JP4368337B2 - Metal film manufacturing method and metal film manufacturing apparatus - Google Patents

Description

  The present invention relates to a metal film manufacturing method and a metal film manufacturing apparatus, and more particularly to etching a member to be etched formed of a metal that forms a high vapor pressure halide with a source gas plasma containing halogen under a predetermined condition. This is useful when applied to film formation.

  The present invention is also useful when applied to a case where a composite metal film is formed by etching a member to be etched having a plurality of types of metal with a source gas plasma containing halogen.

  Conventionally, when a metal film, for example, a copper thin film is produced by a vapor deposition method, for example, a liquid organic metal complex such as copper, hexafluoroacetylacetonate, trimethylvinylsilane, or the like is used as a raw material, and a solid raw material is used as a solvent. The film is formed on the substrate by being dissolved in and vaporized by utilizing a thermal reaction.

JP 2001-284285 A International Publication No. 01/073159 Pamphlet

  In the above-described conventional technology, it is difficult to improve the film formation speed because the film is formed using a thermal reaction. In addition, the metal complex as a raw material is expensive, and hexafluoroacetylacetonate and trimethylvinylsilane associated with copper remain as impurities in the copper thin film, making it difficult to improve the film quality. .

  In view of the above prior art, the present invention provides a metal film manufacturing method and a metal film manufacturing apparatus that can use an inexpensive raw material with a high film forming speed and can reduce impurities in the film as much as possible. With the goal.

  The inventors obtained the following knowledge. That is, chlorine gas is supplied into a vacuum chamber that accommodates the substrate, and this chlorine gas is converted into plasma by plasma generating means, while an etching target member made of a copper plate disposed in the chamber is etched with chlorine gas plasma. In this case, by appropriately controlling the temperature relationship between the copper plate and the substrate, the etched copper can be deposited on the substrate to form a copper thin film. That is, a copper thin film can be formed on a substrate when the copper plate as the member to be etched is heated to a high temperature (for example, 300 ° C. to 400 ° C.) and the substrate is set to a low temperature (about 200 ° C.).

  Therefore, while the copper plate is disposed facing the chlorine gas plasma forming a relatively high temperature atmosphere, the substrate is disposed in a relative low temperature atmosphere facing the copper plate with the plasma atmosphere interposed therebetween, and the temperature of both is set. A Cu thin film manufacturing apparatus can be easily provided by appropriate control.

Here, as the member to be etched, in addition to Cu, for example, any metal that forms a high vapor pressure halide such as Ta, Ti, W, Zn, In, and Cd can be used. Furthermore, a composite metal containing a plurality of these metals, for example, an alloy of In and Cu can be used as the member to be etched. In addition, a composite metal containing a non-metallic element such as S or Se in the metal, for example, an alloy such as CuInSe ₂ , CdS, or ZnSe can be used as the member to be etched. In addition to Cl ₂ , the source gas can be generally used as long as it is a halogen gas.

ここで、Ｃｌ^*はＣｌのラジカルであることを、（ｇ）はガス状態であることを、（ａｄ）は吸着状態であることをそれぞれ表している。 In the above-described Cu thin film production apparatus, the following reaction is considered to occur.

Here, Cl ^* represents a Cl radical, (g) represents a gas state, and (ad) represents an adsorption state.

If there is sufficient Cl ^* in the above formula (1), the reaction to the right side of the formula proceeds and a Cu film can be deposited satisfactorily. However, Cl ₂ , Cl ^{+ and the} like are mixed in the Cl gas plasma, and Cl ^* is not preferentially generated. Therefore, the reaction of the above formula (1) does not proceed uniquely, but conversely, a reaction proceeding to the left side also occurs simultaneously. Furthermore, there is a possibility that the Cu film formed at the corner is etched.

Further, the following reaction may occur if Cl ₂ is not sufficiently extracted from CuCl (ad).
CuCl (ad) → CuCl (s)
That is, a CuCl solid is formed. This CuCl (s) is an insulator. Therefore, the presence of CuCl (s) in the Cu film causes a decrease in the electrical conductivity of the generated Cu film and deteriorates the film quality.

Therefore, in order to realize a metal film manufacturing method based on the above-described knowledge well, further improve the film quality, and at the same time, further increase the film forming speed, first, a sufficient amount of Cl ^* in the chamber ^. This Cl ^* may be replenished separately so as to exist. This may be achieved by generating and supplying high-density Cl ^* in another space having a smaller volume than the chamber. This is because it is easier to adjust the plasma conditions so that Cl ^* is generated in a space with a smaller volume.

On the other hand, it is considered that a reaction represented by the following formula (2) also occurs as another film forming reaction.
2CuCl (ad) → 2Cu + Cl ₂ (2)

The above formula (2) is a reaction in which CuCl (ad) deposits Cu with thermal energy and releases Cl ₂ gas, but it is a reversible reaction that may be in thermal equilibrium. In the above equation (2), if the amount of Cl ₂ is decreased, the reaction goes to the right side. For this purpose, the Cl ₂ gas may be dissociated.

Therefore, in order to achieve a good metal film manufacturing method based on the above-described knowledge, to further improve the film quality, and at the same time, further increase the film formation rate, secondly, Cl generated with the film formation reaction. ₂ The dissociation rate may be increased so that the amount of gas decreases. This can be basically achieved by adjusting the plasma conditions.

  The object of the present invention is achieved by utilizing an etching phenomenon under a predetermined temperature control based on the above knowledge, and the effect is increased by increasing the dissociation rate of the raw material gas adsorbed on the substrate. The structure of the first metal film manufacturing method according to the present invention focusing on the film forming reaction of the above formula (2), which is more remarkable, is characterized by the following points.

  1) A member to be etched formed of a metal that forms a high vapor pressure halide is disposed in a chamber that accommodates a substrate therein, and the temperature of the member to be etched and the substrate is controlled to a predetermined temperature and a temperature difference. Thus, the member to be etched is etched with a source gas plasma containing halogen in the chamber to form a precursor of a metal component and a halogen, and the metal component of the precursor is deposited on the substrate to form a predetermined component. In the metal film preparation method for forming a film, the plasma conditions are controlled so that the dissociation rate of the source gas generated with the film formation reaction is increased.

  2) In the metal film manufacturing method described in 1) above, the plasma conditions are controlled by reducing the supply amount of the source gas.

  3) In the metal film manufacturing method described in 1) above, the control of the plasma conditions should be realized by increasing the amount of high-frequency power used to form the source gas plasma.

  4) In the metal film manufacturing method described in 1) above, the plasma conditions are controlled by supplying a rare gas having a mass of Ne or more into the chamber in addition to the source gas.

  5) In the metal film manufacturing method described in 1) above, the plasma conditions are controlled by supplying electromagnetic waves into the chamber and dissociating the source gas supplied into the chamber.

  The configuration of the first metal film manufacturing apparatus that realizes the first metal film manufacturing method is characterized by the following points.

  6) A cylindrical chamber in which the substrate is accommodated, a member to be etched formed of a metal that forms a high vapor pressure halide disposed in a position facing the substrate in the chamber, the substrate and the member to be etched A raw material gas supply means for supplying a raw material gas containing halogen into the chamber between the member and a plasma of the raw material gas supplied into the chamber by supplying high-frequency power to etch the member to be etched The film forming plasma generating means for forming the source gas plasma in the chamber and the substrate temperature is controlled to a predetermined temperature lower than the temperature of the member to be etched, and the source gas plasma etches the member to be etched. Temperature control means for depositing a metal component on a substrate from a precursor of the metal component and halogen obtained thereby to form a predetermined film; In addition to the source gas, it has a rare gas supply means for supplying a rare gas having a mass of Ne or more into the chamber.

  7) A cylindrical chamber in which a substrate is accommodated, a member to be etched formed of a metal that forms a high vapor pressure halide disposed in a position facing the substrate in the chamber, and a source gas containing halogen Source gas plasma supply means for forming the plasma outside the chamber and supplying the source gas plasma into the chamber between the substrate and the member to be etched, and the substrate temperature higher than the temperature of the member to be etched Temperature control means for depositing a metal component on a substrate from a precursor of a metal component and a halogen obtained by etching the member to be etched by controlling the material gas plasma to a low predetermined temperature, and performing a predetermined film formation; In addition to the source gas, it has a rare gas supply means for supplying a rare gas having a mass of Ne or more into the chamber.

  8) A cylindrical chamber in which a substrate is accommodated, a member to be etched formed of a metal that forms a high vapor pressure halide disposed in a position away from the position facing the substrate in the chamber, and the chamber A shield plate disposed between the substrate and the member to be etched and having a hole directed in the direction of the substrate, and a halogen contained in the chamber between the member to be etched and the shield plate A raw material gas supply means for supplying a raw material gas, and a material gas plasma supplied into the chamber by supplying high-frequency electric power to form a raw material gas plasma in the chamber by etching the member to be etched. The film plasma generating means and the temperature of the substrate are controlled to a predetermined temperature lower than the temperature of the member to be etched, and the source gas plasma is etched. In addition to the temperature control means for depositing the metal component on the substrate from the precursor of the metal component and halogen obtained by etching the ching member to form a predetermined film, and the source gas, a noble gas having a mass of Ne or more is added. A metal film manufacturing apparatus, comprising: a rare gas supply means for supplying the inside of the chamber.

  9) A cylindrical chamber in which the substrate is accommodated, a member to be etched formed of a metal that forms a high vapor pressure halide disposed in a position facing the substrate in the chamber, the substrate, and the substrate to be etched A raw material gas supply means for supplying a raw material gas containing halogen into the chamber between the member and a plasma of the raw material gas supplied into the chamber by supplying high-frequency power to etch the member to be etched The film forming plasma generating means for forming the source gas plasma in the chamber and the substrate temperature is controlled to a predetermined temperature lower than the temperature of the member to be etched, and the source gas plasma etches the member to be etched. Temperature control means for depositing a metal component on a substrate from a precursor of the metal component and halogen obtained thereby to form a predetermined film; An electromagnetic wave generating means for supplying an electromagnetic wave into the chamber to dissociate a raw material gas generated with a film forming reaction.

  10) A cylindrical chamber in which the substrate is accommodated, a member to be etched formed of a metal that forms a high vapor pressure halide disposed in a position facing the substrate in the chamber, and a source gas containing halogen Source gas plasma supply means for forming the plasma outside the chamber and supplying the source gas plasma into the chamber between the substrate and the member to be etched, and the substrate temperature higher than the temperature of the member to be etched Temperature control means for depositing a metal component on a substrate from a precursor of a metal component and a halogen obtained by etching the member to be etched by controlling the material gas plasma to a low predetermined temperature, and performing a predetermined film formation; An electromagnetic wave generating means for supplying an electromagnetic wave into the chamber to dissociate a raw material gas generated with a film forming reaction.

  11) A cylindrical chamber in which a substrate is accommodated, a member to be etched formed of a metal that forms a high vapor pressure halide disposed in a position away from the position facing the substrate in the chamber, and the chamber A shield plate disposed between the substrate and the member to be etched and having a hole directed in the direction of the substrate, and a halogen contained in the chamber between the member to be etched and the shield plate A raw material gas supply means for supplying a raw material gas, and a material gas plasma supplied into the chamber by supplying high-frequency electric power to form a raw material gas plasma in the chamber by etching the member to be etched. The plasma generating means for film and the temperature of the substrate are controlled to a predetermined temperature lower than the temperature of the member to be etched, and the source gas plasma is subjected to the etching. A temperature control means for depositing a metal component on a substrate from a precursor of a metal component and a halogen obtained by etching the etching member to form a predetermined film, and an electromagnetic wave is supplied into the chamber to accompany the film formation reaction. Electromagnetic wave generating means for dissociating the generated raw material gas.

  The configuration of the second metal film production method that realizes the production of a composite metal thin film by applying the first metal film production method is characterized by the following points.

  12) In the metal film manufacturing method according to any one of 1) to 5) above, the member to be etched formed of the metal is formed of a composite metal composed of a plurality of types of metal components, and the source gas Predetermining film formation by depositing a plurality of types of metal components on a substrate from a plurality of types of precursors of metal components and halogen obtained by plasma etching the member to be etched.

  The configuration of the second metal film manufacturing apparatus for realizing the second metal film manufacturing method is characterized by the following points.

  13) In the metal film manufacturing apparatus according to any one of 6) to 11) above, the member to be etched formed of the metal is formed of a composite metal composed of a plurality of types of metal components, and the source gas Predetermining film formation by depositing a plurality of types of metal components on a substrate from a plurality of types of precursors of metal components and halogen obtained by plasma etching the member to be etched.

  The configuration of the third metal film manufacturing method for realizing the composite metal thin film manufacturing by applying the first metal film manufacturing method is characterized by the following points.

  14) In the metal film manufacturing method according to any one of 1) to 5) above, the member to be etched formed of the metal includes one or more kinds of metal components and one or more kinds of nonmetal components. A metal component formed from a metal component, one or more precursors of a metal component and a halogen, a non-metal component and one or more precursors of a halogen, which are formed of a composite metal and are obtained by etching the member to be etched by the source gas plasma And depositing the non-metallic component on the substrate at the same time to form a predetermined film.

  The configuration of the third metal film manufacturing apparatus for realizing the third metal film manufacturing method is characterized by the following points.

  15) In the metal film manufacturing apparatus described in any one of 6) to 11) above, the member to be etched formed of the metal includes one or more kinds of metal components and one or more kinds of nonmetal components. A metal component formed from a metal component, one or more precursors of a metal component and a halogen, a non-metal component and one or more precursors of a halogen, which are formed of a composite metal and are obtained by etching the member to be etched by the source gas plasma And depositing the non-metallic component on the substrate at the same time to form a predetermined film.

According to the present invention, by supplying “a rare gas having a mass of Ne or more into the chamber in addition to the source gas”, in the example, Cl generated in the film formation reaction of 2CuCl to Cu deposition or 2InCl to In deposition ₂ Dissociate Cl ^* As a result, the formation of a Cu or In metal film is promoted. The noble gas functions as a catalyst that increases the dissociation rate. In addition, according to another aspect of the present invention, by supplying "electromagnetic wave into the chamber", Cl in the excitation chamber ^* In this embodiment, Cl is separated from CuCl (ad) or InCl (ad) to promote the formation of a Cu or In metal film.

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

<First Embodiment>
FIG. 1 is a schematic side view of a metal film manufacturing apparatus according to a first embodiment of the present invention. As shown in the figure, a support base 2 is provided in the vicinity of the bottom of a chamber 1 (made of an insulating material) formed in a cylindrical shape, for example, made of ceramics (made of an insulating material). Is placed. The support base 2 is provided with a temperature control means 6 including a heater 4 and a refrigerant flow means 5, and the support base 2 is set to a predetermined temperature (for example, a temperature at which the substrate 3 is maintained at 100 ° C. to 200 ° C.) by the temperature control means 6. ) Is controlled.

  The upper surface of the chamber 1 is an opening, and the opening is closed by a copper plate member 7 as a metal member to be etched. The inside of the chamber 1 closed by the copper plate member 7 is maintained at a predetermined pressure by the vacuum device 8.

  A coil-shaped film-forming plasma antenna 9 wound in the axial direction of the chamber 1 is disposed around the cylindrical portion of the chamber 1 on the copper plate member 7 side. The matching unit 10 and the power source 11 are connected to supply power. The film forming plasma antenna 9, the matching unit 10 and the power source 11 constitute a film forming plasma generating means.

A slit-like opening 23 is formed at a position obliquely above the substrate 3 in the cylindrical portion of the chamber 1, and one end of a cylindrical passage 24 is fixed to the opening 23. A cylindrical excitation chamber 25 formed of an insulator is provided in the middle of the passage 24, and a coiled plasma antenna 26 is wound around the excitation chamber 25. A matching unit 27 and a power source 28 are connected to the plasma antenna 26 to supply power. Here, the opening 23, the associated passage 24, the excitation chamber 25, and the like are disposed at the same height of the chamber 1 and at four locations around the chamber 1 (only two locations are shown in the figure). is there. A flow rate controller 29 is connected to the other end of the passage 24, and Cl ₂ gas for obtaining Cl ^* is supplied into the passage 24 through the flow rate controller 29. The plasma antenna 26, the matching unit 27, the power source 28, and the flow rate controller 29 constitute source gas radical supply means.

In such raw material gas radical supply means, Cl ^* is formed by supplying electromagnetic waves from the plasma antenna 26 into the excitation chamber 25 while supplying Cl ₂ gas into the excitation chamber 25 via the flow rate controller 29. . At this time, the plasma conditions are adjusted so that Cl ^* can be formed at a high density in the excitation chamber 25. The Cl ^* formed in this way is supplied into the chamber 1 through the passage 24 during film formation. This Cl ^* dissociates Cl ₂ gas from CuCl (ad) adsorbed on the substrate 3 and promotes the film formation reaction. That is, the film forming reaction represented by the above formula (1) is promoted.

A source gas containing chlorine (Cl ₂ gas diluted with He to a chlorine concentration of ≦ 50%, preferably about 10%) is supplied to the cylindrical portion of the chamber 1 above the support base 2. Nozzle 12 is connected. The nozzle 12 opens toward the copper plate member 7. In addition, a raw material gas is fed to the nozzle 12 via a flow rate controller 13. The source gas is sent from the substrate 3 side to the copper plate member 7 side along the wall surface in the chamber 1 during film formation.

On the other hand, a nozzle 30 for supplying a rare gas such as Ar gas into the chamber 1 is connected to the upper portion of the cylindrical portion of the chamber 1. Here, the flow rate of a rare gas such as Ar gas is controlled by the flow rate controller 31 to improve the dissociation rate of the Cl ₂ gas in the film formation reaction shown in the above formula (2), and to promote the film formation reaction. Is. Therefore, except for the He gas contained in the source gas as a diluent gas, a rare gas having a mass of Ne or more can be used as a gas that improves the dissociation rate of the Cl ₂ gas and promotes the film formation reaction. However, Ar gas or Kr gas is preferable in view of the function as a catalyst for improving the dissociation rate, and Ar gas is optimal in consideration of cost.

  The mode at the time of film formation in such a metal film manufacturing apparatus is as follows. During film formation, the film formation plasma antenna 9 and the plasma antenna 26 are energized.

First, while supplying the source gas from the nozzle 12 to the inside of the chamber 1, electromagnetic waves are incident on the inside of the chamber 1 from the film forming plasma antenna 9, whereby the Cl ₂ gas is ionized to generate Cl ₂ gas plasma (source gas). Plasma) 14 is generated. The Cl ₂ gas plasma 14 is formed in a space adjacent to the film forming plasma antenna 9 in the chamber 1, that is, a space on the copper plate member 7 side (upper part) of the chamber 1.

The Cl ₂ gas plasma 14 causes an etching reaction in the copper plate member 7 to generate a precursor (CuxCly) 15. At this time, the copper plate member 7 is maintained at a predetermined temperature (for example, 200 ° C. to 400 ° C.) higher than the temperature of the substrate 3 by the Cl ₂ gas plasma 14.

  The precursor (CuxCly) 15 generated inside the chamber 1 is transferred to the substrate 3 controlled to a temperature lower than that of the copper plate member 7. The precursor (CuxCly) 15 transported to the substrate 3 and adsorbed thereto deposits Cu on the substrate 3 by the reaction of the above formulas (1) and (2) representing the film formation reaction. Thus, the Cu thin film 16 is generated on the surface of the substrate 3.

At this time, in the excitation chamber 25, Cl ^* is formed with high efficiency and replenished into the chamber 1, thereby dissociating Cl in the formula (1) and promoting the film formation reaction. Further, Ar gas is supplied from the nozzle 30 into the chamber 1 to dissociate the Cl ₂ gas in the above formula (2) to promote the film formation reaction.

In the metal film manufacturing apparatus having the above configuration, the Cl ₂ gas plasma (raw material gas plasma) 14 is used, so that the reaction efficiency is greatly improved and the film forming speed is increased. In addition, since the Cl ₂ gas is used as the source gas, the cost can be greatly reduced. Further, since the substrate 3 is controlled to a temperature lower than that of the copper plate member 7 by using the temperature control means 6, the residue of impurities such as chlorine can be reduced in the Cu thin film 16, and the high quality Cu thin film 16. Can be generated.

<Second Embodiment>
FIG. 2 is a schematic side view of a metal film manufacturing apparatus according to the second embodiment of the present invention. As shown in the figure, the metal film manufacturing apparatus according to the present embodiment differs from the first embodiment shown in FIG. 1 in the configuration of the plasma antenna and the configuration of related parts, but the same in many parts. It is the composition. Therefore, the same parts as those in FIG.

As shown in FIG. 2, the chamber 41 is a cylindrical member made of metal (for example, aluminum), the upper surface is an opening, and the opening is an insulating member (for example, made of ceramics). It is blocked by a disk-shaped ceiling board 47. The copper etched member 58 composed of the ring portion 59 and the projection portion 60 will be described in detail later with reference to FIG. 3. The member to be etched is divided into a plurality of portions in the circumferential direction in a position facing the substrate 3 in the chamber 41. The protruding portion 60 is protruding from the inner peripheral surface side of the chamber 41 toward the center side. The film-forming plasma antenna 49 is formed in a spiral shape and disposed outside the ceiling plate 47, and forms an electric field by a current supplied from the power source 51 via the matching unit 50. In the internal space on the etched member 58 side (upper part), Cl ₂ gas, which is a raw material gas supplied into the chamber 41, is converted into plasma to form Cl ₂ gas plasma 14. That is, the film forming plasma generating means is constituted by the film forming plasma antenna 49, the matching unit 50 and the power source 51.

  As shown in detail in FIG. 3, a projecting portion 60 that extends to the vicinity of the central portion in the radial direction of the chamber 41 (see FIG. 2) has the same width on the inner peripheral side of the ring portion 59 of the member to be etched 58. A plurality (12 in the illustrated example) are provided in the circumferential direction. The protrusion 60 is attached to the ring portion 59 integrally or detachably. Between the ceiling plate 47 (see FIG. 2) and the inside of the chamber 41, there is a notch 67 (space) formed between the protrusions 60. The ring part 59 is grounded, and the plurality of protrusions 60 are electrically connected by the ring part 59 and have the same potential.

At the time of film formation in such a metal film manufacturing apparatus, the film forming plasma antenna 49 and the plasma antenna 26 are energized. As a result, the electromagnetic wave from the film forming plasma antenna 49 is into the chamber 41, the Cl ₂ gas is ionized to generate a Cl ₂ gas plasma (source gas plasma) 14, the first embodiment The Cu thin film 16 is formed in the same manner as described above.

However, the mode of forming the film-forming plasma in this embodiment is slightly different from that of the metal film manufacturing apparatus shown in FIG. 1, and this will be described with reference to FIG. As shown in the figure, when the Cl ₂ gas plasma 14 (see FIG. 2) is generated below the member to be etched 58, the current direction A of the film-forming plasma antenna 49 is a direction across the protrusion 60. . As a result, an induced current B is generated in the direction shown in the figure on the side of the protrusion 60 facing the film-forming plasma antenna 49. Here, since the notched portion 67 (space) exists in the member to be etched 58, the induced current B flows in the same direction a as the current direction A of the film forming plasma antenna 49 on the lower surface side of each protrusion 60. As a result, when the member 58 to be etched is viewed from the substrate 3 side, the film-forming plasma antenna is effectively provided even if the protrusion 60 as a conductor is present below the film-forming plasma antenna 49, that is, the substrate 3 side. Thus, there is no current in a direction to cancel the current 49, and an alternating electric field can be formed by the film-forming plasma antenna 49 below the protrusion 60. In addition, the ring portion 59 is grounded, and the protrusion 60 is maintained at the same potential. As a result, even when the member to be etched 58, which is a conductor, is present, the electromagnetic wave from the film forming plasma antenna 49 surely enters the chamber 41, and the Cl ₂ gas plasma 14 is placed below the member to be etched 58. It can be formed stably.

In this embodiment as well, in the excitation chamber 25, Cl ^* is formed with high efficiency and replenished into the chamber 41, whereby Cl in the formula (1) is dissociated to promote the film formation reaction. Further, Ar gas is supplied from the nozzle 30 into the chamber 41 to dissociate the Cl ₂ gas in the formula (2) to promote the film formation reaction.

  Further, in this embodiment, it is possible to eliminate the instability of plasma due to the difference in potential by controlling the supply of the source gas without connecting the protrusion 60 to the ring portion 59.

<Third Embodiment>
As shown in FIG. 5, this embodiment removes the film-forming plasma antenna 9 in the first embodiment shown in FIG. 1, and instead of the film-forming plasma antenna 9 on the copper plate member 7 which is a member to be etched. It is a combination of functions. For this reason, the high frequency power from the power source 11 is supplied to the copper plate member 7 via the matching unit 10 and the support base 2 which is a conductive member is grounded. That is, the copper plate member 7 and the support base 2 serve as both electrodes, and a Cl ₂ gas plasma 14 is formed between them in the chamber 1.

  Other configurations in the metal film manufacturing apparatus according to the present embodiment are the same as those in FIG. 1, and thus the same parts are denoted by the same reference numerals and redundant description is omitted.

In this embodiment, source gas is supplied into the chamber 1 from the nozzle 12 and electromagnetic waves are incident on the chamber 1 from the copper plate member 7, whereby the Cl ₂ gas is ionized to generate Cl ₂ gas plasma (source gas). Plasma) 14 is generated. As a result, an etching reaction occurs in the copper plate member 7 by the Cl ₂ gas plasma 14, and a precursor (CuxCly) 15 is generated. At this time, the copper plate member 7 is maintained at a temperature (for example, 200 ° C. to 400 ° C.) higher than the temperature of the substrate 3 by a temperature control means (not shown). Thus, the Cu thin film 16 is formed on the surface of the substrate 3 in the same manner as in the first embodiment.

Also in this embodiment, in the excitation chamber 25, Cl ^* is formed with high efficiency and replenished into the chamber 1, thereby dissociating Cl in the formula (1) and promoting the film formation reaction. Further, Ar gas is supplied from the nozzle 30 into the chamber 1 to dissociate the Cl ₂ gas in the above formula (2) to promote the film formation reaction.

<Fourth embodiment>
As shown in FIG. 6, this embodiment can be positioned as a modification of the third embodiment shown in FIG. 5, but the copper plate member 72 that is the member to be etched is placed on the substrate 3 in the chamber 71. A shield plate 73 having a ground potential serving as a counter electrode is disposed at a position avoiding the facing position. Then, the high frequency power from the power source 11 is supplied to the copper plate member 7 through the matching unit 10, and the raw material gas is supplied between the copper plate member 72 and the shielding plate 73 in the chamber 71 through the nozzle 12. The plasma is formed. Here, a large number of holes 73 a are formed in the shielding plate 73, and the precursor 15 formed between the copper plate member 72 and the shielding plate 73 passes through the holes 73 a and above the substrate 3 in the chamber 71. It is configured to reach the space. The copper plate member 72 is a hollow truncated cone-shaped member, and the shielding plate 73 is formed of a hollow truncated cone-shaped member similar to the copper plate member 72. Therefore, the surfaces facing each other are parallel and are inclined with respect to the substrate 3. This prevents particles that are peeled off from the etched copper plate member 72 from adhering to the substrate 3, and allows the predetermined precursor 15 to be supplied to the space above the substrate 3. This is because the particle 15 is less likely to be shielded by the shielding plate 73 and reach the space above the substrate 3, whereas the precursor 15 can easily pass through the hole 73a.

  Other configurations in the metal film manufacturing apparatus according to the present embodiment are the same as those in FIG. 5, and thus the same parts are denoted by the same reference numerals and redundant description is omitted.

In this embodiment, source gas is supplied from the nozzle 12 into the chamber 71 and electromagnetic waves are incident from the copper plate member 72 into the chamber 71, whereby the Cl ₂ gas is ionized and Cl ₂ gas plasma (source gas is supplied). Plasma) 14 is generated. As a result, the Cl ₂ gas plasma 14 causes an etching reaction in the copper plate member 72 to generate a precursor (CuxCly) 15. The precursor (CuxCly) 15 reaches the space above the substrate 3 in the chamber 71 through the hole 73 a of the shielding plate 73. At this time, the copper plate member 72 is maintained at a temperature (for example, 200 ° C. to 400 ° C.) higher than the temperature of the substrate 3 by a temperature control unit (not shown). Thus, the Cu thin film 16 is formed on the surface of the substrate 3 in the same manner as in the first embodiment.

Here, the precursor (CuxCly) 15 easily passes through the hole 73a. Of the Cl ^* formed in the space between the copper plate member 72 and the shielding plate 73, the precursor (CuxCly) 15 passes through the hole 73a and is above the substrate 3. There is little to reach the space. This is because, among the Cl ^* , those that have collided with the shielding plate 73 are combined to form Cl ₂ gas. That is, a reaction represented by Cl ^* + Cl ^* → Cl ₂ occurs and Cl ^* disappears.

On the other hand, also in this embodiment, in the excitation chamber 25, Cl ^* is formed with high efficiency and replenished into the chamber 71, thereby dissociating Cl in the formula (1) and promoting the film formation reaction. As described above, in this embodiment in which most of the Cl ^* formed in the space between the copper plate member 72 and the shielding plate 73 disappears, the replenishment of Cl ^* becomes more significant, and the film formation reaction is promoted. The contribution is particularly remarkable.

In this embodiment as well, Ar gas is supplied from the nozzle 30 into the chamber 71 to dissociate the Cl ₂ gas in the formula (2) to promote the film formation reaction.

<Fifth embodiment>
In each of the above-described embodiments, the source gas is supplied into the chamber 1 and the like and converted into plasma. However, the source gas plasma may be supplied directly into the chamber. Such a metal film manufacturing apparatus will be described in detail with reference to FIG. As shown in the figure, the metal film production apparatus according to this embodiment is largely different from the metal film production apparatus according to the first embodiment shown in FIG. Although different, it has many common components. Therefore, the same parts as those in FIG.

  As shown in FIG. 7, the upper surface of a chamber 81 made of, for example, ceramic (made of insulating material) is formed as an opening, and the opening is formed by a ceiling plate 100 made of, for example, ceramic (made of insulating material). It is blocked. A metal (copper: Cu) member to be etched 88 is provided on the lower surface of the ceiling plate 100, and the member to be etched 88 has a conical shape. In addition, slit-like openings 89 are formed at four places (only two places are shown in the figure) around the upper part of the tubular portion of the chamber 81, and one end of the tubular passage 90 is formed in the opening 89. Each is fixed. A cylindrical excitation chamber 95 formed of an insulator is provided in the middle of the passage 90, and a coiled plasma antenna 91 is provided around the excitation chamber 95. The plasma antenna 91 includes a matching unit 92 and a power source 93. Is connected to the power supply. The plasma antenna 91, the matching unit 92, and the power source 93 constitute plasma generating means.

A flow rate controller 94 is connected to the other end side of the passage 90, and a raw material gas containing chlorine as a halogen in the passage 90 via the flow rate controller 94 (He has a chlorine concentration ≦ 50%, preferably 10%. Cl ₂ gas diluted to a certain extent) is supplied. When electromagnetic waves are incident on the inside of the excitation chamber 95 from the plasma antenna 91, Cl ₂ gas is ionized to generate Cl ₂ gas plasma (raw material gas plasma) 96. That is, the excitation means is configured to excite the source gas containing chlorine in the excitation chamber 95 isolated from the chamber 81. Due to the generation of the Cl ₂ gas plasma 96, excited chlorine is supplied from the opening 89 to the member to be etched 88 side (upper part) in the chamber 81, and the member to be etched 88 is etched by the Cl ₂ gas plasma 96.

At the time of film formation in such a metal film manufacturing apparatus, a Cl ₂ gas plasma 96 is formed in the excitation chamber 95, and the temperature condition between the member 88 to be etched and the substrate 3 is adjusted in a predetermined manner through the opening 89. The Cl ₂ gas plasma 96 is introduced. Thereby, the member to be etched 88 is etched as in the case of the metal film manufacturing apparatus shown in FIG. 1 and the like, and the Cu thin film 16 can be formed on the substrate 3.

In this embodiment as well, in the excitation chamber 25, Cl ^* is formed with high efficiency and replenished into the chamber 81, thereby dissociating Cl in the formula (1) and promoting the film formation reaction. Further, Ar gas is supplied from the nozzle 30 into the chamber 81 to dissociate the Cl ₂ gas in the formula (2) to promote the film forming reaction.

Next, a case where a member to be etched is a composite metal made of, for example, In and Cu, or a composite metal such as, for example, CuInSe ₂ , CdS, or ZnSe, and a thin film of the composite metal is manufactured will be described.

ここで、Ｃｌ^*はＣｌのラジカル、（ｇ）はガス状態、（ａｄ）は吸着状態をそれぞれ表している。 It is considered that the following reaction occurs in the production of a thin film of a composite metal (for example, an InCu thin film) in the same manner as the production of the Cu thin film described above.

Here, Cl ^* represents a Cl radical, (g) represents a gas state, and (ad) represents an adsorption state.

In addition, as another film forming reaction, the following reaction is also expected to occur in the same manner, corresponding to the formula (2) predicted when the Cu thin film is produced.
2CuCl (ad) → 2Cu + Cl ₂ (5)
2InCl (ad) → 2In + Cl ₂ (6)

Further, in the case of a composite metal such as CuInSe ₂ , CdS, or ZnSe containing a nonmetallic element, it is considered that the nonmetallic element in the composite metal is chlorinated by Cl ^* . That is, as a result of etching with Cl ^* , nonmetallic elements such as Se and S form chlorides and become precursors, which are transported to the substrate and become constituent elements of the thin film.

<Sixth Embodiment>
FIG. 8 is a schematic side view of a metal film manufacturing apparatus according to the sixth embodiment of the present invention. As shown in the figure, a support base 2 is provided in the vicinity of the bottom of a chamber 1 (made of an insulating material) formed in a cylindrical shape, for example, made of ceramics (made of an insulating material). Is placed. The support base 2 is provided with a temperature control means 6 including a heater 4 and a refrigerant flow means 5, and the support base 2 is set to a predetermined temperature (for example, a temperature at which the substrate 3 is maintained at 100 ° C. to 200 ° C.) by the temperature control means 6. ) Is controlled.

  The upper surface of the chamber 1 is an opening, and the opening is closed by a composite metal plate member 101 which is a member to be etched made of a composite metal of In and Cu. Here, the composite metal plate member 101 is obtained by uniformly mixing In and Cu at a ratio of 1: 1, and then press-molding it into a plate shape. According to this manufacturing method, the composite metal plate member 101 can be easily manufactured. Alternatively, the composite metal plate member 101 may be manufactured in a split type in which the right half is formed of In and the left half is formed of Cu. According to this manufacturing method, composition control of the thin film to be formed is facilitated. The inside of the chamber 1 closed by the composite metal plate member 101 is maintained at a predetermined pressure by the vacuum device 8.

  A coil-shaped film-forming plasma antenna 9 wound around the axial direction of the chamber 1 is arranged around the composite metal plate member 101 side of the cylindrical portion of the chamber 1. The matching unit 10 and the power source 11 are connected to the power supply. The film forming plasma antenna 9, the matching unit 10 and the power source 11 constitute a film forming plasma generating means.

A slit-like opening 23 is formed at a position obliquely above the substrate 3 in the cylindrical portion of the chamber 1, and one end of a cylindrical passage 24 is fixed to the opening 23. A cylindrical excitation chamber 25 formed of an insulator is provided in the middle of the passage 24, and a coiled plasma antenna 26 is wound around the excitation chamber 25. A matching unit 27 and a power source 28 are connected to the plasma antenna 26 to supply power. Here, the opening 23, the associated passage 24, the excitation chamber 25, and the like are disposed at the same height of the chamber 1 and at four locations around the chamber 1 (only two locations are shown in the figure). is there. A flow rate controller 29 is connected to the other end of the passage 24, and Cl ₂ gas for obtaining Cl ^* is supplied into the passage 24 through the flow rate controller 29. The plasma antenna 26, the matching unit 27, the power source 28, and the flow rate controller 29 constitute source gas radical supply means.

In such raw material gas radical supply means, Cl ^* is formed by supplying electromagnetic waves from the plasma antenna 26 into the excitation chamber 25 while supplying Cl ₂ gas into the excitation chamber 25 via the flow rate controller 29. . At this time, the plasma conditions are adjusted so that Cl ^* can be formed at a high density in the excitation chamber 25. The Cl ^* formed in this way is supplied into the chamber 1 through the passage 24 during film formation. This Cl ^* dissociates Cl ₂ gas from the metal chloride (CuCl, InCl) adsorbed on the substrate 3 and promotes the film formation reaction. That is, the film forming reaction represented by the above formulas (3) and (4) is promoted.

A source gas containing chlorine (Cl ₂ gas diluted with He to a chlorine concentration of ≦ 50%, preferably about 10%) is supplied to the cylindrical portion of the chamber 1 above the support base 2. Nozzle 12 is connected. The nozzle 12 opens toward the composite metal plate member 101. In addition, a raw material gas is fed to the nozzle 12 via a flow rate controller 13. The source gas is sent from the substrate 3 side to the composite metal plate member 101 side along the wall surface in the chamber 1 during film formation.

On the other hand, a nozzle 30 for supplying a rare gas such as Ar gas into the chamber 1 is connected to the upper portion of the cylindrical portion of the chamber 1. Here, the flow rate of the rare gas such as Ar gas is controlled by the flow rate controller 31 to improve the dissociation rate of the Cl ₂ gas in the film formation reactions shown in the above formulas (5) and (6). It is intended to promote. Therefore, except for the He gas contained in the source gas as a diluent gas, a rare gas having a mass of Ne or more can be used as a gas that improves the dissociation rate of the Cl ₂ gas and promotes the film formation reaction. However, Ar gas or Kr gas is preferable in view of the function as a catalyst for improving the dissociation rate, and Ar gas is optimal in consideration of cost.

  The mode at the time of film formation in such a metal film manufacturing apparatus is as follows. During film formation, the film formation plasma antenna 9 and the plasma antenna 26 are energized.

First, while supplying the source gas from the nozzle 12 to the inside of the chamber 1, electromagnetic waves are incident on the inside of the chamber 1 from the film forming plasma antenna 9, whereby the Cl ₂ gas is ionized to generate Cl ₂ gas plasma (source gas). Plasma) 14 is generated. The Cl ₂ gas plasma 14 is formed in a space adjacent to the film-forming plasma antenna 9 in the chamber 1, that is, a space on the composite metal plate member 101 side (upper part) of the chamber 1.

The Cl ₂ gas plasma 14 causes an etching reaction in the composite metal plate member 101 to generate a precursor 102. At this time, the composite metal plate member 101 is maintained at a predetermined temperature (for example, 200 ° C. to 400 ° C.) higher than the temperature of the substrate 3 by the Cl ₂ gas plasma 14. Here, the precursor 102 comprises Cu _x1 Cl _y1 and In _x2 Cl _y2 .

  The precursor 102 generated inside the chamber 1 is transferred to the substrate 3 controlled to a temperature lower than that of the composite metal plate member 101. The precursor 102 transported to the substrate 3 and adsorbed thereto deposits Cu and In on the substrate 3 by the reactions of the above formulas (3) to (6) representing the film forming reaction. Thus, a composite metal thin film 103 made of Cu and In is generated on the surface of the substrate 3.

At this time, in the excitation chamber 25, Cl ^* is formed with high efficiency and supplied into the chamber 1, thereby dissociating Cl in the above formulas (3) and (4) to promote the film formation reaction. Further, Ar gas is supplied from the nozzle 30 into the chamber 1 to dissociate the Cl ₂ gas in the above formulas (5) and (6) to promote the film formation reaction.

In the metal film manufacturing apparatus having the above configuration, the Cl ₂ gas plasma (raw material gas plasma) 14 is used, so that the reaction efficiency is greatly improved and the film forming speed is increased. In addition, since the Cl ₂ gas is used as the source gas, the cost can be greatly reduced. Furthermore, since the temperature of the substrate 3 is controlled to be lower than that of the composite metal plate member 101 by using the temperature control means 6, it is possible to reduce the residue of impurities such as chlorine in the composite metal thin film 103, and to improve the quality. The composite metal thin film 103 can be generated.

Further, in the metal film manufacturing apparatus according to the present embodiment, the composite metal plate member 101 can be made of a composite metal such as CuInSe ₂ , CdS, or ZnSe, whereby a thin film of these composite metals can be manufactured.

<Seventh embodiment>
FIG. 9 is a schematic side view of a metal film manufacturing apparatus according to the seventh embodiment of the present invention. As shown in the figure, the metal film manufacturing apparatus according to the present embodiment differs from the sixth embodiment shown in FIG. 8 in the configuration of the plasma antenna and the configuration of related parts, but the same in many parts. It is the composition. Therefore, the same parts as those in FIG.

As shown in FIG. 9, the chamber 41 is a cylindrical member made of metal (for example, aluminum), the upper surface is an opening, and the opening is an insulating member (for example, ceramic). It is blocked by a disk-shaped ceiling board 47. The composite metal member 105 composed of the ring portion 106 and the projection portion 107 will be described in detail later with reference to FIG. 10, but is divided into a plurality of portions in the circumferential direction at positions facing the substrate 3 in the chamber 41 and each divided portion. The protrusion 107 protrudes from the inner peripheral surface side of the chamber 41 toward the center side. The film-forming plasma antenna 49 is formed in a spiral shape and disposed outside the ceiling plate 47, and forms an electric field by a current supplied from the power source 51 via the matching unit 50. In the internal space on the side of the composite metal member 105 (upper part), the Cl ₂ gas that is the raw material gas supplied into the chamber 41 is turned into plasma to form the Cl ₂ gas plasma 14. That is, the film forming plasma generating means is constituted by the film forming plasma antenna 49, the matching unit 50 and the power source 51.

As shown in detail in FIG. 10, on the inner peripheral side of the ring portion 106 of the composite metal member 105, protrusions 107a to 107l extending to the vicinity of the central portion in the radial direction of the chamber 41 (see FIG. 9) and having the same width. Are provided in the circumferential direction (12 in the illustrated example). The projecting portions 107a to 107l are attached to the ring portion 106 integrally or detachably. Here, the protrusions 107a, e, and i are made of Cu (copper), the protrusions 107c, g, and k are made of In (indium), and the protrusions 107b, d, f, h, j, and l are made of Se (selenium). It is. That is, each protrusion is formed in accordance with the composition ratio of CuInSe ₂ . Between the ceiling plate 47 (see FIG. 9) and the inside of the chamber 41, there is a notch 67 (space) formed between the protrusions 107a to 107l. The ring portion 106 is grounded, and the plurality of protrusions 107a to 107l are electrically connected by the ring portion 106 and have the same potential.

At the time of film formation in such a metal film manufacturing apparatus, the film forming plasma antenna 49 and the plasma antenna 26 are energized. As a result, by incident electromagnetic waves from the film forming plasma antenna 49 into the chamber 41, the Cl ₂ gas is ionized to generate a Cl ₂ gas plasma (source gas plasma) 14, the sixth embodiment The composite metal thin film 103 is formed in the same manner as described above.

The composite metal thin film 103 in this embodiment is a composite metal thin film made of CuInSe ₂ containing a non-metallic element, but is formed in the same manner as the film formation of the composite metal film made of only the metal element shown in the sixth embodiment. It is thought that a film is performed. That is, it is considered that not only the metallic elements of Cu and In but also Se, which is a nonmetallic element, forms a chloride as a precursor by chlorination with Cl ^* and is transported to the substrate to form a thin film.

Also in this embodiment, in the excitation chamber 25, Cl ^* is formed with high efficiency and replenished into the chamber 41, so that Cl in the above equations (3) and (4) is dissociated to form a film formation reaction. To promote. Furthermore, it is considered that chlorinated Se adsorbed on the substrate also dissociates Cl and promotes the film forming reaction. Further, Ar gas is supplied from the nozzle 30 into the chamber 41 to dissociate the Cl ₂ gas in the above formulas (5) and (6) to promote the film formation reaction.

  Further, in the metal film manufacturing apparatus according to the present embodiment, it is possible to manufacture a thin film of these composite metals by manufacturing the composite metal member 105 from a composite metal such as CdS, ZnSe, InCu or the like.

<Eighth Embodiment>
As shown in FIG. 11, the present embodiment removes the film-forming plasma antenna 9 in the sixth embodiment shown in FIG. 8, and instead forms a film-forming plasma on the composite metal plate member 101 which is a member to be etched. It combines the functions of an antenna. For this reason, the high frequency power from the power source 11 is supplied to the composite metal plate member 101 via the matching unit 10, and the support base 2, which is a conductive member, is grounded. That is, the composite metal plate member 101 and the support base 2 serve as both electrodes, and a Cl ₂ gas plasma 14 is formed between them in the chamber 1. Here, the composite metal plate member 101 is formed of a composite metal of In and Cu.

  Other configurations in the metal film manufacturing apparatus according to this embodiment are the same as those in FIG. 8, and thus the same parts are denoted by the same reference numerals and redundant description is omitted.

In this embodiment, the source gas is supplied from the nozzle 12 to the inside of the chamber 1, and electromagnetic waves are incident on the inside of the chamber 1 from the composite metal plate member 101, whereby the Cl ₂ gas is ionized and Cl ₂ gas plasma ( Source gas plasma) 14 is generated. As a result, the Cl ₂ gas plasma 14 causes an etching reaction in the composite metal plate member 101 to generate the precursor 102. Here, the precursor 102 comprises Cu _x1 Cl _y1 and In _x2 Cl _y2 . At this time, the composite metal plate member 101 is maintained at a temperature (for example, 200 ° C. to 400 ° C.) higher than the temperature of the substrate 3 by a temperature control unit (not shown). Thus, a composite metal thin film 103 made of Cu and In is formed on the surface of the substrate 3 in exactly the same manner as in the sixth embodiment.

Also in this embodiment, in the excitation chamber 25, Cl ^* is formed with high efficiency and replenished into the chamber 1 to dissociate Cl in the above formulas (3) and (4) to form a film formation reaction. To promote. Further, Ar gas is supplied from the nozzle 30 into the chamber 1 to dissociate the Cl ₂ gas in the above formulas (5) and (6) to promote the film formation reaction.

Further, in the metal film manufacturing apparatus according to the present embodiment, the composite metal plate member 101 can be made of a composite metal such as CuInSe ₂ , CdS, or ZnSe, whereby a thin film of these composite metals can be manufactured.

<Ninth embodiment>
In the sixth to eighth embodiments, the source gas is supplied into the chamber 1 and the like and converted into plasma. However, the source gas plasma may be supplied directly into the chamber. Such a metal film manufacturing apparatus will be described in detail with reference to FIG. As shown in the figure, the metal film production apparatus according to the present embodiment is largely different from the metal film production apparatus according to the sixth embodiment shown in FIG. Although different, it has many common components. Therefore, the same parts as those in FIG.

  As shown in FIG. 12, the upper surface of a chamber 81 made of, for example, ceramics (made of an insulating material) is formed as an opening, and the opening is formed by a ceiling plate 100 made of, for example, ceramics (made of an insulating material). It is blocked. A composite metal plate member 101 is provided on the lower surface of the ceiling plate 100, and the composite metal plate member 101 has a conical shape. Here, the composite metal plate member 101 is formed of a composite metal of In and Cu.

  In addition, slit-like openings 89 are formed at four places (only two places are shown in the figure) around the upper part of the tubular portion of the chamber 81, and one end of the tubular passage 90 is formed in the opening 89. Each is fixed. A cylindrical excitation chamber 95 formed of an insulator is provided in the middle of the passage 90, and a coiled plasma antenna 91 is provided around the excitation chamber 95. The plasma antenna 91 includes a matching unit 92 and a power source 93. Is connected to the power supply. The plasma antenna 91, the matching unit 92, and the power source 93 constitute plasma generating means.

A flow rate controller 94 is connected to the other end side of the passage 90, and a raw material gas containing chlorine as a halogen in the passage 90 via the flow rate controller 94 (He has a chlorine concentration ≦ 50%, preferably 10%. Cl ₂ gas diluted to a certain extent) is supplied. When electromagnetic waves are incident on the inside of the excitation chamber 95 from the plasma antenna 91, Cl ₂ gas is ionized to generate Cl ₂ gas plasma (raw material gas plasma) 96. That is, the excitation means is configured to excite the source gas containing chlorine in the excitation chamber 95 isolated from the chamber 81. Due to the generation of the Cl ₂ gas plasma 96, excited chlorine is supplied from the opening 89 to the composite metal plate member 101 side (upper part) in the chamber 81, and the composite metal plate member 101 is etched by the Cl ₂ gas plasma 96.

At the time of film formation in such a metal film manufacturing apparatus, a Cl ₂ gas plasma 96 is formed in the excitation chamber 95, and the temperature condition between the composite metal plate member 101 and the substrate 3 is adjusted in a predetermined manner via an opening 89. Then, the Cl ₂ gas plasma 96 is introduced. Thus, the composite metal plate member 101 is etched in the same manner as in the case of the metal film manufacturing apparatus shown in FIG. 8 and the like, and the composite metal thin film 103 made of Cu and In can be formed on the surface of the substrate 3.

Also in this embodiment, in the excitation chamber 25, Cl ^* is formed with high efficiency and replenished into the chamber 81, so that Cl in the above formulas (3) and (4) is dissociated to form a film formation reaction. To promote. Further, Ar gas is supplied from the nozzle 30 into the chamber 81 to dissociate the Cl ₂ gas in the above formulas (5) and (6) to promote the film formation reaction.

Further, in the metal film manufacturing apparatus according to the present embodiment, the composite metal plate member 101 can be made of a composite metal such as CuInSe ₂ , CdS, or ZnSe, whereby a thin film of these composite metals can be manufactured.

The source gas radical supply means in each of the above embodiments is a coiled plasma antenna 26 wound around a cylindrical excitation chamber 25. Cl ^* is formed in the excitation chamber 25, and this Cl ^* is supplied to the chamber. Although it is configured to replenish the interior of 1 etc., it is not limited to this. It suffices if a radical (for example, Cl ^* ) of a source gas (for example, Cl ₂ gas) is separately formed and replenished into the chamber. For example, source gas radical supply means having the following configuration is conceivable.

  1) A means for supplying microwaves to a cylindrical passage that communicates with the inside of the chamber and circulates the source gas, and the source gas is converted into plasma by the microwave generated by the microwave supply means. This can be easily configured by using a magnetron, for example. In this case, a frequency of about 2.45 (GHz) can be used. Incidentally, the frequency supplied to the plasma antenna 26 in each of the above embodiments is 13.56 (MHz). Therefore, higher density source gas radicals can be formed when microwaves are used.

  2) One having heating means for heating the source gas flowing through the cylindrical passage communicating with the chamber and thermally dissociating the source gas. As such a heating means, a heater formed of a filament is conceivable. With such a heater, a temperature of 1500 ° C. or higher necessary for thermal dissociation can be easily obtained. Therefore, the raw material gas radical replenishing means can be configured at the lowest cost.

3) One having an electromagnetic wave generating means for supplying an electromagnetic wave such as a laser beam or an electron beam to a raw material gas flowing through a cylindrical passage communicating with the inside of the chamber to dissociate the raw material gas. This can generate a desired radical (for example, Cl ^* ) with high efficiency by fixing the wavelength of the laser beam or the electron beam to a specific wavelength. That is, desired radicals can be selectively generated with high efficiency.

In each of the above embodiments, a rare gas supply means is provided as means for improving the dissociation rate of Cl ₂ gas so as to promote the film formation reaction of the above formulas (2), (5), and (6). Instead of this, electromagnetic waves may be supplied into the chamber 1 or the like to dissociate the Cl ₂ gas. That is, an electromagnetic wave having such a wavelength that the source gas (eg, Cl ₂ ) dissociates above the substrate 3 may be supplied, for example, a laser beam having a wavelength of 200 nm to 350 nm. Such a configuration can be easily configured by using a laser oscillation device that emits laser light in the ultraviolet region, such as an excimer laser or a YAG laser.

  Further, in order to increase the dissociation rate in order to promote the film formation reaction of the above formulas (2), (5), and (6), the following control of plasma conditions is effective.

1) Reduce the supply amount of the source gas (for example, Cl ₂ gas). In this case, since the amount of the precursor is also reduced, it is necessary to sacrifice the film formation rate to some extent. However, in principle it is possible. For example, considering the case of each of the above embodiments, it is appropriate to reduce the standard supply amount by about 10% in view of the film formation rate. That is, when the standard supply amount of Cl ₂ gas is 50 (sccm), it is appropriate to reduce it to about 45 (ccm).

2) Increase the amount of high-frequency power to the film-forming plasma antenna that generates plasma inside the chamber 1 or the like. For example, when the standard power is 22 (W / cm ² ), this is set to 30 (W / cm ² ).

The metal film manufacturing apparatus according to each of the above embodiments includes requirements for accelerating the film formation reaction according to the above formulas (1), (3), and (4), and the composition according to the above formulas (2), (5), and (6). Although described as an apparatus that satisfies both of the requirements for promoting the film reaction at the same time, of course, it may be configured as an apparatus that promotes one of the film forming reactions. Further, in order to improve the dissociation rate in order to promote the film forming reaction according to the above formulas (2), (5), and (6), Ar gas is separately supplied, but this is a source gas (for example, Cl ₂ gas). ) Can be used instead of the He gas. In this case, the function as the dilution gas of the source gas and the function as the film formation promoting gas for improving the dissociation rate are combined.

In each of the above-described embodiments, the Cl ₂ gas diluted with He has been described as an example of the source gas. However, the Cl ₂ gas can be used alone. In the case of a member to be etched made of a composite metal, the precursor is Cu _x1 Cl _y1 , In _x2 Cl _y2 , Se or S chloride, and the like. Therefore, the source gas may be a gas containing chlorine. Furthermore, in general, not only chlorine but any halogen gas can be used as the raw material gas of the present invention.

  Further, the member to be etched is not limited to copper, and any metal that forms a high vapor pressure halide such as Ta, Ti, W, Zn, In, and Cd can be used similarly. In this case, the precursor is chloride (halide) such as Ta, Ti, W, Zn, In, and Cd, and the thin film formed on the surface of the substrate 3 is Ta, Ti, W, Zn, In, Cd, and the like. Become.

Furthermore, a composite metal containing a plurality of these metals, for example, an alloy of In and Cu can be used as the member to be etched. In addition, a composite metal containing a non-metallic element such as S or Se in the metal, for example, an alloy such as CuInSe ₂ , CdS, or ZnSe can be used as the member to be etched. In this case, the precursor is a metal chloride and a chloride of a nonmetallic element, and a thin film of a composite metal is generated on the surface of the substrate 3.

  In each of the above embodiments, the case where the radicals of the source gas are replenished has been described. However, it is not always necessary to replenish the radicals of the source gas depending on the film forming conditions. However, it is possible to improve the film forming speed and the film quality by replenishing separately formed radicals of the source gas.

1 is a schematic side view showing a metal film manufacturing apparatus according to a first embodiment of the present invention. It is a schematic side view which shows the metal film preparation apparatus which concerns on the 2nd Embodiment of this invention. It is the II arrow directional view of FIG. It is the II-II arrow directional view of FIG. It is a schematic side view which shows the metal film preparation apparatus which concerns on the 3rd Embodiment of this invention. It is a schematic side view which shows the metal film preparation apparatus which concerns on the 4th Embodiment of this invention. It is a schematic side view which shows the metal film preparation apparatus which concerns on the 5th Embodiment of this invention. It is a schematic side view which shows the metal film preparation apparatus which concerns on the 6th Embodiment of this invention. It is a schematic side view which shows the metal film preparation apparatus which concerns on the 7th Embodiment of this invention. It is the II arrow directional view of FIG. It is a schematic side view which shows the metal film preparation apparatus which concerns on the 8th Embodiment of this invention. It is a schematic side view which shows the metal film preparation apparatus which concerns on the 9th Embodiment of this invention.

DESCRIPTION OF SYMBOLS 1 Chamber 3 Substrate 6 Temperature control means 7 Copper plate member 9 Deposition plasma antenna 12 Nozzle 14 Cl ₂ gas plasma 15 Precursor 16 Cu thin film 24 Passage 25 Excitation chamber 26 Plasma antenna 41 Chamber 47 Ceiling plate 49 Deposition plasma antenna 58 Member to be etched 59 Ring part 60 Projection part 71 Chamber 72 Copper plate member 73 Shielding plate 73a Hole 81 Chamber 88 Member to be etched 90 Channel 91 Plasma antenna 101 Composite metal plate member 102 Precursor 103 Composite metal thin film 105 Composite metal member 106 Ring part 107 protrusion

Claims (9)

A member to be etched formed of a metal that forms a high vapor pressure halide is disposed in a chamber that accommodates the substrate therein, and the temperature of the member to be etched and the substrate is controlled to a predetermined temperature and temperature difference. Then, the member to be etched is etched with a source gas plasma containing halogen in the chamber to form a precursor of a metal component and a halogen, and the metal component of the precursor is deposited on a substrate to form a predetermined film. In the metal film production method to be performed,
In addition to the source gas, a rare gas having a mass of Ne or more is supplied into the chamber. The member to be etched formed of the metal is formed of a composite metal composed of a plurality of types of metal components,
Claims, characterized in that the raw material gas plasma to perform a plurality of types of a plurality of types of metal components is deposited on a substrate from precursor predetermined deposition of the metal component and a halogen obtained by etching the etched member 2. The metal film production method according to 1. The member to be etched formed of the metal is formed of a composite metal composed of one or more types of metal components and one or more types of non-metal components,
A metal component and a non-metal component are obtained from one or more precursors of a metal component and a halogen obtained by etching the member to be etched by the source gas plasma, and one or more precursors of a non-metal component and a halogen. The metal film manufacturing method according to claim 1, wherein the film is deposited on the substrate at the same time and a predetermined film is formed. A cylindrical chamber in which a substrate is accommodated;
A member to be etched formed of a metal that forms a high vapor pressure halide disposed in a position facing the substrate in the chamber;
A source gas supply means for supplying a source gas containing halogen in a chamber between the substrate and the member to be etched;
A film forming plasma generating means for forming a source gas plasma in the chamber by plasmaizing the source gas supplied into the chamber by supplying high-frequency power to etch the member to be etched;
The substrate temperature is controlled to a predetermined temperature lower than the temperature of the member to be etched, and the source gas plasma causes the metal component to deposit on the substrate from a precursor of a metal component and a halogen obtained by etching the member to be etched. Temperature control means for performing predetermined film formation,
In addition to the source gas, there is provided a rare gas supply means for supplying a rare gas having a mass of Ne or more into the chamber. A cylindrical chamber in which a substrate is accommodated;
A member to be etched formed of a metal that forms a high vapor pressure halide disposed in a position facing the substrate in the chamber;
A source gas plasma supply means for forming a source gas plasma containing halogen outside the chamber and supplying the source gas plasma into the chamber between the substrate and the member to be etched;
The substrate temperature is controlled to a predetermined temperature lower than the temperature of the member to be etched, and the source gas plasma causes the metal component to deposit on the substrate from a precursor of a metal component and a halogen obtained by etching the member to be etched. Temperature control means for performing predetermined film formation,
In addition to the source gas, there is provided a rare gas supply means for supplying a rare gas having a mass of Ne or more into the chamber. A cylindrical chamber in which a substrate is accommodated;
A member to be etched formed of a metal that forms a high vapor pressure halide disposed in a position avoiding the position facing the substrate in the chamber;
A shielding plate disposed between the substrate and the member to be etched in the chamber and having a hole facing the substrate;
A source gas supply means for supplying a source gas containing halogen into the chamber between the member to be etched and the shielding plate;
A film forming plasma generating means for forming a source gas plasma in the chamber by plasmaizing the source gas supplied into the chamber by supplying high-frequency power to etch the member to be etched;
The substrate temperature is controlled to a predetermined temperature lower than the temperature of the member to be etched, and the source gas plasma deposits the metal component on the substrate from the precursor of the metal component and halogen obtained by etching the member to be etched. Temperature control means for performing a predetermined film formation,
In addition to the source gas, there is provided a rare gas supply means for supplying a rare gas having a mass of Ne or more into the chamber. A cylindrical chamber in which a substrate is accommodated;
A member to be etched formed of a metal that forms a high vapor pressure halide disposed in a position facing the substrate in the chamber;
A source gas supply means for supplying a source gas containing halogen in a chamber between the substrate and the member to be etched;
A film forming plasma generating means for forming a source gas plasma in the chamber by plasmaizing the source gas supplied into the chamber by supplying high-frequency power to etch the member to be etched;
The substrate temperature is controlled to a predetermined temperature lower than the temperature of the member to be etched, and the source gas plasma causes the metal component to deposit on the substrate from a precursor of a metal component and a halogen obtained by etching the member to be etched. Temperature control means for performing predetermined film formation,
An apparatus for producing a metal film, comprising: an electromagnetic wave generating means for supplying an electromagnetic wave into the chamber to dissociate a source gas generated by a film forming reaction. A cylindrical chamber in which a substrate is accommodated;
A member to be etched formed of a metal that forms a high vapor pressure halide disposed in a position facing the substrate in the chamber;
A source gas plasma supply means for forming a source gas plasma containing halogen outside the chamber and supplying the source gas plasma into the chamber between the substrate and the member to be etched;
The substrate temperature is controlled to a predetermined temperature lower than the temperature of the member to be etched, and the source gas plasma causes the metal component to deposit on the substrate from a precursor of a metal component and a halogen obtained by etching the member to be etched. Temperature control means for performing predetermined film formation,
An apparatus for producing a metal film, comprising: an electromagnetic wave generating means for supplying an electromagnetic wave into the chamber to dissociate a source gas generated by a film forming reaction. A cylindrical chamber in which a substrate is accommodated;
A member to be etched formed of a metal that forms a high vapor pressure halide disposed in a position avoiding the position facing the substrate in the chamber;
A shielding plate disposed between the substrate and the member to be etched in the chamber and having a hole facing the substrate;
A source gas supply means for supplying a source gas containing halogen into the chamber between the member to be etched and the shielding plate;
A film forming plasma generating means for forming a source gas plasma in the chamber by plasmaizing the source gas supplied into the chamber by supplying high-frequency power to etch the member to be etched;
The substrate temperature is controlled to a predetermined temperature lower than the temperature of the member to be etched, and the source gas plasma deposits the metal component on the substrate from the precursor of the metal component and halogen obtained by etching the member to be etched. Temperature control means for performing a predetermined film formation,
An apparatus for producing a metal film, comprising: an electromagnetic wave generating means for supplying an electromagnetic wave into the chamber to dissociate a source gas generated by a film forming reaction.

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