JP2006292896A - Method for forming resist pattern, method for forming thin film pattern, micro device and method for manufacturing same, and crosslinking resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming a resist pattern by which a resist pattern facilitating formation of a sufficiently microfabricated thin film pattern can be obtained. <P>SOLUTION: The method for forming a resist pattern includes the steps of: forming a patterned resist layer 4 containing an acid generating material which generates an acid by heating or exposure on one surface of a substrate 1; depositing a crosslinking resin composition 5 on the resist layer 4; crosslinking a part of the crosslinking resin composition 5 near the surface of the resist layer 4 by heating or exposure to form a crosslinked layer 6 covering the resist layer 4; removing a part except for the crosslinked layer 6 of the crosslinking resin composition 5 to obtain a resist pattern 10 comprising the resist layer 4 and the crosslinked layer 6 covering the resist layer 4. The crosslinking resin composition contains a water-soluble crosslinking resin which crosslinks in the presence of an acid, at least either inorganic particles or a nonwater soluble resin, and a solvent which dissolves the crosslinking resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resist pattern forming method, a thin film pattern forming method, a microdevice and a manufacturing method thereof, and a crosslinkable resin composition.

  In the manufacture of microdevices with thin films, such as thin film magnetic heads, thin film inductors, semiconductor devices, thin film sensors, thin film actuators, etc., conductive materials, soft magnetic materials can be obtained by methods such as frame plating using resist patterns. A thin film pattern made of a predetermined material such as is formed. In general, a thin film pattern is formed by forming a resist pattern on a thin film and using this as a mask pattern to remove a part of the thin film. In this case, dry etching is performed on the thin film that is not covered with the resist pattern, or the plating layer is deposited on the thin film that is not covered with the resist pattern, and then the resist pattern is removed and covered with the plating layer. A predetermined portion of the thin film is removed by a method in which the thin film is removed by dry etching or the like.

Conventionally, as a method for enabling miniaturization of a thin film pattern, a resist layer formed of a resist containing an acid generating material that generates an acid by heating or exposure is patterned, and the resist layer is formed from a crosslinked resin. A method is known in which a resist pattern covered with a cross-linked layer is formed and a thin film pattern is formed using the resist pattern as a mask pattern (see, for example, Patent Documents 1, 2, and 3).
JP-A-11-95418 JP 2001-316863 A JP 2003-195521 A

  For further miniaturization of the thin film pattern, it is effective to form a resist pattern that has been sufficiently miniaturized by narrowing the pattern interval (trench width) and using this as a mask pattern to form a thin film pattern it is conceivable that.

  However, in the case of a conventional resist pattern, the dry etching resistance or the like decreases with the miniaturization, and even if the resist pattern itself is miniaturized, it becomes difficult to form a miniaturized thin film pattern using the resist pattern itself. It became clear.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resist pattern capable of forming a sufficiently miniaturized thin film pattern and a method for forming the resist pattern. Moreover, an object of this invention is to provide the crosslinkable resin composition used for the formation method of this resist pattern.

  Furthermore, the present invention provides a thin film pattern forming method capable of obtaining a sufficiently miniaturized thin film pattern using the resist pattern as a mask pattern, and a sufficiently miniaturized micro device and a manufacturing method thereof. The purpose is to provide.

  In order to solve the above problems, a method for forming a resist pattern of the present invention includes a step of forming a patterned resist layer on one surface of a substrate, which includes an acid generating material that generates an acid by heating or exposure, and a resist. A step of adhering a crosslinkable resin composition to the layer, a step of crosslinking a portion of the crosslinkable resin composition in the vicinity of the resist layer surface by heating or exposure, and forming a crosslinkable layer that covers the resist layer; Removing a portion other than the cross-linked layer from the resin composition to obtain a resist pattern comprising a resist layer and a cross-linked layer covering the resist layer, and the cross-linkable resin composition is cross-linked in the presence of an acid. A water-soluble crosslinkable resin, at least one of inorganic particles and a water-insoluble resin, and a solvent that dissolves the crosslinkable resin.

  When the resist pattern manufactured by the resist pattern forming method of the present invention is used as a mask pattern for forming a thin film pattern, it is possible to form a sufficiently miniaturized thin film pattern. Such an effect is considered to be manifested, for example, by improving the etching resistance of the resist pattern by the inorganic particles or the water-insoluble resin in the crosslinked layer.

  If inorganic particles or the like are contained in the cross-linked layer, the surface of the resist pattern becomes rough, and there is a concern that the resolution of dry etching or the like of a thin film using this as a mask pattern may be lowered. However, even if the crosslinked layer contains inorganic particles and the like, a resist pattern having a smooth surface is formed, and it is possible to form a sufficiently thinned thin film pattern by using the resist pattern. As a result, it became clear. This is because, for example, even when a protruding portion due to inorganic particles or the like is formed on the resist layer surface, when heated or exposed in a state where the crosslinkable resin composition is adhered, in the vicinity of the inorganic particles or the like This is because the diffusion of the acid generated from the resist layer is inhibited, so that the thickness of the cross-linked layer becomes relatively thinner than other parts, and as a result, the surface of the cross-linked layer is smoothed as a whole. It is done.

  The inorganic particles in the crosslinkable resin composition preferably contain a metal or a metal compound. As a result, a resist pattern that is further excellent in terms of dry etching resistance and that suppresses shrinkage of the resist pattern when irradiated with an electron beam can be obtained. If the resist pattern shrinks greatly due to electron beam irradiation, there is a problem in that the reproducibility of repeated measurement of measured values is lost when the resist pattern dimensions are measured with an electron microscope.

  The inorganic particles are preferably conductive. As a result, the shrinkage of the resist pattern when the electron beam is irradiated is suppressed, and the resist pattern is sufficiently prevented from being charged. Therefore, the occurrence of charging when the resist pattern dimension is measured with an electron microscope is reduced.

  The resist pattern of the present invention includes an acid generating material that generates an acid upon heating or exposure, a patterned resist layer, a cured product that covers the resist layer, and is crosslinked with a water-soluble crosslinkable resin, and an inorganic material. And a crosslinked layer containing at least one of the particles and the water-insoluble resin.

  When the resist pattern of the present invention is used as a mask pattern for forming a thin film pattern, it is possible to form a sufficiently thinned thin film pattern. This resist pattern is formed, for example, by the above-described resist pattern forming method of the present invention.

  The method for forming a thin film pattern of the present invention includes a step of forming a resist pattern on the thin film of a substrate provided with a thin film on one surface of a substrate by the method of forming a resist pattern of the present invention, and the resist pattern covering the thin film pattern. A step of removing a thin film portion by etching and a step of removing a resist pattern to obtain a thin film pattern.

  Alternatively, the method of forming a thin film pattern of the present invention includes a step of forming a resist pattern on the thin film of a substrate provided with a thin film on one surface of the substrate by the resist pattern forming method of the present invention, and the resist pattern. The process of removing the resist pattern after forming a plating layer on the thin film of the uncovered part, and the thin film pattern in which the plating layer is laminated by removing the thin film of the part not covered by the plating layer by etching Obtaining.

  According to these thin film pattern forming methods of the present invention, a sufficiently miniaturized thin film pattern is manufactured by using the resist pattern formed by the resist pattern forming method of the present invention as a mask pattern. Can do.

  The present invention is also a microdevice manufacturing method including a step of forming a thin film pattern by the thin film pattern forming method of the present invention, and a microdevice obtained by the manufacturing method. According to the microdevice manufacturing method of the present invention, a sufficiently miniaturized microdevice can be obtained.

  The crosslinkable resin composition of the present invention comprises a water-soluble crosslinkable resin that crosslinks in the presence of an acid, at least one of inorganic particles and a water-insoluble resin, and a solvent that dissolves the water-soluble crosslinkable resin. It is for making it adhere to the resist layer containing the acid generation material which generates an acid by heating or exposure. In this crosslinkable resin composition, the inorganic particles preferably contain a metal or a metal compound, and are preferably conductive.

  This crosslinkable resin composition of the present invention can be suitably used as the crosslinkable resin composition in the resist pattern forming method of the present invention.

  According to the present invention, there are provided a resist pattern capable of forming a sufficiently miniaturized thin film pattern, a method for forming the resist pattern, and a crosslinkable resin used in the method.

  In addition, according to the present invention, there are provided a thin film pattern forming method capable of obtaining a sufficiently miniaturized thin film pattern, a sufficiently miniaturized micro device, and a manufacturing method thereof.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  1 and 2 are cross-sectional views showing an embodiment of a resist pattern forming method. FIG. 1 shows a step of forming a patterned resist layer 4 containing an acid generating material that generates an acid upon exposure on one surface of a substrate 1, and FIG. 2 shows a crosslinkable resin composition on the resist layer 4. The resist layer 4 is formed by the crosslinked layer 6 formed by crosslinking the crosslinkable resin in the vicinity of the surface of the resist layer 4 of the crosslinkable resin composition by heating or exposing in this state. The covering step (b) and the step (c) of removing a portion other than the cross-linked layer 6 in the cross-linkable resin composition are shown.

  In this embodiment, first, as shown in FIG. 1A, ultraviolet rays or the like are passed through a mask M on which a predetermined pattern is drawn on the photosensitive resin layer 3 formed on one surface of the substrate 1. Is irradiated with an actinic ray to solubilize a predetermined portion of the photosensitive resin layer 3 in an alkaline aqueous solution (exposure). Thereafter, the photosensitive resin layer 3 is developed to form a resist layer 4 patterned in a predetermined pattern as shown in FIG. In exposure to the photosensitive resin layer 3, light having a wavelength of 248 nm (KrF excimer laser), a wavelength of 192 nm (ArF excimer laser), or the like is irradiated using a stepper, a scanner, or the like.

The substrate 1 has a structure in which a thin film 12 as a film to be patterned is laminated on a base 11 made of a ceramic material such as Si or Al ₂ O ₃ .TiC. The thin film 12 is made of a material such as a conductive or soft magnetic metal such as Ni, Cu, or NiFe, a conductive metal oxide, or a conductive organic material, and has a thickness of 0.01 to 1.0 μm. It is preferable. The thin film 12 is formed by a method such as sputtering, CVD, vapor deposition, or electroless plating.

  The photosensitive resin layer 3 includes an acid generating material that generates an acid by heating or exposure, and is made of a photosensitive resin that is solubilized in an alkaline aqueous solution by exposure with actinic rays. As for the thickness of the photosensitive resin layer 3, 0.1-10 micrometers is preferable. The photosensitive resin layer 3 is formed by, for example, applying a coating solution in which a photosensitive resin is dissolved or dispersed in a solvent onto the substrate 1 by spin coating or the like, and removing the solvent in the coating solution by heating or the like. Can do. The photosensitive resin layer 3 may be pre-baked by heating before exposure if necessary.

  A conventionally well-known thing can be used as a photosensitive resin containing an acid generating material. For example, NQD-novolak resist containing naphthoquinonediazide derivative (NQD), which is an acid generating material, and novolak resin, NQD esterified novolak resist in which NQD is bonded to novolak resin through an ester bond, and onium salts such as sulfonium salts are generated. A polyhydroxystyrene-based chemically amplified resist contained as a material is preferably used.

  After the photosensitive resin layer 3 was exposed, the photosensitive resin layer 3 was developed and patterned by removing an exposed portion using an alkali developer such as a 2.38 mass% tetramethylammonium hydroxide aqueous solution. A resist layer 4 is formed. After the development, the developer is washed with washing water to remove the attached developer.

  Subsequently, as shown in FIG. 2A, on the substrate 1 and the resist layer 4, at least one of a water-soluble crosslinkable resin that crosslinks in the presence of an acid, inorganic particles, and a water-insoluble resin. Then, a crosslinkable resin composition layer 5 made of a crosslinkable resin composition containing a solvent that dissolves the water-soluble crosslinkable resin is formed, and the crosslinkable resin composition is adhered to the resist layer 4. The crosslinkable resin composition layer 5 is formed by a spin coat method or the like, and a preferable thickness thereof is 0.01 to 0.3 μm. The crosslinkable resin composition layer 5 may be formed in a state where the washing water is attached to the resist layer 4 or after the washing water is removed.

  In this state, the resist layer 4 and the crosslinkable resin composition layer 5 are heated or exposed to crosslink the crosslinkable resin in the crosslinkable resin composition layer 5 near the surface of the resist layer 4 to cover the resist layer 4. Thus, the crosslinked layer 6 is formed (FIG. 2B). Then, the crosslinkable resin composition other than the crosslinkable layer 6 is removed by washing or the like to obtain a resist pattern 10 including the resist layer 4 and the crosslinkable layer 6 covering the resist layer 4 ((c) in FIG. 2). When the crosslinked layer 6 is formed by heating, for example, the whole is heated to 85 to 150 ° C. using a hot plate or the like.

  The water-soluble crosslinkable resin is a resin that forms a crosslinked structure in the presence of an acid and becomes a cured product. This water-soluble crosslinkable resin contains, for example, a water-soluble resin composed of a water-soluble polymer and a water-soluble crosslinking agent that crosslinks the water-soluble resin.

  Examples of water-soluble resins include polyacrylic acid, polyvinyl acetal, polyvinyl pyrrolidone, polyvinyl pyrrolidone-polyvinyl acetate copolymer, polyvinyl alcohol, polyethylene imine, polyethylene oxide, styrene-maleic acid copolymer, polyvinyl amine resin, polyallylamine, oxazoline. Examples include group-containing water-soluble resins, water-soluble melamine resins, water-soluble urea resins, alkyd resins, and sulfonamide resins. These may be used alone or in combination as a water-soluble resin.

  The water-soluble crosslinking agent is a component that crosslinks polymers by reacting with and binding to a polymer that is a water-soluble resin. Specific examples of the water-soluble crosslinking agent include urea, N-alkoxymethylene urea, urea urea crosslinking agents such as ethylene urea and ethylene urea carboxylic acid, melamine crosslinking agents such as melamine and alkoxymethylene melamine, benzoguanamine and glycol. Amino crosslinking agents such as uril can be mentioned.

  Instead of using the water-soluble crosslinking agent as described above, an acid generator such as an acid generator that generates an acid by heating or exposure (for example, an organic acid amine salt such as p-toluenesulfonic acid triethylamine salt). The water-soluble resin may be cross-linked by reacting the polymers in the water-soluble resin with each other in the presence of an acid to be generated. In this case, a water-soluble crosslinking agent and an acid generator can be used in combination.

  The crosslinkable resin composition preferably contains inorganic particles among the inorganic particles and the water-insoluble resin. When the crosslinkable resin composition contains inorganic particles, the inorganic particles are dispersed in the crosslinkable resin composition. The inorganic particles preferably contain a metal or a metal compound, and more preferably consist of a metal or a metal compound. The inorganic particles are preferably conductive.

Examples of the metal used for the inorganic particles include Au, Ag, and Pt. Further, as a metal _{compound, Al 2 O 3, Bi 2} O 3, CeO 2, CuO, Fe 2 O 3, Ho 2 O 3, ITO (Indium-Tin-Oxide), Mn 3 O 4, SiO 2, SnO ₂ , metal oxides such as TiO ₂ , Y ₂ O ₃ , and ZnO, and metal nitrides such as AlN, TiN, and SiN. Among these, ITO, CeO ₂ , CoO, SiO _{2 and the} like are preferable, and ITO is particularly preferable.

  The shape of the inorganic particles is not particularly limited, and for example, spherical or polyhedral inorganic particles are used. The particle size of the inorganic particles is preferably 10 nm or less. When this particle diameter exceeds 10 nm, the smoothness of the resist pattern surface to be formed tends to decrease. Although there is no restriction | limiting in particular about the minimum of an inorganic particle, Usually, what is necessary is just about 1 nm or more. Inorganic particles having a particle size of 10 nm or less can be prepared, for example, by sizing inorganic particles having an average particle size exceeding 10 nm by a solution precipitation method.

  When the crosslinkable resin composition contains a water-insoluble resin, the water-insoluble resin is dissolved or dispersed in the form of particles in the crosslinkable resin composition. This water-insoluble resin is composed of a water-insoluble polymer or oligomer, and examples thereof include novolak resins, silicone resins, polyhydroxystyrene resins, and epoxy resins. As the epoxy resin, “EX-711” which is a powder epoxy resin, “EX-731” which is a powder imide epoxy resin, “EM-150” which is a novolak type epoxy resin (all of which are Nagase ChemteX Corporation) Manufactured, trade name) and the like are preferably used.

  When the water-insoluble resin is in the form of particles, the shape and particle size are preferably the same as those described above for the inorganic particles. Even when the water-insoluble resin is uniformly dissolved in the crosslinkable resin composition, in the cured product formed by crosslinking the crosslinkable resin, the water-insoluble resin is usually in the form of fine particles. It becomes a distributed state.

  As a solvent for dissolving the water-soluble crosslinkable resin, water, a water-soluble organic solvent such as alcohol, or a mixed solution of water and a water-soluble organic solvent can be used.

  The crosslinkable resin composition preferably contains at least one of inorganic particles and water-insoluble resin in an amount of 1 to 3% by mass, and 70 to 95% by mass of a solvent for dissolving the water-soluble crosslinkable resin. It is preferable to contain.

  Moreover, it is preferable that the crosslinkable resin composition contains a surfactant in addition to the above components. As the surfactant, acetylene alcohol and its polyethoxylate, acetylene glycol and its polyethoxylate can be suitably used. Commercially available products that can be used as surfactants include “FLORARD” (trade name) manufactured by 3M, “Nonipol” (trade name) manufactured by Sanyo Kasei Co., Ltd., and “acetylenol EL” manufactured by Kawaken Chemical Co., Ltd. And water-soluble surfactants such as (trade name).

  The resist pattern 10 includes a patterned resist layer 4, a cured product obtained by coating the resist layer 4 and crosslinked with a water-soluble crosslinkable resin, and at least one of inorganic particles and a water-insoluble resin. Layer 6. The resist pattern 10 has high etching resistance because the crosslinked layer 6 contains inorganic particles or a water-insoluble resin, and it is easy to narrow the pattern interval. In addition, it does not easily shrink when it is irradiated with an electron beam for pattern interval measurement or the like.

  The resist pattern 10 is used as a mask pattern for forming a thin film pattern. 3 and 4 are cross-sectional views for explaining an embodiment of a method for forming a thin film pattern. In this embodiment, first, a portion of the thin film 12 not covered with the resist pattern 10 is removed by etching (FIG. 3). The thin film 12 is preferably etched by dry etching such as milling or RIE.

  Subsequently, the resist pattern 10 is removed to obtain a thin film pattern 20 formed on the substrate 11 (FIG. 4). The resist pattern 10 is removed using a solvent such as NMP or acetone.

  5 and 6 are cross-sectional views for explaining another embodiment of a method for forming a thin film pattern. In this embodiment, first, the plating layer 7 is formed on a portion of the thin film 12 that is not covered with the resist pattern 10 (FIG. 5A). The plating layer 7 is formed by deposition of a material capable of forming a plating layer such as NiFe or Cu. The thin film 12 is preferably formed of the same material as the plating layer 7.

  Subsequently, after removing the resist pattern 10 (FIG. 5B), the portion of the thin film 12 that is not covered with the plating layer 7 is removed by etching to obtain a thin film pattern 20 in which the plating layer 7 is laminated. . The removal of the resist pattern 10 and the etching of the thin film 12 are performed in the same manner as in the above-described embodiment described with reference to FIGS.

  The thin film pattern 20 may be used as a constituent member of a micro device after removing a part thereof. In this case, the resist layer 8 patterned so as to cover the portion to be left out of the thin film pattern 20 and the plating layer 7 is formed (FIG. 6A), and the thin film of the portion not covered with the resist layer 8 is formed. After removing the pattern 20 and the plating layer 7 (FIG. 6B), the resist layer 8 is removed, and the thin film pattern 20 in which the plating layer 7 is laminated as shown in FIG. can get. Formation and removal of the resist layer 8 can be performed in the same manner as the formation of the resist layer 4 and the removal of the resist pattern 10.

  The thin film pattern shown in FIG. 4 and FIG. 6C is sufficiently narrow in width and interval, and this thin film pattern can be used as a part of a micro device, for example, in the case of a thin film magnetic head, its magnetic pole. By using as a lead or the like, a sufficiently miniaturized high-density microdevice can be obtained.

  FIG. 7 is a cross-sectional view schematically showing a thin film magnetic head as one embodiment of a micro device obtained by a method of manufacturing a micro device including a step of forming a thin film pattern by the method of forming a thin film pattern as described above. is there. The thin film magnetic head 100 shown in FIG. 7 performs a magnetic information recording operation at a position where the medium facing surface S is disposed to face the recording surface of a recording medium (not shown). 7A shows a cross section perpendicular to the medium facing surface S, and FIG. 7B shows an end surface of the thin film magnetic head viewed from the medium facing surface S side.

The thin film magnetic head 100 includes an insulating layer 41 made of a nonmagnetic insulating material on a base layer 60 made of a ceramic material such as Al ₂ O ₃ .TiC, and a reproducing head unit that reads magnetic information using the magnetoresistance effect. 50, a separation layer 42 made of a nonmagnetic insulating material, a recording head unit 30 for performing a magnetic recording process, and an overcoat layer 45 made of a nonmagnetic insulating material are stacked in this order.

  The recording head unit 30 is provided on the reproducing head unit 50 with the separation layer 42 interposed therebetween. The recording head unit 30 has a configuration in which the auxiliary magnetic pole 36 adjacent to the separation layer 42, the gap layer 38 in which the thin film coil 39 is embedded, and the magnetic pole 31 are laminated in this order. The magnetic pole 31 and the auxiliary magnetic pole 36 are magnetically connected via a coupling portion 37 that is filled in the opening 380 of the gap layer 38 and is made of a magnetic material.

  The magnetic pole 31 is provided adjacent to the gap layer 38. That is, the magnetic pole 31 has a base layer 60, a reproducing head portion 50, a separation layer 42, an auxiliary magnetic pole 36, a gap layer 38 in which a thin film coil 39 is embedded, and a whole laminated body including a connecting portion 37 as a base. It is provided on one side.

  The magnetic pole 31 covers the portion of the magnetic flux emitting portion 32 opposite to the medium facing surface S from the periphery and magnetically connects to the connecting portion 37 while exposing the exposed surface 32S exposed to the medium facing surface S side. And a yoke portion 35 formed so as to be connected.

  The magnetic flux release portion 32 is adjacent to the support portion 32b, a rod-shaped pole portion 32a having an exposed surface 32S exposed on the medium facing surface S side, a support portion 32b provided on the opposite side of the exposed surface 32S of the pole portion 32a. And a seed layer 33 provided.

  The above-described thin film pattern forming method is applied, for example, when the magnetic flux emitting portion 32 is formed. That is, the seed layer 33, which is a thin film, is patterned by the above-described thin film pattern forming method, and the pole portion 32a and the support portion 32b are formed as plating layers on the seed layer 33, whereby the magnetic flux emitting portion 32 is formed. It is formed. In this case, before forming the plating layer, for example, the side surface of the pole portion 32a can be inclined by heating the resist pattern to incline the wall surface of the resist pattern.

  The seed layer 33, the pole portion 32a, and the support portion 32b are preferably formed of a soft magnetic material such as a material containing iron and nitrogen, a material containing iron, zirconia and oxygen, or a material containing iron and nickel. . More specifically, for example, permalloy (Ni: 45%, Fe: 55%), iron nitride (FeN), iron-cobalt alloy, and iron-containing alloys FeM and FeCoM (M is nickel, nitrogen, carbon, Boron, silicon, aluminum, titanium, zirconia, hafnium, molybdenum, tantalum, niobium, and copper can be used.

  The gap layer 38 is composed of three gap layer portions 38a, 38b and 38c. The gap layer portion 38a is provided adjacent to the auxiliary magnetic pole 36. On the gap layer portion 38a, a thin film coil 39 having a winding structure that is wound spirally around the opening 380 is provided. The gap layer portion 38b is provided so as to cover between the windings of the thin film coil 39 and its peripheral region, and the gap layer portion 38c covers the gap layer portion 38b and forms an opening 380.

  The reproducing head unit 50 has a configuration in which a lower read shield layer 51a adjacent to the insulating layer 41, a shield gap film 52, and an upper read shield layer 51a are stacked in this order. A magnetoresistive element 55 as a reproducing element is embedded in the shield gap film 52, and one end surface of the magnetoresistive element 55 is exposed to the medium facing surface S side. The magnetoresistive effect element 55 detects the magnetic information of the recording medium by using, for example, a giant magnetoresistive effect (GMR: Giant Magneto-resistive) or a tunnel magnetoresistive effect (TMR: Tunneling Magneto-resistive). It functions as a reproducing element.

  In the thin film magnetic head 100, the portions other than the magnetic flux emitting portion 32 can be formed by appropriately adopting materials and forming methods normally used in the manufacture of the thin film magnetic head. The microdevice manufacturing method of the present invention is particularly preferably employed in the method of manufacturing a thin film magnetic head. In addition to this, for example, microdevices such as thin film inductors, semiconductor devices, thin film sensors, and thin film actuators are used. It is also suitable as a production method that enables miniaturization in production.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.

<Preparation of crosslinkable resin composition>
Example 1
Polyvinylpyrrolidone-polyvinyl acetate copolymer (PVP-PVAc copolymer) as a water-soluble resin, methoxyethylene urea as a water-soluble crosslinking agent, CeO ₂ particles as inorganic particles, water obtained by distilling ion-exchanged water, and surface activity Acetylene alcohol as an agent was mixed in the ratio (parts by weight) shown in Table 1, and sufficiently stirred to dissolve each component, followed by filtration with a 0.2 μm filter to obtain a crosslinkable resin composition. It was. The CeO ₂ particles used were prepared by sieving a portion having a particle diameter of 10 nm or less from CeO ₂ particles having an average particle diameter of 14 nm manufactured by C.I.

(Example 2)
The same as in Example 1 except that instead of CeO ₂ particles, ITO particles having an average particle size of 30 nm manufactured by CI Kasei Co., Ltd. were used by sizing a portion having a particle size of 10 nm or less by a solution precipitation method. Thus, a crosslinkable resin composition containing each component in the ratio shown in Table 1 was obtained.

(Example 3)
Instead of CeO ₂ particles, from “EM-150” (trade name) manufactured by Nagase ChemteX Corporation, which is an emulsion in which novolak resin particles are dispersed, a portion having a particle size of 10 nm or less is obtained by centrifugal solution precipitation. A crosslinkable resin composition containing each component in the ratio shown in Table 1 was obtained in the same manner as in Example 1 except that the powder prepared by sizing was used.

Example 4
A crosslinkable resin composition containing each component in the ratio shown in Table 1 was obtained in the same manner as in Example 2 except that p-toluenesulfonic acid triethylamine salt as an acid generator was used instead of methoxyethylene urea. .

(Example 5)
A crosslinkable resin composition containing each component in the ratio shown in Table 1 was obtained in the same manner as in Example 2 except that p-toluenesulfonic acid triethylamine salt as an acid generator was further used.

(Comparative Example 1)
A crosslinkable resin composition containing each component in the ratio shown in Table 1 was obtained in the same manner as in Example 1 except that CeO ₂ particles were not used.

(Comparative Example 2)
A crosslinkable resin composition containing each component in the ratio shown in Table 1 was obtained in the same manner as in Example 4 except that ITO particles were not used.

(Example 6)
A Ni thin film (thickness: 100 nm) is formed on one surface of a base made of a 6-inch Si substrate by sputtering, and the Si substrate and a Ni thin film substrate (hereinafter referred to as “Ni substrate”). Got. Then, a patterned resist layer was formed on the Ni substrate as follows.

  "AZ DX5105P" (trade name, AZ Electronic Materials Co., Ltd.), a chemically amplified polyhydroxystyrene (PHS) resist that contains an acid generating material that generates acid when heated, is a resist for a wavelength of 248 nm (KrF excimer laser). )) Was applied onto a Ni substrate by spin coating so as to have a thickness of 500 nm after pre-baking. The coated resist was heated at 100 ° C. for 90 seconds with a hot plate, pre-baked, cooled to room temperature with a cooling plate, and then DUV stepper (“NSR-EX14D” (trade name) manufactured by Nikon, NA = 0.65, σ = 0.7) and exposed through a mask. Furthermore, it was heated at 110 ° C. for 90 seconds with a hot plate, cooled to room temperature with a cooling plate, developed with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds, and 300 nm L / S (pattern A resist layer having a pattern with a line spacing of 300 nm (hereinafter, a resist layer formed in the same manner is referred to as “resist layer A”) was formed.

  Subsequently, the crosslinkable resin composition prepared in Example 1 was applied so as to cover the resist layer A, then heated by a hot plate at 85 ° C. for 90 seconds, cooled to room temperature by a cooling plate, and then uncrosslinked by washing with water. The crosslinkable resin composition was removed to obtain a resist pattern in which the resist layer A was covered with the crosslinkable layer. It was 225 nm when the initial line space | interval of the obtained resist pattern was measured using Hitachi, Ltd. CD-SEM "S9200".

Milling is performed for 3 minutes using this resist pattern as a mask, and the resist pattern cross section before and after the milling is observed with a CD-SEM, whereby the resist pattern milling rate (the amount of the resist pattern removed in 3 minutes from the start of milling ( = Amount of change in resist pattern thickness))) was 40 nm. Here, milling and CD-SEM observation were performed under the following conditions.
<Milling>
・ Milling equipment: “IBE-IBD” (trade name) manufactured by Veeco
・ Gas: Ar
・ Gas flow rate: 10 SCCM
・ Pressure: 2 × 10 ⁻⁴ Torr
・ Milling angle: 90 ° (with respect to the substrate surface)
・ Beam current: 300mA
・ Beam voltage: 300V, DC
・ Acceleration voltage: -500V
<CD-SEM>
・ Device: “S9200” (trade name) manufactured by Hitachi, Ltd.
・ Acceleration voltage: 800V
-Beam current: 10 pA
・ Measurement magnification: 200,000 times ・ Image integration count: 64 times ・ Threshold for automatic measurement: 50%

  In addition, when measuring the occurrence of charge-up (charging) in the resist pattern during CD-SEM measurement, no charge-up was observed.

(Example 7)
A resist pattern was formed and evaluated in the same manner as in Example 6, except that the crosslinkable resin composition prepared in Example 3 was used instead of the crosslinkable resin composition prepared in Example 1. .

(Example 8)
Instead of the resist layer A, a patterned resist layer was formed as follows. First, “ARC29” (trade name) manufactured by Nissan Chemical Co., Ltd., which is an antireflection film material, is applied on a Ni substrate so that the thickness after pre-baking is about 80 nm. Was heated at 120 ° C. for 120 seconds and cooled to room temperature with a cooling plate to form an antireflection film. On this antireflection film, “SAIL-X108” (trade name) is a chemically amplified acrylic resin resist containing an acid generating material that generates an acid by heating with a resist for a wavelength of 192 nm (ArF excimer laser). , Manufactured by Shin-Etsu Chemical Co., Ltd.) was applied by spin coating so that the thickness after pre-baking was 250 nm. The coated resist was pre-baked by heating at 100 ° C. for 90 seconds with a hot plate, cooled to room temperature with a cooling plate, and then ARF scanner (“NSR-S306C” (trade name) manufactured by Nikon, NA = 0.75, σ = 0.7) and exposed through a halftone mask. Furthermore, it was heated at 110 ° C. for 90 seconds with a hot plate, cooled to room temperature with a cooling plate, developed with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds, and 100 nm L / S (pattern A resist layer having a pattern with a line spacing of 100 nm (hereinafter, a resist layer formed in the same manner is referred to as “resist layer B”) was formed.

  Subsequently, in place of the crosslinkable resin composition prepared in Example 1, the resist layer B was coated with the crosslinkable layer in the same manner as in Example 6 except that the crosslinkable resin composition prepared in Example 4 was used. A resist pattern was obtained. The initial line interval of the obtained resist pattern was 170 nm. Further, the line interval after the same measurement of the line interval 10 times was 172 nm, and the level almost the same as the initial level was maintained.

  Further, when the milling rate and charge-up of this resist pattern were evaluated in the same manner as in Example 6, the milling rate was 39 μm, and no charge-up was observed.

Example 9
An Al ₂ O ₃ thin film (thickness: 100 nm) is formed on one surface of a 6-inch Si substrate by sputtering, and the Si substrate and the Al ₂ O ₃ thin film (hereinafter referred to as “Al”). of ₂ O ₃ substrate "referred to.) was obtained. Then, this Al ₂ O ₃ substrate was used in place of the Ni substrate, and the crosslinkable resin composition prepared in Example 2 was used in place of the crosslinkable resin composition prepared in Example 1. Similarly, a resist pattern in which the patterned resist layer A was coated with a crosslinked layer was obtained. The line interval of the obtained resist pattern was 230 nm.

  With respect to this resist pattern, the milling rate and the charge-up were evaluated in the same manner as in Example 6. As a result, the milling rate was 37 μm and no charge-up was observed.

(Example 10)
Resist in which resist layer B was coated with a crosslinked layer in the same manner as in Example 8, except that the crosslinkable resin composition prepared in Example 5 was used instead of the crosslinkable resin composition prepared in Example 4. Got a pattern. The initial line interval of the obtained resist pattern was 160 nm.

  With respect to this resist pattern, the milling rate and the charge-up were evaluated in the same manner as in Example 6. As a result, the milling rate was 39 μm and no charge-up was observed. Further, the line interval after the measurement of the line interval 10 times was 162 nm, and the level almost the same as the initial level was maintained.

(Comparative Example 3)
A patterned resist layer A (line spacing of 300 nm) was produced on a Ni substrate in the same manner as in Example 6, and this was used as it was as a resist pattern to evaluate the milling rate and charge-up in the same manner as in Example 6. As a result, the milling rate was 55 μm, and no charge-up was observed.

(Comparative Example 4)
A patterned resist layer A (line spacing 300 nm) was prepared in the same manner as in Comparative Example 1 except that an Al ₂ O ₃ substrate was used instead of the Ni substrate, and this was used as a resist pattern as in Example 6. When the milling rate and charge-up were evaluated in the same manner as described above, the milling rate was 55 μm, and the occurrence of charge-up was observed.

(Comparative Example 5)
A patterned resist layer B (line spacing 200 nm) was produced on a Ni substrate in the same manner as in Example 8, and this was used as a resist pattern as it was to evaluate the milling rate and charge-up in the same manner as in Example 6. As a result, the milling rate was 61 μm, and no charge-up was observed. Further, the line spacing after the measurement of the line spacing 10 times was expanded to 215 nm (initially +15 nm) due to the shrinkage of the resist pattern due to the irradiation of the electron beam for measurement.

(Comparative Example 6)
Resist in which resist layer A was coated with a crosslinked layer in the same manner as in Example 6 except that the crosslinkable resin composition prepared in Comparative Example 1 was used instead of the crosslinkable resin composition prepared in Example 1. Got a pattern. The initial line interval of the obtained resist pattern was 220 nm.

  With respect to this resist pattern, the milling rate and charge-up were evaluated in the same manner as in Example 6. As a result, the milling rate was 54 μm, and no charge-up was observed.

(Comparative Example 7)
Resist in which resist layer B was coated with a crosslinked layer in the same manner as in Example 8, except that the crosslinkable resin composition prepared in Comparative Example 2 was used instead of the crosslinkable resin composition prepared in Example 4. Got a pattern. The initial line interval of the obtained resist pattern was 165 nm.

  With respect to this resist pattern, the milling rate and charge-up were evaluated in the same manner as in Example 6. As a result, the milling rate was 52 μm and no charge-up was observed. Further, the line spacing after the measurement of the line spacing 10 times was expanded to 173 nm (initially +8 nm) due to the shrinkage of the resist pattern due to the irradiation of the electron beam for measurement.

  Table 2 summarizes the evaluation results for each resist pattern. The resist patterns produced in Examples 6 to 10 have a small line interval and are sufficiently miniaturized. The resist patterns of Examples 6 to 10 are, of course, compared with the resist patterns of Comparative Examples 3 to 5 in which no cross-linked layer is formed, and the resists of Comparative Examples 6 and 7 in which a cross-linked layer is formed. Compared to the pattern, the milling rate is clearly small and the etching resistance is excellent. Further, the resist patterns of these examples had good surface smoothness. That is, a resist pattern in which a cross-linked layer is formed using a cross-linkable resin composition containing inorganic particles or a water-insoluble resin can be miniaturized and has excellent etching resistance. It was confirmed that it can be used as a mask pattern for forming a miniaturized thin film pattern.

  The resist patterns of Comparative Examples 5 and 7 were greatly shrunk by electron beam irradiation, whereas the resist patterns of Examples 8 and 9 were hardly shrunk by electron beam irradiation and were resistant to electron beams. It was confirmed that it was excellent.

Furthermore, in the case of a substrate on which an insulating Al ₂ O ₃ thin film was formed, the resist pattern of Comparative Example 4 was charged up, whereas the resist pattern of Example 8 formed on the same substrate was Since no charge-up was observed, it was confirmed that the resist pattern was sufficiently prevented from being charged especially when conductive inorganic particles were used.

It is sectional drawing for demonstrating one Embodiment of the formation method of the resist pattern by this invention. It is sectional drawing for demonstrating one Embodiment of the formation method of the resist pattern by this invention. It is sectional drawing for demonstrating one Embodiment of the formation method of the thin film pattern by this invention. It is sectional drawing for demonstrating one Embodiment of the formation method of the thin film pattern by this invention. It is sectional drawing for demonstrating other embodiment of the formation method of the thin film pattern by this invention. It is sectional drawing for demonstrating other embodiment of the formation method of the thin film pattern by this invention. 1 is an end view showing a thin film magnetic head as an embodiment of a microdevice according to the present invention. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 3 ... Photosensitive resin layer, 4 ... Resist layer, 5 ... Crosslinkable resin composition layer, 6 ... Crosslinked layer, 7 ... Plating layer, 8 ... Resist layer, 10 ... Resist pattern, 20 ... Thin film pattern, DESCRIPTION OF SYMBOLS 11 ... Base | substrate, 12 ... Thin film, 30 ... Recording head part, 31 ... Magnetic pole, 32 ... Magnetic flux emission part, 32a ... Pole part, 32b ... Support part, 33 ... Seed layer, 35 ... Yoke part, 100 ... Thin film magnetic head.

Claims (13)

Forming a patterned resist layer on one surface of the substrate containing an acid generating material that generates acid upon heating or exposure; and
Attaching a crosslinkable resin composition to the resist layer;
A step of crosslinking a portion near the resist layer surface of the crosslinkable resin composition by heating or exposure to form a crosslinked layer covering the resist layer; and
Removing the portion other than the cross-linked layer from the cross-linkable resin composition to obtain a resist pattern comprising the resist layer and the cross-linked layer covering the resist layer;
With
The crosslinkable resin composition is
A water-soluble crosslinkable resin that crosslinks in the presence of an acid;
At least one of inorganic particles and water-insoluble resin;
A solvent for dissolving the crosslinkable resin;
A method for forming a resist pattern, comprising:   The method for forming a resist pattern according to claim 1, wherein the inorganic particles contain a metal or a metal compound.   The method for forming a resist pattern according to claim 1, wherein the inorganic particles are conductive. A patterned resist layer containing an acid generating material that generates acid upon heating or exposure; and
A cured layer coated with the resist layer and crosslinked with a water-soluble crosslinkable resin, and a crosslinked layer containing at least one of inorganic particles and a water-insoluble resin;
A resist pattern having   The resist pattern according to claim 4, wherein the inorganic particles contain a metal or a metal compound.   The resist pattern according to claim 4, wherein the inorganic particles are conductive. A step of forming a resist pattern by the method of forming a resist pattern according to any one of claims 1 to 3 on the thin film of a substrate provided with a thin film on one surface of a substrate;
Removing the portion of the thin film not covered by the resist pattern by etching;
Removing the resist pattern to obtain a thin film pattern;
A method of forming a thin film pattern comprising: A step of forming a resist pattern by the method of forming a resist pattern according to any one of claims 1 to 3 on the thin film of a substrate provided with a thin film on one surface of a substrate;
Removing the resist pattern after forming a plating layer on the thin film in a portion not covered by the resist pattern;
Removing the thin film in a portion not covered with the plating layer by etching to obtain a thin film pattern in which the plating layer is laminated;
A method of forming a thin film pattern comprising:   A method for manufacturing a microdevice, comprising a step of forming a thin film pattern by the method for forming a thin film pattern according to claim 7 or 8.   A microdevice obtained by the method for manufacturing a microdevice according to claim 9. A water-soluble crosslinkable resin that crosslinks in the presence of an acid;
At least one of inorganic particles and water-insoluble resin;
A solvent for dissolving the water-soluble crosslinkable resin;
Containing
A crosslinkable resin composition for adhering to a resist layer containing an acid generating material that generates an acid by heating or exposure.   The crosslinkable resin composition according to claim 11, wherein the inorganic particles contain a metal or a metal compound. The crosslinkable resin composition according to claim 11, wherein the inorganic particles are conductive.

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