JP2007123853A - Layer forming method and device, base material processing device, wiring forming method, and wiring structure of substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and device for forming a layer that does not require high vacuum and a large chamber when forming a layer. <P>SOLUTION: The layer forming device comprises a material vaporizing part 108 for generating material gas containing organic metal material by heating and vaporizing an organic metal material which is solid or liquid under the pressure ranging from 0.01 Pa to a normal pressure, a base material holding part 100 for holding a base material W, a base material heating part 104 that heats the surface of the base material W up to the temperature higher than the decomposition temperature of the organic metal material vaporized by the material vaporizing part 108, and a material supply part 109 for locally forming the atmosphere of material gas over the surface of the base material W. The material supply part 109 makes at least a part of the surface of the base material exposed to the material gas atmosphere so that a metal layer or metal compound layer is formed on the surface of the base material W. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a layer forming method and apparatus, and in particular, forms a metal layer or a metal compound layer on the surface of a substrate used in a semiconductor device, a flat panel display, a microelectromechanical system (MEMS), a precision electronic device and the like. The present invention relates to a layer forming method and apparatus. The present invention also relates to a substrate processing apparatus, and in particular, a substrate processing apparatus having a wet or dry processing unit for bringing a processing solution or gas such as a chemical solution or pure water into contact with the surface of the substrate or performing a heat treatment. It is about. Furthermore, the present invention relates to a wiring forming method, and more particularly to a semiconductor fine wiring forming method for forming a copper wiring by electrolytic plating on the surface of a substrate on which a barrier metal layer is formed. The present invention also relates to a wiring structure of a substrate formed by such a wiring forming method.

  As a copper wiring technique corresponding to the 45 nm node, a process for directly forming copper on the surface of the barrier metal by electrolytic plating has been proposed. As such a barrier metal material, Ru, Os, and the like have been studied. As such a barrier metal film forming method, a chemical vapor deposition method (CVD), an atomic layer deposition method (ALD), or a physical vapor deposition method is used. (PVD). In particular, the method of forming a metal or metal compound thin film by CVD is positioned as a key technique that can replace the sputtering method because of the superiority of the step coverage of the base material (see, for example, Non-Patent Document 1 described later).

  In a general CVD apparatus, a raw material gas is introduced into the chamber from the outside via a port provided in the chamber, and the raw material gas is exhausted to form a flow of the raw material gas in the chamber. Therefore, a large amount of source gas is required for the film forming process. In addition, the flow of the raw material gas is disturbed due to the consumption due to the chemical reaction of the chamber shape, the installed objects inside the chamber, and the raw material gas, and causes a non-uniform layer formation.

  In order to suppress such disturbance of the gas flow, a rectifying member may be installed in the chamber. However, there is a problem that the capacity of the chamber becomes very large compared to the base material. Furthermore, since the atmosphere in the chamber is controlled by the gas replacement operation in the entire chamber, a large gas vacuum exhaust system is required for gas replacement in a large chamber. For this reason, it has been difficult to incorporate a CVD apparatus as a film forming apparatus unit into a wet apparatus such as a plating apparatus or a dry apparatus such as an annealing apparatus.

  Further, in a fine copper wiring structure formed by the above-described method, improvement in reliability with respect to copper diffusion and adhesion with copper is required.

Yoshida Sadafumi, “Applied Physics Engineering Selection 3 Thin Film”, Baifukan, 1990, p. 64-70

The present invention has been made in view of such problems of the prior art, and is a layer that does not require a large chamber and a large gas vacuum exhaust system as compared with a base material while ensuring good step coverage. It is a first object to provide a forming method and a layer forming apparatus.
In addition, a second object of the present invention is to provide a substrate processing apparatus capable of performing both layer formation processing and wet or dry processing in one apparatus.
Furthermore, a third object of the present invention is to provide a wiring structure of a substrate and a wiring forming method with improved reliability of copper diffusion and adhesion with copper.

  In order to achieve the above object, according to the first aspect of the present invention, the surface of the substrate is heated, and the organometallic material that is solid or liquid is heated under a pressure in the range from 0.01 Pa to normal pressure. Generating a raw material gas containing the organometallic material by vaporizing, locally forming an atmosphere of the raw material gas on the surface of the substrate, and exposing at least a part of the surface of the substrate to the atmosphere; The method for forming a layer is characterized in that a metal layer or a metal compound layer is formed on the surface of the substrate.

Here, a block-like, granular, or powder-like organometallic material can be used as the solid organometallic material. The liquid organometallic material includes a solution in which the organometallic material is dissolved in a solvent such as water (that is, an organometallic solution). That is, any raw material containing an organometallic material that is solid or liquid under a pressure in the range from 0.01 Pa to normal pressure can be used in the layer forming method and apparatus of the present invention.
Further, as the source gas, in addition to the vaporized organometallic material, a mixed gas of a gaseous organometallic material and an inert gas (carrier gas) such as N ₂ gas, or a fine powdery organometallic material The aerosol which consists of is included.

  According to the present invention, since the atmosphere made of the source gas is locally formed on the surface of the substrate, it is not necessary to supply the source gas to the entire chamber, and the amount of the organometallic material used can be greatly reduced. . Moreover, since the volume of the chamber can be reduced, the entire apparatus can be made compact. As a result, it can be combined with a wet or dry processing apparatus.

In a preferred aspect of the present invention, the source gas is supplied to a part of the surface of the substrate, and the source port is maintained while maintaining a constant distance between the source gas supply port and the base material facing the source port. And by relatively moving the base material, an atmosphere composed of the source gas is locally formed on the surface of the base material, and an opening area of the supply port is set to be equal to or less than an area of the surface of the base material. Features.
A preferred embodiment of the present invention is characterized in that a unit in which a material vaporizing unit that vaporizes an organometallic material and the supply port are integrated is provided, and the unit and the base material are relatively moved.

In a preferred aspect of the present invention, the distance from the supply port to the surface of the substrate is not more than 6 times the minimum frontage of the supply port.
In order to ensure good step coverage for the substrate, it is essential to perform the layer formation process in the region where surface reaction rate control is dominant (for example, Nobuyoshi Ashiya, “Survey Report on Highly Integrated Device Wiring Materials”). 2 ", Japan Electronics Industry Promotion Association, 1996, p. 187). However, the gas flow of the organometallic material in the chamber is disturbed by the exhaustion accompanying the chemical reaction of the shape of the chamber, the installation inside the chamber, and the organometallic material. Therefore, a concentration (partial pressure) distribution of the organometallic material is generated in the chamber, and this concentration distribution can also occur on the substrate. For this reason, in the portion where the concentration of the organometallic material on the surface of the base material is low, the supply (transportation) rate is dominant, and it becomes difficult to ensure the uniformity of the layer thickness and good step coverage. There is a case.

  FIG. 1 is a schematic diagram showing a two-dimensional free jet model of a jet J ejected from an ejection port E having an opening width a. As shown in FIG. 1, the jet J violently mixes with the surrounding fluid to create turbulence, and the width of the jet J itself increases. The outer periphery of the injection port E gradually penetrates toward the center line X of the jet J as it moves away from the injection port E, so that the average velocity of the jet J does not decrease at all. A core) P is formed. The length of the potential core P along the center line X of the jet J is 6 times (= 6a) the opening width a of the injection port E. Note that the periphery of the potential core P is called a mixed region.

The above description applies not only to the case where the injection port E is a circle having a diameter a as shown in FIG. 2A, but also to a case where the injection port E is a rectangle having a short side a and a long side b as shown in FIG. apply. That is, when the uniform velocity of the jet J is U ₀ , the velocity of the jet J on the center line X is u _m0 , and the distance along the center line X from the injection port E is x, u _m0 for various b / a. The relationship between / U ₀ and x / a is as shown in the graph of FIG. 3 (N. Rajaratnam, Yasumasa Nomura, Jet, Morikita Publishing Co., p. 1,268, 1981). As can be seen from FIG. 3, the length of the potential core (the region where u _m0 / U ₀ = 1.00) is 6a regardless of the value of b / a.

  Thus, when injecting the vaporized organometallic material from the injection port, the distance from the injection port to the surface of the base material is set to 6 times or less the minimum frontage of the injection port, and the surface of the base material is arranged in the potential core. By doing so, the gas flow of a uniform speed can be supplied to the surface of the base material W, without reducing the ejection speed. Therefore, the concentration of the organometallic material on the surface of the substrate W becomes constant without decreasing from the concentration of the organometallic material at the injection port. As a result, it is possible to form a layer in a state in which a reaction-controlled region is ensured without causing a supply-controlled state, and it is possible to obtain a good step coverage with a uniform layer thickness. At this time, the organometallic material supplied to the surface of the substrate is a fluid that becomes a viscous flow region.

In a preferred embodiment of the present invention, a heater is disposed adjacent to the supply port at a rear portion with respect to the moving direction of the supply port, and the layer is annealed simultaneously with the layer formation by the heater. Repeated twice or more.
In general, a metal layer or a metal compound layer formed from an organometallic material is formed by a chemical reaction of the organometallic material, and therefore, generation of decomposition products such as hydrocarbons and carbon is inevitable. For this reason, at the time of deposition of the layer, these degradation products are taken into the layer, or the surface of the substrate is contaminated with the deposited degradation product, thereby deteriorating the layer quality and improving the adhesion of the layer to the substrate. There is a risk of lowering. In addition, the adhesion of the layer depends on the property unique to the material, that is, the electron cloud of the material constituting the layer and the electron cloud of the material constituting the substrate are easily overlapped.

  In order to prevent such deterioration of the layer quality and reduction of the adhesion of the layer to the substrate, it is necessary to anneal the layer with a heater. As the heater, an infrared lamp furnace capable of controlling the output and heating time, a laser capable of controlling the output and heating time, and capable of local heating can be used.

  By the annealing process using such a heater, the decomposition product taken into the layer diffuses to the surface of the layer and is released to the outside of the layer, thereby improving the layer quality. In addition, by thermally vibrating the atomic lattice that constitutes the layer and the base material, the layer and the base material are sufficiently close to each other regardless of the presence or absence of a decomposition product interposed between the layer and the base material. Furthermore, at the interface, mutual diffusion and substitution of both atoms can be caused, and high adhesion strength can be obtained.

  On the other hand, in this annealing process, if excessive thermal energy is applied to the layer, surface diffusion is promoted, and the layer energy is condensed by the surface energy of the layer itself. And separation of layers occurs. Therefore, instead of forming a layer having a desired thickness at a time, a film thinner than the thickness of the desired layer is first formed, and then the thin film is annealed by a heater adjacent to the injection port. When the thickness of the film to be annealed is reduced in this way, the absolute amount of atomic movement in the surface diffusion of the film is limited, and the progress of film condensation is limited. At the same time, it is possible to shorten the time required for the decomposition products to be discharged to the outside of the membrane, and to obtain a high quality and high adhesion membrane. Furthermore, in this layer formation method, a thin film with good quality and good adhesion is laminated by repeating the steps of layer formation and annealing treatment, and finally, a layer with a desired thickness and high quality and high adhesion is obtained. It can be formed on a substrate.

  From 0.01 MPa to normal pressure, the organometallic material supplied to the surface of the substrate is a fluid that becomes a viscous flow region. In this viscous flow region, since the thermal conductivity of the atmosphere is higher than that in the molecular flow region, heat removal of the layer after annealing is performed quickly.

According to a preferred aspect of the present invention, an impregnating member is disposed opposite to a base material, the liquid organic metal material is impregnated in the impregnated member, and the organic metal material impregnated in the impregnated member is heated and vaporized. A raw material gas containing the organometallic material is generated.
In a preferred aspect of the present invention, the impregnated member is at least one of a porous material, a nonwoven fabric, and a woven fabric.
In a preferred aspect of the present invention, a distance from the surface of the impregnating member to the surface of the base material is 10 mm or less.

In a preferred embodiment of the present invention, a base material having a space inside is prepared, and an atmosphere composed of the source gas is locally formed on the surface of the base material by supplying the source gas into the space, and the space The raw material gas and its decomposition products are discharged from
In a preferred aspect of the present invention, the supply and discharge of the raw material gas are performed using a coaxial double structure flow path.

In a preferred embodiment of the present invention, a coating film of an organometallic material is formed on a material supply member, the material supply member is disposed to face a substrate, and the coating film of the organometallic material on the material supply member is heated. A raw material gas containing the organometallic material is generated by vaporizing, and the distance between the base material and the material supply member is 3 mm or less.
In a preferred aspect of the present invention, the coating film of the organometallic material on the material supply member is heated and vaporized by heat transfer or radiant heat from the heated surface of the substrate.

In a preferred aspect of the present invention, the organometallic material includes at least one of cobalt, tungsten, platinum, aluminum, copper, molybdenum, manganese, and silicon.
In a preferred aspect of the present invention, the base material is at least one of a semiconductor wafer, a ceramic, a resin, and a metal.
In a preferred aspect of the present invention, the surface of the substrate is made of semiconductor, ceramic, resin, Ru, RuO ₂ , Cu, Ta, TaN, Ti, TiN, Si, SiO ₂ , low-k material, Co, P, CoP. , CoWP, W, WSiC, WC, Ni, and Al.

  According to another aspect of the present invention, a step of forming a barrier metal layer on a substrate on which a wiring groove is formed, a step of forming a metal layer or a metal compound layer on the barrier metal layer by the layer forming method, A wiring forming method comprising a step of performing electrolytic plating using the metal layer or the metal compound layer as a seed layer and filling the wiring groove with copper, and a step of removing a part of the copper by chemical mechanical polishing. Provided.

In a preferred aspect of the present invention, the metal layer or the metal compound layer is a metal layer mainly composed of cobalt.
In a preferred aspect of the present invention, the method further includes a step of selectively forming a metal layer mainly composed of cobalt on the surface of copper filled in the wiring groove by electroless plating.

  According to another aspect of the present invention, copper filled in a wiring groove, a barrier metal layer, a metal layer mainly composed of cobalt formed between the copper and the barrier metal layer, and the copper And a metal layer mainly composed of cobalt formed on the exposed surface, and the metal layer formed between the copper and the barrier metal layer is a cobalt layer formed by the layer forming method. A wiring structure of a substrate is provided, wherein the metal layer formed on the exposed surface of copper is a metal layer formed by electroless plating.

  According to another aspect of the present invention, a material vaporization that generates a raw material gas containing an organometallic material by heating and vaporizing a solid or liquid organometallic material under a pressure in a range from 0.01 Pa to normal pressure. A base material heating part that heats the surface of the base material to a temperature higher than the decomposition temperature of the organometallic material vaporized by the material vaporization part, and the raw material. A material supply unit that locally forms an atmosphere composed of gas on the surface of the substrate, and the material supply unit exposes at least a part of the surface of the substrate to the atmosphere to expose the surface of the substrate. There is provided a layer forming apparatus characterized by forming a metal layer or a metal compound layer.

In a preferred aspect of the present invention, the material supply unit includes a supply port for supplying the source gas to a part of the surface of the base material, and maintains a constant interval between the supply port and the base material facing the supply port. However, a moving mechanism for relatively moving the supply port and the base material is provided, and the opening area of the supply port is equal to or smaller than the surface area of the base material.
In a preferred aspect of the present invention, the material vaporization unit and the material supply unit are an integral unit, and the moving mechanism relatively moves the unit and the base material.
In a preferred aspect of the present invention, the distance from the supply port to the surface of the substrate is not more than 6 times the minimum frontage of the supply port.
In a preferred aspect of the present invention, a heater is disposed adjacent to the supply port at a rear portion with respect to the moving direction of the supply port.

In a preferred aspect of the present invention, the material supply unit includes an impregnation member disposed so as to face the base material, and the impregnation member is impregnated with a liquid organometallic material.
In a preferred aspect of the present invention, the impregnated member is at least one of a porous material, a nonwoven fabric, and a woven fabric.
In a preferred aspect of the present invention, a distance from the surface of the impregnating member to the surface of the base material is 10 mm or less.

In a preferred aspect of the present invention, the material supply unit is connected to a space formed in the base material via a sealing material, and has a material supply channel for supplying a source gas to the space. The material discharge path is connected to the space via a sealing material and discharges the source gas and its decomposition product from the space.
In a preferred aspect of the present invention, the material supply channel and the material discharge channel are channels having a coaxial double structure.

In a preferred aspect of the present invention, the material supply unit is a material supply member in which a coating film of an organometallic material is formed, the material supply member is disposed to face a substrate, and the base material and the material supply member The interval is 3 mm or less.
In a preferred aspect of the present invention, the coating film of the organometallic material on the material supply member is heated and vaporized by heat transfer or radiant heat from the heated substrate.

According to another aspect of the present invention, there is provided the layer forming apparatus, and a wet processing unit that performs wet processing on the base material on which the metal layer or the metal compound layer is formed by the layer forming apparatus. A substrate processing apparatus is provided.
In a preferred aspect of the present invention, the wet processing unit is at least one of an electrolytic plating unit, an electroless plating unit, a chemical mechanical polishing unit, an electrolytic etching unit, an electrolytic polishing unit, a chemical etching unit, and a cleaning unit. It is characterized by being.

According to another aspect of the present invention, the apparatus includes: the layer forming apparatus; and a dry processing unit that performs dry processing on the base material on which the metal layer or the metal compound layer is formed by the layer forming apparatus. A substrate processing apparatus is provided.
In a preferred aspect of the present invention, the dry processing unit is at least one of an annealing unit, a CVD unit, and a gas etching unit.

  According to the present invention, downsizing of a film formation space, saving of an organic metal material, good adhesion between a base material and a layer, uniform thickness of a layer, a single apparatus of a layer forming process and a wet or dry process Continuous processing can be realized.

  Hereinafter, embodiments of the present invention will be described in detail with reference to FIGS. 4 to 19B. In FIG. 4 to FIG. 19B, the same or corresponding components are denoted by the same reference numerals, and redundant description is omitted.

  FIG. 4 is a schematic view showing a layer forming apparatus according to an embodiment of the present invention. This layer forming apparatus heats and vaporizes a solid or liquid organometallic material to generate a source gas containing the organometallic material, and locally forms an atmosphere composed of the source gas on the surface of the substrate. The surface of the heated substrate is exposed to the atmosphere to form a metal layer or a metal compound layer on the surface of the substrate.

  As shown in FIG. 4, the layer forming apparatus includes a base material holding unit (susceptor) 100 that holds the base material W upward, and a raw material containing the organometallic material M by heating and vaporizing the organometallic material M. A material vaporization unit 108 that generates gas, and a material supply unit 109 that is connected to the material vaporization unit 108 and supplies the source gas to the base material W are provided.

  The base material holding part 100 has a vacuum chuck mechanism (not shown) on the upper surface thereof, whereby the base material W is held on the upper surface of the base material holding part 100. Instead of the vacuum chuck mechanism, an electrostatic chuck mechanism that holds the substrate W by electrostatic force may be provided. The substrate holding unit 100 can move up and down, and moves downward when the substrate W is loaded and unloaded, and moves upward when the layer is formed. In addition, a first heater (base material heating unit) 104 for heating the base material W adsorbed on the upper surface by a vacuum chuck mechanism is embedded in the base material holding unit 100. By supplying a current to the heater 104, the base material W is heated to a temperature higher than the decomposition temperature of the organometallic material M, for example, 150 ° C. The temperature of the substrate W varies depending on the organometallic material used.

  Connected to the chamber 130 are a gas introduction pipe 121 for introducing an inert gas such as nitrogen or argon into the chamber 130 from an inert gas supply source 131 and a gas discharge pipe 122 for discharging the inert gas. Yes. The gas discharge pipe 122 is connected to the vacuum pump 126 via the flow rate control valve 125. The pressure of the chamber 130 is set to, for example, normal pressure by adjusting the flow rate of the inert gas and the flow rate adjustment valve 125.

  In this layer forming apparatus, a solid or liquid organometallic material is selected as the organometallic material M under a pressure in the range from 0.01 Pa to normal pressure. For example, as organic metal material M, organic cobalt (Co), organic tungsten (W), organic platinum (Pt), organic aluminum (Al), organic copper (Cu), organic molybdenum (Mo), organic manganese (Mn), etc. It is preferable to use an organic metal, organic silicon (Si), hydrocarbon, or a combination thereof. As an example, an organometallic material M can be used in which an alkyl, phenyl, pentadienyl, carbonyl, or the like is coordinated with a metal or a semiconductor material. The organometallic material M preferably has a significantly higher decomposition temperature than the vaporizable temperature.

  The material vaporization unit 108 includes a heater (second heater) 116 that heats the organometallic material M. The organometallic material M is vaporized by heating the organometallic material M with the heater 116, and the organometallic material is heated. A source gas containing the material M is generated. For example, the organometallic material M is heated to 70 ° C. by the heater 116. At this time, an inert gas may be introduced into the material vaporization unit 108 in order to transport the vaporized organometallic material M to the substrate W. In this way, the material vaporization unit 108 is a raw material made of a gaseous organometallic material M, a mixed gas of an inert gas and a gaseous organometallic material M, or an aerosol that is a finely divided organometallic material M. Generate gas.

  The material vaporization unit 108 communicates with the material supply unit 109 through an expandable / contractible flow pipe 111. The material supply unit 109 is disposed so as to face the surface of the substrate W held by the substrate holding unit 100. Further, the material supply unit 109 has substantially the same outer dimensions as the base material W, and has a shape like an enclosure that covers the entire surface of the base material W. The raw material gas generated in the material vaporization unit 108 is transferred to the surface of the substrate W through the flow pipe 111 and stays in the material supply unit 109, thereby causing a local atmosphere made of the raw material gas on the surface of the substrate W. To form. There is a gap between the material supply unit 109 and the base material W, so that an excessive pressure difference between the inside and outside of the material supply unit 109 is eliminated.

  The surface of the substrate W is exposed to a local source gas atmosphere formed in the material supply unit 109, and at the same time, the surface of the substrate W is heated by the heater 104. Thereby, the organometallic material is thermally decomposed, and a metal layer or a metal compound layer is deposited on the surface of the substrate W.

  Some types of organometallic materials produce metal oxides during the pyrolysis reaction. For this reason, the layer formed according to this embodiment is not limited to a metal layer, but also includes a metal compound layer.

During the film forming process, the inert gas is always kept flowing in the chamber 130. Thereby, the source gas supplied via the material supply unit 109 is sequentially replaced with a new source gas, and the temperature in the chamber 130 is kept substantially constant. Further, by supplying an inert gas, O ₂ can be excluded from the chamber 130, and even when an organometallic material that easily ignites is used, the film formation process can be performed safely. it can.

  According to the present embodiment, the chamber 130 is not filled with the source gas, but the source gas atmosphere is formed only in a local space on the surface of the base material W, so that the film formation space can be reduced and the source material can be reduced. The amount of gas used can be reduced.

  Next, another embodiment of the present invention will be described with reference to FIGS. FIG. 5 is a schematic view showing a layer forming apparatus according to another embodiment of the present invention, and FIG. 6 is a schematic view seen from the direction indicated by the arrow VI in FIG. Note that the configuration and operation of the present embodiment not specifically described are the same as the configuration and operation of FIG.

  As shown in FIGS. 5 and 6, the material supply unit 119 is attached to a reciprocating movement mechanism 127 extending in parallel with the surface of the base material W, and the reciprocating movement mechanism 127 causes the material supply unit 119 to be moved to the base material W. It is moved at an arbitrary speed in parallel with the surface. The supply port 119a of the material supply unit 119 has a rectangular shape, and the width in the moving direction is shorter than the width in the direction perpendicular to the moving direction. The width in the longitudinal direction is slightly larger than the width of the substrate W as shown in FIG.

  The material supply unit 119 is retracted away from the substrate W before and after the layer formation, and at the time of layer formation, the material supply unit 119 sweeps horizontally from end to end of the substrate W held on the upper surface of the substrate holding unit 100. To do. At this time, the distance between the supply port 119a of the material supply unit 119 and the surface of the substrate W is kept constant. As described above, since the supply port 119a of the material supply unit 119 is smaller than the surface of the substrate W, the source gas is supplied only to a part of the surface of the substrate W. However, as described above, the material supply unit 119 is provided. Moves in parallel with the surface of the substrate W, so that the source gas can be supplied to a desired region of the substrate W. In addition, what is necessary is just to move the supply port 119a of the material supply part 119 and the base material W relatively, and the base material W can also be moved.

  7 and 8 are schematic views showing a layer forming apparatus according to another embodiment of the present invention, and FIG. 8 is a schematic view seen from a direction indicated by an arrow VIII in FIG. The configuration and operation of the present embodiment that are not specifically described are the same as the configuration and operation of FIG.

  In the layer forming apparatus of this embodiment, the material vaporization supply unit 110 in which the material vaporization unit and the material supply unit are integrated is used. The material vaporization supply unit 110 includes a storage portion 112 that stores an organometallic material (solid or liquid) M, and a slit-like injection port (supply port) 114 that gradually narrows from the storage portion 112 and opens to the lower surface. And are formed. A second heater 116 that heats and vaporizes the organometallic material M is built in the material vaporization supply unit 110.

  An inert gas (carrier gas) such as nitrogen is introduced into the material vaporization supply unit 110 from an inert gas supply source 133. The material vaporization supply unit 110 is disposed such that the injection port 114 faces the surface of the substrate W. According to such a configuration, the gaseous organometallic material is transported to the inert gas and injected as a raw material gas from the injection port 114 toward the base material W, and the raw material gas atmosphere is locally formed on the surface of the base material W. Formed. In order to make the temperature of the entire material vaporization supply unit 110 uniform, it is desirable that the material vaporization supply unit 110 be a thermostat made of metal such as aluminum.

  The material vaporization supply unit 110 is attached to a reciprocating movement mechanism 127 extending in parallel with the surface of the substrate W, and the reciprocating movement mechanism 127 allows the material vaporization supply unit 110 to move at an arbitrary speed parallel to the surface of the substrate W. It is supposed to be moved by. The width in the longitudinal direction of the injection port 114 of the material vaporization supply unit 110 is formed to be slightly larger than the width of the base material W.

  The material vaporization supply unit 110 is retracted away from the base material W before and after the layer formation, and at the time of layer formation, the material vaporization supply unit 110 extends horizontally from end to end of the base material W held on the upper surface of the base material holding unit 100. Sweep. At this time, the distance between the injection port 114 of the material vaporization supply unit 110 and the surface of the substrate W is kept constant. As described above, since the injection port 114 of the material vaporization supply unit 110 is smaller than the surface of the substrate W, the source gas is supplied only to a part of the surface of the substrate W. However, as described above, the material vaporization supply is performed. Since the unit 110 moves in parallel with the surface of the substrate W, the source gas can be supplied to a desired region of the substrate W. In addition, the injection port 114 of the material vaporization supply unit 110 and the base material W should just be moved relatively, and the base material W can also be moved.

  Also in this embodiment, the base material holding part 100 can be moved up and down, and the distance between the base material W and the injection port 114 can be adjusted. Therefore, it is possible to form a layer by adjusting the distance from the injection port 114 to the surface of the substrate W to be 6 times or less the minimum front port of the injection port 114 (see FIG. 1).

  FIG. 9 is a schematic view showing a layer forming apparatus according to another embodiment of the present invention. As shown in FIG. 9, this layer forming apparatus has basically the same configuration as the layer forming apparatus shown in FIGS. 7 and 8, but the third heater is adjacent to the material vaporization supply unit 110. It differs from the above-described layer forming apparatus in that 129 is provided.

  In the present embodiment, the material vaporization supply unit 110 and the heater 129 are attached to a reciprocating movement mechanism 127 extending in parallel with the surface of the substrate W, and the reciprocating movement mechanism 127 causes the material vaporization supply unit 110 and the heater 129 to move. It is moved at an arbitrary speed parallel to the surface of the substrate W. The heater 129 is disposed rearward with respect to the traveling direction of the material vaporization supply unit 110, and the width in the longitudinal direction is substantially the same as the width in the longitudinal direction of the material vaporization supply unit 110.

  At the time of layer formation, the material vaporization supply unit 110 is moved in the direction indicated by the arrow in FIG. 9, and the raw material gas containing the organometallic material M is injected onto the surface of the substrate W. The heater 129 heats and anneals the organometallic material M sprayed from the material vaporization supply unit 110 onto the surface of the substrate W. As described above, the layer 129 is annealed simultaneously with the layer formation by the heater 129, and the layer formation and annealing steps are repeated twice or more to obtain a layer having a desired thickness. In this embodiment, the material vaporization supply unit 110 and the heater 129 are moved. However, the injection port 114 of the material vaporization supply unit 110 and the base material W may be relatively moved, and the base material W is moved. It can also be moved.

  FIG. 10 is a schematic view showing a layer forming apparatus according to another embodiment of the present invention. As shown in FIG. 10, the layer forming apparatus includes a base material holding unit 400 that holds the base material W upward, and a material that holds the material supply member X to which a coating film of an organometallic material is attached downward. A supply member holding unit 402, a spin coater 404 that applies a metal organic material to the material supply member X to form a coating film, and a robot (not shown) that transports the substrate W and the material supply member X are provided. . The substrate holding unit 400 and the material supply member holding unit 402 are accommodated in the chamber 410, and the spin coater 404 is accommodated in the chamber 411. The chamber 410 is placed on the chamber 411, and the entire apparatus is made compact. Note that the chamber 411 may be placed on the chamber 410.

  The material supply member holding unit 402 has a function as a material vaporization unit that generates a raw material gas by vaporizing a solid or liquid organic metal material at room temperature, and the material supply member X coated with the organic metal material is a raw material A material supply unit that locally forms an atmosphere made of a gas on the surface of the substrate W and exposes the surface of the substrate W to the source gas atmosphere to form a metal layer or a metal compound layer on the surface of the substrate W As a function.

  The base material holding part 400 has a vacuum chuck mechanism (not shown) on its upper surface, and the base material W is held on the upper surface of the base material holding part 400 by this vacuum chuck mechanism. In addition, a first heater 414 that heats the substrate W is embedded in the substrate holding unit 400. The substrate W is heated to, for example, 150 ° C. by the heater 414. The base material holder 400 in the present embodiment is configured to be rotatable.

  The material supply member holding unit 402 has a vacuum chuck mechanism (not shown) on its lower surface, and the material supply member X coated with an organic metal material by this vacuum chuck mechanism is the lower surface of the material supply member holding unit 402. Is supposed to be retained. In addition, a second heater 418 for heating the material supply member X is embedded in the material supply member holding portion 402. The material supply member X is heated to, for example, 70 ° C. by the heater 418 so that the organometallic material applied to the material supply member X is vaporized. Note that the organic metal material coating film on the material supply member X may be vaporized by heat transfer or radiant heat from the surface of the substrate W heated by the heater 414.

  The spin coater 404 includes a holding unit 420 that holds and rotates the material supply member X, a nozzle 422 that supplies an organic metal material to the upper surface of the material supply member X, a storage unit 423 that stores the organic metal material, and a holding unit 420. And a cover 424 covering the periphery of the.

  A gas introduction pipe 433 for introducing an inert gas such as nitrogen or argon from the inert gas supply source 430 into the chamber 410 and a gas discharge pipe 434 for discharging the inert gas are connected to the chamber 410. Yes. The gas discharge pipe 434 is connected to the vacuum pump 436 through the flow rate control valve 435. The pressure of the chamber 410 can be maintained at a desired pressure by adjusting the flow rate of the inert gas introduced from the inert gas supply source 430 and the flow rate control valve 435. For example, the pressure in the chamber 410 is set to normal pressure. Similarly, an inert gas supply source, a flow rate control valve, and a vacuum pump (all not shown) are connected to the chamber 411, and a flow of an inert gas such as nitrogen or argon is formed inside the chamber 411. .

  In this layer forming apparatus, first, after the base material W is adsorbed on the upper surface of the base material holding part 400, the material supply member X is transported to the spin coater 404 by a robot. In the spin coater 404, the organic metal material is uniformly applied to the entire surface of the material supply member X by supplying the organic metal material from the nozzle 422 while rotating the material supply member X by the holding unit 420.

  The material supply member X coated with the organometallic material is transferred from the chamber 411 to the chamber 410 by the robot. And the material supply member holding | maintenance part 402 descend | falls and the material supply member X is hold | maintained on the lower surface. The material supply member X is held facing the base material W by the material supply member holding unit 402. The distance between the substrate W and the material supply member X is 3 mm or less, and preferably the distance between the substrate W and the material supply member X is set to 0.5 to 1 mm.

  The material supply member holding unit 402 is preheated by the heater 418. When the material supply member X is heated by the heater 418, the organic metal material is vaporized from the coating film on the material supply member X, and an atmosphere made of a gaseous organic metal material (raw material gas) is formed on the surface of the substrate W. That is, it is locally formed between the substrate W and the material supply member X. Accordingly, the surface of the substrate W is exposed to the source gas, and a metal layer or a metal compound layer is formed on the surface of the substrate W.

  The heating temperature of the heater 418 is a temperature at which the organometallic material can be vaporized, and is preferably a temperature equal to or lower than the decomposition temperature of the organometallic material. In order to vaporize the organometallic material substantially uniformly, it is preferable that the surface of the material supply member X is heated substantially uniformly. The surface temperature of the material supply member X is preferably lower than the surface temperature of the substrate W. That is, the heating temperature of the organometallic material by the heater 418 is preferably lower than the heating temperature of the substrate W by the heater 414. Further, during the layer formation, it is preferable to heat the substrate W by the heater 414 of the substrate holding unit 400 and adjust the temperature of the substrate W so that the layer is formed uniformly. The base material holding part 400 is preferably rotated.

  FIG. 11 is a schematic view showing a layer forming apparatus according to another embodiment of the present invention. This layer forming apparatus impregnates an impregnated member with a liquid organometallic material, and keeps the organometallic material on the surface of the impregnated member at all times so that the atmosphere of the source gas is locally formed on the surface of the substrate. The layer is formed by exposing the surface of the substrate to a source gas atmosphere.

  As shown in FIG. 11, this layer forming apparatus has a base material holding part (susceptor) 600 that holds the base material W facing upward, and the organic metal material M is vaporized and held by the base material holding part 600. A material vaporization supply unit 610 that supplies the surface of the substrate W. The substrate holding unit 600 and the material vaporization supply unit 610 are accommodated inside the chamber 630 and are isolated from the outside by the chamber 630.

  The material vaporization supply unit 610 locally forms on the surface of the substrate W a function as a material vaporization unit that vaporizes a liquid organometallic material at room temperature to generate a raw material gas, and an atmosphere made of the raw material gas, It has a function as a material supply unit that exposes the surface of the substrate W to a source gas atmosphere to form a metal layer or a metal compound layer on the surface of the substrate W.

  The base material holding part 600 has an electrostatic chuck mechanism (not shown) on its upper surface, and the base material W is held on the upper surface of the base material holding part 600 by the electrostatic force of this electrostatic chuck mechanism. It has become. In addition, a first heater (base material heating part) 604 for heating the base material W held on the upper surface is embedded in the base material holding part 600. By supplying an electric current to the heater 604, the substrate W is heated to a temperature higher than the decomposition temperature of the organometallic material M, for example, 150 ° C. The temperature of the substrate W varies depending on the organometallic material used.

  Connected to the chamber 630 are a gas introduction pipe 632 for introducing an inert gas such as nitrogen or argon from the inert gas supply source 631 into the chamber 630 and a gas discharge pipe 634 for discharging the inert gas. Yes. The gas discharge pipe 634 is connected to the vacuum pump 636 via the flow rate control valve 635. The pressure of the chamber 630 can be maintained at a desired pressure by adjusting the flow rate of the inert gas introduced from the inert gas supply source 631 and the flow rate control valve 635. For example, the pressure in the chamber 630 is set to normal pressure.

  A storage unit 612 for storing the organometallic material M is formed in the material vaporization supply unit 610. The reservoir 612 is a thermostatic chamber so that the organometallic material M can be liquefied and held, and the reservoir 612 is filled with the liquefied organometallic material M. An impregnation member 613 for impregnating the liquid organometallic material M in the storage portion 612 is disposed below the storage portion 612, and the impregnation member 613 communicates with the storage portion 612 through an opening 612a. The lower surface of the impregnating member 613 is exposed to the outside and faces the base material W placed on the base material holding part 600. As the impregnation member 613, a porous material, a nonwoven fabric, or a woven fabric is preferably used.

  With such a configuration, the liquefied organometallic material M in the reservoir 612 is always impregnated in the impregnation member 613 by capillary action. On the lower surface of the impregnating member 613, the organometallic material M is vaporized by heat from the surface of the heated substrate W, and an atmosphere (raw material gas atmosphere) composed of the vaporized organometallic material M is locally present on the surface of the substrate W. Formed. Therefore, the surface of the base material W is exposed to the source gas atmosphere, whereby a metal layer or a metal compound layer is formed on the surface of the base material W. By using such an impregnating member 613, the organometallic material M can be stably supplied to the surface of the substrate W. In addition, it is preferable to set the distance from the surface of the impregnation member 613 to the surface of the base material W to 10 mm or less, and it is preferable to set to 3 mm or less further. These numerical values are determined from the viewpoint of forming a local source gas atmosphere on the surface of the substrate W. A heater for heating the organometallic material M impregnated in the impregnation member 613 may be provided adjacent to the impregnation member 613.

  FIG. 12 is a schematic diagram showing another configuration example of the present embodiment. As shown in FIG. 12, this layer forming apparatus has basically the same configuration as the layer forming apparatus shown in FIG. 11, but the base material W, the base material holding part 600, and the impregnation member 613 are vertical. 11 is different from the layer forming apparatus shown in FIG. Thus, by using the impregnation member 613 in the material vaporization supply unit 610, leakage of the organometallic material M can be suppressed even if the installation angle of the impregnation member 613 is changed. The installation angle of the holding unit 600 can be set to an arbitrary value, and the degree of freedom in design increases.

  FIG. 13 is a schematic view showing a layer forming apparatus according to another embodiment of the present invention. In this layer forming apparatus, a raw material gas (a gaseous organometallic material, a mixed gas of an inert gas and a gaseous organometallic material, or an aerosol that is a finely divided organometallic material) is introduced into a space in a base material. The metal layer or the metal compound layer is formed on the surface that supplies and forms the space.

  As shown in FIG. 13, this layer forming apparatus includes a base material holding part (susceptor) 700 that holds the base material W, a material vaporization part 712 that heats and vaporizes the organometallic material to generate a raw material gas, and a raw material A material supply pipe (material supply flow path) 714 that supplies gas to the space S in the substrate W, and a material discharge pipe (material discharge flow path) 718 that discharges a raw material gas and the like from the space S are provided. In this embodiment, the chamber and the inert gas supply source are not provided.

  A first heater (base material heating part) 704 for heating the base material W is embedded in the base material holding part 700. By passing an electric current through the heater 704, the substrate W is heated to a temperature higher than the decomposition temperature of the organometallic material, for example, 150 ° C. The temperature of the substrate W varies depending on the organometallic material used.

  The material supply pipe 714 is connected to the space S in the base material W, and the base material W and the material supply pipe 714 are sealed by a sealing material 716 such as an O-ring. The material discharge pipe 718 is connected to the space S on the opposite side of the material supply pipe 714, and the base material W and the material discharge pipe 718 are sealed with a sealing material 720 such as an O-ring. The material discharge pipe 718 communicates with the vacuum pump 722, and the raw material gas and its decomposition product are exhausted from the space S through the material discharge pipe 718 by the vacuum pump 722. A flow rate adjustment valve 724 is disposed on the upstream side of the vacuum pump 722.

  In such a configuration, by driving the vacuum pump 722, the space S in the base material W is evacuated through the material discharge pipe 718, and the raw material gas from the material vaporization unit 712 passes through the material supply pipe 714 in the space S in the base material W. To be introduced. Thereby, a raw material gas atmosphere is formed in the space S, and a metal layer or a metal compound layer is formed on the surface forming the space S. At the time of layer formation, it is preferable to heat the substrate W with the heater 704 and adjust the temperature of the substrate W so that the layer is formed uniformly.

  The layer forming apparatus in this embodiment is suitable for forming a layer on the surface of a substrate having a complicated shape. For example, even when layer formation is necessary on a curved surface such as the inner peripheral surface of a cylindrical base material, it is easy to optimize the layer formation conditions, and uniformization is possible. That is, since the source gas atmosphere can be locally formed only on the portion where the layer is to be formed (in this embodiment, only on the surface where the space S is formed), the layer forming conditions can be optimized. This eliminates the need to consider the external atmosphere and facilitates layer formation in the reaction rate-determining region.

  FIG. 14 is a schematic view showing a layer forming apparatus according to another embodiment of the present invention. The configuration and operation of the present embodiment that are not specifically described are the same as the configuration and operation of the layer forming apparatus shown in FIG.

  As shown in FIG. 14, this layer forming apparatus forms a layer on the inner surface of the recessed space S formed inside the base material W. More specifically, the layer forming apparatus includes a material supply pipe 814 as a material supply flow path connected to the material vaporization unit 712 and a material discharge pipe 818 as a material discharge flow path connected to the vacuum pump 722. ing. The material supply pipe 814 and the material discharge pipe 818 are constituted by double pipes, and a seal material 816 such as an O-ring is provided between the material discharge pipe 818 as an outer pipe and the base material W. The material supply pipe 814 as the inner pipe is inserted into the recessed space S inside the base material W. According to such a layer forming apparatus, a layer can be formed on the surface of a substrate having various and complicated shapes.

  In the present embodiment, an example of a double pipe in which the material supply pipe 814 is an inner pipe and the material discharge pipe 818 is an outer pipe has been described, but the present invention is not limited to this, and the material supply pipe 814 is an outer pipe. A double pipe having the material discharge pipe 818 as an inner pipe may be used.

  Here, for example, a semiconductor wafer, ceramic, resin, metal, or the like can be used as the base material in each of the above-described embodiments, and the layer forming apparatus according to the present invention is a semiconductor or a micro electro mechanical system (MEMS). Microelectromechanical Systems) and flat panel displays (FPDs) can be used for manufacturing. Hereinafter, a case where the above-described layer forming apparatus is used to form a metal layer or a metal compound layer on the surface of a semiconductor substrate (semiconductor wafer) as a base material will be described with reference to FIGS. 15 to 19B. To do. In FIG. 15 to FIG. 19B, the same or corresponding components are denoted by the same reference numerals, and redundant description is omitted.

  FIG. 15 is a plan view showing the substrate processing apparatus 1 including the layer forming apparatus according to the present invention. As shown in FIG. 15, the substrate processing apparatus 1 includes a layer forming unit 10 that forms a metal layer or a metal compound layer on the surface of a substrate such as a semiconductor wafer (substrate) having a fine concavo-convex structure, and layer formation There are provided four electroplating units 20 that perform electrolytic plating treatment on the subsequent substrate, and two etching / cleaning units 30 that etch, wash, and dry the electroplated substrate. These units are accommodated in a rectangular frame 40. A base material transport container 42 that can store a large number of base materials such as a SMIF (Standard Manufacturing Interface) pod and a FOUP (Front Opening Unified Pod) is detachably attached to an end portion in the longitudinal direction of the frame 40. A chemical solution management unit 44 that manages a chemical solution such as a plating solution is installed outside the frame 40.

  Inside the frame 40, a rail 50 is laid along the base material transport container 42, and a first transport robot 60 is provided on the rail 50. A rail 52 is laid along the electroplating unit 20 and the etching / cleaning unit 30, and a second transfer robot 62 is provided on the rail 52. Further, a third transfer robot 64 is provided at a position adjacent to the layer forming apparatus between the first transfer robot 60 and the second transfer robot 62.

  The first transport robot 60 transports the base material between the base material transport container 42, the third transport robot 64, and the layer forming unit 10, and the third transport robot 64 is configured of the layer forming unit 10 and the second transport robot 62. The substrate is transported between. The second transport robot 62 transports the substrate among the third transport robot 64, the electrolytic plating unit 20, and the etching / cleaning unit 30.

  The base material introduced into the base material processing apparatus 1 by the base material transport container 4 is transported to the layer forming unit 10 by the first transport robot 60. In the layer forming unit 10, as described above, a layer is formed by vaporizing the organometallic material. Thereafter, the base material is transported to the electroplating unit 20 by the third transport robot 64 and the second transport robot 62 and plated there. The base material after plating is transported to the etching / cleaning unit 30 by the second transport robot 62, where etching of the plating film adhering to the edge (bevel) portion of the base material and cleaning and drying of the base material are performed.

  As the layer forming unit 10, the layer forming apparatus of each of the above-described embodiments can be used. In this example, a layer forming unit 10 having substantially the same configuration as the layer forming apparatus shown in FIG. 7 is used. Hereinafter, the layer forming unit 10 will be described with reference to FIG.

  FIG. 16 is a schematic diagram showing the layer forming unit 10 shown in FIG. The layer forming unit 10 uses an organometallic material having a vapor pressure of atmospheric pressure or lower to form a layer made of a substance contained in the organometallic material on the surface of the substrate. As shown in FIG. 16, the layer forming unit 10 includes a base material holding unit 100 that holds the base material W upward and a base material W that vaporizes the organometallic material and is held by the base material holding unit 100. A material vaporization supply unit 110 that injects toward the surface and a plurality of pins 120 that support the substrate W introduced from the first robot 60 to the layer forming unit 10 are provided. The substrate holding unit 100, the material vaporization supply unit 110, and the pin 120 are accommodated in the chamber 130 and are isolated from the outside by the chamber 130.

  The substrate holding unit 100 has a vacuum chuck mechanism 102 on the upper surface thereof, and the substrate W is held on the upper surface of the substrate holding unit 100 by the vacuum chuck mechanism 102. In addition, a heater 104 for heating the substrate W adsorbed on the upper surface by the vacuum chuck mechanism 102 is embedded in the substrate holding unit 100. The substrate W is heated by the heater 104 to a temperature higher than the decomposition temperature of the organometallic material M, for example, 150 ° C. The temperature of the substrate W varies depending on the organometallic material used, but is preferably 120 ° C. or higher and 300 ° C. or lower. The substrate holding unit 100 in the present embodiment is configured to move up and down between a position below the substrate W supported by the pins 120 and a position in the vicinity of the material vaporization supply unit 110.

  As shown in FIG. 16, the material vaporization supply unit 110 includes a storage portion 112 that stores an organometallic material (solid or liquid) M, and an injection port 114 that gradually narrows from the storage portion 112 and opens to the lower surface. Is formed. In addition, a heater 116 for heating the organometallic material M is provided inside the material vaporization supply unit 110. An inert gas such as nitrogen is introduced into the material vaporization supply unit 110.

  The organometallic material M is heated by the heater 116 to a temperature at which the organometallic material M can be vaporized, for example, 70 ° C., thereby vaporizing. This temperature is preferably a temperature at which the vaporized organometallic material M can be supplied to the substrate surface in a controllable manner, and is preferably below the boiling temperature of the organometallic material. The material vaporization supply unit 110 in the present embodiment is configured to be movable in the horizontal direction from end to end of the substrate W held on the upper surface of the substrate holding unit 100.

  A gas introduction port 132 for introducing an inert gas such as nitrogen or argon is provided in the chamber 130 at the lower portion of the chamber 130, and a gas for discharging the inert gas is provided at the upper portion of the chamber 130. A discharge port 134 is provided.

  The base material W introduced into the chamber 130 of the layer forming unit 10 is placed on top of the pins 120. Then, when the substrate holding unit 100 located below is raised, the substrate W is transferred from the pin 120 to the substrate holding unit 100, and the vacuum chuck mechanism 102 sets the substrate holding unit 100 on the upper surface of the substrate holding unit 100. The material W is adsorbed.

  The substrate holding unit 100 holding the substrate W continues to rise to the vicinity of the material vaporization supply unit 110. After the raising of the base material holding unit 100 is completed, the organometallic material M in the storage unit 112 is heated and vaporized by the heater 116 of the material vaporization supply unit 110. The vaporized organometallic material M is sprayed onto the upper surface of the base material W from the injection hole 114 of the material vaporization supply unit 110, whereby a metal layer or a metal compound layer is formed on the upper surface of the base material W. At this time, it is preferable to heat the substrate W by the heater 104 of the substrate holding unit 100 and adjust the temperature of the substrate W so that the layer is formed uniformly. During the film forming process, the material vaporization supply unit 110 is moved in the horizontal direction so that a layer is formed over the entire surface of the substrate W. In order to uniformly supply the vapor of the organometallic material to the base material W, a gas flow from the material vaporization supply unit 110 toward the base material W is formed, and this gas flow is supplied to the base material W through the current plate. May be.

  When unloading the substrate W from the layer forming unit 10, for example, the inside of the chamber 130 is evacuated through the gas discharge port 134 using a vacuum pump having a degree of vacuum of about 0.01 Pa, and the organic metal used for film formation The vapor of the material M is discharged, and then an inert gas such as dry nitrogen is introduced into the chamber 130 via the gas introduction port 132, and then the substrate W after film formation is carried out of the layer forming unit 10. Good. Alternatively, a load lock may be installed in the layer forming unit 10 and the substrate W may be carried out through this load lock.

  FIG. 17 is a schematic diagram showing the electrolytic plating unit 20 shown in FIG. As shown in FIG. 17, the electrolytic plating unit includes a cylindrical plating tank 202 that opens upward and holds a plating solution 200 therein, and a base W that is detachably held downward. And a head unit 204 that arranges the base material W at a position that closes the opening. A plate-like anode 206 that is immersed in the plating solution 200 and serves as an anode electrode is horizontally disposed inside the plating tank 202, and the peripheral portion of the substrate W is a cathode via an electrode contact provided on the head portion 204. It is electrically connected to the electrode. The anode 206 is made of a porous material or a material that forms a mesh.

  A plating solution injection pipe 208 that forms a jet of a plating solution directed upward is connected to the center of the bottom of the plating vessel 202, and a plating solution receiver 210 is disposed outside the upper portion of the plating vessel 202. The plating solution injection pipe 208 extends from the plating solution adjustment tank 212 and is connected to a plating solution supply pipe 218 provided with a pump 214 and a filter 216. The plating solution adjustment tank 212 is connected to a plating solution return pipe 220 extending from the plating solution receiver 210.

  In such a plating apparatus, the substrate W is held downward by the head unit 204, and the substrate W is immersed in the plating solution 200 from the upper part of the plating tank 202. Then, while applying a predetermined voltage between the anode (anode electrode) 206 and the base material (cathode electrode) W, the plating solution in the plating solution adjustment tank 212 is ejected upward from the bottom of the plating tank 202 by the pump 214. Then, a jet of the plating solution 200 is applied perpendicularly to the lower surface of the substrate W. In this way, a plating current is passed between the anode 206 and the substrate W to form a plating film on the lower surface of the substrate W. At this time, the plating solution 200 overflowing the plating tank 202 is collected by the plating solution receiver 210 and flows into the plating solution adjustment tank 212.

This substrate processing apparatus is particularly effective when performing the following processes. First, as shown in FIG. 18A, a wiring groove 310 is formed in the interlayer insulating film 300 of the base material W made of SiO ₂ or a low-k material, and the surface of the interlayer insulating film 300 is made of Ta by sputtering or the like. A barrier metal layer 320 is formed. The base material W on which the barrier metal layer 320 is formed is introduced into the layer forming unit 10 of the base material processing apparatus 1 described above. In the layer forming unit 10, organic Co is vaporized and Co is attached to the barrier metal layer 320. As a result, a Co layer 330 is uniformly formed on the surface of the barrier metal layer 320 as shown in FIG.

  Next, the base material W is introduced into the electrolytic plating unit 20 of the base material processing apparatus 1 described above, and electrolytic plating is performed using the Co layer 330 as a seed layer. As shown in FIG. A copper film 340 is formed. As a result, the copper trench 340 is filled in the wiring trench 310. The base material W in which the wiring groove 310 is filled with the copper film 340 is conveyed from the base material processing apparatus 1 to the CMP apparatus. In this CMP apparatus, as shown in FIG. 19A, excess copper film 340 is removed by chemical mechanical polishing until the surface of interlayer insulating film 300 is exposed. Thereafter, the substrate W is transported from the CMP apparatus to the electroless plating apparatus. In this electroless plating apparatus, electroless CoWP plating is performed, and a CoWP layer 350 is selectively formed on the surface of the copper film 340 filled in the wiring groove 310 as shown in FIG.

  According to the wiring structure thus formed, the Co layer 330 is formed between the copper film 340 filled in the wiring groove 310 and the barrier metal layer 320, and the copper film 340 filled in the wiring groove 310. A CoWP layer 350 is formed on the surface. Therefore, the copper film 340 filled in the wiring trench 310 is covered with the Co layer 330 and the CoWP layer (that is, a metal layer containing Co as a main component) 350 which are the same kind of metal, and the Co layer 330 and the CoWP layer 350 are covered. The reliability of the interface between and the adhesion to copper can be improved. As a result, the reliability with respect to copper diffusion can be improved.

  Here, it is preferable that the decomposition temperature of the organometallic material used in the layer forming unit 10 is significantly higher than the vaporizable temperature. By using such a material, the organometallic material can be vaporized under atmospheric pressure, and the layer forming unit can be combined with a wet processing unit such as an electrolytic plating unit to form a unit. Therefore, the layer forming unit and the wet processing unit can be arranged in one base material processing apparatus, and simplification and space saving of the apparatus can be realized. In addition, since the layer forming unit and the wet processing unit can be arranged in one apparatus, the time between the layer forming process and the wet processing can be shortened, and the time management is facilitated.

In addition, although the example which provided the CMP apparatus and the electroless-plating apparatus separately from the base-material processing apparatus 1 was described here, you may incorporate these CMP apparatuses and an electroless-plating apparatus in the base-material processing apparatus 1. FIG. Further, in the layer forming unit 10 of the substrate processing apparatus 1, Co / Si may be vapor-deposited on the surface of the substrate W, and heat treatment may be performed for silicidation to form a seed layer. Alternatively, the layer forming unit 10 of the substrate processing apparatus 1 may promote the film growth of electrolytic copper plating in the electrolytic plating unit 20 by thinly depositing Co on the surface of the barrier metal layer made of Ru. Moreover, the surface of the base material introduced into the layer forming unit 10 includes semiconductor, ceramic, resin, Ru, RuO ₂ , Cu, Ta, TaN, Ti, TiN, Si, SiO ₂ , low-k material, Co, P Preferably, a layer made of at least one of CoP, CoWP, W, WSiC, WC, Ni, and Al is formed.

  In the above-described embodiment, the example in which the layer forming unit is combined with the electroplating unit has been described, but the wet processing unit combined with the layer forming unit is not limited to the electroplating unit. For example, as the wet processing unit, an electroless plating unit, a chemical mechanical polishing unit, an electrolytic etching unit, an electrolytic polishing unit, a chemical etching unit, or a cleaning unit can be used. In addition, the layer forming unit may be combined with a dry processing unit such as an annealing unit, a CVD unit, or a gas etching unit, and the base material on which the metal layer or the metal compound layer is formed by the layer forming unit may be subjected to dry processing.

  Further, a plurality of layer forming units may be provided, and a metal layer or a metal compound layer made of different substances may be formed in each layer forming unit. Further, a plurality of layers may be formed by exchanging a gas or an organometallic material in a single layer forming unit to form a metal layer or a metal compound layer made of a plurality of substances. As the cleaning of the base material after the layer formation processing in the layer forming unit, contact cleaning such as roll cleaning and pencil cleaning, non-contact cleaning such as ultrasonic liquid cleaning and IPA cleaning, and the like can be considered. Furthermore, you may dry a base material after washing | cleaning of this base material.

  Further, the relationship between the heating target temperature of the organometallic material and the corresponding heating target temperature of the base material corresponding to the substance to be formed on the base material may be stored in advance in a storage device as a database. In this case, for example, a sensor for measuring the temperature of the base material and the heating temperature of the heater is provided, the heating target temperature is obtained by referring to the database based on the temperature signal from these sensors, and the obtained heating is obtained. The heater may be controlled according to the target temperature so that the temperature of the base material and the temperature of the organometallic material are within an appropriate temperature range.

  In addition, the processing recipe of the substrate processing process including the layer forming process is recorded on a computer-readable storage medium, and is read out as necessary. Further, this processing recipe is made into a database according to the type of base material to be processed and the substance to be formed, and these databases are recorded on the recording medium.

  Although one embodiment of the present invention has been described so far, it is needless to say that the present invention is not limited to the above-described embodiment, and may be implemented in various forms within the scope of the technical idea.

It is a schematic diagram which shows the two-dimensional free jet model of the jet ejected from the injection nozzle. FIG. 2A and FIG. 2B are diagrams showing examples of the shape of the injection port of FIG. It is a graph which shows the velocity attenuation | damping of the jet ejected from a rectangular injection port. It is a mimetic diagram showing a layer formation device concerning one embodiment of the present invention. It is a schematic diagram which shows the layer forming apparatus which concerns on other embodiment of this invention. It is the schematic diagram seen from the direction shown by arrow VI of FIG. It is a schematic diagram which shows the layer forming apparatus which concerns on other embodiment of this invention. It is the schematic diagram seen from the direction shown by the arrow VIII of FIG. It is a schematic diagram which shows the layer forming apparatus which concerns on other embodiment of this invention. It is a schematic diagram which shows the layer forming apparatus which concerns on other embodiment of this invention. It is a schematic diagram which shows the layer forming apparatus which concerns on other embodiment of this invention. It is a schematic diagram which shows the other structural example of this embodiment. It is a schematic diagram which shows the layer forming apparatus which concerns on other embodiment of this invention. It is a schematic diagram which shows the layer forming apparatus which concerns on other embodiment of this invention. It is a top view which shows the base-material processing apparatus provided with the layer forming apparatus (layer forming unit) which concerns on this invention. It is a schematic diagram which shows the layer formation unit shown in FIG. It is a schematic diagram which shows the electroplating unit shown in FIG. 18 (a) to 18 (c) are schematic views showing a process using the substrate processing apparatus shown in FIG. FIG. 19A and FIG. 19B are schematic views showing a process using the substrate processing apparatus shown in FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material processing apparatus 10 Layer formation unit (layer formation apparatus)
20 Electrolytic plating unit 30 Etching / cleaning unit 40 Frame 42 Substrate transport container 60, 62, 64 Transport robot 100, 400, 600, 700 Substrate holder 104, 116, 129, 414, 418, 604, 704 Heater 108, 712 Material vaporization unit 109,119 Material supply unit 110,610 Material vaporization supply unit 111 Flow pipe 112,423,612 Storage unit 114 Injection port 127 Reciprocating movement mechanism 131,133,631 Inert gas supply source 130,410,411 630 Chamber 132 Gas introduction port 134 Gas exhaust port 300 Interlayer insulating film 310 Wiring groove 320 Barrier metal layer 330 Co layer 340 Copper film 350 CoWP layer 402 Material supply member holding part 404 Spin coater 613 Impregnation member 714, 814 Material supply pipe 71 , 720,816 sealant 718,818 material discharge pipe M organometal S space W substrate X material supply member

Claims (38)

Heating the surface of the substrate,
A raw material gas containing the organometallic material is generated by heating and vaporizing the organometallic material that is solid or liquid under a pressure in a range from 0.01 Pa to normal pressure,
Forming an atmosphere of the source gas locally on the surface of the substrate;
A layer forming method comprising forming a metal layer or a metal compound layer on a surface of a substrate by exposing at least a part of the surface of the substrate to the atmosphere. While supplying the source gas to a part of the surface of the substrate and maintaining a constant distance between the source gas supply port and the substrate facing the supply port, the supply port and the substrate are relatively To form an atmosphere consisting of the source gas locally on the surface of the substrate,
The layer forming method according to claim 1, wherein an opening area of the supply port is equal to or less than an area of the surface of the base material. A unit in which a material vaporizing unit that vaporizes an organic metal material and the supply port are integrated is provided,
The layer forming method according to claim 2, wherein the unit and the base material are relatively moved.   The layer forming method according to claim 2, wherein a distance from the supply port to the surface of the substrate is not more than 6 times a minimum frontage of the supply port. A heater is disposed adjacent to the supply port at the rear with respect to the moving direction of the supply port,
With the heater, the layer is annealed simultaneously with the layer formation,
The layer formation method according to claim 2, wherein the layer formation and the annealing are repeated twice or more. An impregnated member is placed opposite the substrate,
Impregnating the impregnated member with a liquid organometallic material,
2. The layer forming method according to claim 1, wherein a raw material gas containing the organometallic material is generated by heating and vaporizing the organometallic material impregnated in the impregnating member.   The layer forming method according to claim 6, wherein the impregnated member is at least one of a porous material, a nonwoven fabric, and a woven fabric.   The layer forming method according to claim 6, wherein a distance from the surface of the impregnated member to the surface of the base material is 10 mm or less. Prepare a substrate with space inside,
By supplying the source gas to the space, an atmosphere composed of the source gas is locally formed on the surface of the substrate,
The layer forming method according to claim 1, wherein the source gas and its decomposition product are discharged from the space.   The layer forming method according to claim 9, wherein the supply and discharge of the source gas are performed using a coaxial double structure flow path. Form a coating of organometallic material on the material supply member,
The material supply member is disposed to face the substrate,
A raw material gas containing the organometallic material is generated by heating and vaporizing the coating film of the organometallic material on the material supply member,
The layer forming method according to claim 1, wherein a distance between the base material and the material supply member is 3 mm or less.   The layer forming method according to claim 11, wherein the coating film of the organometallic material on the material supply member is heated and vaporized by heat transfer or radiant heat from the heated surface of the substrate.   The layer forming method according to claim 1, wherein the organometallic material includes at least one of cobalt, tungsten, platinum, aluminum, copper, molybdenum, manganese, and silicon.   The layer forming method according to claim 1, wherein the base material is at least one of a semiconductor wafer, a ceramic, a resin, and a metal. The surface of the substrate, semiconductor, ceramic, _{resin, Ru, RuO 2, Cu,} Ta, TaN, Ti, TiN, Si, SiO 2, low-k material, Co, P, CoP, CoWP , W, WSiC, The layer forming method according to claim 1, wherein the layer is formed of at least one of WC, Ni, and Al. Forming a barrier metal layer on the substrate on which the wiring trench is formed;
Forming a metal layer or a metal compound layer on the barrier metal layer by the method according to any one of claims 1 to 12,
Performing electrolytic plating using the metal layer or the metal compound layer as a seed layer and filling the wiring groove with copper;
And a step of removing a part of the copper by chemical mechanical polishing.   The wiring formation method according to claim 16, wherein the metal layer or the metal compound layer is a metal layer containing cobalt as a main component.   18. The wiring forming method according to claim 17, further comprising a step of selectively forming a metal layer mainly composed of cobalt on the surface of copper filled in the wiring groove by electroless plating. Copper filled in the wiring groove;
A barrier metal layer;
A metal layer mainly composed of cobalt formed between the copper and the barrier metal layer;
A metal layer mainly composed of cobalt formed on the exposed surface of the copper,
The metal layer formed between the copper and the barrier metal layer is a cobalt layer formed by the method according to any one of claims 1 to 12,
The wiring structure of a substrate, wherein the metal layer formed on the exposed copper surface is a metal layer formed by electroless plating. A material vaporization unit that generates a raw material gas containing the organometallic material by heating and vaporizing the solid or liquid organometallic material under a pressure in a range from 0.01 Pa to normal pressure;
A substrate holding part for holding the substrate;
A substrate heating unit that heats the surface of the substrate to a temperature higher than the decomposition temperature of the organometallic material vaporized by the material vaporization unit;
A material supply unit that locally forms an atmosphere made of the source gas on the surface of the substrate;
The said material supply part forms a metal layer or a metal compound layer on the surface of a base material by exposing at least one part of the surface of a base material to the said atmosphere, The layer formation apparatus characterized by the above-mentioned. The material supply unit includes a supply port for supplying the source gas to a part of the surface of the base material,
A moving mechanism is provided for moving the supply port and the base material relatively while maintaining a constant distance between the supply port and the base material facing the supply port,
21. The layer forming apparatus according to claim 20, wherein an opening area of the supply port is equal to or less than an area of the surface of the base material. The material vaporization unit and the material supply unit are an integral unit,
The layer forming apparatus according to claim 21, wherein the moving mechanism relatively moves the unit and the base material.   The layer forming apparatus according to claim 21, wherein a distance from the supply port to the surface of the base material is 6 times or less of a minimum frontage of the supply port.   The layer forming apparatus according to claim 21, wherein a heater is disposed adjacent to the supply port at a rear portion with respect to a moving direction of the supply port. The material supply unit has an impregnation member disposed to face the base material,
The layer forming apparatus according to claim 21, wherein the impregnated member is impregnated with a liquid organometallic material.   26. The layer forming apparatus according to claim 25, wherein the impregnating member is at least one of a porous material, a nonwoven fabric, and a woven fabric.   26. The layer forming apparatus according to claim 25, wherein a distance from the surface of the impregnated member to the surface of the substrate is 10 mm or less. The material supply unit
Connected to a space formed in the base material via a sealing material, and has a material supply channel for supplying a raw material gas to the space;
21. The layer forming apparatus according to claim 20, further comprising a material discharge channel connected to the space via a sealing material and discharging the source gas and its decomposition product from the space.   The layer forming apparatus according to claim 28, wherein the material supply channel and the material discharge channel are channels having a coaxial double structure. The material supply unit is a material supply member in which a coating film of an organometallic material is formed,
21. The layer forming apparatus according to claim 20, wherein the material supply member is disposed to face a substrate, and a distance between a base material and the material supply member is 3 mm or less.   The layer forming apparatus according to claim 30, wherein the coating film of the organometallic material on the material supply member is heated and vaporized by heat transfer or radiant heat from the heated base material.   21. The layer forming apparatus according to claim 20, wherein the organometallic material includes at least one of cobalt, tungsten, platinum, aluminum, copper, molybdenum, manganese, and silicon.   The layer forming apparatus according to claim 20, wherein the base material is at least one of a semiconductor wafer, a ceramic, a resin, and a metal. The surface of the substrate, semiconductor, ceramic, _{resin, Ru, RuO 2, Cu,} Ta, TaN, Ti, TiN, Si, SiO 2, low-k material, Co, P, CoP, CoWP , W, WSiC, 21. The layer forming apparatus according to claim 20, wherein the layer forming apparatus is made of at least one substance selected from WC, Ni, and Al. A layer forming apparatus according to any one of claims 20 to 31,
A substrate processing apparatus comprising: a wet processing unit that performs wet processing on a substrate on which a metal layer or a metal compound layer is formed by the layer forming apparatus.   The wet processing unit is at least one of an electrolytic plating unit, an electroless plating unit, a chemical mechanical polishing unit, an electrolytic etching unit, an electrolytic polishing unit, a chemical etching unit, and a cleaning unit. Item 35. The substrate processing apparatus according to Item 35. A layer forming apparatus according to any one of claims 20 to 31,
A substrate processing apparatus comprising: a dry processing unit that performs dry processing on a substrate on which a metal layer or a metal compound layer is formed by the layer forming apparatus.   38. The substrate processing apparatus according to claim 37, wherein the dry processing unit is at least one of an annealing unit, a CVD unit, and a gas etching unit.

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