TW466583B - A fine pattern forming material and a process for manufacturing a semiconductor device using the same - Google Patents

Abstract

During the formation of resist pattern by exposure of light, it is limited in fineness due to the restriction imposed on the wavelength of exposing light, which is to be solved by the present invention. A thickening material crosslinked upon diffusion of an acid is covered over an underlying resist pattern capable of generating an acid. A predetermined amount of a weak acid is added or a compound capable of generating an acid upon thermal decomposition is added to the thickening material. The acid is caused to diffuse from the inside of the underlying resist pattern into the thickening material by heating to form the crosslinked layer on the boundary as a covering layer for the underlying resist pattern to widen the resist pattern. This reduces the hole size and the isolation width of the resist.

Description

d 6 6583_____ V. Description of the invention 0) [Detailed description of the invention] [Technical field to which the invention belongs] The present invention is a fine separation resistance to reduce the pattern separation size or the opening size of holes when forming a resist pattern in the semiconductor manufacturing process. Materials for agent patterns, and a method for forming an anti-money agent pattern using this material, in particular, a method for manufacturing a semiconductor device using the method for finely separating a resist, and a related semiconductor device manufactured by the method. [Known Technology] With the high integration of semiconductor devices, the wiring and separation width are required to be extremely fine during the manufacturing process. Generally, fine pattern formation is a method of forming an anti-contact agent pattern 'by photolithography, and then using the formed anti-I insect pattern as a mask' to etch various substrate films. This is very important for the formation of fine patterns by photolithography. Photolithography consists of the application of anti-contact agents, mask alignment, exposure, and development. For the miniaturization, the limitation of the exposure wavelength causes a problem of the miniaturization limit. In addition, it has been difficult to control the anti-nicking agent's button-resistance in the conventional film production process. Therefore, it is impossible to control the surface shape of the pattern sidewall surface after etching by controlling the etching resistance. As described above, in the conventional photolithography using exposure, fine patterning used in semiconductors is performed by etching in accordance with a resist pattern formed by coating, exposing, and forming a resist. The size of the pattern made by this method is mainly determined by the performance of the resist, the exposure wavelength, and the exposure lighting conditions. Therefore, it is not a way to obtain higher-grade fine patterns.

89121567.ptd Page 5 533 V. Description of the invention (2) Method ’Therefore, the initial limit for the manufacture of the residual agent is the limit for the fine pattern on the semiconductor substrate. It is heard that in order to solve the above-mentioned conventional problems, the inventor of the present invention has developed a technique disclosed in Japanese Patent Laid-Open Publication No. Hei. 73-927. Nine technologies. This technology firstly applies a few layers of resist pattern on the conventional method, and applies a complete resist, and then bridges and develops to obtain a bridged film. Since = 5 weeks, the bridge film was attached to the initial resist pattern interface, which resulted in a reduction in the pattern's resolution and the opening diameter of the holes. This makes it possible to create a fine pattern beyond the original resist pattern. Tire shuttle limit [Problems to be solved by the invention] However, in the technology announced in the earlier invention, when the process is carried out, once the acid content in the air in the clean room is high, there is a pattern defect such as dry work, mouth defects, etc. This has been confirmed. For this kind of problem, the inventors have made advances in the advance invention. The purpose is to make the clean room air stern in the process ^ $ Improve non-existence 'to prevent the occurrence of pattern defects such as bad openings. Furthermore, the opening of the divided bridge film thickness (edge adhesion amount) is not abnormal due to the local increase. The present invention provides the above-mentioned materials for forming fine patterns. The fine pattern described in item 1 of the scope of the patent application forms the following features: The remaining features include water-soluble resins or two types of water-soluble resins, or copolymers of two or more types of water-soluble resins. Masking points. 々 * 添

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〇 6583 V. Description of the invention (3) Add a certain amount of dipyridamine, as a solvent, or water and a water-soluble organic solvent. Now the acid is supplied from the aforementioned J. The connection part of the above case is: the acid of the pattern is used to form a bridging film with water or water as described in the above-mentioned plan; the non-bridged part is removed in the application of a patent ~ a mixed solvent of each agent as a developing solution. The following features: ⑽ The fine pattern forming material described in item 2 has a compound ϊ: ΐ τ ί or a mixed knife with two or more of the aforementioned water-soluble bridging agents, adding a certain amount of weak age! . ,, f I i organic solvents in the person A, ^, with water or water and water-soluble anti-figure sword map; :: agent as a solvent to dissolve; supply acid in the first ... The connecting part; the acid is used in the non-bridged part to form a bridging membrane by using this raw wooden bridge reaction; it is removed as a developing solution. Or the fine pattern forming material described in the mixed solvent item of the water-soluble organic solvent has a mixture of one or two kinds of water-soluble resins as the water-soluble bridging agent or water and water-solubility, and a predetermined amount is added. Weak acid; dissolve with a mixed solvent of water-supplying acid in the first solvent as the solvent to dissolve the 'pattern of the acid and the pattern; described in the second figure j, the soil τ is formed from the above-mentioned resist to form a bridge Membrane, two: the mixed solvent of the cross-linking agent produces a mixed solvent as a disgrace: 2 part of the water or water and water-soluble organic solvents are removed. The fine pattern-forming material tailored in the patent application item No. $ ^^ has members of 466583 V. Description of the invention (4) The following characteristics: "Appropriate use in the record of any of the patent application items 1 to 3" A weak acid of 3 or more is used as the weak acid. The micrographs described in item 5 of the scope of the patent application have the following characteristics: The war material has the records in any of the items} to 4 of the scope of the patent application: aromatic acid acids such as succinic acid and benzoic acid: : Vinegar is weak. It is the other fine feature described in item 6 of the scope of the patent application: The war material 枓 has a copolymer of one water-soluble resin or two or more of the foregoing water-soluble resins as a copolymer: thermal decomposition to generate acid The compound is dissolved by using water or a mixed solvent of water and liquid agent as a solvent, and the paper-forming acid is formed on the first organic solution. Agent pattern phase: :::: Water or a mixed solvent of water and water-soluble organic solvent ::: The second fine pattern described in item 7 of the patent scope has a mixture of: 桥 桥 bridge type-or Two or more of the aforementioned water-soluble bridging agents are water and water. 1 The main component is a compound that is added to generate thermal decomposition; it is dissolved in water or a mixed solvent of the first organic solvent and the solvent; The anti-resistant pattern is formed from the aforementioned first resist pattern

89121567.ptd Page 8 466583 V. Description of the invention (5) The acid in the proposal forms a bridging film with the front ridge. The second: the thorn = the bridging reaction occurs, and the mixed solvent is used as the liquid y or the water and the solubility. The organic solvent in the patent application ", the following characteristics: the fine pattern forming material described in the member has a water-soluble resin ~ a mixture of more than a variety of-as a water-soluble bridging agent-species or two substances, to water or water; Adding thermal decomposition to generate an acid to dissolve the compound; supplying a mixed solvent of 醆 = organic solvent as a solvent to enter the resist pattern. The acid formed on the second and the agent pattern @ 'from the aforementioned bridge reaction to form a bridge film. The mixed non-bridged part where the soluble organic solvent is generated at the contact part of the first resist pattern uses water separation or water and water in the scope of patent application; ΓΛ is removed by the developing solution. The following features: The fine pattern described in the first member The material has a compound that decomposes to generate an acid as described in any one of the items 6 to 8 of the scope of the patent application, and is used as the above-mentioned hot nitrogen salt. The application of nuclear acid that generates a counter anion is important The scope of the patent No. 10 Φ ^ 4 ^ θ & The following characteristics: The 5 already contained city ridge pattern forming material has the description in the scope of the patent application No. 9 as the use of alkanoic acid and aromatic acid Anion. Ion has the following characteristics in item 11 of the scope of patent application: r ° The already loaded Seita pattern forming material has a water-soluble polymer with an ethylene structure on the main chain and is generated under acid catalysis.

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The bridging reaction has alkoxymethylamino bridging agent two components as the main component; adding a certain amount of weak acid; dissolved in pure water or a mixed solvent of pure water and a water-soluble solvent; when the acid is supplied The micro-pattern forming material described in Item 12 of the scope of application for a bridging membrane machine has the following features on the right: ~ It has a water-soluble polymer with an ethylene structure on the main chain and an alkane that produces a bridging reaction under acid catalysis. The two components of the oxymethylamino bridging agent are composed as the main component; a compound that is thermally decomposed to generate an acid; is dissolved in pure water or a mixed solvent of pure water and a water-soluble organic solvent, and forms a bridging film when supplying acid . The fine pattern forming material described in item 13 of the scope of the patent application is: In the item 11 or 12 of the scope of the patent application, polyvinylacetal and polyvinylpyrrolidone are used as the water-soluble polymer. One, or a mixture of two or more of polyvinyl alcohol, polyaziridine, polyoxyethylene, polyvinylamine, polyacrylic acid, and polypropylene amine. The fine pattern forming material described in the scope of application patent No. 14 is: f. In the scope of the patent application scope No. Π or No. 12, as the aforementioned bridging agent, melamine inducer and urea are used alone or in combination. The inducer acts as a backbone of the oxymethylamino bridging agent. The method for manufacturing a semiconductor device described in item 15 of the scope of patent application has the following characteristics: it includes a step of supplying an acid on the first resist semiconductor substrate to form a first resist pattern; and the first resist pattern The step of forming the second layer using the fine pattern forming material described in any one of the claims 1 to 14 of the scope of patent application

89121567.ptd Page 10 466583 V. Description of Invention (7)

The first resist pattern is connected to the second non-bridged part of the first resist pattern. The second resist pattern is used as the shape of the invention. A step of forming a bridge film on the second layer and the aforementioned portion; a step of separating the aforementioned forming a second resist pattern; and a step of etching the aforementioned semiconductor substrate for the mask. FIG. 1 is a schematic diagram of a mask pattern used in the present invention to form a finely divided resist; FIG. 2 is an example of the pattern; 圊 1 (a) represents a fine hole mask pattern 1 〇 ′ ′ FIG. 1 b represents a mask pattern 2 0 0 with fine gaps; FIG. 1 (c) shows an isolated residual pattern 300. Fig. 2 is a flow chart for explaining a method for forming an anti-money agent pattern according to an embodiment of the present invention. -^ " First, "the method for forming a finely divided anti-surface pattern of this embodiment" will be described with reference to Figs. 1 and 2 and the second method of manufacturing a semiconductor device using this method, as shown in Fig. 2 (a). On the semiconductor substrate (semiconductor wafer) 3, a first resist 1 (for example, a thickness of 0, 7 to 1 μm) for applying an acid is applied. Various materials can be used for the material of the first resist 1 and the acid supply mechanism. Details will be described later. This first resist 1 ′ is applied on the semiconductor substrate 3 by a spin coater, and then pre-baking (at 70 to 110 ° (heat treatment at a temperature of 1 minute) to make the first anti-I insecticide The solvent evaporates in 1. Secondly, in order to form the first resist pattern (base resist pattern), g-line, i-line, or deep-UV, KrF excimer laser, ArF excimer laser are applied. The light source corresponding to the photosensitive wavelength of the first anti-agent 1 such as X-ray, EB (electron beam), X-rap, etc., is covered with a mask containing a pattern as shown in 圊 1.

8912) 567.ptd page 11 4 6 6583 Description of the invention (8) Screen projection exposure. After the exposure to the first anti-synthetic agent 1 is performed, p E b (heating after exposure) C is performed as needed (for example, the PEB temperature is 50 to 13 CTC). This improves the resolution of the resist 1. After that, it was developed with TMAH (tetramethylammonium hydroxide), etc. at about 0.05 to 3.0 wt. Fig. 2 (b) shows the first anti-surname agent pattern 1a (basic anti-surname agent pattern) thus formed. = After image processing, post-development baking (eg, baking temperature C ~ 120 ° C, 60 seconds) may be required as required. This heat treatment requires the first reaction or the second resist material to be considered in combination with the reaction, and it is desirable to set an appropriate temperature. As described in "t", there is a difference except that the first resist i for supplying acid is used. 'The other process is similar to the conventional resist pattern formation method-as shown in Figure 2 (c), on the semiconductor substrate 3, the bridge that causes the bridge is formed # 好 社 & & VII IA 2 : The second household 2 composed of a fine pattern-forming material that is dissolved in a resist 1 U> cereal with insoluble acid as a component. Off, the fine pattern of the material of the second layer 2 depends on the material) With the coating method of the second layer 2 of the second and second pass, both the Shanghai and the Shanghai cages are coated: there is no special restriction on the first anti-axial agent pattern 1 (... Mouth spray coating, spin coating or dipping in the second layer of material solution 466583 V. Description of the invention (9) (for example, 8 5 ° C, 60 seconds). Secondly, as shown in Figure 2 (d), On the semiconductor substrate}, a first agent is formed: FIG. 1a, and a second layer 2 is formed thereon for heat treatment. (Mixed baking, the following is MB as required. The heating temperature is, for example, 85 to 15). Diffusion of the acid from the first anti-contact agent pattern 1 a into the first layer 2 causes bridging between the second layer 2 and the first resist case 1 a. In this case , Mixing baking temperature / time such as * μ 1 5 〇C / 6 〇 ～ 120 seconds. If the most suitable conditions can be set according to the type of resist used and the thickness of the Bing layer 5, it is the best The bridging agent la of the bridging layer 4 which causes the bridging reaction due to the mixing and baking is formed in the second layer 2. This is shown in 2 (e), 'Use water or Ding etc. Pattern ^ I of the aqueous solution is not bridged, and the second layer 2 is peeled off to form a second resist red. After the above treatment, the hole diameter of the hole pattern or the separation width of the line pattern will be = ^, or isolated residue may be obtained. The resist with an enlarged pattern area ^,-The method of supplying the material and acid of the first resist 1 is described below: The first example is that the trace amount of acid remaining in the first resist can be used in the manufacturing process = clear condition 'There are cases where acid is added or not added, and residual acid is moved by means such as heating. The first example is the case where the first anti-silver agent material contains some acidic substances. In this case, there is no It is necessary to generate acid by exposure, etc., the body of the anti-antibiotic material contains acid to adjust, and the heat treatment makes the acid diffuser

4 6 6583 V. Description of invention (ίο) Bridge. In this case, as the acid, for example, a carbonic acid-based low-molecular acid is suitably used. If it can be mixed with a resist, there is no particular limitation. In the third example, the mechanism of generating acid inside by proper heating. In this case, no acid is generated during the 'exposure' and the like, and a bridge reaction can be achieved by heat treatment only. The fourth example is a case where an acid is generated by exposure instead of heat treatment. For example, in a chemically amplified resist, light and electron beams, X-rays, and the like are used to cause an acid catalyst to generate a reaction, and a generated acid catalyst is used to cause an amplification reaction. In this case, after the second resist 2 is applied and exposed, an acid can be generated in the first resist pattern. Furthermore, if an exposure method is used, an appropriate exposure mask is used to select exposure for the first pattern, and the exposed portion and the unexposed portion are distinguished to form a bridged area and a non-bridged area. f 'This selective exposure can also be performed by electron beam irradiation. The fifth example 'is that after the first resist pattern is formed, the surface is treated with an acidic solution or an acid gas, and in a later step, bridging can also be achieved by using a heat-treated diffusion acid'. If the material of the first resist 1 is a material capable of supplying an acid, both positive and negative resists are suitable. + For example, as a specific example, a positive resist composed of a linear novolac resin, Cai Nong *, and a nitrogen (hetero) benzene-based photosensitizer mixture may be mentioned. In addition, a chemically amplified resist that generates a sharp mechanism is also applicable. Next ’apply the material (fine patterning material) for the second layer 2

89121567.ptd Page 14 4 6 6583 V Description of the invention (11) Description. As the main component resin of the second layer 2 material, a mixture of two or more kinds. J meters use a bridging water solvent, or a mixture of two or more types, and j 'uses a mixture of a water-soluble bridging agent and a water-soluble bridging agent alone. This water > cereal resin and, in the present invention, it is a weak acid of this kind. An appropriate amount of weak acid is added to the eye-knife material to add an appropriate amount of surrounding atmosphere, that is, the ancient people in the clean room air to prevent x from affecting the process. Preventing the damage of acid to the second layer of materials Preventing pattern defects caused by snakes, Tian Ye / Formation of film thickness Yudang, Ahum County 17 shang ', · Anomalous pixels attached (weak bridging film =: In order to improve the environment Adaptability: From the effects of the addition, the following considerations are considered:-Generally, the acidic PH film is difficult to absorb: new adsorption, which is due to the presence of the acid added in advance, and the 'relative acid :: flowing acid concentration' film side concentration is close to equilibrium. It becomes difficult to integrate the new I. 1 π It is better to add an acid t to the second layer 2 material and use a weak acid above ρΗ3, J should be. We hope to use the weakest acid as possible. Its concentration is the same as that of the second layer 2 body. It is better not to cause bridging under Rittiwin. For example, for the second layer 2 material as a whole, a concentration of about 500 ppm is required. Therefore, the storage stability of the first layer 2 material can be ensured. ^ The specific examples of adding acid to the layer 2 material are as follows: As a good example, any one or two of the aromatic acids such as thiobenzoic acid and benzoic acid such as acid can be used. Pure ifϊ 二层 2 材 肖(Fine pattern forming material) is water (for example, or water (for example, Water) and water-soluble organic solvent as a mixed solvent

Page 15 η 4 6 6583 V. Description of the invention (12) Line: Solution: Materials. And ... give the acid formed on the first 'from the first resist pattern of the acid in the case: a bridging reaction occurs, forming a bridge agent or a mixed solvent of ^ and ^ soluble organic solvents as imaging液 脱。 Liquid removed. In addition, when the above mixture is used as the main component of the second layer 2 material: In the case, the composition of these materials is based on the application of the first resist material, and there is no other special two. OK, as a specific example of the water-soluble resin composition used on the second layer 2 material: 'as shown in Figure 3, polyacrylic acid, polypropylene ammonium, polyethylene, polyethylene, polyethylene, etc. 、 Polyaziridine 、 Polyoxyethylene J ethylene maleic acid copolymer, polyvinylamine resin, &: Dioxazoline-based water-soluble resin, water-soluble trimeramine, water-soluble, resin , Alkyd resin, sulfa resin, etc. can be effectively applied. In addition, the composition that generates a bridging reaction in the presence of acidic components, or a mixture of water-soluble bridging agents that may not produce right bridging reactions, can be used alone. Use these components in mixtures :: Yes; One or two or more of these water-soluble resins are suitable for use as a mixture. It can be appropriately adjusted according to the amount of reaction with the first resist 1 on the substrate and the reaction stripe & In addition, the use of some water-soluble resins is to increase the solubility in water, and it is also suitable to use salts such as hydrochloride. X 马 目 _Second ’As a water-soluble bridging agent that can be used in the second layer 2 material, as shown in FIG. 4 for summer ’s urea, alkoxymethyl urea, ν-alkoxy%

4 6 6583 5. Description of the invention (13) Base urea, vinyl urea, 7 aw melamine, alkoxymethene Jf, etc., stringent bridging agents, agents, phenyl uramine , Melamine, and other melamine-based bridgers, and ammonia-based bridgers do not have :::, etc. Amino-based: bridgers can be used, and sexual bridgers have no special restrictions. If the bridging water generated from the acid is dissolved in the specific water-soluble anti-surgical agent material as described in I, use one of the resins or mix A with j φ $, θ, and one of the water-soluble bridging agents described above, θ 〇. 4 intermix S as above, for example, specifically; is effective. The product is made of polyvinyl acetal * ', and the water-soluble resin group-poly-ammonia or ethanoic bridging side " oxygen base is based on high water solubility, mixed: use. In this case, from 2 farts σ, the liquid storage stability is excellent. The suitable materials for the second resist require water-soluble or materials that can be added to Kariya solution in the presence of insoluble acid components, and there is no particular limitation. The material of the 纟 成 木桥 反应, if so, is hot, solid: Exposure: 醆 is only added, as the second wood ~, the situation has been explained before attack. In this case, # 4: wood 枓 hope to choose a suitable material with good reactivity and suitable heat treatment (for example, in this case, for example, the stem of the body is two α b0 C) acetaldehyde Polyethylene condensate for the first layer and 2 materials of each individual and body, or the water-soluble material composition which mixes them at a ratio of 1 kT of the mixed effect of vinyl alcohol and ethyl urea. There is \\ 312 \ 2d * code \ 9〇.〇i \ 89121567.

Ptd Page 17 〇583 〇583

From another point of view, the description is as described in V. Description of the Invention (14) In the above description of the fine pattern forming material: That is, the fine pattern forms a suitable structure of the water-soluble resin and the acid-catalyzed methylamino group bridging agent is decomposed into two components. Acid compounds; dissolved in a pure water mixed solvent and supplied with acid; in addition, as a water-soluble local molecular alkoxymethylamino bridging agent with a thin pattern formed of a vinyl structure, a thermal decomposition compound generates an acid; It is dissolved in a mixed solvent and is supplied in this case as a mixture of hydroaldehyde, polyvinylpyrrolidone, polyethylene polyvinylamine, polyacrylic acid, and polypropylene. Examples of materials: The main chain is composed of a cross-linking reaction on the main chain, and has a main component. When tuli or pure water and a water-soluble organic solvent are used, a bridging film is formed. Examples of suitable materials for holding materials: The main component is composed of the main chain and the acid-catalyzed cross-linking reaction as the main component; Tim Li Kou 'pure water or pure water and water-soluble organic ^ When acid is given, bridging 骐 is formed. 'Polymers' use melamine derivatives, urea, polyaziridine, polyoxyethylene return, fine brewed amines, or two or more of them as bridging agents alone or in combination with melamine derivatives and urea ^ Alkoxyfluorenyl-based bridging agent of the physical skeleton. Dingsheng Secondly, plasticizers such as ethylene glycol, glycerin, and trivinyl glycerol can be added to the material of the second layer 2 as an additive. • Adding For the second layer of 2 materials, in order to improve the film-forming property, surfactants such as Florart manufactured by 3M Corporation and Nonel manufactured by Sanyo Chemical Co., Ltd. can be added as additives. The solvent for the material (fine patterning material) of the second layer 2 is described as follows

Fifth invention description (15): r η λ ^ 2 The solvent for the material should be water (for example, pure water)-¾ (for example, pure water) such as > uJ or 水 笛 一 # 水 / gluten organic solvent. Mixed solvents. The solvent used for the second material must not dissolve the first resist and the material can be fully dissolved. If it is a full pattern U ', there are no other special restrictions. 1 solvent

Pure: 々-¾: a solvent for the second layer of material. Water (suitable for water such as I, M, M, Λ, or water and N-as a mixed solvent of organic solvents. Restricted with water ... Solvent, if it is water-soluble 1 There are no other specific examples of ethanol, methanol, isopropyl — etc. can be used. If the mixture reaches 41, butadiene, acetone on 1: 2: No: solution of the first anti-axial agent pattern la,: 4 The specific embodiment of application mode 1 is described as follows. Add 20 PPM acetic acid to the second layer 2 as described above; (fine pattern forming material) when this acid is used as an additive material, when 5OPPb, the above-mentioned mou Λ, until the sulfuric acid concentration in the air is in the past two processes without adding acid materials. Adding acid materials, the opening will not occur _ Shi Ruliang occurred 2 000. And using this method can get air c Forming materials, that is, can be gray and s is a solid micro-pattern made of acid attached to the second layer 2 material body,

\\ 3l2 \ 2d-code \ 90-01 \ 89I2J567.ptd Page 19 ^ 66583 V. Description of the invention (16) --- Reduce pattern defects and abnormal opening sizes. Example 2 ': A material to which 200 PPM acetic acid was added was prepared as the second layer 2 material.

4 is a comparative article. A material B to which 1,000 ppM sulfuric acid was added was prepared as the second layer material. I Material A can maintain its performance even after 9 days. = Material B 'The liquid itself becomes white and turbid, and the resin's bridging progresses differently and becomes a material that cannot be used practically. ^ = Sample, can obtain a fine pattern that is solid with respect to the acid concentration in the air "μ material. And adding an appropriate amount of a weak acid 'makes it possible to obtain a stable resist material. That is, it can inhibit the acid from adhering to the second layer 2 material body, and can reduce pattern defects and abnormal opening sizes. Using a weak acid with a pH of 3 or more can prevent material stability from being impaired even if acid is added to the anti-agent. The second embodiment of the present invention is described below. The second embodiment is related to the second resist-forming material, and the bridge film formation flow is the same as that described in the first embodiment. In the second embodiment, the second layer 2 uses the same main component of the material (fine-circle-forming material) as that described in the first embodiment, and the main component material is added with a thermal decomposition compound that generates an acid. In other words, the "second layer 2 material added compound thermally decomposes to generate acid" to ensure storage stability at normal temperature. The purpose of adding these compounds in an appropriate amount is to prevent the atmosphere that is solid during the process, that is, the bad influence of the acid contained in the clean room on the second layer 2. To prevent possible pattern defects and abnormal edge adhesion (bridge bridging)

89121567.ptd

466583 V. Description of the invention (π) The film thickness is abnormal). That is, to improve environmental adaptability. A suitable example of such a compound that generates an acid by heat is a diazonium salt which contains an acid and generates a counter anion. Fig. 5 shows an example of a diazonium salt. Suitable examples of the counter anion of the heat-generating acid compound include an alkylsulfonic acid-based anion and an aromatic sulfonic acid-based anion, or two anions. If such a compound is added, the adhesion of the acid to the second layer 2 material body can be suppressed, and pattern defects and abnormal opening sizes can be reduced. Even the addition of acid can avoid compromising the stability of the material. In addition, because “acids are generated during the process of forming the bridging film”, there is no need to worry about the occurrence of adverse forces during storage at room temperature, and the range of choice of the type of acid to be added and the concentration can be expanded. Island police, the specific embodiment of the second embodiment of the 疋 κ is described as follows: Re-application Example 1 As described in the first embodiment, according to the embodiment of the present invention (fine pattern forming material) Timing force is prepared: 1 in the first The material A of the compound of the second layer 2 was heated to generate an acid as a comparative object, and a second layer 2 B was prepared. ^ _Material The material A can be maintained even after 90 days: the body itself is white and thirsty, and the resin is bridged. , Material B, Material that cannot be used in the world. Unusual, becomes solid S is a solid material. Moreover, even if heating is added: in the end of life: it is affected by soil

★ In this way, you can get 6583 for the second layer and 2 materials. 5. Description of the invention (18) --- You can also obtain stable materials. The method of forming the finely divided resist pattern on the semiconductor substrate 3 has been described in detail above. The finely divided resist pattern of the present invention is not limited to the semiconductor substrate 3, and may be used in the case where an insulating layer such as a silicon oxide film is formed in the manufacturing process of a corresponding semiconductor device, and a conductive layer such as polycrystalline stone may also be used. The formation of the finely divided resist pattern of the present invention is not limited by the substrate 臈, as long as it can be applied to a substrate capable of forming a resist pattern, it can be formed on a substrate corresponding to a desired substrate. These substrates are collectively referred to as a semiconductor substrate. Furthermore, in the present invention, the fine separation resist pattern formed as described above is used as a mask, and a semiconductor substrate such as a base or a semiconductor thin plate such as various thin films is fused and etched to form fine gaps or fine holes on the semiconductor substrate. 'It is an invention for manufacturing a semiconductor device. The present invention includes the following inventions in addition to the inventions described in the patent claims. As the water-soluble resin described in item 1 or item 6 of the scope of the patent application, polyacrylic acid, polyvinyl acetal, polyvinylpyrrolidone, polyvinyl alcohol, azetolide, polyoxyethylene, styrene-anhydrous butane One of oxalic acid copolymer, polyethyleneamine, polyacrylamine, water-soluble resin containing oxazoline group, water-soluble polyamine resin, water-soluble urea resin, alkyd resin, and sulfonamide A fine pattern forming material containing two or more compounds or salts of these compounds as a main component. As the water-soluble bridging J described in the second or seventh item of the patent application scope, melamine derivatives, urea derivatives, phenyluridine,

89121567, ptd page 22 6583 V. Description of the invention (19) _ One or a mixture of two or more kinds of spreading alcohols. Fine pattern forming materials. As the main component, as the aforementioned melamine derivative ', a amine of oxymethylmelamine or a blended amine and a fine pattern forming material are used. The main component of the F horse is as follows. As the urea inducer, one or two or more mixtures of urea, urea, N-alkyloxymethylurea, and ethylene-based swollen methylurea are used as alkenyl urea. Carbonate. The knife-shaped M fine pattern forming material is used as any one of a mixture of polyvinylacetal and polyvinylalcohol = soluble resin in item 3 of the scope of patent application, and is made of a derivative of polyethyleneacetal. "Urea derivative or:;: agent, using melamine cyanide" in any one of the species ^ = ^ = biological and urea-derived manufacturing method of the invention: the invention of the :: method or the above devices. 4 仃 Semiconductor manufactured by using this feature [Effect of the invention] As described in detail above, the etching resist separation pattern and hole pattern α can be obtained by using the present invention;% 4:., ' Micro: Refine the method of forming a pattern that can be used to transcend the wavelength limit, the material of Guo'an, and use this material to form a pattern in the process of forming a bridge film. In addition, a material having a finely divided resist pattern at the time of storage can be obtained or obtained. material. Of Reactive Anti-Agent Patterns

89l2l567.ptd Page 23 -〇 6 5 8 3 V. Description of the invention ¢ 20) In this way, the aperture size of the hole-based resist pattern can be reduced compared with the conventional method, and the separation width of the gap-based resist pattern can be reduced than the conventional method. Furthermore, by using the finely divided resist pattern thus formed as a mask, finely divided gaps and holes can be formed on the semiconductor substrate. In addition, by using such a manufacturing method, a semiconductor device that finely separates gaps and holes can be obtained. [Explanation of the element number] 1 The first anti 14 agent 1a The first resist pattern 2 The second layer 2 a The second resist pattern 3 The semiconductor substrate (semiconductor substrate) 4 The bridge layer 100 The micro hole mask pattern 2 0 0 Fine gap mask pattern 3 0 0 Isolated residual pattern

89121567.ptd Page 24 U 6 5 83 Simple description of the formula Figures 1 (a)-(c) are diagrams showing a mask pattern of a resist pattern forming method according to the first embodiment of the present invention. Figures 2 (a)-(e) are flowcharts showing the steps of a resist pattern forming method according to the first embodiment of the present invention. Fig. 3 is a view showing an example of a water-soluble resin composition used in the resist pattern forming method according to the first embodiment of the present invention. Fig. 4 is a diagram showing an example of a water-soluble bridging agent used in the resist pattern forming method according to the first embodiment of the present invention. Fig. 5 is a view showing an example of an acid-producing compound used in the method for forming an anti-tin agent pattern according to the second embodiment of the present invention.

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Claims (1)

b 6 5 83 VI. Patent application scope _ 1 _ One kind of fine pattern forming material, one or two of the aforementioned water-soluble resins, two, two, and two or more copolymers of sexual resins of water-soluble resins as a proportion = 0 Or water-soluble acid; water: water and water-soluble; two :: force :: quantitative weak dissolve, supply the acid in the first resist 7 and 3 as the solvent for the pattern of the etchant. Formed on the aforementioned _3, from the first reaction, a plum tree film is formed; and a mixed solvent that generates a bridging reaction solvent is removed as a developing solution. Water or water and water-solubility have 2. — a kind of fine pattern forming material, one of the material and the two water-soluble bridging agent I, divided by water-soluble bridging agent; add a certain amount of weak acid to water;: mixture As the main component, a mixed solvent is used as a solvent to dissolve a soluble organic solvent, and a frame is generated from the contact portion of the resist pattern on the resist pattern of the first resist pattern, and the first resist is water or water. And the water-soluble organic bridge H is not bridged. A mixed solvent of a mixture is used as a developing solution ^ A fine pattern forming material, on; a mixture of water-soluble bridging agent wax and organic solvent ::::; the amount of weak acid; water or water; The formation of the two-two solution; supply 醆: the bridge part is water or ^ / 卞 bridge reaction 'to form a bridging film. "-Remove the image liquid. 117 soluble organic solvents are now mixed together! Work: Shelf 4 〇6 5 83 Six, Scope of patent application material 4 _ As for the fine pattern shape in any of the scope of patent application items 1 to 3, in which a weak acid with a pH of 3 or more is used as the above weak acid. Take Ke 5. If the scope of patent application is 1 to 3 The fine pattern jealous material according to any one of the items, wherein the weak acid is an acid of an alkylcarboxylic acid such as acetic acid or a dicarboxylic acid such as benzoic acid. It is characterized in that a water-soluble species or a mixture of two or more of the foregoing water-soluble resins or a copolymer of one or more of the aforementioned water-based "lipids" is used as a main component; :: : The solvent is dissolved, and the acid is supplied to form two first resist patterns on the first resist pattern. The contact portion with the first resist pattern = bridge reaction to form a bridging film; instead of bridging water Then use a mixed solvent of amidine and organic solvents as the developing solution to remove it. — And water-soluble 7. — a kind of fine pattern forming material, one of which is the aforementioned water-soluble _ bridge 丨, 4 —, water> glutinous bridging agent; adding thermal decomposition produces two: a mixture of ^ as the main machine The mixed solvent of the solvent is used as a solvent: two = water or water and a water-soluble solvent, which is generated on the case of the first resist pattern and the first resist pattern is produced by the first step of cryolysis and the first step of the resist pattern. The acid and the first resist are water or water and water soluble to form a bridging film; not the bridging part is removed. Organic solvent mixed solvent is used as the developing solution. ① The fine pattern forming material is the main component, and 1 is heated to decompose one or two or more kinds of mixture to make the compound; it is water or water and water. 89121567.ptd page 27 — one or more species and water-soluble plus + z, characterized by water-soluble resin 166583 6. The scope of the patent application is to dissolve the mixed solvent of ϋ Ϊ as a solvent to dissolve it. ## The acid is generated on the flute-resist map; the salt is added from the first resist-resist map plus eight ; $ * $ Of acid: If a bridging reaction occurs in the junction with the first machine etched dish, the bridged part is removed with water or water and a water-soluble organic solvent ^ called a developing solution. As a fine material as described in any one of claims 6 to 8 of the scope of the patent application, the cardiotropic agent: ′ uses a counter-anion-containing diazo to generate an acid: It is a compound that generates an acid by the above thermal decomposition. 'Operation 10. For example, if the fine pattern of item 9 in the scope of the patent application is to form a curry, an alkylsulfonic acid-based and aromatic sulfonic acid-based anion is used as the di-ion. The above-mentioned reverse anion 11. A fine pattern forming material, characterized by a water-soluble noble molecule with a dilute structure on the main chain, and a bridging agent with a oxymethylamino group that generates a bridging corridor under the catalysis of an acid The two components are used as the main component ^. Add a certain amount of weak acid; dissolve in pure water or a mixed solvent of pure water and a water-soluble organic solvent; form a bridging film when supplying acid. , 1 2. A fine pattern forming material, which is characterized by a water-soluble molecule with a vinyl structure on the main chain and an alkoxymethylamino bridging agent which generates a bridging reaction under the catalysis of an acid. It is composed as a main component; a compound that is generated by thermal decomposition to add an acid; is dissolved in pure water or a mixed solvent of pure water and a water-soluble organic solvent; and when a acid is supplied, a bridging film is formed. '1 3 · As for the fine pattern forming material in the scope of application for patent No. 丨 or 12, where' Using polyvinyl acetal 'polyvinylpyrrolidine rim, polyvinyl alcohol, polyaziridine, polyoxyethylene, Polyvinylamine, polyacrylic acid, polyacrylic acid country \\ 312 \ 2d-code \ 90-01 \ 8912l567.ptd Page 28 466583 6. Scope of patent application One or more mixtures of two or more kinds are used as the above water-soluble polymers. 1 4. The fine pattern forming material according to item 11 or 12 of the scope of patent application, wherein alkoxyfluorenylamino groups having a melamine derivative or a zoline derivative as a skeleton are used alone or in combination. The bridging agent serves as the aforementioned bridging agent. 1 5. A method for manufacturing a semiconductor device, comprising the step of forming a first resist pattern by supplying an acid on a first resist semiconductor substrate; Any one of the items 1 to 14 describes a step of forming a second layer of the fine pattern forming material; a bridge film is formed at the portion where the second layer and the first resist pattern meet by the supply acid of the first resist pattern. A step of removing the non-bridged portion of the second layer to form a second resist pattern; and the aforementioned semiconductor substrate step of etching the second resist pattern as a mask. 89121567.ptd Page 29