WO1995006900A1 - Procede et appareil de realisation de motifs - Google Patents

Procede et appareil de realisation de motifs Download PDF

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Publication number
WO1995006900A1
WO1995006900A1 PCT/JP1994/001449 JP9401449W WO9506900A1 WO 1995006900 A1 WO1995006900 A1 WO 1995006900A1 JP 9401449 W JP9401449 W JP 9401449W WO 9506900 A1 WO9506900 A1 WO 9506900A1
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WO
WIPO (PCT)
Prior art keywords
chamber
film
organic compound
forming
mask
Prior art date
Application number
PCT/JP1994/001449
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English (en)
Japanese (ja)
Inventor
Issei Takemoto
Tomoko Hiraiwa
Yoshitada Oshida
Toru Otsubo
Original Assignee
Hitachi, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi, Ltd. filed Critical Hitachi, Ltd.
Publication of WO1995006900A1 publication Critical patent/WO1995006900A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/167—Coating processes; Apparatus therefor from the gas phase, by plasma deposition

Definitions

  • the present invention relates to a pattern forming method and a pattern forming apparatus, and more particularly, to a pattern forming method and a pattern forming apparatus suitable for forming fine patterns in the field of semiconductor devices and electronics. .
  • a film to be processed is formed on the entire surface of the substrate.
  • a photo resist is coated, exposed, and developed to form a mask of the photo resist of a predetermined pattern.
  • the above-mentioned processes include various processes ranging from those performed in a vacuum such as a sputter ring to those performed in the atmosphere or a solution such as exposure and development. As a result, the number of processes increases, the complexity increases, the amount of substrate movement, and the time increases. There were many factors that hindered shortening and cleanliness.
  • the selection method of this is in the. Presence of N 0 2 gas, and through a predetermined mask to S i layer (or A 1 layer), Ri by the and this is irradiated with an excimer laser, a surface Oxidized to form a SiO 2 (A 1 O x) film with a thickness of, for example, about 2 nm, which is used as an etching mask, and the surface area that is not oxidized is dry-etched.
  • a predetermined pattern is formed by selective etching by a computer.
  • this method is limited to the case where the film to be processed is at least a metal to be photo-oxidized.
  • photo-oxidation using ⁇ O 2 ′ has a problem that it is difficult to obtain a sufficiently thick etching mask since it is a reaction on the very outermost surface with a depth of several nm.
  • a plasma polymerized film which is a photoresist formed using monoalkylsilane as a raw material
  • a plasma polymerized film is exposed to excimer laser light via a predetermined mask in the presence of O 2.
  • the exposure area S i - 0 - S i structures make patterns that have a, the error pitch in g selectivity between the unexposed portion was raw time difference, C 1 2 d
  • this method requires the use of monoalkylsilane, a compound that is difficult to handle in terms of safety (generally flammable gas in the atmosphere at room temperature), and also takes into consideration the removal of photo-resist. Did not. Disclosure of the invention
  • an object of the present invention is to solve the above-mentioned problems of the prior art, and a first object of the present invention is to perform an all-dry integrated process.
  • An object of the present invention is to provide an improved pattern forming method for forming a turn, and a second object of the present invention is to provide an apparatus for forming the pattern.
  • the first object of the present invention is to provide a first step of depositing a film to be processed on a substrate, a second step of forming a photoresist on the film to be processed, and a photo resist.
  • the sixth In the pattern forming method in which the photo-etching process including at least the above steps is an integrated process for all the drives, the second step is a non-oxidizing atmosphere under reduced pressure, and is a solid or liquid.
  • the exposure is performed by irradiating the photoresist through the mask with an electromagnetic wave having an energy sufficient to cleave the Si—Si bond of the organic compound.
  • Photo-resist having a stage for developing with the same This is achieved by a pattern forming method including a mask pattern forming step.
  • the organic compound in order to decompose the vaporized organic compound to generate Si radical, is decomposed by heating, for example, overnight or an infrared lamp, or by electromagnetic wave irradiation.
  • Decomposition power for example, UV irradiation at a wavelength of 350 nm or less, practically preferably about 190 nm
  • decomposition by low-temperature plasma irradiation preferable plasma irradiation area
  • the starting material for forming the photoresist film is An organic compound containing Si and having 2 or less H bonds to Si, for example, a cyclic dialkylsilane compound (2) represented by the following chemical structural formula (1) Any one or more of the fluorosilane compound represented by the formula (1) or the chain-like dialkylsilane compound or the polysilane compound represented by the formula (3) used.
  • R and R 2 represent organic groups selected from an alkyl group and an aryl group
  • R 3 R 4 represents a fusoleo group, an alkyl group having 0 to phenolic group, and a phenyl group.
  • Perfluorophenyl
  • R Si- (Si) n 2 -S i- R ;
  • hexamesylcyclopropyl preferably, hexamesylcyclopropyl.
  • the photoresist formed in the second step is combined with an organic compound having at least two or more Si-Si bonds in which the organic compound once decomposed is recombined.
  • the third step of exposing the photo resist and the fourth step of developing the exposed photo resist are integrated and performed in the same step.
  • the exposure is performed by applying a predetermined mask to the photo-register having the Si-Si bond.
  • This is performed by irradiating electromagnetic waves having a wavelength and energy sufficient to cleave the Si-Si bond through the turn.
  • electromagnetic waves having a wavelength of 350 nm or less in the vacuum ultraviolet region is effective, and at present, a light source up to about 19 O nm can be used as a practically preferable one. If a light source with a shorter wavelength is developed in the future, it can be naturally used as an effective light source.
  • the irradiation dose varies depending on the composition of the photoresist used (organic compound having a Si—Si bond), but practically at least 500 mJ / cm 2. Required.
  • organic compounds having Si—Si bonds in the exposed areas of the photoresist are selectively decomposed, and decomposition products containing Si are converted into gaseous substances under vacuum evacuation. , And is removed from the system, and development proceeds with exposure.
  • the carrier gas is placed in the exposure atmosphere to efficiently exhaust and remove decomposition products out of the system. It is also effective to introduce a source and perform exposure and development under a gas flow.
  • the carrier gas may be, for example, an inert gas such as Ar or N 2, and in some cases, a gas such as hydrogen, so as not to degrade the photoresist forming the mask. Use gas.
  • the sixth step of removing the turn (resist mask) is performed in the same manner as the third and fourth exposure-development steps of forming a photo resist pattern.
  • the Si-Si bond that constitutes the photoresist is formed.
  • This is a step of decomposing an organic compound having the above, and exhausting and removing the decomposition product as a gaseous substance to the outside of the system.
  • the entire surface of the substrate is formed in a gaseous phase represented by di-p-xylylene, polyamic acid, polyimide, polyurea, or the like.
  • a step of forming an organic flattening film using an organic compound having a relatively small molecular weight and having the property of being softened and deformed when heated is provided.
  • a step of forming the aforementioned photo-register may be provided.
  • a film having a sufficient etching selectivity with the film to be processed on the substrate to be processed for example, a phenolic resin, a polyimide resin, a carbon film, etc.
  • a step of forming an etching mask typified by, and a step of forming the photo-register on the etching mask.
  • a second object of the present invention is to provide at least a first chamber for forming a photoresist on a substrate and a second chamber for exposing the photoresist.
  • a turn forming apparatus including at least a third chamber for transferring a substrate, wherein each of the chambers is configured to be vacuum-sealed, and the first chamber and the second chamber are The first chamber, which is connected to the third chamber via a separately provided gate valve and forms the photoresist, has a non-oxidizing atmosphere and a solid or liquid state.
  • the second chamber which exposes the photo-registries, is at least responsible for breaking the recombination.
  • a means for irradiating the photo-register with electromagnetic waves having sufficient energy for example, an electromagnetic wave by irradiating ultraviolet rays having a wavelength of 350 nm or less in a vacuum ultraviolet region; irradiation means).
  • a vacuum ultraviolet region Decomposition means such as an electromagnetic wave irradiation means by irradiating ultraviolet rays having a wavelength of 350 nm or less and a low-temperature plasma irradiation means by microwave discharge are used.
  • the first chamber is used to form a thin film using an organic compound as a raw material, the first chamber is used not only for forming a photoresist but also for forming a photoresist.
  • An organic flattening film or an etching mask that serves as a ground film may be formed.
  • the step of vaporizing is performed at a safety level including Si, which is a raw material of a solid or liquid photo resist at room temperature. Vaporize the easy-to-handle organic compounds in a non-oxidizing atmosphere under vacuum evacuation for the dry process so that the Si 10-Si structure does not occur due to oxidation reaction and the like.
  • electromagnetic waves for example, with ultraviolet light having a wavelength of 350 nm or less
  • low-temperature plasma for example, using a part of the low-temperature plasma of Ar gas
  • the reacting further comprises cooling the Si radical under vacuum exhaust and recombining it to at least two or more Si-Si bonds. That is, a Si—Si bond film is deposited on the substrate to form a photo resist thin film.
  • the step of decomposing the organic compound under vacuum evacuation using an organic compound that is easy to handle for safety supplies the material for the thin film, and the step of reacting is the process of depositing the film.
  • a photo resist having a desired thickness can be formed on a substrate or a non-metal substrate such as a flattening film (including an etching mask such as a carbon film). It can be formed safely and easily.
  • this film formation process can form a thin film of an organic compound, not only film formation of a photo resist but also etching masks such as an organic planarization film and a carbon film. Film formation is also possible.
  • an electromagnetic wave having sufficient energy to cleave the Si—Si bond of the organic Si compound (ultraviolet light having a wavelength of 350 nm or less, for example, a wavelength of 248 nm since irradiated to preparative Les Soo DOO; irradiation) at dose 5 0 0 m J / cm 2 or more of K r F excimer laser, selectively off via the Ma scan click the desired pattern is formed
  • many Si—Si bonds are broken, and a gaseous Si laser large enough to exhaust molecules out of the system. Can be decomposed into dicals. That is, when exposure is performed under vacuum evacuation, the exposed portion is decomposed into a low-molecular gaseous substance, removed and developed (development proceeds with exposure).
  • the photo-resist generated by the exposure can be reduced. This has the effect that the decomposition products can be efficiently exhausted and removed out of the system together with the carrier gas.
  • the photoresist is selectively etched and a resist mask with a positive image pattern is obtained.
  • the etching of the film to be processed using the photo resist and the turn as a mask can be performed by a well-known dry etching method.
  • the step of removing the photoresist resist is carried out in the same manner as the step in which the exposure step and the development step are integrated.
  • the entire surface of the substrate is irradiated with electromagnetic waves, and the photo resist pattern is decomposed into gaseous Si radicals and removed by the cleavage of the Si-Si bond.
  • the reduction and simplification of the process and the reduction in the amount of substrate movement are further promoted, and it is possible to provide an integrated dry process that further shortens the pattern formation time and improves the yield.
  • a carrier gas such as an inert gas
  • the first chamber for forming a photoresist film is composed of a vaporization chamber, a decomposition chamber, and a reaction chamber, and the vaporization chamber is provided with heating means. It has gas introduction and exhaust means, and at room temperature, introduces a solid or liquid organic compound that is easy to handle for safety, including Si, which is a raw material for photo resist, at room temperature. , Drive Heating under vacuum evacuation for the process and vaporizing in a non-oxidizing atmosphere so that the Si 10-Si structure does not occur due to oxidation reaction or the like.
  • the decomposition chamber has a heating means such as a heater, an electromagnetic wave irradiation means, or a decomposition means such as a plasma irradiation means (low-temperature plasma), and is capable of forming a Si—Si bond of a vaporized organic Si compound into a vacuum. It decomposes by the above-mentioned means under exhaust gas to produce a Si radical in which the Si—Si bond is broken.
  • a heating means such as a heater, an electromagnetic wave irradiation means, or a decomposition means such as a plasma irradiation means (low-temperature plasma)
  • the reaction chamber has at least a substrate support and an exhaust means, and the Si radical generated in the decomposition chamber is cooled under vacuum evacuation, and at least two or more S i radicals are cooled. Rejoins to one Si bond. That is, a recombination film having Si-Si bonds is deposited on the surface of the substrate placed on the substrate support provided with the cooling means, and a thin film of a photoresist is formed.
  • a vaporized compound for a dry process that is safe and easy to handle is created, decomposed in the decomposition chamber to produce low molecular Si radicals, and recombined in the reaction chamber. This is collected by forming a thin film on the substrate surface.
  • a solid or liquid organic compound that is easy to handle for safety is handled outside the pattern forming device, so that there is little restriction on the installation location, and a highly safe pattern forming device that is easy to handle. realizable.
  • the vaporization chamber, decomposition chamber, reaction chamber, and each detailed process are separated and connected via a gate valve so that each chamber can be separated, so process control is easy and simple control. so, A photo resist having a desired thickness can be easily formed even on a substrate or a film other than a metal such as an organic planarization film or an etching mask.
  • the substrate forming the photoresist can be set in the reaction chamber adjacent to the transfer chamber. Therefore, the pattern can be reduced by simplifying the process and reducing the amount of substrate movement.
  • a pattern forming apparatus capable of shortening the forming time and improving the yield can be realized.
  • the second chamber is a means for irradiating electromagnetic waves (ultraviolet light having a wavelength of 350 nm or less) having a wavelength and energy sufficient to cleave the Si—Si bond of the organic Si compound.
  • This is an exposure chamber provided with an exhaust unit and an exhaust means.
  • exposure and development in forming a photo resist pattern in a conventional photo etching process, and a resist pattern are masked. Perform the entire process of removing the photoresist after it has been used as a tool.
  • the second chamber can reduce the pattern formation time and improve the yield by reducing and simplifying the process and reducing the amount of substrate movement in each process, and can improve the yield. There is no room at all, just one light source.
  • a common, compact and economical pattern forming device can be realized o
  • the second chamber is an exposure chamber for performing a process of exposing and patterning a photo resist
  • the second chamber includes an exposure optical system, and thus does not like vibration. It is desirable to provide a processing chamber, for example, an exposure chamber capable of performing precise exposure by providing an anti-vibration structure in a connection portion with a third chamber for transporting a substrate.
  • FIG. 1 is a top view showing one configuration example of the pattern forming apparatus of the present invention.
  • Fig. 2 is a cross-sectional view of the film formation chamber of the photoresist.
  • Fig. 3 is a sectional view of the exposure and development chamber.
  • FIG. 4 is a cross-sectional view showing another example of the structure of the photo resist film formation chamber.
  • FIG. 5 is a cross-sectional view showing another example of the structure of the photo-resist film forming chamber.
  • FIG. 6 is a top view showing another configuration example of the pattern forming apparatus.
  • 7A to 7E are process diagrams showing one embodiment of a butter-forming method in the same manner.
  • 8A to 8G are process diagrams showing another embodiment of the pattern forming method in the same manner.
  • 9A to 9H are process diagrams showing another embodiment of the same pattern formation method.
  • FIG. 1 An example of the configuration of a pattern forming apparatus that performs the pattern forming method according to the present invention will be described with reference to FIGS. 1, 2, and 4.
  • FIG. 1 An example of the configuration of a pattern forming apparatus that performs the pattern forming method according to the present invention will be described with reference to FIGS. 1, 2, and 4.
  • FIG. 1 An example of the configuration of a pattern forming apparatus that performs the pattern forming method according to the present invention will be described with reference to FIGS. 1, 2, and 4.
  • Fig. 1 is a top view showing the main part of the pattern forming apparatus.
  • the pattern forming apparatus has a low lock chamber 1 for taking in and out a substrate holder 10 for holding and transporting a substrate (not shown).
  • a substrate pretreatment chamber 2 for cleaning the substrate, a film formation chamber 3 for a film to be processed, a film formation chamber 4 for an etching mask, and a film formation chamber 5 for an organic planarization film.
  • a film forming chamber 6 (corresponding to a first chamber of the present invention) of a photo resist comprising three chambers, a vaporization chamber 6-1, a decomposition chamber 6-2, and a reaction chamber 6-3.
  • Room 9 (corresponding to the third room of the present invention).
  • the transfer of the photo resist to the film forming chamber 6 is performed only in the reaction chamber 6-3.
  • a low-lock chamber 1 a substrate pretreatment chamber 2, a film formation chamber 3 for a film to be processed, a film formation chamber for an etching mask 4.
  • Each of the developing chamber 7, the etching chamber 8, the transfer chamber 9 and the transfer chamber 9 is configured to be able to evacuate the chamber, and a vacuum exhaust device (not shown) for evacuating the interior of the chamber is provided in the decomposition chamber 6-.
  • a vacuum exhaust device not shown for evacuating the interior of the chamber is provided in the decomposition chamber 6-.
  • Each is provided except for 2.
  • a load lock chamber 1 a substrate pre-treatment chamber 2, a film formation chamber 3 for a film to be processed, a film formation chamber 4 for an etching mask, a film formation chamber 5 for an organic planarization film, and a photoreceptor.
  • the deposition chamber 6 reaction chamber 6-3
  • the exposure and development chamber 7, and the etching chamber 8 are arranged around the transfer chamber 9, and the gate chambers 9a, 9b, 9c , 9d, 9e, 9f, 9g, and 9h were connected to the transfer room 9 respectively.
  • the load lock chamber 1 has a gate la connected to the transfer chamber 9, a door la through which the substrate holder 10 can be moved in and out, and a reaction chamber 6-3.
  • the decomposition chamber 6-2 is connected to the decomposition chamber 6-2 via a valve 6c.
  • the vacuum in the decomposition chamber 6-2 and the reaction chamber 6-3 is maintained and the sample (photoresist membrane) is vaporized.
  • a valve 6b and a sample bottle (or sample cylinder) are placed between the decomposition chamber 6-2 and the vaporization chamber 6-1.
  • a door 6a was provided to allow access to the outside with the door.
  • the substrate pre-processing chamber 2 has a function capable of cleaning by sputtering etching. It is done by evening etching. If equipped with an ion gun, it can be used instead of a spatula etching. It can also be cleaned with on-beam etching.
  • the film forming chamber 3 for the film to be processed is a normal sputtering chamber, it may be replaced by a well-known vacuum deposition or a film forming chamber by plasma CVD. Further, the etching mask film forming chamber 4 used for forming the two-layer resist film was a film forming chamber using a notter ring or a plasma CVD.
  • a plurality of deposition chambers 4 for an organic flattening film to be formed in order to eliminate a step when a substrate has a step need to be provided depending on the film forming material.
  • two evaporation sources are used.
  • FIG. 2 is an example of a cross-sectional view showing a detailed configuration of the film forming chamber 6 of the photoresist.
  • the vaporization chamber 6-1 includes a boat 11 for holding the organic compound sample 12, a support 13 for holding the boat 11, and a heating means for vaporizing the sample 12 (in this embodiment, an infrared ray). (A lamp may be used, but an ultraviolet lamp may be used.)
  • a gas such as N 2 gas is introduced to bring the vaporization chamber to atmospheric pressure.
  • the decomposition chamber 6-2 is composed of a port 15 and an exhaust port 16, and the decomposition chamber 6-2 is a cylindrical tube (a quartz tube is used in this embodiment) suitable for uniformly transmitting heat for decomposing a vaporized sample. And a heating means (in this example, an infrared lamp is used) 18 and a decomposition chamber 6-2 to prevent the heat from deforming and deteriorating the degree of vacuum And a water cooling mechanism 19.
  • the reaction chambers 6 and 3 support the substrate holder 10 It was composed of a table 20 (with built-in temperature control means such as cooling, but not shown), a film thickness monitor 21 for measuring the film thickness, and an exhaust port 22.
  • the film forming chamber 6 of the photoresist can form a thin film using an organic compound as a raw material, a thin film of an organic compound other than the photoresist as shown in the examples described later can be formed. It can also be used for formation.
  • the support 20 is provided with a heating means so that an organic compound having a property of softening and deforming when heated can be processed in order to form an organic flattening film as shown in an example described later. Was.
  • FIG. 3 is a cross-sectional view showing the configuration of the exposure and developing chamber 7.
  • the exposure and development chamber 7 exposes a light source 27 for transmitting a KrF excimer laser, an illumination optical system 28, a photomask 29 having a predetermined pattern, and a projection optical system 30.
  • the exposure and development chamber 7 carries out a step of forming a resist pattern by exposing and developing the photoresist, and a step of removing the photoresist, which is a subsequent step. Make it possible.
  • the carrier gas inlet 33 is provided on the upstream side of the exhaust system.
  • the inert gas such as Ar gas is used.
  • the carrier gas of the type corresponding to the raw material of the photoresist thin film flows.
  • the thin film can be processed by exposure to light while the decomposition products of the photo resist decomposed by exposure are efficiently exhausted and removed to the outside by this carrier gas. As a result, it was made possible to use a less volatile raw material as a raw material for the photo resist thin film.
  • the etching chamber 8 of the film to be processed was configured to be capable of reactive ion etching using RF plasma.
  • a method of generating plasma by microwaves can be used.
  • FIG. 4 is a sectional view showing another configuration example corresponding to the film forming chamber 6 of the photoresist shown in FIG. 2 of the first embodiment.
  • the difference from FIG. 2 of Example 1 is the configuration of the vaporization chamber 6-1 of the sample 12 and the decomposition chamber 6_2.
  • the vaporization chamber 6-1 contains the sample 1 of the organic compound. 2 is composed of a sample cylinder 23 for heating the sample, heating means for vaporizing the sample (heating wires are used in this embodiment) 24 and a temperature controller (not shown).
  • a plasma irradiation means for irradiating a vaporized sample with plasma to decompose it was provided.
  • the decomposition chamber 6-2, 2-5 is a plasma generation unit (microwave power supply is used in this embodiment), and Ar gas, which is a raw material gas for generating plasma, is a gas.
  • a low-temperature plasma is generated when it is sent from the inlet 26 to the plasma generator 25 via the flow control valve 6d. Has become.
  • the organic compound gas sent from the vaporization chamber 6-1 is exposed to this plasma, it decomposes and generates Si radicals.
  • the position exposed to this plasma is set so as to be part of the low temperature plasma's afterglow, which is a condition under which organic compounds are easily decomposed and Si radicals are easily generated. ing.
  • the valve 6 e connecting the sample cylinder 23 in the vaporization chamber 6-1 with the gas supply pipe 17 a made of quartz is constituted by an electromagnetic valve, and the quartz pipe 17 in the decomposition chamber 6-2
  • the valve 6b connecting b to the gas supply pipe 17a of the vaporization chamber 6-1 is composed of a flow control valve.
  • the thin film forming chamber 6 of the photoresist can form a thin film using an organic compound as a raw material, a thin film of an organic compound other than the photoresist as described in Examples described later is used. It can also be used to form
  • FIG. 5 is a cross-sectional view showing a modification in which a decomposition unit by electromagnetic wave irradiation is provided in place of the decomposition unit by plasma irradiation in the film formation chamber 6 of the photoresist shown in FIG. It is.
  • the configuration is the same as that of Example 2, but only the configuration of decomposition chamber 6-2 is different. That is, electromagnetic waves are radiated from the light source 27 arranged outside the quartz tube 17 b of the decomposition chamber 6-2 to the vaporized organic compound in the quartz tube 17 b by the illumination optical system 28. Generate S i radicals.
  • the light source 27 emits ultraviolet light having a wavelength of 350 nm or less.
  • a mercury lamp or a KrF excimer laser used in the exposure-development chamber shown in FIG. 3 is used.
  • FIG. 6 is a top view showing another embodiment of the pattern forming apparatus.
  • the device configuration is basically the same as the configuration shown in FIG. 1 of the first embodiment. However, it differs from FIG. 1 in that the film forming chamber 4 for the etching mask and the film forming chamber 5 for the organic planarizing film are removed from FIG.
  • Other configurations and functions of the device are the same as those described with reference to FIG. 1 of the first embodiment, and a description thereof will not be repeated.
  • the film formation chamber 6 of the photoresist all of the configuration shown in FIG. 2 of the first embodiment, the configuration shown in FIG. 4 of the second embodiment, and the configuration shown in FIG. 5 of the third embodiment. Can be used.
  • Embodiment 1 Next, an embodiment in which a pattern is actually formed using the pattern forming apparatus of the present invention shown in Embodiment 1 will be described with reference to FIGS. 1 to 3 and FIGS. 7A to 7E.
  • 7A to 7E are cross-sectional views of a substrate showing the steps of pattern formation according to the present embodiment.
  • the Si substrate 35 is set in the substrate holder 110 of the pattern forming apparatus shown in FIG. 1, and is put into the load lock chamber 1 through the door 1a.
  • the chamber is evacuated to 1.3 X 10 — 3 Pa or less with a vacuum exhaust device (not shown). I care.
  • the transport chamber 9 is always evacuated I by the vacuum exhaust device (not shown), a vacuum degree of 1 3 X 1 0 - was earthenware pots by keeping the 3 following pressures.
  • the gate valve 9a is opened, the substrate holder 10 is moved to the transfer chamber 9, and the gate valve 9a is closed.
  • the substrate pretreatment chamber 2 was evacuated to a vacuum of 5 X
  • the process of forming the film to be processed 36 shown in FIG. 7A was performed as follows.
  • the film formation chamber 3 (the sputtering ring chamber in this embodiment) for the film to be processed is evacuated to a vacuum of 5 ⁇ 10 15 Pa or less, and Open the valve 9 c and transfer the substrate holder 10 to the film forming chamber 3 for the film to be processed. Close valve 9c.
  • an Ar gas of 80 sccm was flowed into the film formation chamber 3 for the film to be processed, the pressure in the chamber was adjusted to 0.5 Pa, and RF power of 500 W was applied to the film to be processed.
  • a certain Si02 film 36 was formed to a thickness of 20 O nm.
  • the chamber is evacuated to a vacuum degree of below 5 XI 0- 5 P a.
  • the gate valve 9c is opened, the substrate holder 10 is moved to the transfer chamber 9, and the gate valve 9c is closed.
  • Deposition chamber of the film to be processed 3 is a vacuum 5 X 1 0 is evacuated - 5 P a in the following contact Ku.
  • the process of forming the photoresist film 37 shown in FIG. 7B was performed as follows. As shown in FIGS. 1 and 2, the valve 6 b between the vaporization chamber 6-1 and the decomposition chamber 6-2 of the film formation chamber 6 of the photoresist is closed. Open valve 6c between decomposition chamber 6-2 and reaction chamber 6-3. The reaction chamber 6 - 3 and decomposition chamber 6 - 2 is evacuated to a vacuum degree of 5 XI 0 - to below 5 P a, open the gate Tobarubu 9 f, conveying the substrate holder 1 0 to the reaction chamber 6 one 3 , Close gate valve 9 ⁇ .
  • the door 6a is opened, and an organic compound containing Si as a raw material for forming a photoresist film is opened.
  • the door 6a to dodeca main Chirushiku Russia the Kisashira in as the sample 1 2 was filled in a sample boat 1 1 is, the door 6 a to close, evacuated to a vacuum degree of below 5 XI 0- 5 P a .
  • the internal temperature of the quartz tube 17 is adjusted to 600 ° C. using the infrared lamp 18 of the decomposition chamber 6-2.
  • open the valve 6b and heat the sample 12 with the infrared lamp 14 and keep it at 150 ° C.
  • the dodecamethylcyclohexasilane is heated to 150 ° C in the vaporization chamber 6-1 to be vaporized, and furthermore, to the temperature (at 600) inside the quartz tube 17 in the decomposition chamber 6-2.
  • the Si-Si bond is broken, and several species containing Si are generated. These species are recombined in the reaction chamber 6-3 and deposited on the substrate in the form of Si-Si bonded film.
  • a temperature control means capable of setting the substrate temperature to room temperature or lower is provided on the support 20 in the reaction chamber 6-3 (not shown in FIG. 2). Then, deposition was performed with the substrate temperature set to room temperature.
  • a photo resist 37 having a thickness of 50 nm was formed on the substrate in the reaction chamber 6-3. The thickness is controlled by closing the valve 6c when the desired thickness is obtained by the thickness monitor 21.
  • the exposure and development steps shown in FIG. 7C were performed as follows.
  • the exposure and development chamber 7 shown in FIG. 3 is evacuated to a vacuum of 5 ⁇ 1 (J— 5 Pa or less), the gate valve 9 g is opened, and the substrate holder 10 is moved to the exposure and development chamber. And the gate valve 9 g is closed, and then the wavelength of 248 nm oscillated by the KrF excimer laser of the light source 27 is used.
  • the laser beam is uniformly irradiated by the illumination optical system 28 onto the photomask 29 having a predetermined pattern (in this embodiment, a line-and-space pattern of 1 ⁇ m).
  • the pattern image of the mask 29 is formed by the projection optical system 30 on the surface of the photoresist 37 on the substrate 35 through a quartz window 31.
  • the Si-Si bond of the photo-resist molecule is cleaved, and the low-molecular-weight chemical species is converted into a gaseous substance from the exhaust port 34 to the outside. Exhausted.
  • This photo register 37 is a photo mask. Gives a positive image to the turn image. In this way, the photo mask 29 is no. The turn image was transferred to the photo register 37.
  • the etching process of the film to be processed (Sio2) 36 shown in FIG. 7D was performed as follows.
  • CH 2 F 2 gas is introduced at a flow rate of 20 sccm as an etching gas, and the degree of vacuum in the room is adjusted to 7 Pa.
  • 300 W RF Power was applied to etch the SiO 2 film 36 as the film to be processed.
  • the gate valve 9 h is opened, the substrate holder 10 is transferred to the transfer chamber 9, and the gate valve 9 h is closed.
  • the removal process of the photoresist 37 shown in FIG. 7E was performed as follows. 1, the exposure and developing chamber 7 a vacuum by evacuation 5 XI 0 shown in FIG. 3 - is under 5 P a following, open the gate Tobarubu 9 g, exposing the substrate holder 1 0 and developed Transfer to chamber 7 and close gate valve 9 g. Next, a laser beam having a wavelength of 248 nm oscillated by the KrF excimer laser of the light source 27 is irradiated with the photo-residue remaining on the substrate 35 by the illumination optical system 28. Focus on the outermost surface of step 37, and irradiate and expose the entire surface. As a result, the photo resist 37 can be disassembled, exhausted outside the room, and removed. After the removal of the photo resist 37, the gate valve 9g is opened, the substrate holder 10 is transferred to the transfer chamber 9, and the gate valve 9g is closed.
  • FIGS. 7A to 7E are cross-sectional views of a substrate showing the steps of pattern formation according to the present embodiment.
  • 7A and FIGS. 7C to 7E were performed in the same manner as in Example 4 except for the process in FIG. 7B, so that the description of these processes is omitted here. The explanation will focus on process 7B.
  • the formation process of the photo resist film 37 shown in FIG. 7B was performed as follows. Open the valve 6c between the decomposition chamber 6-2 and the reaction chamber 6-3 of the film formation chamber 6 shown in Fig.4. Evacuate the reaction chamber 6-3 and decomposition chamber 6-2 to reduce the vacuum to 5X.
  • phenylfluorosilan an organic compound containing Si, which is a raw material for forming a photo resist film, was previously charged into a sample cylinder 23, which is a vaporization chamber 6-1. Please keep it.
  • the sample cylinder 23 is separated by a vaporization chamber 6-1 and a flow control valve 6b via a solenoid valve 6e, and an electric heater 24 and a temperature controller are used to keep the temperature constant at all times. (Not shown).
  • the decomposition chamber 6-2 is evacuated, and the degree of vacuum is reduced by 5 X
  • phenylfluorosilane an organic compound containing Si as a raw material
  • the phenylfluorosilane is broken down by two Si—H bonds to form Si radicals, which are cooled and recombined in the reaction chamber 6-3.
  • Si—Si bonds are generated and deposited on the substrate 35 in a film form.
  • a photo-resist 37 having a thickness of 30 O nm can be formed on the substrate 35 in the reaction chamber 6-3.
  • the film thickness is controlled by stopping the supply of the source gas when the film thickness monitor 21 reaches a desired film thickness.
  • a 1-m line-and-space pattern of the Si02 film 36 could be formed.
  • Deposition of film to be processed 36, formation of photoresist 37, exposure, development, etching of film to be processed The process of removing the photoresist and photoresist was able to be performed consistently in a state where the air was cut off and the pressure was reduced.
  • FIGS. 1 to 3 and FIGS. 8A to 8G are process diagrams showing the steps of forming a pattern and a pattern according to the present embodiment in a cross-sectional view of the substrate, which will be sequentially described below with reference to these figures.
  • the pretreatment of the substrate 38 and the step of forming the film to be processed 39 shown in FIG. 8A were performed as follows.
  • the pretreatment of the substrate 38 was performed on the substrate 38 having a step, using the substrate pretreatment chamber 2 of the apparatus shown in FIG.
  • the film formation chamber 3 (spring ring chamber in this embodiment) of the film to be processed is evacuated to a vacuum degree of 5 XI 0 — 5 Pa or less, the gate valve 9 C is opened, and the substrate holder 1 1 Is transferred to the film forming chamber 3 for the film to be processed, and the gate valve 9c is closed.
  • 50 sccm of Ar gas is flowed into the film forming chamber 3 for the film to be processed, the pressure in the chamber is adjusted to 0.5 Pa, and a length of ⁇ is applied to the film to be processed.
  • the introduction of the Ar gas is stopped, the room is evacuated to a vacuum, and the degree of vacuum is reduced to 5 X 10 — 5 Pa or less.
  • the gate knob 9c is opened, the substrate holder 10 is moved to the transfer chamber 9, and the gate valve 9c is closed.
  • Deposition chamber 3 of the film to be processed is evacuated to 5 XI degree of vacuum 0 - 5 P a below to your Ku.
  • the step of forming the organic planarization film 40 for planarizing the substrate 38 having the step shown in FIG. 8B is performed by using the organic planarization film deposition chamber (in this embodiment, a vapor deposition apparatus) 5 shown in FIG.
  • the organic planarization film deposition chamber in this embodiment, a vapor deposition apparatus 5 shown in FIG.
  • N 2 gas was introduced into the organic flattening film deposition chamber 5
  • the vacuum was returned to the atmospheric pressure
  • the door 5 a was opened
  • the two deposition boats were opened.
  • equimolar amounts of pyromellitic dianhydride and 4,4′-diaminodiphenyl ether are provided. Close door 5a and evacuate to a vacuum of 5 X 10 — 5 Pa or less.
  • the gate valve 9 e is opened, the substrate holder 10 is transferred to the organic flattening film forming chamber 5, and the gate valve 9 e is closed.
  • pyromellitic dianhydride was heated to 100 ° C.
  • 4,4′-diammino diphenyl ether was heated to 150 ° C.
  • a polyamic acid film was deposited on the substrate.
  • the substrate was heated under vacuum evacuation, kept at 200 ° C., and changed into a polyimide to form an organic planarization film 40.
  • the process of forming the photoresist 41 shown in FIG. 8C was performed as follows. In the same manner as in Example 5, dodecamethylcyclohexasilane was used in the film formation chamber 6 of the photoresist. Photoresist 41 was formed on organic flattened film 40, which had been flattened.
  • the exposure and development steps shown in FIG. 8D were performed as follows.
  • the photo-resist 41 is obtained in the same manner as in the fifth embodiment.
  • the etching step of the organic flattening film 40 shown in FIG. 8E was performed as follows.
  • the etching chamber 8 for the film to be processed in FIG. 1 is evacuated to 5 ⁇ 10 ⁇ 5 Pa or less, the gate valve 9 h is opened, and the substrate holder 10 is moved to the etching chamber for the film to be processed. Move to 8 and close gate valve 9 h.
  • As the error pitch down Gugasu introducing 0 2 gas at a flow rate of 8 0 sccm, adjusting the vacuum degree of the chamber l OP a.
  • RF power of 300 W was applied, and the organic flattening film 40 was etched.
  • This etching treatment is based on a well-known plasma asher which removes the exposed organic planarization film 40 by burning it with oxygen plasma.
  • the etching process of the film to be processed 39 shown in FIG. 8F was performed as follows. After carrying out the error pitch ranging organic planarization layer 4 0, with preferred or same chamber (E pitch in g chamber 8), stopping the supply of 0 2 gas, and evacuated, the vacuum degree 5 x The film to be processed, for example, an A1 film 39 was etched to 10 ⁇ 5 Pa or less in the same manner as in the step of FIG. 7D of Example 5.
  • a photo resist 41 removal process shown in FIG. 8G was performed as follows. In the same manner as in the step of FIG. Photoregister 41 was removed.
  • the process can be performed by a dry integrated process throughout the entire process. .
  • FIGS. 1, 2, and 9A to 9H Another embodiment in which a pattern is actually formed by using the pattern forming apparatus of the first embodiment will be described with reference to FIGS. 1, 2, and 9A to 9H.
  • a carbon film is formed as a second resist film under the photo resist film, a two-layer resist film is formed, and the film to be processed is etched. It shows how to do this.
  • the manufacturing process is based on an integrated all-dry process as in the previous examples.
  • description will be given sequentially according to the cross-sectional process drawings shown in FIGS. 9A to 9H.
  • the pretreatment of the substrate and the process of forming the film to be processed 43 shown in FIG. 9A were performed as follows. After the pretreatment of the substrate is performed on the substrate 42 using the substrate pretreatment chamber 2 and the film formation chamber 3 of the film to be processed as shown in FIG. The film 43 was formed to a thickness of 500 nm.
  • a carbon film 44 as an etching mask was formed to a thickness of 40 O nm.
  • the introduction of the Ar gas is stopped, the room is evacuated, and the degree of vacuum is reduced to 5 X 10 — 5 Pa or less.
  • the gate knob 9 d is opened, the substrate holder 10 is moved to the transfer chamber 9, and the gate valve 9 d is closed.
  • D pitch Ngumasu deposition chamber 4 of the clause is the degree of vacuum and vacuum exhaust 5 XI 0 - 5 P a be less than or equal to your clause.
  • the process of forming the photoresist film 45 shown in FIG. 9C was performed as follows. In the same manner as in the photo resist film formation step shown in FIG. 7B of Example 5, dodecamethylcyclohexasilane was used as a raw material in the photo resist film formation chamber 6. Photoresist 45 was formed on carbon film 44 as a quality.
  • the exposure and development steps shown in FIG. 9D were performed as follows. Using the exposure and development chamber 7, a positive pattern is obtained in the same manner as in the process shown in FIG.
  • the etching step of the etching mask 44 shown in FIG. 9E was performed as follows.
  • RF power of 300 W One was applied to etch the carbon film 44.
  • the etching process of the film to be processed 43 shown in FIG. 9F was performed as follows. After performing the etching of the etching mask 44, the supply of the second gas is stopped in the same chamber (etching chamber 8), and the vacuum is exhausted. There 5 XI 0 - 5 P a to the Tsu Na et al., were subjected to image pitch in g of a 1 film 4 3 is a film to be processed similarly to FIG. 8 F process of example 7.
  • the removal process of the photoresist 45 shown in FIG. 9G was performed as follows. As in Example 5, the photo resist 45 was removed in the exposure and development chamber 7 of FIG.
  • the etching mask 44 removal step shown in FIG. 9H was performed as follows. 5 XI degree of vacuum e Tsu Chi in g chambers 8 of the film to be processed in Figure 1 0 - 5 to less than P a, open the gate Toba Lube 9 h, et pitch down of the film to be processed and the substrate holder 1 0 Move to chamber 8 and close gate valve 9 h. As a d Tsu Chi down Gugasu introducing 0 2 gas at a flow rate of 5 0 sccm, to adjust the interior of the vacuum degree to 1 0 P a. A length of 300 ⁇ and a pressure of 1 ⁇ were applied to remove the carbon film 44.
  • 35, 38, and 42 are substrates. Industrial applicability
  • the intended purpose has been achieved by the present invention. That is, the steps of forming the film to be processed, forming a photoresist, exposing, developing, etching the film to be processed, and removing the photoresist are cut off from the atmosphere, and the pressure is reduced. It was possible to perform consistently in the state that was done. This eliminates the process of exhausting vacuum from the atmospheric pressure between each process and the associated processes such as washing and drying after solution treatment, which were conventionally required, and shortens the manufacturing time. For example, productivity can be improved.

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  • Condensed Matter Physics & Semiconductors (AREA)
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Abstract

Ce procédé de réalisation totalement à sec de motifs sur toutes sortes de couches minces en réduit le nombre d'opérations et diminue les temps d'attente entre les opérations. Ce procédé apporte une amélioration de la qualité en réduisant les risques d'adhérence de poussière. L'invention concerne également un appareil permettant la réalisation totalement à sec des motifs en employant des composés ne présentant aucun risque et facile à utiliser. Une technique à sec de production de photorésist de ce procédé comprend les étapes: 1) d'évaporation sous vide d'un composé organique ne présentant aucun risque et facile à utiliser, et 2) de décomposition des composés organiques vaporisés. Pour réaliser ou éliminer un motif de photorésist, le procédé utilise une irradiation au moyen d'une onde électromagnétique véhiculant une énergie suffisante pour décomposer les composés organiques afin qu'ils se vaporisent, décomposer et éliminer les composés organiques.
PCT/JP1994/001449 1993-09-03 1994-09-02 Procede et appareil de realisation de motifs WO1995006900A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP5/219529 1993-09-03
JP21952993 1993-09-03
JP737494 1994-01-27
JP6/7374 1994-01-27

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0812477A1 (fr) * 1995-02-28 1997-12-17 Chip Express Corporation Materiau ameliore pouvant subir une ablation par un rayonnement laser
US6255718B1 (en) 1995-02-28 2001-07-03 Chip Express Corporation Laser ablateable material
US7670754B2 (en) 2003-12-03 2010-03-02 Canon Kabushiki Kaisha Exposure apparatus having a processing chamber, a vacuum chamber and first and second load lock chambers

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61230140A (ja) * 1985-04-04 1986-10-14 Mitsubishi Electric Corp 有機シリコ−ン系遠紫外線感光性レジスト
JPS63184746A (ja) * 1984-04-05 1988-07-30 アメリカ合衆国 基板表面にポジ像を形成する方法
JPH02263981A (ja) * 1989-02-15 1990-10-26 Internatl Business Mach Corp <Ibm> 被膜形成方法
JPH0463414A (ja) * 1990-07-03 1992-02-28 Canon Inc 半導体装置の製造方法および製造装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63184746A (ja) * 1984-04-05 1988-07-30 アメリカ合衆国 基板表面にポジ像を形成する方法
JPS61230140A (ja) * 1985-04-04 1986-10-14 Mitsubishi Electric Corp 有機シリコ−ン系遠紫外線感光性レジスト
JPH02263981A (ja) * 1989-02-15 1990-10-26 Internatl Business Mach Corp <Ibm> 被膜形成方法
JPH0463414A (ja) * 1990-07-03 1992-02-28 Canon Inc 半導体装置の製造方法および製造装置

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0812477A1 (fr) * 1995-02-28 1997-12-17 Chip Express Corporation Materiau ameliore pouvant subir une ablation par un rayonnement laser
EP0812477A4 (fr) * 1995-02-28 1998-10-07 Chip Express Corp Materiau ameliore pouvant subir une ablation par un rayonnement laser
US6255718B1 (en) 1995-02-28 2001-07-03 Chip Express Corporation Laser ablateable material
US7670754B2 (en) 2003-12-03 2010-03-02 Canon Kabushiki Kaisha Exposure apparatus having a processing chamber, a vacuum chamber and first and second load lock chambers

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