film production method - Google Patents

Description

  The present invention relates to a thin film manufacturing apparatus and a thin film manufacturing method capable of forming an alloy film in one chamber.

  Currently, in the manufacture of semiconductors and the like, film formation using a plasma CVD (Chemical Vapor Deposition) apparatus is known. A plasma CVD apparatus is a plasma reaction of a gas such as an organometallic complex that becomes a material of a film introduced into a chamber by a high frequency incident from a high frequency antenna, and a chemical reaction on the substrate surface by active excited atoms in the plasma. Is a device for forming a metal thin film or the like by promoting the above.

  On the other hand, the present inventors installed a member to be etched, which is a metal component that forms a high vapor pressure halide, and is made of a metal component desired to be formed into a film, and the member to be etched is formed by plasma of halogen gas. A plasma CVD apparatus (hereinafter referred to as a new type of plasma CVD apparatus) and a film forming method for forming a precursor which is a halide of a metal component by etching and forming only the metal component of the precursor on a substrate. Developed (for example, see Patent Document 1 below).

JP 2003-147534 A

In the above-described plasma CVD apparatus of the new type, the metal film is formed on the substrate by controlling the temperature of the substrate to be lower than the temperature of the member to be etched which is a metal source to be formed. For example, when the metal of the member to be etched is M and the halogen gas is Cl ₂ , the member to be etched is controlled to a high temperature (for example, 300 ° C. to 700 ° C.) and the substrate is controlled to a low temperature (for example, about 200 ° C.). Thus, an M thin film can be formed on the substrate. This is thought to be due to the following reaction.

(1) Plasma dissociation reaction; Cl ₂ → 2Cl ^*
(2) Etching reaction; M + Cl ^* → MCl (g)
(3) Adsorption reaction to the substrate; MC1 (g) → MC1 (ad)
(4) Film formation reaction; MCl (ad) + Cl ^* → M + Cl ₂ ↑ (1)
Here, Cl ^* represents a Cl radical, (g) represents a gas state, and (ad) represents an adsorption state.

  In the above-described new CVD apparatus, a metal thin film with few impurities can be produced uniformly and at high speed. The application of this new type of CVD apparatus has been studied to produce an alloy thin film. Since the state of the vapor pressure of metal varies depending on the type, it is necessary to finely control the deposition rate and deposition conditions in order to produce an alloy thin film, and there is no established technique at present.

  The present invention has been made in view of the above circumstances, and provides a thin film production apparatus and a thin film production method capable of producing a metal thin film of an alloy with few impurities uniformly and at high speed in the above-described CVD apparatus of the new method. The purpose is to do.

In order to achieve the above object, a thin film manufacturing apparatus of the present invention according to claim 1 is provided.
A first plasma antenna and a second plasma antenna are provided above the ceiling plate, and an interior is provided in two chambers, a first chamber and a second chamber, corresponding to the first plasma antenna and the second plasma antenna. A partitioned chamber;
A member to be etched , which is disposed in the first chamber and the second chamber, each formed of a different metal;
A swivel table disposed at the bottom of the chamber and capable of moving a substrate between the first chamber and the second chamber;
Each said at positions corresponding to the etched member, and the source gas supply means for supplying a source gas containing a halogen at a flow rate controller,
Each said to correspond to the etched member, the precursor of the metal components by etching the first chamber and the etched member with internally to generate plasma of the material gas into plasma of the second chamber Generating the plasma generating means including the first plasma antenna and the second plasma antenna ;
Each said to correspond to the etched member, and a temperature control means for depositing the metal component of the precursor on the substrate by the temperature of the substrate is controlled lower than the temperature of each of the etched member
Driving time of the turning table, flow rate and supply timing of the source gas supplied via the flow rate controller, feeding power to the first plasma antenna and the second plasma antenna,
A plasma CVD apparatus comprising: stacking control means for individually controlling the metal component of each member to be etched to move the substrate between the first chamber and the second chamber to stack the dissimilar metals. It is characterized by that.

In order to achieve the above object, the thin film manufacturing method of the present invention according to claim 2 comprises:
A first plasma antenna and a second plasma antenna are provided above the ceiling plate, and an interior is provided in two chambers, a first chamber and a second chamber, corresponding to the first plasma antenna and the second plasma antenna. A partitioned chamber;
A member to be etched, which is disposed in the first chamber and the second chamber, each formed of a different metal;
A swivel table disposed at the bottom of the chamber and capable of moving a substrate between the first chamber and the second chamber;
Source gas supply means for supplying a source gas containing halogen to a portion corresponding to each of the members to be etched with a flow rate controller,
Corresponding to each of the members to be etched, the inside of the first chamber and the second chamber is converted into plasma to generate plasma of the source gas to etch the member to be etched, thereby forming a precursor with a metal component. Generating the plasma generating means including the first plasma antenna and the second plasma antenna;
Corresponding to each member to be etched, temperature control means for controlling the temperature of the substrate to be lower than the temperature of each member to be etched to form the metal component of the precursor on the substrate. A step of preparing a plasma CVD apparatus; and the source gas is supplied into the first chamber and the second chamber in which the substrate disposed on the turntable is accommodated, and the source gas is converted into plasma to generate plasma. A precursor of a metal component and a halogen is formed by etching and etching each member to be etched in the first chamber and the second chamber with plasma of the source gas, and the temperature of the substrate is set to each member to be etched. A first film forming step of forming a film on each of the substrates at a temperature lower than the temperature of the substrate, and then turning off the supply gas and turning the turntable to A swirling step of exchanging the substrates in the chamber and the second chamber, respectively, and then supplying the source gas to the substrates exchanged in the first chamber and the second chamber to convert the source gas into plasma. A plasma is generated to etch each member to be etched with the plasma of the source gas to form a precursor of a metal component and a halogen, and the temperature of each substrate is lower than the temperature of each member to be etched. And a second film forming step of forming a film on each of the substrates .

  In the first aspect of the present invention, a dense multi-layer film structure can be formed, the film forming conditions of each layer can be optimized, and an alloy metal thin film having desired characteristics can be easily obtained. For this reason, it becomes a thin film production apparatus which can produce the metal thin film of an alloy with few impurities uniformly and at high speed.

According to the second aspect of the present invention, a dense multi-layer film structure can be formed, the film forming conditions of each layer can be optimized, and an alloy metal thin film having desired characteristics can be easily obtained. For this reason, it becomes a thin film preparation method which can produce the metal foil film | membrane of an alloy with few impurities uniformly and at high speed.

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

  FIG. 1 is a schematic plan view of a thin film production apparatus according to an embodiment of the present invention, FIG. 2 is a schematic side view of a thin film production apparatus according to an embodiment of the present invention, and FIG. A time chart is shown, and FIG. 4 shows an explanation showing the lamination state of the metal films.

  As shown in FIGS. 1 and 2, a swivel table 2 is provided at the bottom of a chamber 1 made of, for example, ceramic (made of an insulating material), which is formed in a cylindrical shape. It is swiveled (moving means). The interior of the chamber 1 is partitioned into a first chamber 5 and a second chamber 6 by a partition plate 4. The shape of the chamber is not limited to a cylindrical shape, and for example, a rectangular chamber can be applied.

  Note that the first chamber 5 and the second chamber 6 are not necessarily partitioned by the partition plate 4. Further, the moving means is not limited to the turntable 2, and means for transporting the substrate can be applied.

  The turntable 2 is provided with a first support base 7 corresponding to the first chamber 5 and a second support base 8 corresponding to the second chamber 6. The first support base 7 and the second support base 8 are provided. A substrate (glass substrate) 9 is placed on each. The first support base 7 and the second support base 8 are respectively provided with temperature control means 12 including a heater 10 and a refrigerant circulation means 11. The first support base 7 and the second support base 8 are predetermined by the temperature control means 12. The temperature is controlled (for example, the temperature at which the substrate 9 is maintained at 100 ° C. to 300 ° C.).

  The upper surface of the chamber 1 is an opening, and the opening is closed by a ceiling plate 13 on a ceramic (insulating) plate, for example. The inside of the chamber 1, which is a sealed space, is evacuated by a vacuum device 20 and maintained at a predetermined low pressure.

  Plasma antennas 14 and 15 are provided above the ceiling plate 13 corresponding to the first chamber 5 and the second chamber 6, respectively, and the gas inside the first chamber 5 and the second chamber 6 is provided by the plasma antennas 14 and 15. Are converted into plasma. The plasma antennas 14 and 15 are each formed in a planar ring shape parallel to the surface of the ceiling plate 13. Matching devices 16 and 17 and power sources 18 and 19 are connected to the plasma antennas 14 and 15, respectively, and a high frequency current is supplied. The plasma antennas 14 and 15, the matching units 16 and 17, and the power sources 18 and 19 constitute plasma generation means.

  An etched member 21 made of, for example, Fe is provided between the substrate 9 and the plasma antenna 14 in the first chamber 5, and, for example, an Ni-made member is formed between the substrate 9 and the plasma antenna 15 in the second chamber 6. A member to be etched 22 is provided. The members to be etched 21 and 22 are disposed in a discontinuous state between the substrate 9 and the ceiling plate 13 with respect to the electric flow of the plasma antennas 14 and 15.

  For example, the members to be etched 21 and 22 are composed of a rod-like projection 23 and a support 24 to the chamber 1, and the projection 24 is disposed between the plasma antennas 14 and 15 and the substrate 9. As a result, the members to be etched 21 and 22 are structurally discontinuous with respect to the circumferential direction, which is the flow direction of electricity of the plasma antennas 14 and 15. In addition, as a structure which makes it a discontinuous state with respect to the electric flow of the plasma antennas 14 and 15, it is also possible to form a to-be-etched member in a grid | lattice form, or to comprise a mesh shape.

Nozzles 26 and 27 for supplying a source gas (Cl ₂ gas) containing chlorine as a halogen gas are connected to the cylindrical portion of the chamber 1 in the first chamber 5 and the second chamber 6. Cl ₂ gas is sent through the flow rate controllers 28 and 29. In addition, fluorine, bromine, iodine, etc. are applicable as halogen contained in source gas. Although one nozzle 26 and one nozzle 27 are shown for each of the first chamber 5 and the second chamber 6, a plurality of nozzles 26 and 27 may be provided equally as appropriate depending on the size of the chamber 1 and the like.

The stacking control means 51 individually controls the drive timing of the swivel table 2 by the drive means 3, the flow rate and supply timing of the Cl ₂ gas supplied via the flow rate controllers 28 and 29, and the power supply to the plasma antennas 14 and 15. Is done. Thus, Fe and Ni are laminated on the substrate 9 to form a film, and permalloy, which is an alloy of Fe and Ni, is produced on the substrate 9 by the action described below.

  In addition, although Fe and Ni were mentioned as an example as a material of the to-be-etched members 21 and 22, a Co / Ni alloy was produced using Co and Ni, or a Ta / SiN alloy was produced using Ta and SiN. It is also possible to make it and apply it to a barrier metal. Further, Ti / SiN alloy is produced using Ti and SiN as materials of the members to be etched 21 and 22, or a Co / Si alloy is produced using Co and Si and applied to the gate electrode of the integrated circuit. Is also possible.

In the thin film manufacturing apparatus described above, Cl ₂ gas is supplied from the nozzle 26 into the first chamber 5. By entering electromagnetic waves from the plasma antenna 14 into the first chamber 5, Cl ₂ gas is ionized to generate Cl ₂ gas plasma. The plasma is generated in the region shown by the gas plasma 55. The reaction formula at this time can be expressed by the following formula.
Cl ₂ → 2Cl ^* (1)
Here, Cl ^* represents a chlorine radical.

When the gas plasma 55 acts on the Fe member to be etched 21, the member to be etched 21 is heated and an etching reaction occurs in Fe. The reaction at this time is represented by the following formula, for example.
Fe (s) + Cl ^* → FeCl (g) (2)
Here, s represents a solid state and g represents a gas state. Formula (2) is a state in which Fe is etched by the gas plasma 55 to be a precursor 57.

The member to be etched 21 is heated by generating the gas plasma 55 (for example, 300 ° C. to 700 ° C.), and the temperature of the substrate 9 is lower than the temperature of the member to be etched 21 by the temperature control means 12 (for example, 100 ° C. to 300 ° C.). As a result, the precursor 57 is adsorbed (deposited) on the substrate 9. The reaction at this time is represented by the following formula, for example.
FeCl (g) → FeCl (ad) (3)

FeCl adsorbed on the substrate 9 is reduced by the chlorine gas radical Cl ^* to become an Fe component, whereby an Fe thin film can be produced. The reaction formula at this time is represented by the following formula, for example.
FeCl (ad) + Cl ^* → Fe (s) + Cl ₂ ↑ (4)

Further, a part of the gasified FeCl (g) generated in the above formula (2) is reduced by the chlorine gas radical Cl ^* before being adsorbed on the substrate 9 (see the above formula (3)), and is in a gaseous state. Fe. The reaction formula at this time is represented by the following formula, for example.
FeCl (g) + Cl ^* → Fe (g) + Cl ₂ ↑ (5)
Thereafter, the gaseous Fe component is deposited on the substrate 9 and an Fe thin film can be produced.

The supply state of Cl ₂ gas at this time is controlled from time T1 to t1 shown in FIG.

On the other hand, in the second chamber 6, a Ni thin film is simultaneously formed on the same principle as the first chamber 5. That is, the supply state of the Cl ₂ gas is controlled from time T1 to t1 shown in FIG.

Cl ₂ gas is supplied from the nozzle 27 into the second chamber 6. By entering electromagnetic waves from the plasma antenna 15 into the second chamber 6, the Cl ₂ gas is ionized to generate Cl ₂ gas plasma. The plasma is generated in the region shown by the gas plasma 56. The reaction formula at this time can be expressed by the following formula.
Cl ₂ → 2Cl ^* (6)
Here, Cl ^* represents a chlorine radical.

When the gas plasma 56 acts on the Ni member 22 to be etched, the member 22 to be etched is heated and an etching reaction occurs in Ni. The reaction at this time is represented by the following formula, for example.
Ni (s) + Cl ^* → NiCl (g) (7)
Here, s represents a solid state and g represents a gas state. Formula (7) is a state in which Ni is etched by the gas plasma 56 to form a precursor 58.

The member to be etched 22 is heated by generating the gas plasma 56 (for example, 300 ° C. to 700 ° C.), and the temperature control means 12 sets the temperature of the substrate 9 to a temperature lower than the temperature of the member to be etched 22 (for example, 100 ° C. to 300 ° C.). As a result, the precursor 58 is adsorbed (deposited) on the substrate 9. The reaction at this time is represented by the following formula, for example.
NiCl (g) → NiCl (ad) (8)

NiCl adsorbed on the substrate 9 is reduced by the chlorine gas radical Cl ^* to become a Ni component, so that, for example, a Ni thin film having a thickness of 1 nm to 10 nm can be produced. The reaction formula at this time is represented by the following formula, for example.
NiCl (ad) + Cl ^* → Ni (s) + Cl ₂ ↑ (9)

Furthermore, a part of the gasified NiCl (g) generated in the above formula (7) is reduced by the chlorine gas radical Cl ^* before being adsorbed to the substrate 9 (see the above formula (8)), and is in a gaseous state. Ni. The reaction formula at this time is represented by the following formula, for example.
NiCl (g) + Cl ^* → Ni (g) + Cl ₂ ↑ (10)
Thereafter, the Ni component in the gas state is formed on the substrate 9 to make a Ni thin film.

  The film formation of the Fe layer and the film formation of the Ni layer in the thin film production apparatus described above are performed simultaneously, and the temperature conditions of the first chamber 5 and the second chamber 6 are individually controlled according to the vapor pressure characteristics of Fe and Ni. The When the formation of the Fe layer and the Ni layer is completed, the driving unit 3 drives the turning table 2 to place the substrate 9 on which the Fe layer is formed in the second chamber 6, and the Ni layer is formed. The substrate 9 thus placed is placed in the first chamber 5 (from time t1 to time T2 shown in FIG. 3). In this state, the above-described film formation is performed (from time T2 to t2 shown in FIG. 3). By repeating the formation of the Fe layer and the Ni layer and the turning of the turntable 2, as shown in FIG. 4, an alloy 60 having a film thickness of 50 nm, for example, having a Fe layer and a Ni layer laminated on the substrate 9 is produced. Is done.

  When the above-described permalloy (for example, Fe: Ni is 2: 8) is manufactured as the alloy 60, the thickness of each of the Fe layer and the Ni layer is formed at a ratio of, for example, 2: 8. Is possible. Further, it is possible to form the film with the same number of Fe layers and Ni layers having a ratio of, for example, 2: 8. In addition, when laminating the Fe layer and the Ni layer, the alloy 60 can be formed by appropriately performing a heat treatment.

The thin film fabrication described above includes a member to be etched made of different kinds of metal, and a metal thin film is formed by adsorbing a metal component of a precursor obtained by plasmaizing Cl ₂ gas and etching each member to be etched to the substrate 9. The alloy is produced by moving the substrate and laminating the metal thin films. For this reason, even if it is a dissimilar metal from which vapor pressure characteristics differ, an optimal condition can be set, respectively, and a thin film can be formed and an alloy can be produced.

  Therefore, a dense multi-layer film structure can be formed, the film forming conditions of each layer can be optimized, an alloy metal thin film with desired characteristics can be easily obtained, and an alloy metal thin film with few impurities can be uniformly and at high speed. Can be produced.

  The present invention can be used in the industrial field of producing a thin film of an alloy in one chamber.

1 is a schematic plan view of a thin film manufacturing apparatus according to an embodiment of the present invention. 1 is a schematic side view of a thin film manufacturing apparatus according to an embodiment of the present invention. It is a time chart showing the supply condition of source gas. It is explanatory drawing showing the lamination | stacking condition of a metal film.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Chamber 2 Turning table 3 Drive means 4 Partition plate 5 1st chamber 6 2nd chamber 7 1st support stand 8 2nd support stand 9 Substrate 10 Heater 11 Refrigerant distribution means 12 Temperature control means 13 Ceiling plate 14, 15 Plasma antenna 16 , 17 Matching device 18, 19 Power source 20 Vacuum device 21, 22 Member to be etched 23 Projection portion 24 Support portion 26, 27 Nozzle 28, 29 Flow rate control means 51 Stacking control means 55, 56 Gas plasma 57, 58 Precursor 60 Alloy

Claims (3)

A first plasma antenna and a second plasma antenna are provided above the ceiling plate, and an interior is provided in two chambers, a first chamber and a second chamber, corresponding to the first plasma antenna and the second plasma antenna. A partitioned chamber;
A member to be etched , which is disposed in the first chamber and the second chamber, each formed of a different metal;
A swivel table disposed at the bottom of the chamber and capable of moving a substrate between the first chamber and the second chamber;
Each said at positions corresponding to the etched member, and the source gas supply means for supplying a source gas containing a halogen at a flow rate controller,
Each said to correspond to the etched member, the precursor of the metal components by etching the first chamber and the etched member with internally to generate plasma of the material gas into plasma of the second chamber Generating the plasma generating means including the first plasma antenna and the second plasma antenna ;
Each said to correspond to the etched member, and a temperature control means for depositing the metal component of the precursor on the substrate by the temperature of the substrate is controlled lower than the temperature of each of the etched member
Driving time of the turning table, flow rate and supply timing of the source gas supplied via the flow rate controller, feeding power to the first plasma antenna and the second plasma antenna,
And stacking control means for individually controlling the metal component of each member to be etched to move the substrate between the first chamber and the second chamber to stack the different metals. A plasma CVD apparatus. A first plasma antenna and a second plasma antenna are provided above the ceiling plate, and an interior is provided in two chambers, a first chamber and a second chamber, corresponding to the first plasma antenna and the second plasma antenna. A partitioned chamber;
A member to be etched, which is disposed in the first chamber and the second chamber, each formed of a different metal;
A swivel table disposed at the bottom of the chamber and capable of moving a substrate between the first chamber and the second chamber;
Source gas supply means for supplying a source gas containing halogen to a portion corresponding to each of the members to be etched with a flow rate controller,
Corresponding to each of the members to be etched, the inside of the first chamber and the second chamber is converted into plasma to generate plasma of the source gas to etch the member to be etched, thereby forming a precursor with a metal component. Generating the plasma generating means including the first plasma antenna and the second plasma antenna;
Corresponding to each member to be etched, temperature control means for controlling the temperature of the substrate to be lower than the temperature of each member to be etched to form the metal component of the precursor on the substrate. A step of preparing a plasma CVD apparatus; and the source gas is supplied into the first chamber and the second chamber in which the substrate disposed on the turntable is accommodated, and the source gas is converted into plasma to generate plasma. A precursor of a metal component and a halogen is formed by etching and etching each member to be etched in the first chamber and the second chamber with plasma of the source gas, and the temperature of the substrate is set to each member to be etched. A first film forming step of forming a film on each of the substrates at a temperature lower than the temperature of the substrate, and then turning off the supply gas and turning the turntable to A swirling step of exchanging the substrates in the chamber and the second chamber, respectively, and then supplying the source gas to the substrates exchanged in the first chamber and the second chamber to convert the source gas into plasma. A plasma is generated to etch each member to be etched with the plasma of the source gas to form a precursor of a metal component and a halogen, and the temperature of each substrate is lower than the temperature of each member to be etched. And a second film forming step of forming a film on each of the substrates. The thin film manufacturing method according to claim 2, wherein a series of steps from the first film forming step to the second film forming step through the turning step is repeated twice or more.

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