JP5490024B2 - Method of curing porous low dielectric constant dielectric film - Google Patents

Description

  The present invention relates to a method of processing a dielectric film. More particularly, the present invention relates to a method of treating low dielectric constant (low-k) dielectric films with electromagnetic (EM) radiation.

  As known to those skilled in the semiconductor arts, interconnect delay is a major factor in drives that limits the speed and performance improvement of integrated circuits (ICs). One way to minimize interconnect delay is to reduce the capacitance of the interconnect by using a low dielectric constant (low-k) material for the insulator for the metal wires in the IC device. Thus, recently, low-k materials have been developed to replace insulating materials with relatively high dielectric constants, such as silicon dioxide. In particular, the low-k film is used as an interlayer between metal wires and an inner layer film in a semiconductor element. In addition, in order to further reduce the dielectric constant of the insulating material, a material film having a hole, that is, a porous low-k dielectric film is formed. Such a low-k film may be formed by a spin-on dielectric film formation (SOD) method or a chemical vapor deposition method (CVD) similar to the application of a photoresist. Thus, the use of low-k materials can be readily adapted to existing semiconductor manufacturing processes.

  Low-k materials are not as strong as conventional silicon dioxide. Moreover, the mechanical strength of the low-k material is further reduced by introducing holes. Because the porous low-k membrane is easily damaged during plasma treatment, a process that improves mechanical strength may be required. It is understood that improving the material strength of the porous low-k dielectric is necessary for successful integration. In order to improve the mechanical strength, a different curing method is used to make the porous low-k membrane stronger and more suitable for integration.

  Polymer curing can be accomplished by treating thin films deposited using, for example, spin-on deposition (SOD) or vapor deposition (such as chemical vapor deposition (CVD)). A process in which crosslinking occurs in the membrane is included. During the curing process, free radical polymerization is understood to be the basic route of crosslinking. Crosslinking of polymer chains improves low-k film manufacturing strength by improving mechanical properties such as Young's modulus, film hardness, fracture toughness, and interfacial bonding.

Since there are various methods for forming a porous dielectric film having a very small dielectric constant, the purpose of post-deposition treatment (curing) may vary depending on the film. Such purposes include, for example, removal of moisture, removal of solvent, combustion removal of porogen used to form pores in the porous insulating film, improvement of the mechanical properties of such films, and the like.
US Pat. No. 5,739,915 US Patent No. 5714437

  Low dielectric constant (low-k) materials are conventionally thermally cured at a temperature range of 300 ° C. to 400 ° C. for CVD deposited films. For example, furnace curing was sufficient to produce strong and dense low-k films having a dielectric constant of less than about 2.5. However, the degree of crosslinking that can be achieved by heat treatment (or thermosetting) is no longer sufficient to produce a film with adequate strength for a strong interconnect structure.

  During thermal curing, a suitable amount of energy is supplied to the membrane, where the membrane is not damaged. However, only a small amount of free radicals can be generated within the temperature range of interest. Due to the loss of heat energy when applying heat to the substrate and the loss of heat in the surrounding environment, in practice only a small amount of heat energy can be absorbed into the curing low-k film. Thus, typical low-k film furnace curing requires high temperatures and long curing times. Even when the heat balance is high, the generation of initiator during thermosetting is insufficient, and the presence of a large amount of methyl termination in the as-deposited low-k film, It will be very difficult to achieve cross-linking.

  The present invention relates to a method of processing a dielectric film. More particularly, the present invention relates to a method for curing a low-k dielectric film.

  The invention further relates to a method of treating a low-k dielectric film with electromagnetic (EM) radiation.

  According to one embodiment of the present invention, a method for curing a low-k dielectric film having a dielectric constant on a substrate of less than about 4 is described. The method includes exposing the low-k dielectric film to infrared (IR) radiation and ultraviolet (UV) radiation.

  According to another embodiment of the present invention, a method for curing a low-k dielectric film having a dielectric constant on a substrate of less than about 4 is described. The method includes the steps of forming a low-k dielectric film on a substrate, exposing the low-k dielectric film to a first infrared (IR) radiation, and applying the low-k dielectric film to the first IR. Exposing the low-k dielectric film to second infrared (IR) radiation following exposure to the UV radiation; and exposing the low-k dielectric film to the UV radiation following the radiation exposure.

  According to another embodiment of the present invention, a method for curing a low-k dielectric film on a substrate is described. The method is a step of forming a low-k dielectric film on a substrate, wherein the low-k dielectric film includes a structure-forming material and a hole-generating material, and the low-k dielectric film is a first step. Exposing to infrared (IR) radiation for a period of time and exposing the low-k dielectric film to ultraviolet (UV) radiation for a second period during the first period. Here, the second period is a small part of the first period, and the second period starts at a first time after the start of the first period, and before the end of the first period. Finish at 2 points.

  According to another embodiment of the present invention, a method for curing a low-k dielectric film on a substrate is described. The method includes a step of forming a low-k dielectric film on a substrate, wherein the low-k dielectric film includes a structure-forming material and a hole generating material, and the hole is formed from the low-k dielectric film. Forming a porous low-k dielectric film by substantially removing the resulting material; generating a crosslinking initiator in the porous low-k dielectric film following the removal; and Cross-linking the porous low-k dielectric film following the generation of the cross-linking initiator.

  In the following description, for purposes of explanation and not limitation, specific details are set forth, such as specific configurations of processing systems and descriptions of various components, to assist in a thorough understanding of the present invention. However, it should be noted that the invention may be practiced in other embodiments that depart from these specific details.

  The present inventors have discovered that a different curing method solves some of the drawbacks of thermosetting. For example, a different curing method provides energy more efficiently than a thermal curing process. For example, high energy levels found in energetic particles or energetic photons, such as accelerated electrons, ions, or neutrons, can easily excite the electrons in the low-k film, effectively creating chemical bonds. Break and dissociate side chains. These unprecedented curing methods can promote the formation of crosslinking initiators (free radicals) and improve the energy application required for actual crosslinking. As a result, the degree of crosslinking can increase even if the heat balance decreases.

  In addition, the inventors have found that the strength of the film is an important issue for the integration of ultra-low-k (ULK) dielectric films (dielectric constants less than about 2.5), so different curing methods have been used. It was thought that the mechanical properties of such a film could be improved. For example, electron beam (EB), ultraviolet (UV) radiation, infrared (IR) radiation, and microwave (MW) radiation can be used to cure the ULK film to improve mechanical strength. On the other hand, the dielectric properties and hydrophobicity of the ULK film are not sacrificed.

  However, even though EB, UV, IR and MW curing all have their own advantages, these methods have limitations. For example, high energy curing sources such as EB and UV can provide higher energy levels that produce more free radicals than crosslinks to crosslink. This significantly improves the mechanical properties while heating the substrate in a complementary manner. On the other hand, electrons and UV photons can adversely affect the electrical and physical properties of the desired film by indiscriminately dissociating chemical bonds. Adverse effects include, for example, loss of hydrophobicity, increased residual stress in the film, destruction of the porous structure, densification of the film, and increased dielectric constant. In addition, low energy curing sources such as IR and MW curing can significantly improve heat application efficiency in most cases. However, low energy cure sources, on the other hand, have side effects such as surface densification (IR) and arcing or transistor damage (MW).

  According to one embodiment of the present invention, a method for curing a low-k dielectric film having a dielectric constant on a substrate of less than about 4 is described. The method includes exposing the low-k dielectric film to non-ionizing electromagnetic (EM) radiation. Non-ionizing EM radiation includes ultraviolet (UV) radiation and infrared (IR) radiation. The UV exposure may have multiple UV exposures. Each UV exposure may or may not have a different intensity, power, power density, or wavelength range, or a combination of two or more of the above. The IR exposure may have multiple IR exposures. Each IR exposure may or may not have a different intensity, power, power density, or wavelength range, or a combination of two or more of the above.

  During the UV exposure, the low-k dielectric film may be heated by raising the substrate temperature to a UV heat treatment temperature that ranges from about 200 ° C to about 600 ° C. Alternatively, the UV heat treatment temperature ranges from about 300 ° C to about 500 ° C. Alternatively, the UV heat treatment temperature ranges from about 350 ° C to about 450 ° C. Substrate heating may be performed by heat transfer heating, convection heating, or radiant heating, or a combination of two or more of the above.

  During the IR exposure, the low-k dielectric film may be heated by raising the substrate temperature to an IR heat treatment temperature ranging from about 200 ° C. to about 600 ° C. Alternatively, the IR heat treatment temperature ranges from about 300 ° C to about 500 ° C. Alternatively, the IR heat treatment temperature ranges from about 350 ° C to about 450 ° C. Substrate heating may be performed by heat transfer heating, convection heating, or radiant heating, or a combination of two or more of the above.

  In addition, heating may be performed before UV exposure, during UV exposure, or after UV exposure, or a combination of two or more of the above. In addition, heating may be performed before IR exposure, during IR exposure, after IR exposure, or a combination of two or more of the above. Heating may be performed by heat transfer heating, convection heating, or radiant heating, or a combination of two or more of the above.

  Furthermore, IR exposure may be performed before UV exposure, during UV exposure, after UV exposure, or at a combination of two or more of the above. In addition, UV exposure may occur before IR exposure, during IR exposure, after IR exposure, or at a combination of two or more of the above.

  Prior to UV exposure and / or IR exposure, the low-k dielectric film may be heated by raising the substrate temperature to a pre-heat treatment temperature in the range of about 200 ° C to about 600 ° C. Alternatively, the pre-heat treatment temperature is in the range of about 300 ° C. to about 500 ° C., desirably in the range of about 350 ° C. to about 450 ° C.

  Following UV exposure and / or IR exposure, the low-k dielectric film may be heated by raising the substrate temperature to a post-heat treatment temperature that ranges from about 200 ° C to about 600 ° C. Alternatively, the post heat treatment temperature is in the range of about 300 ° C to about 500 ° C, and desirably in the range of about 350 ° C to about 450 ° C.

Referring now to FIG. 1, a method for processing a dielectric film on a substrate according to another embodiment is described. The substrate to be processed may be a semiconductor, a conductor, or any other substrate on which a dielectric film is formed. The dielectric film has a dielectric constant of SiO ₂ (before and / or after drying and / or curing) —this value is about 4 (for example, the dielectric constant of thermal SiO 2 is 3.8 to 3.9) — It may have a dielectric constant of less than. In various embodiments of the invention, the dielectric film (before drying and / or curing and / or after drying and / or curing) has a dielectric constant of less than 3.0, a dielectric constant of less than 2.5, a dielectric constant of less than 2.2. Or a dielectric constant less than 1.7.

  The dielectric film may be described as a low dielectric constant (low-k) film or an ultra-low-k film. The dielectric film may include at least one of an organic material, an inorganic material, and an inorganic-organic hybrid material. In addition, the dielectric film may be porous or non-porous.

  The dielectric film may include, for example, a single-phase or two-phase porous low-k film having a structure-forming material and a pore-generating material. The structure-forming material may comprise atoms, molecules, or molecular fragments obtained from structure-forming precursors. The pore-generating material may comprise atomic, molecular, or molecular fragments obtained from pore-generating precursors. The dielectric constant of a single-phase or two-phase porous low-k film is considered to be higher before removal of the pore-generating material than after removal of the pore-generating material.

  For example, the step of forming a single-phase porous low-k film is a step of depositing structure-forming molecules, wherein the structure-forming molecules are side chains of pore-forming molecules that are weakly bound to the structure-forming molecules on the substrate surface. A step of having a group. In addition, for example, the step of forming a two-phase porous low-k film may include a step of copolymerizing structure-forming molecules and pore-generating molecules on the substrate surface.

  In addition, the dielectric film has moisture, water, solvents and / or other contaminants that make the dielectric constant before drying and / or curing higher than the dielectric constant after drying and / or curing. You can do it.

  The dielectric film may be formed by chemical vapor deposition (CVD) or spin-on dielectric (SOD). The spin-on dielectric (SOD) method is a clean track act 8SOD (spin-on dielectric), clean track act act 12SOD, and Lithius coating system (Lithius coating) commercially available from Tokyo Electron Limited (TEL). systems). The Clean Track Act 8 (200 mm), Clean Track Act 12 (300 mm), and Rissius (300 nm) coating systems provide coating, baking, and curing equipment for SOD materials. The track system may be equipped to process 100 mm, 200 mm, 300 mm, and larger size substrates. Other systems and methods for forming a dielectric film on a substrate are well known to those skilled in the art of spin-on dielectric (SOD) and vapor deposition methods.

  For example, the dielectric film may comprise an inorganic silicate base material, such as silicon oxide (or organosilicate) doped with carbon, deposited using a CVD method. Examples of such membranes include Black Diamond® CVD organosilicate glass (OSG) commercially available from Applied Materials, or commercially available from Novellus Systems. Coral (R) CVD films are included.

  In addition, for example, the porous dielectric film may comprise a single phase material. Single phase materials are, for example, silicon oxide based matrices with terminal organic side groups that produce small bubbles (pores) by showing cross-linking during the curing process. In addition, for example, the porous dielectric film may comprise a two-phase material. A two-phase material is, for example, a silicon oxide-based matrix that includes an organic material that decomposes and evaporates during the curing process.

  Alternatively, these dielectric layers may be formed from inorganic silicate-based materials, such as hydrogen silsesquioxane (HSQ) or methyl silsesquioxane (MSQ), deposited using SOD (spin-on dielectric) methods. -May have. Examples of such membranes include FOX® HSQ commercially available from Dow Corning, XLK porous HSQ commercially available from Dow Corning, and commercially available from JSR Microelectronics. JSR LKD-5109 is included.

  Alternatively, the dielectric film may comprise an organic material deposited using the SOD method. Examples of such membranes include SiLK-I, SiLK-J, SiLK-H, SiLK-D, porous SiLK-Y, and porous SiLK-, commercially available from Dow Chemical. Z semiconductor dielectric resin, and FLARE ™ and Nanoglass ™ commercially available from Honeywell.

  The method has a flow chart 500 that begins at 510 with the optional drying of the dielectric film on the substrate in the first processing system. The first processing system has a drying system. The drying system may be equipped to (partially) remove one or more contaminants in the dielectric film. Contaminants include, for example, moisture, solvents, porogens, or other contaminants that can interfere with subsequent curing processes.

  At 520, the dielectric film is exposed to UV radiation. UV exposure may be performed in the second processing system. The second processing system has a curing system. The curing system may be provided to cure the dielectric film, for example, to improve the mechanical properties of the dielectric film. Such curing is accomplished by (partially) causing cross-linking within the dielectric film. After the drying process, the substrate may be transferred from the first processing system to the second processing system in a vacuum environment to minimize contamination.

  Exposure of the dielectric film to UV radiation includes UV from one or more UV lamps, one or more UV LEDs (light emitting diodes), or one or more UV lasers, or a combination of the two or more. Exposure of the dielectric film to radiation may be included. UV radiation belongs to the wavelength range of about 100 nanometers (nm) to about 600 nm. Alternatively, the UV radiation may belong to a wavelength range of about 200 nm to about 400 nm. Alternatively, the UV radiation may belong to a wavelength range of about 150 nm to about 300 nm. Alternatively, the UV radiation may belong to a wavelength range of about 170 nm to about 240 nm. Alternatively, the UV radiation may belong to a wavelength range of about 200 nm to about 240 nm.

  During exposure of the dielectric film to UV radiation, the dielectric film may be heated by raising the substrate temperature to a UV heat treatment temperature that falls in the range of about 200 ° C to about 600 ° C. Alternatively, the UV heat treatment temperature may range from about 300 ° C to about 500 ° C. Alternatively, the UV heat treatment temperature may range from about 350 ° C to about 450 ° C. Alternatively, the dielectric film may raise the substrate temperature before exposure of the dielectric film to UV radiation, after exposure of the dielectric film to UV radiation, or both before and after the exposure. Can be heated by. The heating of the substrate may comprise heat transfer heating, convection heating, or radiant heating, or a combination of two or more.

  Optionally, during exposure of the dielectric film to UV radiation, the dielectric film may be exposed to IR radiation. Exposure of dielectric films to IR radiation can include IR from one or more IR lamps, one or more IR LEDs (light emitting diodes), one or more IR lasers, or a combination of two or more Exposure of the dielectric film to radiation may be included. IR radiation belongs to a wavelength range of about 1 μm to about 25 μm. Alternatively, the IR radiation may belong to a wavelength range of about 2 μm to about 20 μm. Alternatively, the IR radiation may belong to a wavelength range of about 8 μm to about 14 μm. Alternatively, the IR radiation may belong to a wavelength range of about 8 μm to about 12 μm. Alternatively, the IR radiation may belong to a wavelength range of about 9 μm to about 10 μm.

  At 530, the dielectric film is exposed to IR radiation. Exposure of dielectric films to IR radiation can include IR from one or more IR lamps, one or more IR LEDs (light emitting diodes), one or more IR lasers, or a combination of two or more Exposure of the dielectric film to radiation may be included. IR radiation belongs to a wavelength range of about 1 μm to about 25 μm. Alternatively, the IR radiation may belong to a wavelength range of about 2 μm to about 20 μm. Alternatively, the IR radiation may belong to a wavelength range of about 8 μm to about 14 μm. Alternatively, the IR radiation may belong to a wavelength range of about 8 μm to about 12 μm. Alternatively, the IR radiation may belong to a wavelength range of about 9 μm to about 10 μm. IR exposure may occur before UV exposure, during UV exposure, after UV exposure, or at two or more of these times.

  Further, during exposure of the dielectric film to IR radiation, the dielectric film may be heated by raising the substrate temperature to an IR heat treatment temperature belonging to the range of about 200 ° C to about 600 ° C. Alternatively, the IR heat treatment temperature may range from about 300 ° C to about 500 ° C. Alternatively, the IR heat treatment temperature can range from about 350 ° C to about 450 ° C. Alternatively, the dielectric film may raise the substrate temperature before exposure of the dielectric film to IR radiation, after exposure of the dielectric film to IR radiation, or both before and after the exposure. Can be heated by. The heating of the substrate may comprise heat transfer heating, convection heating, or radiant heating, or a combination of two or more.

  As mentioned above, during IR exposure, it is possible to heat the dielectric film via absorption of IR energy. However, the heating may further include a step of heat transfer heating by providing the substrate on the substrate holder and a step of heating the substrate holder by using a heating device. For example, the heating device may include a resistance heating element.

  The inventors have recognized that the energy supplied (hν) may vary at various stages of the curing process. The curing process has mechanisms for moisture and / or contaminant removal, pore-generating material removal, pore-generating material degradation, cross-linking initiator generation, dielectric film cross-linking, and cross-linking initiator diffusion. good. Each mechanism may be required to have different levels and ratios of energy supplied to the dielectric film.

  For example, during removal of the pore-generating material, the removal process may be facilitated by photon absorption at the IR wavelength. The inventors have discovered that IR exposure promotes removal of pore-generating material more efficiently than heating or UV exposure.

  In addition, for example, during removal of the pore-generating material, the removal process may be facilitated by decomposition of the pore-generating material. The removal process may have IR exposure that is supplemented by UV exposure. The inventors may facilitate the removal process with IR exposure by breaking the bonds between the pore-generating material (eg, pore-generating molecules and / or pore-generating molecular fragments) and the structure-forming material. For example, the removal and / or decomposition process may be facilitated by photon absorption at UV wavelengths (eg, from about 300 nm to about 450 nm).

  Further, for example, during the generation of the cross-linking initiator, the cross-linking initiator generation process may be facilitated by utilizing photons and bond decomposition within the structure-forming material induced by photons. The present inventors have discovered that the cross-linking initiator production process can be accelerated by UV exposure. For example, it is considered that an energy level having a wavelength of about 300 to 400 nm or less is required for bond decomposition.

  Further, for example, during crosslinking, the crosslinking process may be facilitated by sufficient thermal energy for bond formation and reorganization. The inventors may be facilitated by IR exposure and / or heating. For example, bond formation and reorganization may require an energy level having a wavelength of about 9 μm, corresponding to the main absorption peak of, for example, a siloxane-based organosilicate low-k material.

  The dielectric film drying process, the IR exposure of the dielectric film, and the UV exposure of the dielectric film may be performed in the same processing system or in separate processing systems. For example, a drying process may be performed in the first processing system, and IR exposure and UV exposure may be performed in the second processing system. Alternatively, for example, IR exposure of the dielectric film may be performed in a processing system that is different from the processing system in which the UV exposure was performed. The IR exposure of the dielectric film may be performed in the third processing system. At this time, the substrate may be transferred from the second processing system to the third processing system in a vacuum state in order to minimize contamination.

  In addition, following the optional drying process, UV exposure process, and IR exposure process, the dielectric film is optionally post-processed in a post-processing system equipped to modify the cured dielectric film. good. For example, the post treatment may include heating the dielectric film. Alternatively, for example, post-processing may include spin coating or vapor deposition of another film on the dielectric film to improve the bonding or hydrophobicity of subsequent films. Alternatively, for example, bonding promotion may be realized in the post-processing system by lightly colliding the dielectric film with the ions. In addition, the post-processing includes a step of performing one or more of a step of depositing another film on the dielectric film, a step of cleaning the dielectric film, and a step of exposing the dielectric film to plasma. You can do it.

  Referring now to FIG. 2, a method for processing a dielectric film on a substrate according to another embodiment is described. The method includes a flowchart 600 that begins at step 610 of forming a dielectric film, eg, a low-k dielectric film, on a substrate. Optionally, the drying process may be performed to (partially) remove one or more contaminants in the dielectric film. The contaminants include, for example, moisture, solvents, or other contaminants that can interfere with the production of high quality low-k dielectric films or the execution of subsequent processes.

  At 620, the dielectric film is exposed to the first IR radiation. Exposure of the dielectric film to the first IR radiation results in moisture, moisture, contaminants, pore-generating materials, residual pore-generating materials, pore-generating materials containing pore-generating molecules (fragments), substances that inhibit cross-linking, residual The complete removal or partial removal of the substance that suppresses crosslinking can be promoted. Dielectric film exposure suppresses all moisture, moisture, contaminants, pore-generating material, residual pore-generating material, pore-generating material including (pore fragments), cross-linking inhibiting substances, residual cross-linking For a period of time sufficient to substantially remove the material to be removed, or a mixture of two or more of these.

The exposure of the dielectric film to the first IR radiation comprises exposure of the dielectric film to multicolor IR radiation, monochromatic IR radiation, pulsed IR radiation, or continuous wave IR radiation, or a combination of two or more thereof. good. For example, exposure of the dielectric film to the first IR radiation can be IR radiation from one or more IR lamps, one or more IR LEDs (light emitting diodes), or one or more IR lasers, or a combination of the two. There may be exposure of the dielectric film to. The first IR radiation may have a power density of up to about 20 W / cm ² . For example, the first IR radiation may have a power density in the range of about 1 W / cm ² to about 20 W / cm ² . The first IR radiation may range in wavelength from about 1 μm to about 25 μm. Alternatively, the first IR radiation may range in wavelength from about 2 μm to about 20 μm. Alternatively, the first IR radiation can range in wavelength from about 8 μm to about 14 μm. Alternatively, the first IR radiation can range in wavelength from about 8 μm to about 12 μm. Alternatively, the first IR radiation may range in wavelength from about 9 μm to about 10 μm. The first IR power density and / or the first IR wavelength may change during the first IR exposure.

  Optionally, during the first IR exposure, the dielectric film may be heated by raising the substrate temperature to a first IR heat treatment temperature in the range of about 200 ° C. to about 600 ° C. Alternatively, the first IR heat treatment temperature may range from about 300 ° C to about 500 ° C. Alternatively, the first IR heat treatment temperature may range from about 350 ° C to about 450 ° C.

  At 630, the dielectric film is exposed to UV radiation following the first IR exposure. For example, exposure of the substrate to UV radiation may facilitate the generation of cross-linking initiators (or free radicals) in the dielectric film.

The exposure of the dielectric film to UV radiation may include exposure of the dielectric film to multicolor UV radiation, monochromatic UV radiation, pulsed UV radiation, or continuous wave UV radiation, or a combination of two or more thereof. . For example, exposure of a dielectric film to UV radiation can be to UV radiation from one or more UV lamps, one or more UV LEDs (light emitting diodes), or one or more UV lasers, or a combination of the two. Exposure of the dielectric film. The UV radiation may have a power density in the range of about 0.1 W / cm ² to about 2000 W / cm ² . The UV radiation can range in wavelength from about 100 nanometers (nm) to about 600 nm. Alternatively, the UV radiation can range in wavelength from about 200 nm to about 400 nm. Alternatively, the UV radiation can range in wavelength from 150 nm to about 300 nm. Alternatively, the UV radiation can range in wavelength from about 170 nm to about 240 nm. Alternatively, the UV radiation can range in wavelength from about 200 nm to about 240 nm.

  Optionally, during UV exposure, the dielectric film may be heated by raising the substrate temperature to a UV heat treatment temperature in the range of about 200 ° C to about 600 ° C. Alternatively, the UV heat treatment temperature may range from about 300 ° C to about 500 ° C. Alternatively, the UV heat treatment temperature may range from about 350 ° C to about 450 ° C.

  At 640, the dielectric film is exposed to the second IR radiation. For example, a dielectric film to the second IR radiation can promote cross-linking of the dielectric film.

The exposure of the dielectric film to the second IR radiation comprises exposure of the dielectric film to polychromatic IR radiation, monochromatic IR radiation, pulsed IR radiation, or continuous wave IR radiation, or a combination of two or more thereof. good. For example, exposure of the dielectric film to the second IR radiation can be IR radiation from one or more IR lamps, one or more IR LEDs (light emitting diodes), or one or more IR lasers, or a combination of the two. There may be exposure of the dielectric film to. The 2IR radiation may have a power density of up to about 20W / cm ^2. For example, the second IR radiation may have a power density in the range of about 1 W / cm ² to about 20 W / cm ² . The second IR radiation may range in wavelength from about 1 μm to about 25 μm. Alternatively, the second IR radiation may range in wavelength from about 2 μm to about 20 μm. Alternatively, the second IR radiation can range in wavelength from about 8 μm to about 14 μm. Alternatively, the second IR radiation can range in wavelength from about 8 μm to about 12 μm. Alternatively, the second IR radiation can range in wavelength from about 9 μm to about 10 μm. The second IR power density and / or the second IR wavelength may change during the second IR exposure.

  Optionally, during the second IR exposure, the dielectric film may be heated by raising the substrate temperature to a second IR heat treatment temperature in the range of about 200 ° C. to about 600 ° C. Alternatively, the second IR heat treatment temperature may range from about 300 ° C to about 500 ° C. Alternatively, the second IR heat treatment temperature can range from about 350 ° C to about 450 ° C.

Optionally, during at least a portion of the first IR exposure, the dielectric film may be exposed to the second UV radiation. For example, exposure of the dielectric film to the second UV radiation can aid in the removal of the various materials described above and thus promote bond breakage or decomposition in the dielectric film. The second UV radiation may have a power density in the range of about 0.1 W / cm ² to about 2000 W / cm ² . The second UV radiation can range in wavelength from about 100 nanometers (nm) to about 600 nm. Alternatively, the UV radiation can range in wavelength from about 200 nm to about 400 nm. Alternatively, the UV radiation can range in wavelength from 150 nm to about 300 nm. Alternatively, the UV radiation can range in wavelength from about 170 nm to about 240 nm. Alternatively, the UV radiation can range in wavelength from about 200 nm to about 240 nm.

Optionally, during at least part of the UV exposure, the dielectric film may be exposed to the third IR radiation. The 3IR radiation may have a power density of up to about 20W / cm ^2. For example, the third IR radiation may have a power density in the range of about 1 W / cm ² to about 20 W / cm ² . The third IR radiation can range in wavelength from about 1 μm to about 25 μm. Alternatively, the third IR radiation may range in wavelength from about 2 μm to about 20 μm. Alternatively, the third IR radiation may range in wavelength from about 8 μm to about 14 μm. Alternatively, the third IR radiation may range in wavelength from about 8 μm to about 12 μm. Alternatively, the third IR radiation may range in wavelength from about 9 μm to about 10 μm. The third IR power density and / or the third IR wavelength may change during the third IR exposure.

  Prior to UV exposure and / or IR exposure, the dielectric film may be heated by raising the substrate temperature to a pre-heat treatment temperature in the range of about 200 ° C to about 600 ° C. Alternatively, the pre-heat treatment temperature can range from about 300 ° C to about 500 ° C. Alternatively, the pre-heat treatment temperature can range from about 350 ° C to about 450 ° C.

  Following UV exposure and / or IR exposure, the dielectric film may be heated by raising the substrate temperature to a post-heat treatment temperature in the range of about 200 ° C to about 600 ° C. Alternatively, the post heat treatment temperature may range from about 300 ° C to about 500 ° C. Alternatively, the post heat treatment temperature may range from about 350 ° C to about 450 ° C.

  According to another embodiment, a method for curing a low dielectric constant (low-k) film on a substrate is described. The method includes generating a low-k dielectric film having a structure forming material and a hole generating material on a substrate. The low-k dielectric film is exposed to infrared (IR) radiation for a first period. During the first period, the low-k film is exposed to ultraviolet (UV) radiation during the second period. The second period is a part of the first period. The second period starts at a first time point at which the first period begins and ends at a second time point before the first period ends.

  Referring to FIG. 3, a method for curing a low-k dielectric film on a substrate according to another embodiment of the present invention is described. The method includes a flowchart 700 that begins at step 710 of generating a low-k dielectric film on a substrate having a structure-forming material and a pore-generating material. At 720, the pore-generating material is substantially removed from the low-k dielectric film to produce a porous low-k dielectric film. Furthermore, at 720, substances that inhibit crosslinking can be substantially removed. Substances that inhibit cross-linking include moisture, moisture, contaminants, pore-generating materials, residual pore-generating materials, pore-generating materials that contain pore-generating molecules (fragments thereof), or a mixture of two or more of these.

  In 730, following removal of the pore-generating material, a crosslinking initiator is generated in the porous low-k dielectric film. At 740, the structure-forming material of the porous low-k dielectric film is crosslinked following the generation of the crosslinking initiator.

  Further, the method is optional and may optionally include a step of breaking the bonds in the low-k dielectric film to assist in removal of the pore-generating material.

  Referring to FIG. 4, a method for curing a low-k dielectric film on a substrate according to another embodiment of the present invention is described. The method includes a flowchart 800 that begins at step 810 of forming a low-k dielectric film having a structure-forming material and a substance that inhibits crosslinking. Substances that inhibit crosslinking with the above include moisture, moisture, contaminants, pore-generating materials, residual pore-generating materials, pore-generating materials containing pore-generating molecules (fragments thereof), or a mixture of two or more of these. . For example, the substance that inhibits cross-linking may include a pore-generating material. A low-k dielectric film having a structure-forming material and a substance that suppresses crosslinking has a copolymer of structure-forming molecules and pore-generating molecules on the substrate surface. In addition, for example, the substance that suppresses cross-linking has a deposit of structure-forming molecules, and the structure-forming molecules have side-chain groups of pore-generating molecules that weakly bind to the structure-forming molecules on the substrate surface.

  At 820, the low-k dielectric film is exposed to infrared (IR) radiation. Exposure of a low-k dielectric film to IR radiation may be low-k dielectric film exposure to polychromatic IR radiation, monochromatic IR radiation, pulsed IR radiation, or continuous wave IR radiation, or a combination of two or more of these. May have exposure. For example, exposure of the low-k dielectric film to the second IR radiation may include exposure of the low-k dielectric film to IR radiation in the wavelength range of about 9 μm to about 10 μm.

  Optionally, the low-k dielectric film may be exposed to ultraviolet (UV) radiation. The exposure of the dielectric film to UV radiation may include exposure of the dielectric film to multicolor UV radiation, monochromatic UV radiation, pulsed UV radiation, or continuous wave UV radiation, or a combination of two or more thereof. . Exposure of the low-k dielectric film to UV radiation may include exposing the low-k dielectric film to UV radiation having a wavelength in the range of about 100 nanometers (nm) to about 600 nm. UV exposure may occur following IR exposure. Alternatively, UV exposure may be performed during a portion of the IR exposure or during the entire period. For example, the UV exposure performed during IR exposure may have a wavelength in the range of about 300 nm to about 450 nm.

  In 830, the amount of low-k dielectric film mechanical properties, electrical properties, optical properties, pore size, or porosity, or a combination of two or more of these, adjusts the remaining amount of substances that inhibit crosslinking. Is adjusted. The amount of material that inhibits cross-linking can affect other properties including carbon concentration, hydrophobicity, and plasma resistance.

  The mechanical property may have an elastic modulus (E) and / or hardness (H). The electrical property may have a dielectric constant (k). The optical property may have a refractive index (n).

  The step of adjusting the remaining amount of the substance that inhibits crosslinking may include the step of substantially removing the substance that inhibits crosslinking from the low-k dielectric film during IR exposure. For example, the cross-linking inhibiting material may be substantially removed prior to exposing the low-k dielectric film to ultraviolet (UV) radiation.

  Alternatively, the adjustment of the remaining amount of the substance that suppresses cross-linking may include adjustment of the IR exposure period, IR intensity of IR exposure, IR irradiation amount of IR exposure, or a combination of two or more of these.

  Alternatively, the remaining amount of the substance that inhibits crosslinking can be adjusted by adjusting the UV exposure period during IR exposure, the UV intensity of UV exposure, or the UV dose of UV exposure, or a combination of two or more of these. May have.

  The method further includes exposing the low-k dielectric film to first ultraviolet (UV) radiation following IR exposure, and exposing the low-k dielectric film to second UV radiation during IR exposure. There may be a step of performing. Here, the first UV exposure is different from the second UV exposure. Adjustment of the remaining amount of the substance that inhibits cross-linking includes adjusting the duration of the second UV exposure during IR exposure, the intensity of the second UV exposure, or the dose of the second UV exposure, or a combination of two or more of these. good. The exposure of the dielectric film to the second UV radiation may have a wavelength in the range of about 300 nm to about 450 nm.

  Optionally, the low-k dielectric film may be heated before IR exposure, during IR exposure, or after IR exposure, or at two or more of these times.

  The (multiple) IR treatment may be performed under vacuum conditions or controlled atmospheric pressure.

  According to one example, the structure-forming material comprises diethoxymethylsilane (DEMS) and the pore-generating material is terpene, norbornene, 5-dimethyl-1,4-cyclooctadiene, decahydronaphthalene, ethylbenzene, or limonene, or these It may have a mixture of two or more. For example, the pore-generating material may comprise α-terpinene (ATRP).

  According to another example of the present invention, a method for preparing a porous low-k dielectric film on a substrate is described. The method includes: forming a SiCOH-containing dielectric film on a substrate using a chemical vapor deposition (CVD) method, wherein the CVD method uses diethoxymethylsilane (DEMS) and a pore-generating material. Exposing the SiCOH-containing dielectric film to IR radiation for a first period of time that is sufficiently long to substantially remove the pore-generating material; following the IR exposure, the SiCOH-containing dielectric film Exposing the body film to UV radiation for a second period; and heating the SiCOH-containing dielectric film during part or all of the second period.

  Exposure of the SiCOH-containing dielectric film to IR radiation may include IR radiation having a wavelength in the range of about 9 μm to about 10 μm (eg, 9.4 μm). The exposure of the SiCOH-containing dielectric film to UV radiation can include UV radiation having a wavelength in the range of about 170 nm to about 240 nm (eg, 222 nm). Heating the SiCOH-containing dielectric film may include a step of heating the substrate to a temperature in the range of about 300 ° C to about 500 ° C.

  IR exposure and UV exposure may be performed in separate processing chambers. Alternatively, IR exposure and UV exposure may be performed in the same processing chamber.

  The pore-generating material may comprise terpenes, norbornene, 5-dimethyl-1,4-cyclooctadiene, decahydronaphthalene, ethylbenzene, or limonene, or a mixture of two or more thereof. For example, the pore-generating material may comprise α-terpinene (ATRP).

  Table 1 provides data for a porous low-k dielectric film intended to have a dielectric constant of about 2.2-2.5. A porous low-k dielectric film is a porous SiCOH-containing dielectric formed by a CVD method using a structure-forming material having diethoxymethylsilane (DEMS) and a hole-generating material having α-terpinene (ATRP) Has a membrane. An “untreated” SiCOH-containing dielectric film having a nominal thickness (angstrom, Å) and refractive index (n) is first exposed to IR radiation resulting in an “after IR” thickness (Å) and “after IR” Refractive index (n). The “post-IR” SiCOH-containing dielectric film is then heated at the same time as UV radiation, resulting in a “post-UV + heat” thickness (厚) and a “post-UV + heat” refractive index (n). .

さらに表1を参照すると、IR後及びUV後＋加熱後での膜厚の収縮度(%)が与えられている。それに加えてUV波長及びUV暴露時間（分、min）が与えられている。さらに結果として硬化したlow-k誘電体膜についての誘電率(k)及び弾性モジュラス(E)が与えられている。表1に示されているように、UV放射線及び加熱の前にIR放射線を利用することで、誘電率は2.3未満でかつ2.09程度になる。しかも低誘電率−つまりk=2.11−が実現可能である一方で、許容可能な機械特性−つまりE=4.44GPa−もまた実現可能である。

Further referring to Table 1, the degree of shrinkage (%) of the film thickness after IR and after UV + heating is given. In addition, UV wavelength and UV exposure time (min, min) are given. Furthermore, the dielectric constant (k) and elastic modulus (E) for the cured low-k dielectric film are given as a result. As shown in Table 1, the dielectric constant is less than 2.3 and about 2.09 by using IR radiation before UV radiation and heating. Moreover, while a low dielectric constant—that is, k = 2.11—can be achieved, acceptable mechanical properties—that is, E = 4.44 GPa—can also be achieved.

  For comparison purposes, a SiCOH-containing dielectric formed using the same CVD method was cured without exposure to IR radiation. If IR exposure is not performed, the “after UV + heat” refractive index will range from about 1.408 to about 1.434. This is a much higher value than the results given in Table 1. A high refractive index suggests that there is an excess of residual pore-generating material in the film-for example, the porous film is insufficient and / or the film is oxidized.

  According to another example of the present invention, a method for preparing a porous low-k dielectric film on a substrate is described. The method includes: forming a SiCOH-containing dielectric film on a substrate using a chemical vapor deposition (CVD) method, wherein the CVD method uses diethoxymethylsilane (DEMS) and a pore-generating material. Exposing the SiCOH-containing dielectric film to IR radiation for a first period of time that is sufficiently long to substantially remove the pore-generating material; following the IR exposure, the SiCOH-containing dielectric film Exposing the body film to UV radiation for a second period; exposing the SiCOH-containing dielectric film to the second IR radiation for a third period during the UV exposure; and following the UV exposure; Exposing the SiCOH-containing dielectric film to third IR radiation only for a fourth period.

  The method may further include a step of heating the SiCOH-containing dielectric film during a part of the second period or during the entire period of the second period. The third period may coincide with the second period.

  Exposure of the SiCOH-containing dielectric film to the first IR radiation may include IR radiation having a wavelength in the range of about 9 μm to about 10 μm (eg, 9.4 μm). The exposure of the SiCOH-containing dielectric film to UV radiation can include UV radiation having a wavelength in the range of about 170 nm to about 230 nm (eg, 222 nm). Exposure of the SiCOH-containing dielectric film to the second IR radiation may include IR radiation having a wavelength in the range of about 9 μm to about 10 μm (eg, 9.4 μm). Exposure of the SiCOH-containing dielectric film to the 31st IR radiation may include IR radiation having a wavelength in the range of about 9 μm to about 10 μm (eg, 9.4 μm). The heating of the SiCOH-containing dielectric film may include a step of heating the substrate to a temperature in the range of about 300 ° C to about 500 ° C.

  The pore-generating material may comprise terpenes, norbornene, 5-dimethyl-1,4-cyclooctadiene, decahydronaphthalene, ethylbenzene, or limonene, or a mixture of two or more thereof. For example, the pore-generating material may comprise α-terpinene (ATRP).

  Table 2 provides data for a porous low-k dielectric film intended to have a dielectric constant of about 2.2-2.25. A porous low-k dielectric film is a porous SiCOH-containing dielectric formed by a CVD process using a structure-forming material with diethoxymethylsilane (DEMS) and a hole-generating material with α-terpinene (ATRP). Has a body membrane. An “untreated” SiCOH-containing dielectric film having a nominal thickness (angstrom, Å) and refractive index (n) is cured by using two processes. Specifically, (1) conventional UV heat treatment (ie without IR exposure), and (2) untreated film is exposed to IR radiation (9.4 μm), followed by IR radiation (9.4 μm) A process that is exposed to UV radiation (222 nm) and then to IR radiation (9.4 μm).

表2は、従来のUV/熱処理についての「UV/熱処理後」の厚さ（Å）及び「UV/熱処理後」の屈折率(n)、並びに、IR+UV/IR+IRプロセスについての「IR+UV/IR+IR後」の厚さ（Å）及び「IR+UV/IR+IR後」の屈折率(n)を与えている。それに加えて、UV/熱処理後及びIR/UV/IR+UV後の膜厚の収縮度(%)も与えられている。さらに、処理の結果硬化した有孔性low-k誘電体膜の誘電率(k)、弾性モジュラス(E)(GPa)及び硬度(H)(GPa)も与えられている。表2に示されているように、UV暴露中及びUV暴露後だけではなく、UV放射線及び加熱に先立ってIR放射線を用いることで、誘電率は2.1未満となる。しかも低誘電率−つまりk=2.1−を実現することができる一方で、受容可能な機械特性−つまりE=4.71GPa及びH=0.46GPa−をも実現することができる。比較すると、IR+UV/IR+IR硬化プロセスは、膜厚の収縮度を従来よりも小さくしながら低誘電率(k=2.1)を実現する。しかも2つの硬化プロセスの機械特性（E及びH）はほぼ同一である。

Table 2 shows the “UV / post-heat” thickness (Å) and “UV / post-heat” refractive index (n) for conventional UV / heat treatment, and the IR + UV / IR + IR process “ The thickness (の) after IR + UV / IR + IR and the refractive index (n) after IR + UV / IR + IR are given. In addition, the shrinkage (%) of the film thickness after UV / heat treatment and after IR / UV / IR + UV is also given. Furthermore, the dielectric constant (k), elastic modulus (E) (GPa) and hardness (H) (GPa) of the porous low-k dielectric film cured as a result of the treatment are also given. As shown in Table 2, using IR radiation prior to UV radiation and heating, as well as during and after UV exposure, the dielectric constant is less than 2.1. Moreover, while a low dielectric constant—that is, k = 2.1—can be achieved, acceptable mechanical characteristics—that is, E = 4.71 GPa and H = 0.46 GPa—can also be achieved. In comparison, the IR + UV / IR + IR curing process achieves a low dielectric constant (k = 2.1) while reducing the shrinkage of the film thickness. Moreover, the mechanical properties (E and H) of the two curing processes are almost identical.

  As a result, porous dielectric films based on diethoxymethylsilane (DEMS) can be formed using IR exposure and UV exposure. The diethoxymethylsilane (DEMS) based porous dielectric film has a dielectric constant of about 2.1 or less, a refractive index of about 1.31 or less, an elastic modulus of about 4 GPa or more, and a hardness of about 0.45 GPa or more.

  Table 3 provides data for a porous low-k dielectric film intended to have a dielectric constant of about 2. A porous low-k dielectric film is a porous SiCOH-containing dielectric formed by a CVD process using a structure-forming material with diethoxymethylsilane (DEMS) and a hole-generating material with α-terpinene (ATRP). Has a body membrane. An untreated SiCOH-containing dielectric film having a nominal thickness (angstrom, Å) and refractive index (n) is cured by using four processes. Specifically, (1) conventional UV heat treatment (ie, no IR exposure), (2) process in which untreated film is exposed only to IR radiation, (3) untreated film is IR radiation (9.4 μm) And then a conventional UV / heat treatment process, and (4) the untreated film is exposed to IR radiation (9.4 μm) followed by IR radiation (9.4 μm) and UV radiation (222 nm) A process that is exposed and then exposed to IR radiation (9.4 μm).

表3は、各硬化プロセス後に得られた屈折率(n)、収縮度(%)、誘電率(k)、弾性モジュラス(E)(GPa)、及び硬度(H)(GPa)を与えている。表3に示されているように、（UV放射線の有無にかかわらず）IR放射線を用いることで、誘電率は（1.9より大きいのとは対照的に）1.7未満となる。IR放射線のみを用いて未処理膜を硬化させるときには、低誘電率−つまりk=1.66−を実現することができる一方で、受容可能な機械特性−つまりE=1.2GPa及びH=0.1GPa−をも実現することができる。しかしIR放射線とUV放射線を用いて未処理膜を硬化させるときには、低誘電率−つまりk=1.68−を実現することができる一方で、機械特性の改善−つまりE=2.34GPa及びH=0.28GPa−をも実現することが可能である。それに加えてIR放射線を用いた硬化プロセスは、膜厚の収縮度を従来よりも小さくしながら低誘電率(k=1.66〜1.68)を実現する。さらにIR放射線が用いられるときには、機械特性（E及びH）はUV放射線を用いることによって改善することができる。

Table 3 gives the refractive index (n), shrinkage (%), dielectric constant (k), elastic modulus (E) (GPa), and hardness (H) (GPa) obtained after each curing process. . As shown in Table 3, with IR radiation (with or without UV radiation), the dielectric constant is less than 1.7 (as opposed to greater than 1.9). When curing an untreated film using only IR radiation, a low dielectric constant--that is, k = 1.66--can be achieved, while acceptable mechanical properties--that is, E = 1.2 GPa and H = 0.1 GPa- Can also be realized. However, when curing an untreated film using IR and UV radiation, a low dielectric constant—that is, k = 1.68—can be achieved while improving mechanical properties—that is, E = 2.34 GPa and H = 0.28 GPa. -Can also be realized. In addition, the curing process using IR radiation achieves a low dielectric constant (k = 1.66 to 1.68) while reducing the shrinkage of the film thickness. In addition, when IR radiation is used, the mechanical properties (E and H) can be improved by using UV radiation.

  As a result, porous dielectric films based on diethoxymethylsilane (DEMS) can be formed using IR exposure and UV exposure. The diethoxymethylsilane (DEMS) based porous dielectric film has a dielectric constant of about 1.7 or less, a refractive index of about 1.17 or less, an elastic modulus of about 1.5 GPa or more, and a hardness of about 0.2 GPa or more.

  FIG. 5A illustrates a processing system 1 for processing a dielectric film on a substrate, according to one embodiment of the present invention. The processing system 1 includes a drying system 20 and a curing system 10 coupled to the drying system 20. For example, the drying system 20 may be provided to remove or reduce one or more contaminants in the dielectric film to a sufficient level. Contaminants include, for example, moisture, moisture, contaminants, pore-generating materials, residual pore-generating materials, side-chain groups that bind weakly with structure-forming materials, pore-generating materials that contain pore-generating molecules Material that inhibits residual crosslinking, or other contaminants that may interfere with the curing process performed within the curing system 10.

  For example, a significant reduction in a particular contaminant present in the dielectric film before and after the drying process includes a reduction of about 10% to about 100% of that particular contaminant. The level of contaminant reduction can be measured using Fourier Transform Infrared (FTIR) spectroscopy or mass spectrometry. Alternatively, for example, a significant reduction in certain contaminants present in the dielectric film may range from about 50% to about 100%. Alternatively, for example, a significant reduction in certain contaminants present in the dielectric film may range from about 80% to about 100%.

  Still referring to FIG. 5A, a curing system 10 may be provided to cure the dielectric film, eg, to improve the mechanical properties of the dielectric film. Such curing is accomplished by (partially) causing cross-linking within the dielectric film. Further, the curing system 10 may be equipped to cure the dielectric film by causing (partially) initiation of cross-linking, removal of the pore-generating material, decomposition of the pore-generating material, and the like. Curing system 10 may include one or more radiation sources. The one or more radiation sources are provided to expose the substrate having the dielectric film to a variety of wavelengths of electromagnetic (EM) radiation. For example, the one or more radiation sources may comprise an infrared (IR) radiation source and an ultraviolet (UV) radiation source. Exposing the substrate to both IR and UV radiation can occur simultaneously, sequentially, or in situations where they partially overlap each other. During sequential exposure, exposure of the substrate to UV radiation may precede, for example, exposure of the substrate to IR radiation, or vice versa. In addition, during sequential exposure, exposure of the substrate to IR radiation may occur, for example, prior to exposure of the substrate to UV radiation or after exposure of the substrate to UV radiation. However, it may be performed both before and after.

  For example, the IR radiation may have an IR radiation source in the range of about 1 μm to about 25 μm. In addition, for example, IR radiation may have an IR radiation source in the range of about 2 μm to about 20 μm, about 8 μm to about 14 μm, about 8 μm to about 12 μm, or about 9 μm to about 10 μm. In addition, for example, the UV radiation source may comprise a UV wavelength band source that generates radiation in the range of about 100 nanometers (nm) to about 600 nm. Further, for example, the UV radiation can range from about 200 nm to about 400 nm, from about 150 nm to about 300 nm, from about 170 nm to about 240 nm, or from about 200 nm to about 240 nm.

  Also, as shown in FIG. 5A, the transfer system 30 is coupled to the drying system 20 to carry the substrate in and out of the drying system 20 and the curing system 10 and to exchange the substrate in the multi-component manufacturing system 40. good. The transport system 30 maintains a vacuum state while allowing the substrate to be carried into and out of the drying system 20 and the curing system 10. The drying system 20, the curing system 10, and the transfer system 30 may include processing elements within the multi-element manufacturing system 40, for example. For example, the multi-element manufacturing system 40 enables loading and unloading of substrates with respect to the processing elements. Processing elements include devices such as etching systems, film deposition systems, coating systems, patterning systems, metrology systems, and the like. In order to isolate the processes performed in the first system and the processes performed in the second system, an isolation assembly 50 may be used to combine the systems. For example, the isolation assembly 50 may include at least one of a thermal isolation assembly for thermal isolation and a gate valve assembly for vacuum isolation. The drying system 20, the curing system 10, and the transport system 30 may be provided in any order.

  The substrate IR exposure may be performed in the drying system 20, may be performed in the curing system 10, or may be performed in another processing system (not shown).

  Alternatively, in another embodiment of the invention, FIG. 5B illustrates a processing system 100 for processing a dielectric film on a substrate. The processing system 100 includes a “cluster tool” configuration of a drying system 110 and a curing system 120. For example, the drying system 110 may be provided to remove or reduce one or more contaminants in the dielectric film to a sufficient level. Contaminants include, for example, moisture, moisture, contaminants, pore-generating materials, residual pore-generating materials, side-chain groups that bind weakly with structure-forming materials, pore-generating materials that contain pore-generating molecules Material that inhibits residual cross-linking, or other contaminants that may interfere with the curing process performed within the curing system 120.

  In addition, for example, a curing system 120 may be provided to cure the dielectric film, for example, to improve the mechanical properties of the dielectric film. Such curing is accomplished by (partially) causing cross-linking within the dielectric film. Further, the processing system 100 may further optionally include a post-processing system 140 that is equipped to modify the cured dielectric film. For example, the post treatment may include heating. For example, the post-processing system 140 may include a procedure for spin coating or vapor deposition of other films on the dielectric film to promote subsequent film bonding or to improve hydrophobicity. Alternatively, for example, bonding promotion may be achieved by lightly irradiating the dielectric film with ions in the post-processing system.

  Also shown in FIG. 5B, the transfer system 130 couples with the drying system 110 to load and unload the substrate to and from the drying system 110 and cures to load and unload the substrate to and from the curing system 120. It may be coupled to the system 120 and coupled to the post-processing system 140 for loading and unloading substrates from the post-processing system 140. The transport system 130 can carry substrates into and out of the drying system 110, the curing system 120, and optionally the post-processing system 140 while maintaining a vacuum environment.

  In addition, the transfer system 130 can exchange substrates in one or more cassettes (not shown). Although only a few processing systems are shown in FIG. 5B, other processing systems may also access the transport system 130. Examples of other processing systems include an etching system, a film forming system, a coating system, a patterning system, and a measurement system. Isolation assemblies 150 can be used to combine the systems to isolate the processes performed in the drying and curing systems. For example, the isolation assembly 150 may include at least one of a thermal isolation assembly that provides thermal isolation and a gate valve assembly that provides vacuum isolation. In addition, the transport system 130 may function as a part of the isolation assembly 150, for example.

  The substrate IR exposure may be performed in the drying system 120, may be performed in the curing system 110, or may be performed in another processing system (not shown).

  Alternatively, in another embodiment of the invention, FIG. 5C illustrates a processing system 200 for processing a dielectric film on a substrate. The processing system 200 includes a drying system 210 and a curing system 220. For example, the drying system 210 may be provided to remove or reduce one or more contaminants in the dielectric film to a sufficient level. Contaminants include, for example, moisture, moisture, contaminants, pore-generating materials, residual pore-generating materials, side-chain groups that bind weakly with structure-forming materials, pore-generating materials that contain pore-generating molecules Material that inhibits residual cross-linking, or other contaminants that may interfere with the curing process performed within the curing system 220.

  In addition, for example, a curing system 220 may be provided to cure the dielectric film, for example, to improve the mechanical properties of the dielectric film. Such curing is accomplished by (partially) causing cross-linking within the dielectric film. Further, the processing system 200 may further optionally include a post-processing system 240 that is equipped to modify the cured dielectric film. For example, the aftertreatment system may have heating. In addition, for example, the post-processing system 240 may include a procedure for spin coating or vapor deposition of other films on the dielectric film to facilitate subsequent film bonding or to improve hydrophobicity. . Alternatively, for example, bonding promotion may be achieved by lightly irradiating the dielectric film with ions in the post-processing system.

  The drying system 210, the curing system 220, and the post-processing system 240 may be arranged horizontally or arranged vertically (stacked). Also, as illustrated in FIG. 5C, the transfer system 230 is coupled to the drying system 210 for loading and unloading the substrate to and from the drying system 210 and is cured to load and unload the substrate to and from the curing system 220. Coupled to the system 220 and may be coupled to the post-processing system 240 for loading and unloading substrates to and from the post-processing system 240. The transport system 230 can carry substrates into and out of the drying system 210, the curing system 220, and optionally the post-processing system 240 while maintaining a vacuum environment.

  In addition, the transfer system 230 can exchange substrates in one or more cassettes (not shown) in FIG. 5C. Although only a few processing systems are shown, other processing systems may also access the transport system 230. Examples of other processing systems include an etching system, a film forming system, a coating system, a patterning system, and a measurement system. Isolation assemblies 250 can be used to combine the systems to isolate the processes performed in the drying and curing systems. For example, the isolation assembly 250 may include at least one of a thermal isolation assembly that provides thermal isolation and a gate valve assembly that provides vacuum isolation. In addition, for example, the transport system 230 may function as part of the isolation assembly 250.

  The substrate IR exposure may be performed in the drying system 220, may be performed in the curing system 210, or may be performed in another processing system (not shown).

  At least one of the drying system 10 and the curing system 20 of the processing system 1 illustrated in FIG. 5A has at least two transport openings through which the substrate can pass. For example, as illustrated in FIG.1A, the drying system 10 has two transfer openings, the first transfer opening allows the substrate to pass between the drying system 10 and the transfer system 30, and The second transfer opening allows the substrate to pass between the drying system 10 and the curing system 20. However, for the processing system 100 illustrated in FIG. 5B and the processing system 200 illustrated in FIG. 5C, each processing system 110, 120, 140, and 210, 220, 240 has at least one transport opening through which the substrate can pass. Have

  Referring now to FIG. 6, a drying system 300 according to another embodiment of the present invention is illustrated. The drying system 300 has a drying chamber 310. The drying chamber 310 is provided to create a clean and contaminant-free environment for drying a substrate provided on the substrate holder 320. The drying system 300 can include a heat treatment apparatus 330. The heat treatment apparatus 330 is coupled to the drying chamber 310 or the substrate holder 320 and is provided to evaporate contaminants such as moisture and residual solvent by increasing the substrate temperature. Further, the drying system 300 may include a microwave processing device 340. A microwave processing device 340 is coupled to the drying chamber 310 and is provided to locally heat the contaminants in the presence of an oscillating electric field. The drying process may utilize a heat treatment device 330 and / or a microwave processing device 340 to help dry the dielectric film on the substrate 325.

  The heat treatment apparatus 330 may include one or more conductive heating elements embedded in a substrate holder 320 that is coupled to a power source and temperature control apparatus. For example, each heating element may have a resistive heating element that couples to a power source that is equipped to supply power. Alternatively, the heat treatment device 330 may include one or more radiant heating elements coupled to a power source and a control device. For example, each radiant heating element may have a heating lamp that is coupled to a power source that is equipped to supply power. The temperature of the substrate 325 is, for example, in the range of about 20 ° C. to about 600 ° C., and desirably in the range of about 200 ° C. to about 600 ° C. For example, the temperature of the substrate 325 may range from about 300 ° C. to about 500 ° C. or from about 350 ° C. to about 450 ° C.

  The microwave processing source 340 may comprise a variable microwave source equipped to sweep the microwave frequency over a frequency band. Charge accumulation is prevented by changing the frequency. Therefore, it is possible to apply a microwave drying method that does not cause damage to sensitive electronic elements due to such frequency changes.

  In one example, the drying system 300 may include a drying system that incorporates both a variable frequency microwave device and a heat treatment device. Such a drying system is, for example, a microwave furnace sold by Lambda Technologies.

  The substrate holder 320 may be provided to fix the substrate 325 or may not be provided to fix. For example, the substrate holder 320 may be provided to fix the substrate 325 mechanically or electrically.

  Further, the drying system 300 may include an IR radiation source that exposes the substrate 325 to IR radiation.

  Referring again to FIG. 6, the drying system 300 may further include a gas injection system 350. The gas injection system 350 is coupled to the drying chamber 310 and is equipped to introduce a purge gas into the drying chamber 310. The purge gas may comprise a noble gas or an inert gas such as nitrogen, for example. In addition, the drying system 300 can include an evacuation system 355. An evacuation system 355 is provided to couple to the evacuation chamber 310 and evacuate the drying chamber 310. During the drying process, the substrate 325 may be affected by an inert gas environment regardless of vacuum conditions.

  Further, the drying system 300 may include a control device 360, a substrate holder 320, a heat treatment device 330, a microwave processing device 340, a gas injection system 350, and a vacuum exhaust system 355 coupled to the drying chamber 310. The control device 360 has a microprocessor, a memory, and a digital I / O port. The digital I / O port can not only monitor the output from the drying system 300, but can also generate a control voltage sufficient to interact with the drying system 300 and provide input to the drying system 300. The program stored in the memory is used to interact with the drying system 300 according to the stored process recipe. The controller 360 may be used to configure any number of processing components (310, 320, 330, 340, 350 or 355). Controller 360 may collect, provide, process, store, and display data from processing components. Controller 360 may include a number of applications that control one or more processing components. For example, the controller 360 may include a graphical user interface (GUI) component (not shown). The GUI component can provide an interface that allows a user to monitor and / or control one or more processing components.

  Referring now to FIG. 7, a curing system 400 according to another embodiment of the present invention is illustrated. Curing system 400 has a curing chamber 410. The curing chamber 410 is provided to create a clean and contaminant-free environment for curing the substrate provided on the substrate holder 420. Curing system 400 may have more than one radiation source. The two or more radiation sources are provided to expose the substrate 425 having a dielectric film to a variety of wavelengths of electromagnetic (EM) radiation. The two or more radiation sources may include an infrared (IR) radiation source 440 and an ultraviolet (UV) radiation source 445. Exposing the substrate to both IR and UV radiation can occur simultaneously, sequentially, or in situations where they partially overlap each other.

The IR radiation source 440 may include a broadband (eg, multicolor) IR source or a narrowband (eg, monochromatic) IR source. The IR radiation source 440 may comprise one or more IR lamps, or one or more IR lasers (continuous wave (CW), tunable or pulsed), or combinations thereof. The range of IR power density can be up to about 20 W / cm ² . The range of IR power density can be from about 1 W / cm ² to about 20 W / cm ² . The range of wavelengths of IR radiation can be from about 1 μm to about 25 μm. Alternatively, the IR radiation wavelength range may be from about 8 μm to about 14 μm. Alternatively, the IR radiation wavelength range may be from about 8 μm to about 12 μm. Alternatively, the IR radiation wavelength range may be from about 9 μm to about 10 μm. For example, the IR radiation source 440 may include a CO ₂ laser system. In addition, for example, IR radiation source 440 may include an IR element having a spectral output in the range of about 1 μm to about 25 μm, such as a ceramic element or a silicon carbide element. Alternatively, the IR radiation source 440 may comprise a semiconductor laser (diode), an ion laser, a Ti: sapphire laser, or a dye laser with optical parametric amplification.

The UV radiation source 445 may include a broadband (eg, multicolor) UV source or a narrowband (eg, monochromatic) UV source. The UV radiation source 445 may comprise one or more UV lamps, or one or more UV lasers (continuous wave (CW), tunable or pulsed), or combinations thereof. UV radiation can be generated, for example, by a microwave source, arc discharge, dielectric barrier discharge, or electron impact. The range of UV power density can be from about 0.1 mW / cm ² to about 2000 W / cm ² . The range of UV wavelengths can be from about 100 nanometers (nm) to about 600 nm. Alternatively, the UV wavelength range may be from about 200 nm to about 400 nm. Alternatively, the UV wavelength range may be from about 150 nm to about 300 nm. Alternatively, the UV wavelength range may be from about 170 nm to about 240 nm. Alternatively, the UV wavelength range may be from about 200 nm to about 240 nm. For example, the UV radiation source 445 may comprise a direct current (DC) or pulsed lamp having a spectral output in the range of about 180 nm to about 500 nm, such as a deuterium (D ₂ ) lamp. Alternatively, the UV radiation source 445 may comprise a semiconductor laser (diode), a (nitrogen) gas laser, a triple frequency Nd: YAG laser, or a Cu vapor laser.

  The IR radiation source 440 and / or the UV radiation source 445 may include an optical element for adjusting one or more characteristics of the output radiation. For example, each radiation source may further include an optical fiber, an optical lens, a beam expander, a beam collimator, and the like. Such optical manipulations known to those skilled in the art of optical and EM wave propagation are suitable for the present invention.

  The substrate holder 420 may further include a temperature control system that is equipped to increase and / or control the temperature of the substrate 425. The temperature control system may be part of the heat treatment apparatus 430. The substrate holder 420 may have one or more conductive heating elements coupled with a power source and temperature control device and embedded therein. For example, each heating element may have a resistive heating element that couples to a power source that is equipped to supply power. The substrate holder 420 is optional and may include one or more radiant heating elements. The temperature of the substrate 425 is, for example, in the range of about 20 ° C. to about 600 ° C., and desirably in the range of about 200 ° C. to about 600 ° C. For example, the temperature of the substrate 425 may range from about 300 ° C. to about 500 ° C. or from about 350 ° C. to about 450 ° C.

  In addition, the substrate holder 420 may be provided to fix the substrate 425 or may not be provided to fix. For example, the substrate holder 420 may be provided to mechanically or electrically secure the substrate 425.

Referring again to FIG. 7, the curing system 400 may further include a gas injection system 450. A gas injection system 450 is provided to couple with the cure chamber 410 and introduce purge gas into the cure chamber 410. The purge gas may comprise a noble gas or an inert gas such as nitrogen, for example. Or purge gas instead, for example _{H 2, NH 3, C x} H y or may contain other gases such as a mixed gas thereof. In addition, the curing system 400 can include an evacuation system 455. An evacuation system 455 is provided to couple to and evacuate the curing chamber 410. During the drying process, the substrate 425 may be affected by an inert gas environment regardless of vacuum conditions.

  Further, the curing system 400 may include a controller 460 coupled to the curing chamber 410, a substrate holder 420, a heat treatment device 430, an IR radiation source 440, a UV radiation source 445, a gas injection system 450, and an evacuation system 455. The control device 460 includes a microprocessor, a memory, and a digital I / O port. The digital I / O port can generate sufficient control voltage to not only monitor the output from the curing system 400, but also to interact with and provide input to the curing system 400. The program stored in the memory is used to interact with the drying system 300 according to the stored process recipe. The controller 360 may be used to configure any number of processing components (410, 420, 430, 440, 450 or 455). Controller 460 may collect, provide, process, store, and display data from processing components. The controller 460 may include a number of applications that control one or more processing components. For example, the controller 460 may include graphic user interface (GUI) components (not shown). The GUI component can provide an interface that allows a user to monitor and / or control one or more processing components.

  Controllers 360 and 460 may be implemented with DELL PRECISION WORKSTATION 610 ™ sold by Dell Corporation. Controllers 360 and 460 may also be implemented with general purpose computers, processors, digital signal processors, and the like. The control device is responsive to the control devices 360 and 460 for executing one or more sequences relating to one or more instructions stored in the control device from a computer readable medium in the substrate processing apparatus. A part or all of the processing steps are performed. A computer readable medium or memory retains instructions programmed in accordance with the teachings of the present invention and has the data structures, tables, records, or other data described herein. Examples of computer readable media include compact discs (eg CD-ROM) or other optical media, hard disks, floppy disks, tapes, magneto-optical disks, PROMs (EPROM, EEPROM, flash EPROM), DRAM, There are SRAM, SDRAM or other magnetic media, punch cards, paper tape or other physical media with a pattern of holes, or other media that can be read by a carrier wave (described below) or by a computer.

  The controllers 360 and 460 may be installed locally with respect to the drying system 300 and the curing system 400, or installed remotely with respect to the drying system 300 and the curing system 400 via the Internet or an intranet. May be. Thus, controllers 360 and 460 may exchange data with drying system 300 and curing system 400 using at least one of a direct connection, an intranet, the Internet, and a wireless connection. Controllers 360 and 460 may be coupled to, for example, a customer-side (ie, device manufacturer) intranet, or may be coupled to, for example, a seller-side (ie, device manufacturer) intranet. Further, another computer (that is, a control device, a server, etc.) may exchange data via at least one of a direct connection, an intranet, and the Internet by accessing the control device, for example.

  Even if only certain exemplary embodiments of the present invention are described in detail above, those skilled in the art will recognize that many modifications are possible without departing substantially from the novel teachings and advantages of the present invention. Immediately understand. Accordingly, it is understood that many such modified types are included within the technical scope of the present invention.

5 is a flowchart of a dielectric film processing method according to an embodiment of the present invention. 6 is a flowchart of a dielectric film processing method according to another embodiment of the present invention. 6 is a flowchart of a dielectric film processing method according to another embodiment of the present invention. 6 is a flowchart of a dielectric film processing method according to another embodiment of the present invention. A-C schematically represents a transport system for a drying system and a curing system according to one embodiment of the present invention. FIG. 3 is a schematic cross-sectional view of a drying system according to another embodiment of the present invention. FIG. 3 is a schematic cross-sectional view of a curing system according to another embodiment of the present invention.

Claims (44)

A method for curing a low-k dielectric film having a dielectric constant on a substrate of less than 4 comprising:
Forming a low-k dielectric film having a structure-forming material and a pore-generating material on a substrate;
Prior to exposing the low-k dielectric film to ultraviolet (UV) radiation, affecting the formation of a porous low-k dielectric film by removal of the pore-generating material from the low-k dielectric film. And exposing the low-k dielectric film to a first infrared (IR) radiation comprising a monochromatic electromagnetic wave (EM) having a narrow wavelength band selected to be in a wavelength range of 8 μm to 12 μm;
Exposing the low-k dielectric film to ultraviolet (UV) radiation that affects the formation of a crosslinking initiator in the porous low-k dielectric film after removal of the pore-generating material; and
Following the exposure of the low-k dielectric film to the UV radiation, a second infrared (IR) radiation that affects the crosslinking of the porous low-k dielectric film after generation of the crosslinking initiator. Exposing the low-k dielectric film to:
Having a method.   The method of claim 1, further comprising heating the low-k dielectric film during the first IR exposure by raising the substrate temperature to a first IR heat treatment temperature in a range of 200 ° C to 600 ° C. The method described. The method of claim 2, wherein the first IR heat treatment temperature is in the range of 350 ° C to 450 ° C.   The method of claim 1, further comprising heating the low-k dielectric film during the UV exposure by increasing the substrate temperature to a UV heat treatment temperature that is in the range of 200 ° C to 600 ° C. Method. The method according to claim 4, wherein the UV heat treatment temperature is in the range of 300 ° C to 500 ° C.   The method of claim 1, further comprising heating the low-k dielectric film during the second IR exposure by raising the substrate temperature to a second IR heat treatment temperature in a range of 200 ° C to 600 ° C. The method described. The method of claim 6, wherein the second IR heat treatment temperature is in the range of 350 ° C to 450 ° C.   The step of exposing the low-k dielectric film to UV radiation comprises polychromatic UV radiation, monochromatic UV radiation, pulsed UV radiation, or continuous wave UV radiation, or a combination of two or more of the low-k dielectrics. 2. The method of claim 1, comprising exposing the body membrane.   The step of exposing the low-k dielectric film to UV radiation comprises from one or more UV lamps, one or more UV LEDs, or one or more UV lasers, or a combination of the two or more. The method of claim 1, comprising exposing the low-k dielectric film to UV radiation.   The method of claim 1, wherein exposing the low-k dielectric film to UV radiation comprises exposing the low-k dielectric film to UV radiation having a wavelength in the range of 200 nm to 400 nm. .   The method of claim 1, wherein exposing the low-k dielectric film to UV radiation comprises exposing the low-k dielectric film to UV radiation having a wavelength in the range of 200 nm to 240 nm. . Wherein the said low-k dielectric film exposing to the 1IR radiation, one or more IR LED or one or more IR lasers, or IR radiation from a combination of the two or more low- The method of claim 1, comprising exposing the k dielectric film.   2. The step of exposing the low-k dielectric film to UV radiation further comprises exposing the low-k dielectric film to a third IR radiation at least at some time during the UV exposure. the method of. Exposing the of the low-k dielectric film to the 3IR radiation comprises exposing said low-k dielectric film to IR radiation having a wavelength in the range of 8Myuemu～12myuemu, according to claim 13 Method.   Subsequent to the second IR exposure, performing one or more of depositing another film on the dielectric film, cleaning the dielectric film, or exposing the dielectric film to plasma. The method of claim 1, further comprising: treating the dielectric film by:   The method of claim 1, wherein the low-k dielectric film comprises a structure-forming material and a pore-generating material. The method of claim 1, further comprising exposing the low-k dielectric film to a second UV radiation during the first IR exposure,
The method wherein the second UV exposure is different from the first UV exposure following the first IR exposure. Exposing the of the low-k dielectric film to the 2UV radiation comprises exposing said low-k dielectric film to UV radiation having a wavelength in the range of 300 nm to 450 nm, according to claim 17 Method. A method for preparing a porous low dielectric constant (low-k) film on a substrate comprising:
forming a low-k dielectric film, wherein the low-k dielectric film has a structure-forming material and a substance that suppresses crosslinking in a state of being formed on the substrate;
Exposing the low-k dielectric film to infrared (IR) radiation to remove at least a portion of the cross-linking inhibitor, wherein the exposure to IR radiation is to ultraviolet (UV) radiation And the IR radiation includes monochromatic electromagnetic (EM) radiation having a narrow wavelength band selected to be in the wavelength range of 8 μm to 12 μm, performed prior to exposure of the low-k dielectric film A process; and
By selecting one or more IR characteristics of the exposure of the low-k dielectric film to the IR radiation, the mechanical characteristics, electrical characteristics, optical characteristics, pore size, or presence of the low-k dielectric film are selected. Adjusting the remaining amount of the substance that suppresses the cross-linking remaining in the low-k dielectric film in order to adjust the porosity or the characteristics of a combination of the two or more types;
Having a method. The substance that suppresses cross-linking is moisture, moisture, contaminants, pore-generating material, residual pore-generating material, side chain groups that bind weakly to the structure-forming material, pore-generating molecules (fragments thereof), or two or more of the above 20. A method according to claim 19 , comprising a mixture of: The step of forming the low-k dielectric film having the pore-forming material having the pore-forming material and the substance for suppressing the crosslinking with the structure-forming material includes the step of forming the structure-forming molecule and the pore on the substrate surface. Having a step of copolymerizing the product molecules,
20. A method according to claim 19 . The step of forming a low-k dielectric film having a pore-generating material and a material that suppresses crosslinking with the structure-forming material deposits structure-forming molecules on the substrate surface. The structure-forming molecule has a side chain group of a pore-forming molecule that weakly binds to the structure-forming molecule,
20. A method according to claim 19 . Step of adjusting the remaining amount of the substance that inhibits crosslinking of the during the IR exposure, a step of substantially removing a substance that inhibits the cross-linking from the low-k dielectric film, according to claim 19 the method of. Said one or more IR characteristic period of the IR exposure, the IR intensity of the IR exposure, or IR irradiation amount of the IR exposure, or a step of adjusting the two or more combinations, according to claim 19 the method of. 20. The method according to claim 19 , wherein the mechanical property has an elastic modulus (E) and / or hardness (H). The method of claim 19 , wherein the electrical property has a dielectric constant (k). 20. The method of claim 19 , wherein the optical property has a refractive index (n). 20. The method of claim 19 , further comprising exposing the low-k dielectric film to ultraviolet (UV) radiation. 30. The method of claim 28 , wherein the UV exposure occurs following the IR exposure. 29. The method of claim 28 , wherein the UV exposure is performed during some or all of the IR exposure. Adjusting the remaining amount of the substance that inhibits cross-linking includes the duration of the UV exposure during the IR exposure, the UV intensity of the UV exposure, or the UV dose of the UV exposure, or the two or more 30. The method of claim 28 , comprising adjusting the combination. Exposing the low-k dielectric film to ultraviolet (UV) radiation following the IR exposure; and
Exposing the low-k dielectric film to a second IR radiation during the UV exposure;
20. The method of claim 19 , further comprising: 35. The method of claim 32 , further comprising exposing the low-k dielectric film to a third IR radiation following the UV exposure. Exposing the low-k dielectric film to first ultraviolet (UV) radiation following the IR exposure; and
Exposing the low-k dielectric film to a second UV radiation during the first UV exposure;
The method of claim 19 , further comprising:
The second UV exposure is different from the first UV exposure;
Method. The step of adjusting the remaining amount of the substance that suppresses crosslinking includes the period of the second UV exposure during the IR exposure, the UV intensity of the second UV exposure, or the UV irradiation amount of the second UV exposure, or the 2 35. The method of claim 34 , comprising adjusting one or more combinations. 20. The method of claim 19 , further comprising heating the substrate before the IR exposure, during the IR exposure, after the IR exposure, or at the two or more times. A method for preparing a porous low-k dielectric film on a substrate comprising:
Forming a SiCOH-containing dielectric film on a substrate using a chemical vapor deposition (CVD) method, wherein the CVD method uses diethoxymethylsilane (DEMS) and a pore-generating material;
Exposing the SiCOH-containing dielectric film to IR radiation for a first period that is long enough to substantially remove the pore-generating material;
Following the IR exposure, exposing the SiCOH-containing dielectric film to UV radiation for a second period; and
Heating the SiCOH-containing dielectric film during a part or all of the second period;
Having a method. 38. The method of claim 37 , wherein the pore-generating material comprises terpene, norbornene, 5-dimethyl-1,4-cyclooctadiene, decahydronaphthalene, ethylbenzene, or limonene, or a mixture of the two or more. 38. The method of claim 37 , wherein the pore-generating material comprises α-terpinene (ATRP). A method for preparing a porous low-k dielectric film on a substrate comprising:
Forming a SiCOH-containing dielectric film on a substrate using a chemical vapor deposition (CVD) method, wherein the CVD method uses diethoxymethylsilane (DEMS) and a pore-generating material;
Exposing the SiCOH-containing dielectric film to IR radiation for a first period that is long enough to substantially remove the pore-generating material;
Following the IR exposure, exposing the SiCOH-containing dielectric film to UV radiation for a second period;
Exposing the SiCOH-containing dielectric film to a second IR radiation for a third period during the UV exposure; and
Subsequent to the UV exposure, exposing the SiCOH-containing dielectric film to a third IR radiation for a fourth period;
Having a method. 41. The method according to claim 40 , further comprising heating the SiCOH-containing dielectric film during a part of the second period or during the entire period of the second period. 42. The method of claim 41 , wherein the third period coincides with the second period. 41. The method of claim 40 , wherein the pore-generating material comprises terpene, norbornene, 5-dimethyl-1,4-cyclooctadiene, decahydronaphthalene, ethylbenzene, or limonene, or a mixture of the two or more. 41. The method of claim 40 , wherein the pore-generating material comprises α-terpinene (ATRP).

Images