GB2343453A - Apparatus for forming polymer film and method of forming film with the apparatus - Google Patents

Apparatus for forming polymer film and method of forming film with the apparatus Download PDF

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GB2343453A
GB2343453A GB9921965A GB9921965A GB2343453A GB 2343453 A GB2343453 A GB 2343453A GB 9921965 A GB9921965 A GB 9921965A GB 9921965 A GB9921965 A GB 9921965A GB 2343453 A GB2343453 A GB 2343453A
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organic monomer
polymer film
monomer
carrier gas
forming
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GB9921965D0 (en
GB2343453B (en
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Jun Kawahara
Yoshihiro Hayashi
Akinori Nakano
Mikio Shimizu
Tomohisa Nishikawa
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NEC Corp
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NEC Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/60—Deposition of organic layers from vapour phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/62—Plasma-deposition of organic layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Formation Of Insulating Films (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polymerisation Methods In General (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The present invention provides an apparatus for forming an organic polymer film having a thickness controlled with high accuracy. The apparatus efficiently vaporizes an organic monomer and sprays the vaporized organic monomer onto a substrate, so as to cause polymerization of the organic monomer to proceed on the substrate. The apparatus has a cleaning mechanism to improve the operation stability. Concretely, the apparatus comprises: a vaporization controller 6 that vaporizes an organic monomer while keeping a partial pressure of the organic monomer lower than a saturated vapor pressure of the organic monomer by introducing a carrier gas; a reaction chamber 11 that sprays the vaporized organic monomer with the carrier gas onto a substrate, so as to form a polymer film, which includes the organic monomer as a skeleton thereof, on the substrate; a cleaning mechanism that charges a cleaning solvent, which dissolves the organic monomer, into the vaporization controller 6 and a vaporized material supply conduit 35 that connects the vaporization controller 6 with the reaction chamber 11 for cleaning; and a discharge mechanism that discharges an exhaust flow of the cleaning solvent without being flown through the reaction chamber.

Description

APPARATUS FOR FORMING POLYMER FILM AND METHOD OF FORMING FILM WITH THE APPARATUS BACKGROUND OF THE INVENTION 1. Field of the Invention: The present invention relates to a method of forming a film that insulates semiconductor elements and wiring for connecting the semiconductor elements with each other, and also to an apparatus for the same.
2. Description of the Prior Art: The recent design policy of semiconductor integrated circuits is size reduction, which may cause deterioration of the performance due to a delay in wiring.
The delay of the wiring signals in the semiconductor integrated circuit depends upon a wiring CR time constant (where C denotes a wiring capacity and R denotes a wiring resistance). An increase in wiring resistance due to a decrease in wiring width and an increase in wiring capacity due to a decrease in wiring interval may cause the wiring CR time constant not to sufficiently follow but to be behind the improved switching speed of a transistor. Aluminum alloy is generally used for the material of the wiring in the semiconductor integrated circuits. The applicability of copper and silver for the wiring has been examined for the purpose of lowering the wiring resistance.
With a view to lowering the wiring capacity, on the other hand, the applicability of various dielectric materials having the lower dielectric constant than that of silica (Si02), which is generally used, for the insulator film have been examined. Known examples of the insulator films having the low dielectric constant include fluorine-substituted silica (SiOF), porous silica, and organic polymer films (organic insulator films). The fluorine-substituted silica may, however, cause corrosion of the wiring metal by hydrofluoric acid, which is produced by the reaction of fluorine with the moisture or hydrogen in the film, or increase the dielectric constant due to a release of fluorine. The porous silica is expected to have the dielectric constant of not greater than 2.
In the case of the porous silica, however, condensation of the water content in fine pores may cause the dielectric constant or lower the dielectric strength.
It is thus highly demanded to develop an organic polymer film having the excellent heat resistance and hygroscopic resistance as the inter-layer insulator film that insulates multi-layered wiring on the semiconductor integrated circuit. As for the hygroscopic resistance, it is important that an organic monomer does not include any hydrophilic group. It is also desirable that the polymerization reaction from an organic monomer, which is the skeleton of the organic polymer film, is not via the condensation polymerization reaction of water. The organic monomer here implies a unit which causes polymerization reaction to form an organic polymer.
The method of spin coating the organic monomer is widely used to form such a functional organic polymer film. In this method, the organic monomer is dissolved in a solvent, and in the film-forming process, while removing the solvent, the organic monomer is heated so as to cause the polymerization of the organic monomer to proceed. As a result, a two-dimensional or threedimensional network-structured film or a polymer film is formed. The skeleton of the resulting organic insulator film is the structure of the organic monomer which had been dissolved in the organic solvent.
In"REAL-TIME FT-IR STUDIES OF THE REACTION KINETICS FOR THE POLYMERIZATION OF DIVINYL SILOXANE BIS BENZOCYCLOBUTENE MONOMERS" (Material Research Symposium Proceedings Vol. 227, p. 103, 1991) T. M. Stokich Jr., W.
M. Lee, R. A. Peters (hereinafter referred to as Reference 1), for example, there is a description with respect to a film formation, where a solution, in which divinylsiloxane bis (benzocyclo) butene monomer (hereinafter referred to as DVS-BCB monomer) is dissolved in mesitylene, is spin-coated, subsequently the coat is baked at 100 C to remove the solvent, mesitylene, and further the coat is heated to the temperature of 300 C to 350 C. This heating causes a thermal ring-opening polymerization reaction of the carbon four-membered ring in the benzocyclobutene to proceed and forms an organic polymer film of a three-dimensional molecular chain structure having, as the skeleton, divinylsiloxane bis (benzocyclo) butene monomer, which structure is represented by a chemical formula given below.
In the spin-coating method, the organic monomer is dissolved in a solvent and the dissolved substance is spin-coated. In the course of the spin-coating, however, approximately 90% of the dissolved substance is flown off out of a substrate. This results in a poor utilization efficiency of the starting material. In the spin-coating, the spin-coated film is heated in a baking furnace to remove the solvent and the coat is further heated at higher temperatures to cause a polymerization reaction of the organic monomer to proceed thereby forming an organic polymer film. In the case where oxygen is present in the baking furnace, the oxygen may react with a part of the organic monomers and may interfere with the formation of the intended organic polymer film. For example, after a solution, in which divinylsiloxane bis (benzocyclo) butene monomer is dissolved in mesitylene, is spin-coated, and when the coat is baked, said bake should be carried out in an atmosphere having the allowable oxygen concentration of not greater than 100 ppm. It is thus required to replace the whole atmosphere in the baking furnace with nitrogen gas. This needs a relatively large cost. Further, since oxygen dissolved in the solvent may also react with a part of the organic monomers in the course of baking, the strict regulation of the atmosphere is necessary. This strict regulation is, however, difficult in the spin-coating method. Further, the spincoating is carried out in a spin-coating chamber which is locally evacuated, and on this occasion floating dust particles or fine particles of the organic monomer, which had been stuck to the inner wall of the spin coating chamber dried and solidified, may contaminate the spincoated film. This may deteriorate the quality of the resulting film. The spin-coating method also requires a large quantity of the organic solvent, which results in large loading of the waste treatment.
The present inventors have proposed an evaporation method of the organic monomer to form a functional organic polymer film as disclosed in Japanese Patent Application Laid-open No. 17006/1999. According to this method, an organic monomer is evaporated and the monomer in the gas phase is polymerized on a substrate to obtain an organic polymer film. Fig. 22 shows an apparatus for forming an organic film by this direct vaporization of the organic monomer. An organic monomer 1 included in a reservoir 55 is heated under reduced pressure to be vaporized. A reaction chamber 51 is subsequently evacuated with an evacuation pump 50, and the vaporized organic monomer 1 is fed to the reaction chamber 51 via a vaporized material supply conduit 56. The organic monomer molecules adhere to the surface of a semiconductor substrate 53, on which a semiconductor integrated circuit has been provided, and undergo a polymerization reaction with thermal energy supplied from a substrate heating unit 54, thereby constructing a bridging structure and forming an organic insulator film 52 on the surface of the semiconductor substrate 53.
The method disclosed in Japanese Patent Application Laid-open No. 17006/1999 has the extremely improved utilization efficiency of the starting material, compared with the spin-coating method. This proposed method adopts the technique of vaporizing the organic monomer from the gas-liquid interface. Since evaporation of the organic monomer significantly depends upon the vapor pressure of the organic monomer, it is required to heat the organic monomer at high temperatures. Further, the organic monomer has certain reactivity, on the other hand, and undergoes the polymerization reaction at high temperatures. This makes the vaporization of the organic monomer undesirably unstable and needs an improvement of the method.
SUMMARY OF THE INVENTION In view of the above problem, the present inventors have proposed an MVP (Monomer-vapor Polymerization) method to form a functional organic polymer film as disclosed in Japanese Patent Application No. 170016/1998 (hereinafter referred to as Reference 2), which has not yet been laid open. In this method, an organic monomer, which is a skeleton of the polymer film, is vaporized, the vaporized organic monomer is transported in the gas phase with a carrier gas, and the vaporized organic monomer is sprayed on the surface of a substrate located in a reaction chamber, thereby forming an organic polymer film on the surface of the substrate. In the conventional CVD method, for example, when TEOS (tetraethyl ortho-silicate: Si (OCH2CH3) 4), which is a liquid organic silica source, is vaporized to obtain a silicon oxide film in a reaction chamber, the vaporized TEOS is caused to chemically react with ozone or oxygen, which is supplied via a separate pathway, in the gas phase in a reaction chamber to form a silicon dioxide (SiO2) film. In this case, the resulting film (SiO2) has a different chemical structure from that of the starting material (TEOS). In the case where the organic monomer is vaporized as described in Reference 2, on the other hand, the organic monomer transported in the gas phase undergoes the polymerization reaction on the substrate.
This method, therefore, enables to obtain a remarkable effect that a film having a structure of the starting material as its skeleton can be formed on the substrate with high accuracy. For the purpose of distinction from the conventional CVD method, the method of forming a polymer film disclosed in Japanese Patent Application No.
170016/1998 is hereinafter referred to as the MVP (Monomer-Vapor Polymerization) method.
The proposed MVP method, however, still has several technical problems. The first problem regards vaporization of the organic monomer used as the starting material. By way of example, when a thermally polymerizing material is used, vaporization of the material, in general, significantly depends upon the vapor pressure of the starting material. A high vaporization temperature is thus preferable to improve the vaporization efficiency. Heating the organic monomer at the high temperature in a vaporization controller, however, causes the organic monomer to start polymerization in the vaporization controller. This may result in an unstable operation or malfunction of the vaporization controller.
The second problem regards the phenomenon that the material once vaporized in the vaporization controller may be liquefied again according to the pressure and temperature conditions in a supply conduit leading to the reaction chamber. The temperature, the pressure, and the saturated vapor pressure of the starting material determine whether the starting material is kept in the gas phase or returned to the liquid phase. When there is a specific part having a relatively small cross section of the pathway, for example, a valve, in the supply conduit connecting the vaporization controller to the reaction chamber, said specific part may have a higher pressure or a lower temperature, which causes the material to be liquefied again inside said specific part.
The re-liquefaction of the starting material may cause the supply of material to be unstably varied or make the operation of the valve unstable.
The third problem is difficulty in removing the material liquefied in the supply conduit, if once the starting material has been re-liquefied in the conduit.
Heat is continuously applied to the supply conduit to keep the vaporizing state of the material. In the event that the material is liquefied again in the supply conduit due to the reason discussed above as the second problem and that the re-liquefied material is present in the supply conduit for a relatively long time, a polymerization reaction of said re-liquefied material will start in the supply conduit. The starting material may be liquefied at a specific part having a relatively small cross section of the pathway in the supply conduit, which connects the vaporization controller with the reaction chamber. The polymerized material accordingly may block said specific part of the pathway and interferes with a further supply of the material.
Further, a flow of the starting material from the reaction chamber to the evacuation pump may cause the unstable operation or malfunction of the evacuation pump, in the event that the starting material is fed in the evacuation pump, in accordance with the circumstances in the pump.
The fourth problem is that a cleaning solvent, which is used to remove the material liquefied again in the supply conduit, causes undesirable contamination. In order to prevent the contamination, the cleaning should be performed without feeding the solvent to any nonrequired places, especially to the reaction chamber.
Like the above third problem, in the event that the solvent is fed in the evacuation pump, in accordance with the circumstances in the pump, it may cause the malfunction of the evacuation pump.
An object of the present invention is thus to provide an apparatus for forming an organic polymer film having a thickness controlled with high accuracy. The apparatus efficiently vaporizes an organic monomer and sprays the vaporized organic monomer onto a substrate, so as to cause polymerization of the organic monomer to proceed on the substrate. The apparatus further has a cleaning mechanism to improve the operation stability.
The present invention is directed to an apparatus for forming a polymer film. The apparatus comprises: a vaporization controller that vaporizes an organic monomer while keeping a partial pressure of the organic monomer lower than a saturated vapor pressure of the organic monomer by introducing a carrier gas; a reaction chamber that sprays the vaporized organic monomer with the carrier gas onto a substrate, so as to form a polymer film, which includes the organic monomer as a skeleton thereof, on the substrate; a cleaning mechanism that charges a cleaning solvent, which dissolves the organic monomer, into the vaporization controller and a vaporized material supply conduit that connects the vaporization controller with the reaction chamber for cleaning; and a discharge mechanism that can discharge an exhaust flow of the cleaning solvent without being flown through the reaction chamber.
The present invention is also directed to a method of forming a polymer film. The method comprises the steps of: feeding a supply of an organic monomer to a vaporization controller; heating the organic monomer in the vaporization controller to vaporize the organic monomer while keeping a partial pressure of the organic monomer lower than a saturated vapor pressure of the organic monomer by introducing a carrier gas; transporting the carrier gas containing the vaporized organic monomer from the vaporization controller to a reaction chamber and spraying the carrier gas containing the vaporized organic monomer via a shower head disposed in the reaction chamber onto surface of a substrate located in the reaction chamber, so as to form a polymer film, which includes the organic monomer as a skeleton thereof, on the substrate; charging a cleaning solvent, which dissolves the organic monomer, into the vaporization controller and a vaporized material supply conduit that connects the vaporization controller with the reaction chamber for cleaning, and discharging an exhaust flow of the cleaning solvent after the cleaning; and making a flow of the carrier gas into the vaporization controller and the vaporized material supply conduit connecting the vaporization controller with the reaction chamber while evacuating the reaction chamber, so as to purge remains of the cleaning solvent.
The technique of the present invention quantitatively sprays the organic monomer onto the surface of the substrate and thereby has a high utilization efficiency of the starting material. The organic polymer film obtained as the resulting product has the skeleton of the organic monomer, which is the starting material. Namely the technique enables the excellent control of the polymer film structure that can obtain a polymer film which corresponds to the structure of the starting material monomer.
The organic monomer quickly initiates the polymerization reaction especially under the conditions of the low vapor pressure and the high temperature. In the technique of the present invention, a carrier gas is introduced to make the partial pressure of the organic monomer lower than the saturated vapor pressure of the organic monomer. This enables the organic monomer to be sufficiently vaporized even under the heating condition of relative low temperatures having an extremely slow polymerization rate. The carrier gas containing the organic monomer is sprayed onto the substrate located in the reaction chamber, which is sealed and evacuated with a pump, so that the polymerization reaction of the organic monomer proceeds on the substrate. This effectively prevents the organic monomer from reacting with a reactive gas, such as oxygen, and doe not cause deterioration of the specific properties, for example, an increase in dielectric constant due to partial oxidation of the resulting polymer film.
Even if the organic monomer is liquefied again in either the vaporization controller or in the vaporized material supply conduit and stuck to the inner wall thereof, in the technique of the present invention, the cleaning solvent is charged into and cleans the vaporization controller and the vaporized material supply conduit, so that the inside of the vaporized material supply conduit and of the vaporization controller is kept clean. It is required to discharge an exhaust flow of the cleaning solvent without being flown through the reaction chamber. This arrangement favorably prevents the reaction chamber from being contaminated with the cleaning solvent after cleaning.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 schematically illustrates an apparatus for forming a polymer film in one embodiment according to the present invention; Fig. 2 is a sectional view schematically illustrating a vaporization controller in one embodiment of the present invention; Fig. 3 is a graph showing the unreacted monomer remaining rate plotted against the heating time when the DVS-BCB monomer is heated; Fig. 4 is a graph showing the total pressure P in a vaporizing chamber in the vaporization controller of one embodiment of the present invention plotted against the flow of the He carrier gas; Fig. 5 is a vaporization characteristic diagram showing the relationship between the vaporizing temperature of the DVS-BCB monomer and the maximum supply of the monomer in the vaporization controller of one embodiment of the present invention; Fig. 6 is a graph showing the comparison between infrared absorption characteristics of a DVS-BCB polymer film formed with the apparatus of the Example 1 of the present invention and those of a DVS-BCB polymer film formed by the prior art spin coating method; Fig. 7 shows a cleaning process in the apparatus for forming a polymer film according to the Example 1 of the present invention; Fig. 8 shows a cleaning process in the apparatus for forming a polymer film according to Example 1 of the present invention; Fig. 9 shows a cleaning process in the apparatus for forming a polymer film according to Example 1 of the present invention; Fig. 10 shows a cleaning process in the apparatus for forming a polymer film according to Example 1 of the present invention; Fig. 11 shows a cleaning process in the apparatus for forming a polymer film according to Example 1 of the present invention; Fig. 12 shows a cleaning process in the apparatus for forming a polymer film according to Example 1 of the present invention; Fig. 13 shows a cleaning process in the apparatus for forming a polymer film according to Example 1 of the present invention; Fig. 14 shows a cleaning process in the apparatus for forming a polymer film according to Example 1 of the present invention; Fig. 15 shows a cleaning process in the apparatus for forming a polymer film according to Example 1 of the present invention; Fig. 16 shows a cleaning process in the apparatus for forming a polymer film according to Example 1 of the present invention; Fig. 17 shows a cleaning process in the apparatus for forming a polymer film according to Example 1 of the present invention; Fig. 18 shows a cleaning process in the apparatus for forming a polymer film according to Example 1 of the present invention; Fig. 19 shows a cleaning process in the apparatus for forming a polymer film according to Example 1 of the present invention; Fig. 20 shows a cleaning process in the apparatus for forming a polymer film according to Example 1 of the present invention; Fig. 21 shows a cleaning process in the apparatus for forming a polymer film according to Example 1 of the present invention; and Fig. 22 shows a conventional method in which an organic monomer is evaporated to obtain a polymer film.
Fig. 23 shows a growth flow sheet of a DVS-BCB polymer film using the polymer film growth system of Example 2 according to the present invention.
Fig. 24 shows an infrared spectrum chart of a DVS BCB polymer film formed by using the polymer film growth system of Example 2 according to the present invention.
In the respective drawings, 1 denotes an organic monomer, 2 denotes a carrier gas, 3 denotes a cleaning solvent reservoir, 3a denotes a cleaning solvent, 4 denotes a pressure gas, 5 denotes a liquid flow indicator, 6 denotes a vaporization controller, 6a denotes a head, 6b denotes a body, 6c denotes a shield, 6d denotes a carrier gas supply inlet, 6e denotes an organic monomer supply inlet, 6f denotes a vaporizing chamber, 6g denotes a heater, 6h denotes a valve in the vaporization controller, 7a and 7b denote gas flow regulators, 8 denotes a filter, 9 denotes a thermocouple, 10 denotes an evacuation pump, 11 denotes a reaction chamber, 12 denotes a pipe heater, 13 denotes an organic insulator film, 14 denotes a semiconductor substrate on which a semiconductor integrated circuit is formed, 15 denotes a substrate heating unit, 16 denotes a water-cooling trap, 17 denotes an organic monomer reservoir, 18 denotes a shower head, 20 denotes a valve A, 21 denotes a valve B, 22 denotes a valve C, 23 denotes a valve D, 24 denotes a valve E, 25 denotes a valve F, 26 denotes a valve G, 27 denotes a valve H, 28 denotes a valve I, 29 denotes a valve J, 30 denotes a valve K, 31 denotes a valve L, 32 denotes a valve M, 33 denotes a valve N, 34 denotes a cleaning gas, 35a and 35b denote vaporized material supply conduits, 36 denotes an organic monomer supply conduit, 37a and 37b denote cleaning solvent supply conduits, 38 denotes a carrier gas supply conduit, 39 denotes a waste discharge conduit, 40 denotes an exhaust discharge conduit, 41 denotes a cleaning gas supply conduit, 42 denotes a matching box, 43 denotes an RF power source, 44 denotes an RF cable, 45a and 45b denote earth wires, 46 denotes a plasma, 50 denotes an evacuation pump, 51 denotes a reaction chamber, 52 denotes an organic insulator film, 53 denotes a semiconductor substrate, 54 denotes a substrate heating unit, 55 denotes a reservoir, and 56 denotes a vaporized material supply conduit.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention applies a direct liquid injection technique to vaporize a liquid material. In the bubbling technique or another vaporization technique with a baking system, a greater quantity of the material than required is heated. In the technique of the present invention, however, only a supply of the material and a little quantity of the material existing in the vaporization controller are heated. This accordingly minimizes the amount of the chemical reaction of the starting material by heating other than when vaporizing the starting material.
Fig. 2 is a sectional view schematically illustrating a vaporization controller 6 shown in Fig. 1.
The following description refers to Figs. 1 and 2. The vaporization controller 6 has a vaporizing chamber 6f, which is a small clearance between a head 6a and a body 6b arranged across a shield 6c. A supply of carrier gas 2 is fed through a carrier gas supply inlet 6d of the body 6b into the vaporizing chamber 6f, whereas a supply of DVS-BCB monomer (organic monomer 1) is fed through an organic monomer supply inlet 6e into the vaporizing chamber 6f. The organic monomer 1 is heated to a preset temperature with a heater 6g for heating the periphery of the organic monomer supply inlet 6e and the vicinity of the surface of the body 6b. The vaporizing chamber 6f is evacuated via a vaporized material supply conduit 35a that connects with a reaction chamber 11, which is evacuated with an evacuation pump 10. The vaporized organic monomer 1 is carried out by the carrier gas 2. A diaphragm valve 6h attached to the head 6a immediately above the monomer supply inlet 6e is vertically driven by a piezoelectric element, so that the opening of the organic monomer supply inlet 6e is closed after a fixed flow rate of the organic monomer 1 is fed. This vaporization controller implements the vaporization only by heating a small quantity of the organic monomer fed into the vaporization controller and thereby has a good thermal efficiency. Especially this vaporization controller is favorably. applied to the case where an organic monomer used has a low saturated vapor pressure and is readily polymerized under application of heat of high temperature for a relatively long time, like the present invention.
The conditions of vaporization using the vaporization controller 6 are given below. In the case where the evacuation pump has a constant evacuation capacity, the total pressure P of the vaporizing chamber 6f is a function of the flow of the carrier gas. Here the saturated vapor pressure of the organic monomer is significantly small and is thus negligible. The essential condition is that the carrier gas contains neither oxygen nor water. It is desirable that the carrier gas has a high thermal conductivity since the organic monomer has a low saturated vapor pressure and is sensitive to the temperature. He is the most suitable candidate of the carrier gas, but Ar or N2 that does not react with the organic monomer may be used instead. Fig.
4 is a graph showing an exemplified plot of the total pressure P (torr) in the vaporizing chamber of the vaporization controller used in the present invention against the flow C (sccm) of the He carrier gas. The total pressure P in the vaporizing chamber increases with an increase in the flow C of the carrier gas. The total pressure P in the vaporizing chamber is accordingly expressed as P (C).
The saturated vapor pressure Pm of the DVS-BCB monomer (organic monomer 1) exponentially increases with an increase in temperature. For example, the saturated vapor pressure Pm varies as 0.0078 torr at 125 C, 0.047 torr at 150 C, and 0.21 torr at 175 C. Namely the saturated vapor pressure Pm of the organic monomer is a function of the temperature and expressed as Pm (T).
In the presence of the carrier gas, the organic monomer can be vaporized in the case where the partial pressure of the organic monomer is lower than the saturated vapor pressure of the organic monomer. The partial pressure of the organic monomer is the product of the total pressure P (C) and the molar fraction of the organic monomer in the vaporization controller.
On the assumption that all of the organic monomer supplied is vaporized, the molar fraction Rm of the organic monomer in the vaporization controller is approximately calculated as: Rm = {(Sl (g/min). Mm (g/mol)) x 22400 (cc/mol)}- C(sccm) where C (sccm) denotes the flow of the carrier gas, Sl (g/min) denotes the supply rate of the organic monomer, and Mm (g/mol) denotes the molecular weight of the organic monomer.
The vaporizing condition is accordingly given as: P (C) x Rm < Pm (T) (Expression 1) In the case where the flow of the carrier gas is significantly large and the supply rate of the organic monomer is negligible, the molar fraction Rm of the organic monomer becomes significantly small. The total pressure P (C) in the vaporization controller that is required for vaporization of the organic monomer and satisfies the vaporizing condition may thus be as small as several torr. The vaporizing condition of the organic monomer in the presence of the carrier gas is given as Expression 1 and is rewritten as: Sl < v (C, T) (Expression 2) v (C, T) = (MmxC/22400) x (Pm (T)/P (C)) where C (sccm) denotes the flow of the carrier gas, Sl (g/min) denotes the supply rate of the organic monomer, Mm=390 (g/mol) denotes the molecular weight of the organic monomer, P denotes the total pressure in the vaporization controller, and T denotes the vaporizing temperature.
This determines the range of the flow (C) of the carrier gas and the vaporizing temperature (T) required to vaporize a specified quantity of the organic monomer supplied to the vaporization controller.
In the concrete procedure, the relationship between the total pressure P and the flow of the carrier gas (Fig.
4) and the relationship between the saturated vapor pressure of the DVS-BCB monomer and the temperature (vaporizing temperature T) are substituted into Expression 2, and a vaporization safety rate ss (where ss=0. 5) is multiplied by the right side of Expression 2.
This gives the relationship between the vaporizing temperature T and the maximum supply C of the monomer with regard to the flow of the carrier gas as the parameter. The vaporization characteristic curves thus obtained depend upon the configuration of the vaporization controller and vary according to the setting of the vaporization safety rate ss. The graph of Fig. 5 shows exemplified vaporization characteristic curves.
In the event that the flow of the carrier gas is fixed, the maximum supply of the organic monomer increases with an increase in vaporizing temperature.
This is ascribed to the fact that the saturated vapor pressure of the organic monomer increases with an increase in vaporizing temperature. The vaporization of the organic monomer stably proceeds in the lower area of the characteristic curve. This stable vaporization area is expanded with an increase in flow of the carrier gas.
The polymerization rate of the organic monomer increases with an increase in vaporizing temperature. It is thus necessary to take into account the fact that the polymerization interferes with vaporization of the monomer. The graph of Fig. 3 shows the temperature dependency of the polymerization rate of the organic monomer, where the organic monomer used is divinylsiloxane bis (benzocyclo) butene monomer. The variation in molecular weight against the heating time is measured by the GPC (Gel Permeation Chromatography), and the non-polymerization ratio (1-a) of the divinylsiloxane bis (benzocyclo) butene monomer is calculated. The graph of Fig. 3 shows the logarithm of the non-polymerization ratio (1-a) plotted against the heating time. The logarithm of the non-polymerization ratio (1-a), that is, log (1-a), linearly decreases against the heating time.
This shows that the polymerization reaction proceeds according to a first-order reaction rate equation. The slope of log (1-a) against the heating time increases with an increase in heating temperature.
By way of example, the monomer is heated at various temperatures for one minute. In the case of heating at 150 C, only 0.03% of the monomer undergoes the polymerization reaction. In the case of 170 C, the polymerization rate increases to 0.24%. In the case of 180 C, the polymerization rate reaches 1% or higher.
Namely the polymerization reaction more rapidly proceeds with an increase in vaporizing temperature. During the stand-by of the apparatus, the divinylsiloxane bis (benzocyclo) butene monomer held in the vaporization controller is subjected to the polymerization little by little. In the event that the apparatus is stood by for a relatively long time, for example, for several days of the stand-by, the polymerization reaction becomes not negligible even at the temperature of 150 C where the polymerization rate is significantly small.
As discussed above, the relationship between the vaporization rate and the polymerization rate of the organic monomer is important for the MVP method. The present inventors have found that the polymerization rate of the organic monomer that is not greater than 1/100 of the vaporization rate of the organic monomer is practically negligible.
In the vaporization technique applied in the present invention, the carrier gas is supplied to the vaporization controller, in order to improve the vaporizing condition and enable transport of the vaporized material. It is here desirable that the supplied carrier gas has the temperature substantially equal to the vaporizing temperature. In one exemplified configuration, a metal filter is located in a carrier gas supply conduit of the vaporization controller and is heated to heat the carrier gas. A thermocouple is disposed in the conduit to indirectly measure the temperature of the carrier gas and confirm the sufficient heating.
Referring to Fig. 1, which schematically illustrates one embodiment according to the present invention, a supply of the carrier gas 2 is fed via a gas flow regulator 7a to a filter 8 located in a conduit leading to a valve K30. The filter 8 is heated by the heater 12. By this mechanism, the carrier gas is heated and the heated carrier gas is fed to the vaporization controller 6 via the valve K30. A thermocouple 9 is located in the conduit connecting the filter 8 with the valve K30 to measure the temperature of the carrier gas indirectly.
The carrier gas 2 supplied to the vaporization controller 6 does not take heat from the vaporization controller 6, so that the heat in the vaporization controller 6 is used only to vaporize the organic monomer 1, which is the liquid starting material. This arrangement accordingly improves the efficiency of vaporization. The arrangement also reduces the heat exchange with the vaporized organic monomer 1 and effectively prevents the vaporized organic monomer 1 from being liquefied again.
The vaporized material is kept in the gas phase as long as the pressure of the vaporized material does not exceed its saturated vapor pressure. The supply conduit including the valve, which connects the vaporization controller with the reaction chamber, is heated by the heater. By using the pipe and the valve which have sufficiently large cross sections of the pathway, the pressure does not increase locally, and thus the vaporized starting material can be prevented from being liquefied again.
The following describes a cleaning mechanism of the apparatus and a discharge mechanism of a cleaning solvent after the cleaning process. The starting material in the vaporization controller is exposed to the heat of the vaporization controller all the time, even at the time other than the time for vaporization (for example, at the stand-by time). This may cause the undesirable reaction of the material with the heat. As shown in Fig. 1, the apparatus of one embodiment of the present invention has a mechanism in which the conduit and the vaporization controller are filled with a specific liquid (cleaning solvent), which can dissolve the starting material, after the formation of the film and before the progress of the undesirable reaction of the starting material. This arrangement enables the piping to be sufficiently washed and prevents the pathway from being blocked.
An exhaust pathway that is not via the reaction chamber is disposed to discharge the cleaning solvent as shown in Fig. 1. This arrangement can avoid the potential contamination of the reaction chamber due to the use of the cleaning solvent. The exhaust pathway can be heated like the supply conduit leading to the reaction chamber. This arrangement effectively prevents the vaporized material from being re-liquefied in the pathway to a water-cooling trap (described later) and enhances the discharge rate of the cleaning solvent.
Both the starting material after the formation of the film and the cleaning solvent after the cleaning process are discharged via a water-cooling trap arranged before the evacuation pump. This arrangement enables the starting material and the cleaning solvent to be collected in the water-cooling trap and thereby can avoid the potential trouble which may occur by an introduction of the starting material and the cleaning solvent to the evacuation pump.
A reaction chamber 11 is evacuated with an evacuation pump 10. A substrate heating unit 15 is disposed inside the reaction chamber 11, and a semiconductor substrate 14, on which a semiconductor integrated circuit is formed, is fixed on the substrate heating unit 15. The liquid starting material 1 for the organic film is supplied to the vaporization controller 6 via valves 26 and 23 and a liquid flow indicator 5. The vaporization controller 6 is heated and carries out vaporization while controlling the supply. The organic monomer 1 vaporized in the vaporization controller 6 is fed to the reaction chamber 11 via a vaporized material supply conduit 35 equipped with the heater 12. The organic monomer 1 is then exposed to the thermal energy from the substrate heating unit 15 on the surface of the semiconductor substrate 14, on which the semiconductor integrated circuit is formed, or is alternatively exposed to the plasma energy generated by an RF electric power which is applied to a shower head. The organic monomer 1 thus undergoes the polymerization reaction to form an organic insulator film 13 on the surface of the semiconductor substrate 14.
Since the reaction chamber 11 is evacuated with the evacuation pump 10, the unreacted material is kept in the gas phase and sent to a water-cooling trap 16 via the exhaust conduit which is heated with the heater 12. The starting material can not be kept in the gas phase since the temperature in the water-cooling trap 16 is sufficiently low, and is liquefied in the trap 16. This arrangement prevents the starting material from being flown into the evacuation pump 10 but enables the starting material to be collected in the water-cooling trap 16.
The conduit and the vaporization controller 6 are filled with a cleaning solvent 3a while valves D23 and E24 and the valve 6h in the vaporization controller 6 are all set in closed positions. The cleaning solvent 3a dissolves the material partially reacted in the conduit and the vaporization controller 6. When the cleaning process is concluded, valves C22 and A20 are set in closed positions, a valve B21 is set in an open position, and the valve 6h in the vaporization controller 6 is set in an open position. This causes the cleaning solvent 3a and the starting material dissolved therein to be sent to the water-cooling trap 16. This arrangement prevents the dissolved starting material as well as the cleaning solvent 3a from being flown into the evacuation pump 10 but enables both the dissolved starting material and the cleaning solvent 3a to be collected in the liquid form in the water-cooling trap 16.
The cleaning solvent 3a used in the present invention is a liquid solvent of the organic monomer.
When the organic monomer used is the DVS-BCB monomer, mesitylene, hexamethylketone, or tetralin may be used for the cleaning solvent 3a.
The carrier gas used in the present invention may be gaseous hydrogen, gaseous nitrogen, gaseous helium, gaseous argon, gaseous neon, or another inert gas to the organic monomer.
As discussed above, the present invention adopts the vaporization technique with the minimum thermal loading to vaporize the liquid monomer material for the organic insulator film. Other characteristics of the present invention include heating the carrier gas used for the vaporization of the starting material, using the pipes and valves with smaller heating and pressure losses to prevent the vaporized starting material from being reliquefied, and applying the mechanism for cleaning the whole supply system with a cleaning liquid, the mechanism for discharging the cleaning solvent after the cleaning process without being flown through the reaction chamber, and the mechanism for enabling the exhaust mixture of the starting material and the cleaning solvent to be collected at the inlet of the evacuation pump.
Example 1 One embodiment of the present invention is described in detail with reference to Fig. 1. An apparatus for forming a polymer film according to the present invention mainly includes an organic monomer reservoir 17, the liquid flow indicator 5, the vaporization controller 6, the filter 8 for heating the carrier gas, the gas flow regulators 7a and 7b, the reaction chamber 11, the heater 12 for heating the piping, the cooling trap 16, the evacuation pump 10, and a cleaning solvent reservoir 3. The apparatus also includes pipes and control valves for introducing the carrier gas 2, a cleaning gas 34, a purge gas 19, and a pressure gas 4. The organic monomer reservoir 17 stores divinylsiloxane bis (benzocyclo) butene monomer (DVS-BCB monomer), and the cleaning solvent reservoir 3 stores mesitylene. Gaseous helium (He) is used for all the carrier gas 2, the purge gas 19, and the pressure gas 4.
The cleaning gas 34 is a gaseous mixture of SF6 and oxygen or ozone. Alternatively the cleaning gas 34 may be a gaseous mixture of a fluorocarbon gas, such as CF4 or C2F6, and oxygen or ozone.
The following describes a series of processes from vaporization of the DVS-BCB monomer to formation of a DVS-BCB polymer film with the apparatus for forming the polymer film with reference to Fig. 1. At the initial stage, the diaphragm valve 6h in the vaporization controller 6 and the valves B21 and I28 are set in"open't positions. The reaction chamber 11, an exhaust discharge conduit 40, a waste discharge conduit 39, the vaporization controller 6, the liquid flow indicator 5, the vaporized material supply conduits 35a and 35b, and organic monomer supply conduits 36c and 36d are evacuated with the evacuation pump 10. The heater 12 for heating the piping heats a carrier gas supply conduit 38, the vaporized material supply conduits 35a and 35b, the waste discharge conduit 39, and the exhaust discharge conduit 40 to a specific temperature that may be identical with the preset vaporizing temperature of the organic monomer or a little higher than the preset vaporizing temperature in a specified range where the polymerization reaction of the organic monomer is not significant (the polymerization rate > 1%/min).
For example, when the vaporizing temperature of the DVS-BCB monomer is 150 C, the heating temperature of the piping is set equal to 170 C. The piping temperature is monitored by the thermocouples 9 which are located at appropriate places in the piping, and the heater 12 for heating the piping is regulated to keep the specific temperature.
While the diaphragm valve 6h in the vaporization controller 6 and the valve B21 are set in"closed" positions and the valves K30 and A20 are set in"open" positions, the carrier gas (He) 2 is flown through the carrier gas supply conduit 38, fed to the vaporization controller 6 via the gas flow regulator 7a and the filter 8 for supplying the carrier gas, further flown to the reaction chamber 11 via the vaporized material supply conduits 35a and 35b, and flown out of the apparatus via the exhaust discharge conduit 40 with the evacuation pump 10.
The vaporization controller 6 is heated to the temperature of 150 C, and the He gas is heated to a specific temperature that is identical with the vaporizing temperature with the filter 8 for heating the carrier gas. Pre-heating the He gas introduced to the vaporization controller 6 to the vaporizing temperature effectively prevents the vaporized DVS-BCB monomer from being re-liquefied due to a temperature decrease. The preliminary heating temperature of the carrier gas is set, in principle, equal to the vaporizing temperature, but may be set a little higher than the vaporizing temperature in a specified range where the polymerization reaction of the organic monomer is not significant (polymerization rate > 1%/min). In the case of the DVS BCB monomer, for example, the preliminary heating temperature may be set up to about 175 C. The preliminary heating temperature should, however, be lower than the heat-resistant temperature (for example, 200 C) of the valves which are used in the apparatus for forming the polymer film. The flow of the He carrier gas is set equal to 500 sccm according to the vaporization characteristic curve at the vaporizing temperature 150 C of the DVS-BCB monomer. Under such conditions, the total pressure P in the vaporization controller 6 is 7 torr, and the pressure in the reaction chamber 11 is 2.0 torr.
The silicon substrate (semiconductor substrate) 14, on which the semiconductor integrated circuit is formed, is heated to 300 C by the substrate heating unit 15 which is located in the reaction chamber 11. The appropriate heating temperature of the substrate ranges 250 C to 400 C in the case of the DVS-BCB monomer.
In the process, the valve D23 is then opened and a supply the DVS-BCB monomer is caused to be fed from the organic monomer reservoir 17 via the organic monomer supply conduits 36a, 36b, and 36c to the liquid flow indicator 5, using the pressure gas (He) 4. In the process, the DVS-BCB monomer is fed to the vaporization controller 6 while accurately regulating the supply rate of the DVS-BCB monomer. Under the vaporizing conditions of the He carrier gas flow set equal to 500 sccm and the vaporizing temperature set equal to 150 C, the supply rate of the DVS-BCB monomer is regulated to 0.03 g/min.
At this stage, the diaphragm valve 6h in the vaporization controller 6 is set in"closed"position.
In the process, the diaphragm valve 6h in the vaporization controller 6 is then subsequently opened to vaporize the DVS-BCB monomer. The vaporized DVS-BCB monomer is dispersed in the He carrier gas in a shower head 18 which is disposed in the reaction chamber 11 and sprayed onto the silicon substrate 14. The DVS-BCB monomer undergoes the polymerization reaction on the surface of the silicon substrate 14 which is heated to 300 C, so as to form a DVS-BCB polymer film (organic insulator film) 13. In the case where the adsorption efficiency of the monomer is 20%, the required supply of the DVS-BCB monomer is approximately 0.15 g to form a DVS-BCB film having a thickness of 1 Mm on an 8-inch substrate. In the process, accordingly, the DVS-BCB monomer is supplied from the liquid flow indicator 5 at the flow rate of 0.03 g/min for 5 minutes. On this occasion, the non-polymerized DVS-BCB monomer is present in the exhaust discharge conduit 40. The vaporized and non-polymerized DVS-BCB monomer is re-liquefied in the water-cooling trap 16, which is cooled down to approximately 20 C by water, and accordingly does not flow into the evacuation pump 10.
After a preset quantity of the DVS-BCB monomer is vaporized, the diaphragm valve 6h in the vaporization controller 6 is closed. Then, the valve K30 is closed to stop the supply of the He carrier gas 2 and the silicon substrate 14 is taken out of the reaction chamber 11.
Fig. 6 is a graph showing the comparison between an infrared absorption spectrum of a DVS-BCB polymer film obtained from the DVS-BCB monomer vaporized with the apparatus for forming the polymer film according to the present invention and that of a DVS-BCB polymer film formed by the prior art spin coating method disclosed in Reference 1. The absorption spectrum of the DVS-BCB polymer film of the present invention is similar to the absorption spectrum of the DVS-BCB polymer film by the spin coating method. The DVS-BCB polymer film by the spin coating method has a large absorption of infrared ray in a specific wavelength range of 1700 to 1900 (cm~l).
It is considered that this absorption is ascribed to oxidation of the DVS-BCB polymer film due to contamination with oxygen in the film forming process by the spin coating method. Since the process of the present invention carries out formation of the DVS-BCB polymer film under the strict control of the oxygen-free atmosphere, on the other hand, the DVS-BCB polymer film obtained from the DVS-BCB monomer vaporized with the apparatus for forming the polymer film does not have such absorption of infrared ray. The dielectric constant of this DVS-BCB polymer film is 2.7.
The following describes a series of cleaning processes to clean the piping and the vaporization controller 6 after formation of the polymer film with the apparatus of the present invention, with reference to Figs. 7 through 21.
In the initial state (Fig. 7) immediately after conclusion of the formation of the polymer film, the valve A20 is set in"open"position and the reaction chamber 11, the exhaust discharge conduit 40, the waste discharge conduit 39, the vaporization controller 6, and the vaporized material supply conduits 35a and 35b are evacuated with the evacuation pump 10. In the course of formation of the polymer film, the heater 12 for heating the piping heats the carrier gas supply conduit 38, the vaporized material supply conduits 35a and 35b, the waste discharge conduit 39, and the exhaust discharge conduit 40 to a specific temperature that may be identical with the preset vaporizing temperature of the organic monomer or a little higher than the preset vaporizing temperature in a specified range where the polymerization reaction of the organic monomer is not significant (the polymerization rate > 18/min). In the course of cleaning, on the other hand, the temperature of the piping is set in a range that does not vaporize the cleaning solvent, that is, set not greater than the boiling point of the cleaning solvent. In the case where mesitylene that is the solvent of the DVS-BCB monomer is used for the cleaning solvent, the temperature of the piping is set equal to 120 C, which is sufficiently lower than the boiling point 164 C of mesitylene. The piping temperature is monitored by the thermocouples 9 which are located at appropriate places in the piping, and the heater 12 for heating the piping is regulated to keep the specific temperature.
Referring to Fig. 8, the valves A20 and G26 are set in"closed"positions and the valves E24 and I28 in "open"positions, and the organic monomer supply conduits 36c and 36d are evacuated with the evacuation pump 10 via the organic monomer supply conduit 36b and the waste discharge conduit 39. This enables the remaining organic monomer to be discharged and collected in the cooling trap 16. Collection of the organic monomer with the cooling trap effectively reduces the quantities of the organic monomer flown into the evacuation pump and flown out of the apparatus. Reduction of the quantity of the organic monomer flown into the evacuation pump avoids the potential trouble of the evacuation pump. Reduction of the quantity of the organic monomer flown out of the apparatus reduces the loading of the waste treatment.
Referring to Fig. 9, in the process, the diaphragm valve 6h in the vaporization controller 6 and the valve K30 are opened to feed the carrier gas (He) 2 from the carrier gas supply conduit 38 to the vaporization controller 6 via the gas flow regulator 7a and the filter 8 for supplying the carrier gas. The carrier gas (He) 2 is further fed to the organic monomer supply conduits 36c and 36d via the diaphragm valve 6h in the vaporization controller 6, so as to press out the remaining organic monomer. This further accelerates the discharge of the organic monomer in Fig. 8. This process continues several minutes, for example, one minute.
Referring to Fig. 10, the valves E24,128, and K30 are set in"closed"positions and the valve B21 in"open" position, and the organic monomer supply conduit 36c is evacuated via the liquid flow indicator 5, the organic monomer supply conduit 36d, the diaphragm valve 6h in the vaporization controller 6, the vaporized material supply conduit 35a, the valve B21, and the waste discharge conduit 39. The piping in the liquid flow indicator 5 is very narrow. This arrangement enables the organic monomer to be discharged at a higher rate from both the directions shown in Figs. 9 and 10.
Referring to Fig. 11, the valves M32 and C22 are set in"open"positions and the cleaning solvent 3a is supplied from the cleaning solvent reservoir 3 via the cleaning solvent supply conduit 37 to the organic monomer supply conduits 36c and 36d. The cleaning solvent used here enables dissolution of the organic monomer and preferably has the excellent safety with regard to the toxicity and inflammability. The organic monomer is thus dissolved in the cleaning solvent. Here mesitylene is used for the cleaning solvent. The supplied cleaning solvent is discharged with the evacuation pump 10 via the valve 6h in the vaporization controller 6, the vaporized material supply conduit 35a, the valve B21, and the waste discharge conduit 39. This process continues several minutes, for example, one minute. The flow of the cleaning solvent simultaneously dissolves and presses out the organic monomer remaining in or adhering to the piping, so as to clean the piping.
Referring to Fig. 12, the valve B21 is set in "closed"position while continuing the supply of the cleaning solvent shown in Fig. 11, so as to fill the vaporized material supply conduit 35a, the valve 6h in the vaporization controller 6, the liquid flow indicator 5, and the organic monomer supply conduits 36c and 36d with the cleaning solvent. When the piping is filled with the sufficient quantity of the cleaning solvent, the valves C22 and M32 are set in"closed"positions as shown in Fig. 13. This enables the organic monomer, which has not yet been dissolved in the process of Fig. 11 and still remains in the piping, to be dissolved in the cleaning solvent.
After the organic monomer in the piping is sufficiently dissolved in the cleaning solvent, the valves C22, E24, and I28 are set in"open"positions as shown in Fig. 14 and the piping is evacuated with the evacuation pump 10, so as to cause the cleaning solvent with the organic monomer dissolved therein, which is present in the cleaning solvent supply conduit 37b and the organic monomer supply conduit 36c, to be discharged via the waste discharge conduit 39. The exhaust flow of the cleaning solvent with the organic monomer dissolved therein is collected in the cooling trap 16. This arrangement reduces the quantities of the cleaning solvent flown into the exhaust pump 10 and flown out of the apparatus.
Referring to Fig. 15, the valves E24 and 128 are closed in"closed"positions and the valve B21 and the valve 6h in the vaporization controller 6 in"open" positions, so as to discharge the cleaning solvent with the organic monomer dissolved therein, which remains in the liquid flow indicator 5, the organic monomer supply conduit 36d, the vaporization controller 6, and the vaporized material supply conduit 35a, under reduced pressure with the evacuation pump 10.
The processes shown in Figs. 11 through 15 show the procedure of cleaning the piping and the vaporization controller 6. This series of processes is repeated several time, for example, three times, according to the requirements. This enables the organic monomer remaining in the pathway except the inside of the valve A20 to be all discharged.
After this series of processes, the valve B21 is set in"closed"position and the valves A20 and M32 in "open"positions as shown in Fig. 16, so as to discharge the cleaning solvent via the reaction chamber 11 and the exhaust discharge conduit 40. This process shown in Fig.
16 cleans the inside of the valve A20, which has not been cleaned by the series of processes to Fig. 15.
Referring to Fig. 17, the valve M32, the valve 6h in the vaporization controller 6, and the valve A20 are set in"closed"positions and the valves E24 and I28 in "open"positions, so as to discharge the cleaning solvent used in the process of Fig. 16 via the waste discharge conduit 39. This process enhances the discharge rate, which is affected by the very narrow piping in the liquid flow indicator 5, and prevents any unnecessary substances other than those relating to formation of the film from being fed into the reaction chamber 11. This series of processes enables all the organic monomer existing in the pathway to be discharged.
Further, referring to Fig. 18, the valves E24 and I28 are set in"closed"positions and the valve L31, the valve 6h in the vaporization controller 6, and the valve B21 in"open"positions, and the purge gas 19, gaseous helium in this embodiment, is supplied into the pathway via a purge gas supply conduit 42. The purge gas 19 purges out the cleaning solvent remaining in the vaporized material supply conduit 35a, the vaporization controller 6, the liquid flow indicator 5, and the organic monomer supply conduits 36c and 36d. Since the cleaning solvent is also a liquid, only a simple evacuation requires a long time for discharge. This process significantly improves the discharge rate of the cleaning solvent.
Referring to Fig. 19, the valve B21 is set in position and the valve A20 in"open"position while continuing the supply of the purge gas 19. This enables the cleaning solvent remaining inside the valve A20 to be purged out. This series of processes completely purges out the cleaning solvent remaining in the pathway.
Further, referring to Fig. 20, the valve K30 is set in"open"position while continuing the supply of the purge gas 19, and the carrier gas 2 is fed into the vaporization controller 6 via the carrier gas supply conduit 38. This enables the respective parts inside the vaporization controller 6 to be sufficiently purged.
Referring to Fig. 21, the valves C22 and L31 are set in"closed"positions to keep the apparatus in the stand-by state, and the organic monomer supply conduits 36c and 36d and the vaporized material supply conduit 35a are evacuated with the evacuation pump 10.
The cleaning process discussed above favorably removes the organic monomer which has been partly reacted or re-liquefied and ensures the operation stability of the apparatus.
In the course of cleaning discussed above, the cleaning solvent and the organic monomer dissolved in the cleaning solvent, which are discharged from the piping and the vaporization controller 6 by means of the evacuation pump 10, are flown through the piping heated by the heater and reach the water-cooling trap 16 to be re-liquefied and collected in the liquid form in the water-cooling trap 16. This prevents the cleaning solvent and the organic monomer dissolved therein from being flown into the evacuation pump 10 and thereby avoids the potential trouble of the evacuation pump 10.
After formation of an organic film on the surface of plural semiconductor substrates, the cleaning gas 34, the gaseous mixture of oxygen and C2F6 in this embodiment, is introduced into the reaction chamber 11 via the gas flow regulator 7 and the valve N33 and the inside of the reaction chamber 11 is kept at the pressure of 0.5 through 5 torr with the evacuation pump 10. The process then applies a high frequency of 13.56 MHz to the metal shower head 18 to generate the oxygen plasma. This removes the organic insulator film formed on the inner wall of the reaction chamber 11 and keeps the inside of the reaction chamber 11 clean.
The series of processes discussed above implements formation of a polymer film and cleaning of the organic substance adhering to the inside of the pathway. This process is repeated during the manufacture.
Example 2 This example is to explain a growth method of a polymer film. A further cleaning process in the apparatus for forming the polymer film was carried out in accordance with the procedures described in Example 1 above.
In Example 2, an attempt was made to reduce the growth temperature of the organic polymer film by introducing the vaporized organic monomer in a plasma gas ambience thereby to promote the polymerization reaction of the organic monomer. A configuration of an apparatus, wherein the ring-opening polymerization reaction of the DVS-BCB monomer in the vapor phase is promoted by utilizing a plasma gas, is shown in Fig. 23. In this example, the ring-opening reaction of a carbon fourmembered ring in a benzocyclobutene skeleton is initiated at low temperature by generating plasma, thereby to obtain a polymer film composed of a three-dimensional molecular chain comprising a DVS-BCB monomer as a principal skeleton at lower substrate temperature.
First, the diaphragm valve 6h in the vaporization controller 6 was opened and the DVS-BCB monomer was vaporized. The vaporized DVS-BCB monomer was dispersed by the shower head 18 in the reaction chamber 11, together with the He carrier gas, and then sprayed on the silicon substrate 14 on which a semiconductor integrated circuit is formed. In that case, the substrate heating portion 15 as an electrode is grounded through an earthing wire 45b, while the showed head 18 as an electrode is connected with a RF power source 43 and a matching box 42 through a RF cable 44.
RF power was applied to such a shower head 18, thereby to generate plasma 46 between the substrate heating portion 16 and the shower head 18. In this example, RF power was adjusted to 50 W and a frequency of RF power was adjusted to 13.56 MHz. The pressure in the reaction chamber 11 on film-forming was adjusted to 0.77 Torr. The ring-opening reaction of the carbon fourmembered ring in the benzocyclobutene skeleton in the vapor phase initiated at a low temperature by means of energy of plasma. On the surface of the heated substrate, the polymerization reaction of the ring-opened DVS-BCB monomer occurred thereby to form a DVS-BCB polymer film (organic insulating film) 13. By increasing such power, the reaction is further promoted and the film-forming temperature is also increased. However, when power of not less than 200 W is applied, the composition of the DVS-BCB itself is initiated. Therefore, RF power is preferably within a range from 20 to 190 W. To generate plasma, the pressure of the reaction chamber is preferably within a range from 0.5 to 10 Torr.
The substrate temperature can be reduced by generating plasma and the film can be formed from 100 C.
In the case where the adsorption efficiency of the monomer became 25% as a result of promotion of the reaction by generating plasma, it is necessary to supply about 0.15 g of the DVS-BCB monomer so as to grow a DVS BCB film of 1 g m on the surface of a 8 inch substrate.
Accordingly, the DVS-BCB monomer was supplied from the liquid flow indicator 5 at a flow rate of 0.03 g/min for 4 minutes. In this case, unpolymerized DVS-BCB monomer is contained in an exhaust piping 40, but the DVS-BCB monomer was accumulated in a cooling trap cooled to about 20 C by water cooling and did not penetrate into the exhaust pump 10.
Fig. 24 is an infrared spectrum chart of the DVS BCB polymer film of the example according to the present invention. In this example, the substrate temperature was adjusted to 240 C. In the drawing, an infrared absorption spectrum of a DVS-BCB polymer film, which is obtained by coating a DVS-BCB monomer dissolved in a solvent using a spincoating method, removing the solvent, baking and polymerizing in an electric furnace under a nitrogen ambience at 350 C for 30 minutes, is also described. In the infrared absorption spectrum of this DVS-BCB polymer film, absorptions corresponding to C=C, C6H4 (benzene ring), CH3Si-,-SiO-,-Si (CH3) 2- and-SiCHg were recognized. An increase in infrared absorption at 1700-1900 (cm-1) is caused by partial oxidation of DVS BCB. In the case of the spincoating method, the DVS-BCB monomer film is heated in an electric furnace under a nitrogen ambience. That is, it is assumed that contamination with oxygen occurred in the case of putting the substrate in the furnace, thereby to cause partial oxidation of DVS-BCB.
When the substrate heating temperature was 240 C, a specific peak was not recognized in the DVS-BCB polymer film in the case where RF power for generating plasma is 10 W. In the case where RF power is 30 W, 50 W or 100 W, specific peaks corresponding to C=C, C6H4 (benzene ring), CH3Si-,-SiO-,-Si (CH3) 2- and-SiCH3 were recognized in the DVS-BCB polymer film. In addition, absorption at 1700-1900 (cm-1) due to partial oxidation of DVS-BCB was not recognized. This reason is assumed that the MVP method does not include the process of causing contamination with oxygen. The dielectric constant of this DVS-BCB polymer film was from 2.7 to 2.8. On the other hand, when RF power becomes 200 W or higher, absorption at about 1500 (cm-1), which corresponds to the benzene ring, becomes very weak. Therefore, it is assumed that partial decomposition reaction of the DVS BCB skeleton is caused by a plasma gas.
The same results as those described above were recognized up to the substrate heating temperature of 100 C and effectiveness of the plasma promoting action to reduction in temperature of the polymer film growth by the MVP method was recognized. In such way, the polymerization of the organic monomer in the vapor phase is promoted by He plasma. The plasma gas may be any one, which does not react with the organic monomer, and argon or neon may be used.
In the apparatus for forming the polymer film according to the present invention, the carrier gas for vaporization of the organic monomer is utilized and the organic monomer is directly sprayed onto the substrate, thereby enabling the efficient formation of the polymer film. The organic monomer has a low vapor pressure and is readily re-liquefied and polymerized in the piping or the vaporization controller. The apparatus of the present invention, however, has the cleaning mechanism to keep the pathway in the clean state and improves the operation stability of the apparatus.

Claims (54)

1. An apparatus for forming a polymer film, comprising: a vaporization controller that vaporizes an organic monomer while keeping a partial pressure of the organic monomer lower than a saturated vapor pressure of the organic monomer by introducing a carrier gas; a reaction chamber that sprays the vaporized organic monomer together with the carrier gas onto a substrate, so as to form a polymer film, which includes the organic monomer as a skeleton thereof, on the substrate; a cleaning mechanism that charges a cleaning solvent, which dissolves the organic monomer, into said vaporization controller and a vaporized material supply conduit that connects said vaporization controller with said reaction chamber for cleaning; and a discharge mechanism that discharges an exhaust flow of the cleaning solvent without being flown through said reaction chamber.
2. The apparatus for forming a polymer film according to claim 1, further comprising: an inlet for introducing a flow of oxygencontaining gas to said reaction chamber; a shower head disposed in said reaction chamber to enable the vaporized organic monomer together with the carrier gas to be sprayed onto the substrate; and a high frequency generator that applies a high frequency to said shower head, so as to generate a plasma of the organic monomer, the carrier gas, and the oxygencontaining gas.
3. The apparatus for forming a polymer film according to claim 1, further comprising: a cooling trap that collects the exhaust flow of the cleaning solvent discharged by said discharge mechanism.
4. The apparatus for forming a polymer film according to claim 2, further comprising: a cooling trap that collects the exhaust flow of the cleaning solvent discharged by said discharge mechanism.
5. The apparatus for forming a polymer film according to any one of claim 1, wherein the organic monomer comprises divinylsiloxane bis (benzocyclo) butene monomer represented by a chemical formula given below:
6. The apparatus for forming a polymer film according to any one of claim 2, wherein the organic monomer comprises divinylsiloxane bis (benzocyclo) butene monomer represented by a chemical formula given below:
7. The apparatus for forming a polymer film according to any one of claim 3, wherein the organic monomer comprises divinylsiloxane bis (benzocyclo) butene monomer represented by a chemical formula given below:
8. The apparatus for forming a polymer film according to any one of claim 4, wherein the organic monomer comprises divinylsiloxane bis (benzocyclo) butene monomer represented by a chemical formula given below:
9. The apparatus for forming a polymer film according to claim 1, wherein the carrier gas of the organic monomer is an inert gas that is inert to the organic monomer.
10. The apparatus for forming a polymer film according to claim 2, wherein the carrier gas of the organic monomer is an inert gas that is inert to the organic monomer.
11. The apparatus for forming a polymer film according to claim 3, wherein the carrier gas of the organic monomer is an inert gas that is inert to the organic monomer.
12. The apparatus for forming a polymer film according to claim 4, wherein the carrier gas of the organic monomer is an inert gas that is inert to the organic monomer.
13. The apparatus for forming a polymer film according to claim 5, wherein the carrier gas of the organic monomer is an inert gas that is inert to the organic monomer.
14. The apparatus for forming a polymer film according to claim 6, wherein the carrier gas of the organic monomer is an inert gas that is inert to the organic monomer.
15. The apparatus for forming a polymer film according to claim 7, wherein the carrier gas of the organic monomer is an inert gas that is inert to the organic monomer.
16. The apparatus for forming a polymer film according to claim 8, wherein the carrier gas of the organic monomer is an inert gas that is inert to the organic monomer.
17. The apparatus for forming a polymer film according to claim 9, wherein the inert gas is gaseous helium.
18. The apparatus for forming a polymer film according to claim 10, wherein the inert gas is gaseous helium.
19. The apparatus for forming a polymer film according to claim 11, wherein the inert gas is gaseous helium.
20. The apparatus for forming a polymer film according to claim 12, wherein the inert gas is gaseous helium.
21. The apparatus for forming a polymer film according to claim 13, wherein the inert gas is gaseous helium.
22. The apparatus for forming a polymer film according to claim 14, wherein the inert gas is gaseous helium.
23. The apparatus for forming a polymer film according to claim 15, wherein the inert gas is gaseous helium.
24. The apparatus for forming a polymer film according to claim 16, wherein the inert gas is gaseous helium.
25. A method of forming a polymer film, which comprises the steps of: feeding a supply of an organic monomer to a vaporization controller; heating the organic monomer in said vaporization controller to vaporize the organic monomer while keeping a partial pressure of the organic monomer lower than a saturated vapor pressure of the organic monomer by introducing a carrier gas; transporting the carrier gas containing the vaporized organic monomer from said vaporization controller to a reaction chamber and spraying the carrier gas containing the vaporized organic monomer via a shower head disposed in said reaction chamber onto surface of a substrate located in said reaction chamber, so as to form a polymer film, which includes the organic monomer as a skeleton thereof, on the substrate; charging a cleaning solvent, which dissolves the organic monomer, into said vaporization controller and a vaporized material supply conduit that connects said vaporization controller with said reaction chamber for cleaning, and discharging an exhaust flow of the cleaning solvent after the cleaning; and making a flow of the carrier gas into said vaporization controller and said vaporized material supply conduit connecting said vaporization controller with said reaction chamber while evacuating said reaction chamber, so as to purge remains of the cleaning solvent.
26. The method according to claim 25, wherein said step of vaporizing the organic monomer vaporizes the organic monomer in a specific temperature range that causes a polymerization rate of the organic monomer in said vaporization controller to be not greater than 1/100 of a supply rate of the organic monomer to said vaporization controller.
27. The method according to claim 25, wherein an inner wall of said vaporized material supply conduit connecting said vaporization controller with said reaction chamber and an inner wall of said reaction chamber are heated to be not lower than a vaporizing temperature of the organic monomer in said vaporization controller.
28. The method according to claim 26, wherein an inner wall of said vaporized material supply conduit connecting said vaporization controller with said reaction chamber and an inner wall of said reaction chamber are heated to be not lower than a vaporizing temperature of the organic monomer in said vaporization controller.
29. The method according to claim 25, further comprising the step of: collecting the organic monomer included in the carrier gas at least with a cooling trap, which is kept at a temperature of not higher than a vaporizing temperature of the organic monomer, said cooling trap being disposed before an evacuation pump for evacuating said vaporization controller, said vaporized material supply conduit, and said reaction chamber.
30. The method according to claim 26, further comprising the step of: collecting the organic monomer included in the carrier gas at least with a cooling trap, which is kept at a temperature of not higher than a vaporizing temperature of the organic monomer, said cooling trap being disposed before an evacuation pump for evacuating said vaporization controller, said vaporized material supply conduit, and said reaction chamber.
31. The method according to claim 27, further comprising the step of: collecting the organic monomer included in the carrier gas at least with a cooling trap, which is kept at a temperature of not higher than a vaporizing temperature of the organic monomer, said cooling trap being disposed before an evacuation pump for evacuating said vaporization controller, said vaporized material supply conduit, and said reaction chamber.
32. The method according to claim 28, further comprising the step of: collecting the organic monomer included in the carrier gas at least with a cooling trap, which is kept at a temperature of not higher than a vaporizing temperature of the organic monomer, said cooling trap being disposed before an evacuation pump for evacuating said vaporization controller, said vaporized material supply conduit, and said reaction chamber.
33. The method according to claim 25, wherein the organic monomer comprises divinylsiloxane bis (benzocyclo) butene monomer represented by a chemical formula given below:
34. The method according to claim 26, wherein the organic monomer comprises divinylsiloxane bis (benzocyclo) butene monomer represented by a chemical formula given below:
35. The method according to claim 27, wherein the organic monomer comprises divinylsiloxane bis (benzocyclo) butene monomer represented by a chemical formula given below:
36. The method according to claim 28, wherein the organic monomer comprises divinylsiloxane bis (benzocyclo) butene monomer represented by a chemical formula given below:
37. The method according to claim 25, wherein the carrier gas of the organic monomer is an inert gas that is inert to the organic monomer.
38. The method according to claim 26, wherein the carrier gas of the organic monomer is an inert gas that is inert to the organic monomer.
39. The method according to claim 27, wherein the carrier gas of the organic monomer is an inert gas that is inert to the organic monomer.
40. The method according to claim 28, wherein the carrier gas of the organic monomer is an inert gas that is inert to the organic monomer.
41. The method according to claim 33, wherein the carrier gas of the organic monomer is an inert gas that is inert to the organic monomer.
42. The method according to claim 34, wherein the carrier gas of the organic monomer is an inert gas that is inert to the organic monomer.
43. The method according to claim 35, wherein the carrier gas of the organic monomer is an inert gas that is inert to the organic monomer.
44. The method according to claim 36, wherein the carrier gas of the organic monomer is an inert gas that is inert to the organic monomer.
45. The method according to claim 37, wherein the inert gas is gaseous helium.
46. The method according to claim 38, wherein the inert gas is gaseous helium.
47. The method according to claim 39, wherein the inert gas is gaseous helium.
48. The method according to claim 40, wherein the inert gas is gaseous helium.
49. The method according to claim 41, wherein the inert gas is gaseous helium.
50. The method according to claim 42, wherein the inert gas is gaseous helium.
51. The method according to claim 43, wherein the inert gas is gaseous helium.
52. The method according to claim 44, wherein the inert gas is gaseous helium.
53. An apparatus for forming a polymer film, substantially as herein described with reference to Figure 1 of the drawings.
54. A method of forming a polymer film, substantially has herein described with reference to the drawings other than Figure 22 thereof.
GB9921965A 1998-09-21 1999-09-16 Apparatus for forming polymer film and method of forming film with the apparatus Expired - Fee Related GB2343453B (en)

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