JP2011133750A - Member with protective film for forming resist pattern, and method for producing the same, and method for producing resist pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a member for forming a resist pattern with a new protective film formed on the member. <P>SOLUTION: The member with a protective film for forming a resist pattern comprises: a member for forming a resist pattern having a surface containing an oxide and used by adhering to a resist film 2 for forming a resist pattern; and a protective film 4 formed on the member for forming the resist pattern which contains a straight-chain amphiphilic molecule containing a perfluoro polyether in a main chain and a hydroxyl group in a terminal group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resist pattern forming technique.

  In some semiconductor devices or mounting circuit boards, the processing dimensions are shifting from micron order to submicron order, and as a result, the exposure method used for resist pattern formation is contact from the conventional projection method or proximity method. The system and the reduced projection system are shifting.

  Among them, the contact exposure method can realize sub-micron processing at a relatively low cost, but exposure is performed by bringing the photomask and the substrate into close contact with each other. There is a problem.

  If foreign matter adheres to the light transmitting portion (glass, quartz, etc.) of the photomask, light does not reach the resist during contact exposure, resulting in poor resolution. In addition, when foreign matter adheres to the light shielding portion (such as chromium) of the photomask, a gap is generated between the photomask and the resist during contact exposure, and resolution is deteriorated. Therefore, in order to suppress a decrease in yield, photomask cleaning and repair are required for each exposure process.

  Attempts have been made to suppress contamination due to adhesion of resists and foreign substances by coating a photomask with a fluororesin to form a protective film. However, if the protective film is too thick, the protective film itself becomes a gap between the resist and the mask, and resolution is deteriorated.

  In recent years, nanoimprint technology for transferring a pattern by pressing a mold having a concavo-convex pattern against a liquid resist or the like on a substrate has been actively developed in order to realize microfabrication on the order of nanometers relatively easily. Also in this pattern formation technique, when the mold and the substrate after pattern transfer are separated from each other, resist and foreign matters are attached to the mold, and the yield during repeated processing tends to be reduced.

JP 2008-178984 A US Patent No. 6300042

  One object of the present invention is to provide a novel protective film forming technique for a member to be in close contact with a resist material for forming a resist pattern, such as a contact exposure photomask or a nanoimprint mold, or such a protective film is formed. And providing a resist pattern forming technique using such a protective film.

  According to one aspect of the present invention, a resist pattern forming member having a surface containing an oxide and used in close contact with a resist film for forming a resist pattern is formed on the resist pattern forming member. There is provided a resist pattern forming member with a protective film having a chain and a protective film containing an amphiphilic molecule having a main chain containing perfluoropolyether and a terminal group containing a hydroxyl group.

  A protective film containing an amphiphilic molecule that is linear and has a perfluoropolyether and a terminal hydroxyl group is formed on the surface of the resist pattern forming member containing an oxide with good adhesion by hydrogen bonding. The

1A to 1D are cross-sectional views schematically showing a resist pattern forming process by contact exposure. 2A to 2C are cross-sectional views schematically showing a resist pattern forming process by nanoimprint.

  First, first and second embodiments relating to a resist pattern forming technique by contact exposure will be described. 1A to 1D are cross-sectional views schematically showing a resist pattern forming process by contact exposure.

  As shown in FIG. 1A, a resist film 2 is formed on a substrate 1 with a photoresist material. The substrate 1 is a substrate on which a pattern is desired to be formed using a resist pattern formed by the resist film 2, and is, for example, a semiconductor substrate on which a semiconductor element, an insulating film, a wiring, or the like is formed in a previous process as necessary.

  The photomask 3 includes a translucent substrate 3a and a light shielding film 3b. The translucent substrate 3a is made of glass or quartz, for example. On the surface of the translucent substrate 3a facing the resist film 2, the light shielding film 3b is formed of, for example, chromium on the region to be the light shielding portion Pb, and the region where the light shielding film 3b is not formed becomes the light transmitting portion Pa.

  A protective film 4 is formed on the surface of the photomask 3 facing (at least) the resist film 2 so as to cover the light shielding film 3b and the exposed translucent substrate 3a. Details of the materials of the first and second embodiments suitable for forming the protective film 4 will be described later.

  As shown in FIG. 1B, the surface of the photomask 3 on the light-shielding film 3b side is brought into close contact with the resist film 2 through the protective film 4, and the resist film 2 is irradiated with light L from the translucent portion Pa to perform contact exposure. Do. The photosensitive portion of the resist film 2 is 2a, and the non-photosensitive portion is 2b.

  As shown in FIG. 1C, after contact exposure, the photomask 3 is separated from the resist film 2.

  As shown in FIG. 1D, a resist pattern RP1 is formed by development to remove the photosensitive portion 2a and leave the non-photosensitive portion 2b. Although a positive resist material has been exemplified, a negative resist material can also be used.

  The protective film 4 is interposed between the resist 2 and the photomask 3 during contact exposure, thereby preventing the resist material from adhering to the photomask 3. The protective film 4 is required to have characteristics such that resist material is difficult to adhere and resolution is hardly deteriorated. The inventors of the present invention have studied a suitable protective film forming material as described below.

  First, as a first example, first to fourth experiments in which a first material (an amphiphilic molecule and a solvent) is used as a protective film forming material will be described.

In the first example, a fluorine-containing amphiphilic molecule (solveisosodium) having a linear shape and a main chain containing perfluoropolyether and hydroxyl groups at both terminal groups as represented by the following general formula (1): Lexis) was used as a raw material.

  In addition, a fluorine-containing (fluorine-based) solvent (HGALDEN: manufactured by Solvay Solexis) was used as a solvent for dissolving the adjusted amphiphilic molecule.

  The first experiment will be described. In the first experiment, a supercritical extraction device (SCF-201; manufactured by JASCO Corporation) was used from raw material amphiphilic molecules (having a molecular weight distribution suitable for preparing amphiphilic molecules having an average molecular weight of 2000). Then, supercritical extraction with carbon dioxide gas was performed at a temperature of 50 ° C. to 70 ° C. and a pressure of 10 MPa to 30 MPa to prepare amphiphilic molecules having an average molecular weight of 2000. The degree of dispersion (weight average molecular weight / number average molecular weight) determined by gel permeation chromatography (GPC) decreased to 1.40 after supercritical extraction, compared to 1.45 before supercritical extraction.

  The adjusted amphiphilic molecule was dissolved in the solvent at a concentration of 0.5%. Then, this solution was applied on a photomask by dip coating to form a protective film.

  The photomask of the first experiment is such that a line and space pattern is formed on a quartz blank with a chromium light-shielding film. Multiple line and space patterns with line width and line spacing changed by 0.1 μm from line and space pattern with 0.5 μm line width and 0.5 μm between lines to line and space pattern with 2 μm line width and 2 μm between lines Is formed.

  Using the C1s spectrum of X-ray photoelectron spectroscopy (ESCA) and an infrared spectrophotometer (JIR-100; manufactured by JEOL), the thickness of the obtained protective film is measured for the absorption strength of stretching vibration of CF. As a result, the film thickness was 9 nm.

  Further, the surface energy of a photomask having a protective film formed on the surface was determined by a change in contact angle measured using a contact angle meter (CA-QI; manufactured by Kyowa Interface Science). As a result, the surface free energy of the photomask translucent part (quartz part) and the light shielding part (chrome part) before forming the protective film was larger than 50 mN / m, whereas the surface free energy after forming the protective film was 30 mN / m. m or less.

  A commercially available (positive type) novolak resist material (TMMR P-W1000PM; manufactured by Tokyo Ohka Kogyo Co., Ltd.) was spin-coated on a silicon substrate to a thickness of 1 μm, and then baked at 110 ° C. for 90 seconds. A resist film was formed.

  Using a contact aligner (PEM-2000; Union Optics), the photomask and the resist film were brought into close contact, and contact exposure was performed using a low-pressure mercury lamp as an ultraviolet light source. After separation of the photomask, development was performed for 90 seconds using a 2.38% aqueous tetramethylammonium hydroxide (TMAH) solution to form a resist pattern. For comparison, a resist pattern was similarly formed using a photomask without a protective film.

  The critical resolution was measured for a resist pattern formed with a photomask with a protective film and a resist pattern formed with a photomask without a protective film. As a result, the limit resolution was 1.1 μm regardless of the presence or absence of the protective film. Thus, it was found that the protective film formed of the material of the first example can perform contact exposure while suppressing the deterioration of resolution.

  Note that it is considered that if the flatness of the protective film is not good, the resolution is deteriorated. From the viewpoint of ensuring the flatness of the protective film, it is considered preferable that the degree of dispersion of the amphiphilic molecules is 1.4 or less.

  The second experiment will be described. In the second experiment, similarly to the first experiment, a protective film was formed on the photomask using a material in which amphiphilic molecules adjusted to an average molecular weight of 2000 were dissolved in the solvent at a concentration of 0.5%.

  However, the photomask of the second experiment is one in which a line and space pattern having a line width of 1.5 μm and a line spacing of 1.5 μm is formed. Using this photomask, a pattern was exposed on one wafer in one exposure. Repeated exposure was performed to form resist patterns on a plurality of wafers. For the resist pattern of each wafer, the yield of 21 points in the wafer surface was evaluated. For comparison, the same evaluation was performed for a photomask without a protective film.

  When a photomask without a protective film was used, the yield decreased to 71% by the second exposure. On the other hand, when a photomask with a protective film was used, the yield was 90% or more even after 20 exposures.

  A photomask without a protective film is considered to be difficult to form a good pattern when repeatedly exposed due to adhesion of a resist material. On the other hand, it is considered that a photomask with a protective film can form a good pattern even when repeated exposure is performed by suppressing the adhesion of a resist material due to low surface free energy. When the surface free energy of the protective film is 50 mN / m or less, the adhesion of the resist material is preferably suppressed as compared with the case without the protective film.

  A third experiment will be described. In the third experiment, amphiphilic molecules having average molecular weights adjusted to 1000 and 5000, respectively, were prepared.

  An amphiphilic molecule having an average molecular weight of 1000 is obtained from a raw material amphiphilic molecule (having a molecular weight distribution suitable for preparing an amphiphilic molecule having an average molecular weight of 1000) by using a supercritical extraction apparatus and a temperature of 50 ° C. to It was prepared by performing supercritical extraction with carbon dioxide gas at 70 ° C. and pressure of 10 MPa to 30 MPa. The degree of dispersion determined by GPC decreased to 1.40 after supercritical extraction, compared to 1.50 before supercritical extraction.

  An amphiphilic molecule having an average molecular weight of 5000 is obtained from a raw material amphiphilic molecule (having a molecular weight distribution suitable for preparing an amphiphilic molecule having an average molecular weight of 5000) by using a supercritical extraction apparatus and a temperature of 50 ° C. to It was prepared by performing supercritical extraction with carbon dioxide gas at 70 ° C. and pressure of 10 MPa to 30 MPa. The degree of dispersion determined by GPC decreased to 1.35 after supercritical extraction, compared to 1.40 before supercritical extraction.

  As in the first and second experiments, amphiphilic molecules having an average molecular weight of 1000 and 5000 were dissolved in the solvent at a concentration of 0.5% to form a protective film forming material, respectively. In addition to evaluating the resolution, the yield was evaluated in the same manner as in the second experiment.

  When an amphiphilic molecule having an average molecular weight of 1000 was used, the limit resolution was 1.1 μm, and the yield decreased to 86% in the second exposure. When an amphiphilic molecule having an average molecular weight of 5000 was used, the limit resolution was 1.3 μm, and the yield was 90% or more even after 20 exposures.

  The smaller the average molecular weight, the lower the heat resistance and coverage of the protective film, and the lower the coverage, the lower the yield in repeated exposure. In addition, it is considered that the higher the average molecular weight, the lower the flatness of the protective film and the more likely the resist pattern resolution failure occurs.

  The yield is reduced to 86% by the second exposure in the sample having an average molecular weight of 1000, but the effect of the protective film can be seen as compared with the case without the protective film. From this, the lower limit of the preferred average molecular weight may be considered to be 1000. It would be more preferable if the average molecular weight is 1500 or more.

  The limit resolution deteriorates to 1.3 μm (from 1.1 μm without a protective film) in the sample having an average molecular weight of 5000, but this limit resolution deterioration is allowed. From this, a preferable upper limit of the average molecular weight may be considered to be 5000. It would be more preferable if the average molecular weight is 4500 or less.

  A fourth experiment will be described. In the fourth experiment, similarly to the first experiment, a protective film was formed on the photomask with a material in which amphiphilic molecules having an average molecular weight adjusted to 2000 were dissolved in the solvent. However, the concentration dissolved in the solvent was increased to 1% (compared to 0.5% in the first experiment).

  The thickness of the protective film measured by X-ray photoelectron spectroscopy and infrared spectrophotometer was 10 nm, which was thicker than 9 nm in the first experiment. Further, when the resolution was evaluated in the same manner as in the first experiment, the limit resolution was 1.2 μm, which was slightly deteriorated compared to 1.1 μm in the first experiment.

  It is considered that the higher the concentration of the amphiphilic molecule, the thicker the protective film, and the resolution is likely to deteriorate due to the wide gap between the photomask and the resist film. From this viewpoint, the upper limit of the amphiphilic molecule concentration is estimated to be 1%, and the upper limit of the thickness of the protective film is estimated to be 10 nm.

  If the concentration of amphiphilic molecules is too low, it is difficult to form a uniform protective film. From this viewpoint, the lower limit of the concentration of the amphiphilic molecule seems to be about 0.01%, and the lower limit of the thickness of the protective film seems to be about 0.5 nm.

  As described with reference to the first to fourth experiments, by using the protective film formed of the material of the first embodiment, the resist material adhesion to the photomask is suppressed while suppressing the resolution degradation. Thus, a resist pattern can be formed by contact exposure.

  Next, as a second example, fifth and sixth experiments in which a second material (amphiphilic molecules and a solvent) is employed as a protective film forming material will be described.

In the second example, a fluorine-containing amphipathic molecule (solveisosodium) having a linear shape and a main chain containing perfluoropolyether and hydroxyl groups at both terminal groups, as represented by the following general formula (2): Lexis) was used as a raw material. The difference from the first example is that two types of end groups of the amphiphilic molecule are mixed, and one type of end group is the same type as the first example and contains one hydroxyl group. Another type of terminal group contains two hydroxyl groups.

  As a solvent for dissolving the adjusted amphiphilic molecule, a fluorine-based solvent (FC-77: manufactured by Solvay Solexis) different from the first example was used.

  The fifth experiment will be described. In the fifth experiment, a supercritical extraction device (SCF-201; manufactured by JASCO) was used from the amphiphilic molecules of the raw material (having a molecular weight distribution suitable for preparing an amphiphilic molecule having an average molecular weight of 2500). Then, supercritical extraction with carbon dioxide gas was performed at a temperature of 50 ° C. to 70 ° C. and a pressure of 10 MPa to 30 MPa to prepare amphiphilic molecules having an average molecular weight of 2500. The degree of dispersion determined by GPC decreased to 1.2 after supercritical extraction, compared to 1.3 before supercritical extraction.

  The adjusted amphiphilic molecule was dissolved in the solvent at a concentration of 0.3%. Then, this solution was applied on a photomask by dip coating to form a protective film. The photomask of the fifth experiment is the same as that of the first experiment, in which a plurality of line and space patterns having a line width and a line spacing of 0.5 μm to a line width and a line spacing of 2 μm are formed.

  When the thickness of the protective film was determined by X-ray photoelectron spectroscopy and infrared spectrophotometer, the film thickness was 6 nm.

  Moreover, when the surface energy of the photomask having the protective film formed thereon was measured using a contact angle meter, the surface free energy of the photomask light transmitting part (quartz part) and the light shielding part (chrome part) before the protective film was formed was measured. While it was larger than 50 mN / m, the surface free energy after the formation of the protective film decreased to 35 mN / m or less.

  A silicon substrate on which a resist film was formed was prepared, contact exposure was performed, and development was performed to form a resist pattern. The resist film formation method, contact exposure method, and development method are the same as in the first experiment. For comparison, a resist pattern was similarly formed using a photomask without a protective film.

  The critical resolution was measured for a resist pattern formed with a photomask with a protective film and a resist pattern formed with a photomask without a protective film. As a result, the limit resolution was 1.1 μm regardless of the presence or absence of the protective film.

  A sixth experiment will be described. In the sixth experiment, similarly to the fifth experiment, a protective film was formed on the photomask using the protective film forming material of the second example.

  The photomask of the sixth experiment is the same as the second experiment, in which a line and space pattern having a line width and a line spacing of 1.5 μm is formed. Similar to the second experiment, repeated exposure was performed to form resist patterns on a plurality of wafers, and the yield of 21 points in the wafer plane was evaluated for the resist patterns of each wafer. For comparison, the same evaluation was performed for a photomask without a protective film.

  When a photomask without a protective film was used, the yield decreased to 71% by the second exposure. On the other hand, when a photomask with a protective film was used, the yield was 90% or more even after 20 exposures.

  As described with reference to the fifth and sixth experiments, even when the protective film formed of the material of the second embodiment is used, the resist material adhesion to the photomask is suppressed while suppressing the deterioration of resolution. Thus, a resist pattern can be formed by contact exposure.

  As shown in the above formulas (1) and (2), the fluorine-containing amphiphilic molecules of the first and second examples are linear and the main chain contains a perfluoropolyether, and both end groups have Contains a hydroxyl group.

  The light transmitting portion of the photomask is formed of quartz or glass and includes silicon oxide on the surface, and the light shielding portion is formed of chromium and includes chromium oxide formed by natural oxidation on the surface. Since the amphiphilic molecule of the example has a polar hydroxyl group arranged at the terminal, it can hydrogen bond to the oxide surface (oxygen) of both the light transmitting part and the light shielding part of the photomask. It is considered that a high protective film is formed. On the other hand, the portion of the nonpolar perfluoropolyether in the main chain is exposed to the resist film side, so that the surface free energy is lowered and the adhesion of the resist material to the protective film is suppressed.

  Next, a description will be given of a third embodiment according to a resist pattern formation technique by nanoimprint. 2A to 2C are cross-sectional views schematically showing a resist pattern forming process by nanoimprint.

  As shown in FIG. 2A, a resist film 12 is formed on a substrate 11 with a liquid resist material for nanoimprinting. The substrate 11 is a substrate on which a pattern is to be formed by a resist pattern formed using the resist film 12, and is, for example, a semiconductor substrate on which a semiconductor element, an insulating film, a wiring, or the like is formed in a previous process as necessary.

  A mold corresponding to a desired resist pattern is formed on the surface of the mold 13 on the side facing the resist film 12. The mold 13 is made of, for example, quartz.

  A protective film 14 is formed on the surface of the mold 13 facing (at least) the resist film 12 so as to cover the mold. Details of the material of the third embodiment suitable for forming the protective film 14 will be described later.

  As shown in FIG. 2B, the mold 13 is pressed and brought into close contact with the resist film 12 through the protective film 14, and unnecessary resist material is pushed out of the mold to transfer the mold shape to the resist film 12. Then, the resist film 12 is cooled and cured to form a resist pattern RP11.

  As shown in FIG. 2C, when the resist pattern RP11 is sufficiently cured, the mold 13 is pulled away.

  The protective film 14 is interposed between the resist 12 and the mold 13 during pressing, thereby preventing the resist material from adhering to the mold 13. The contact exposure photomask protective film forming material described in the first embodiment can also be used as a nanoimprint mold protective film forming material as described below.

  A seventh experiment according to the third embodiment will be described. In the seventh experiment, as in the first experiment of the first example, an amphiphilic molecule represented by the above formula (1) (manufactured by Solvay Solexis) was adjusted to an average molecular weight of 2000, It was dissolved at a concentration of 0.5% in a system solvent (HGALDEN: manufactured by Solvay Solexis).

  And this solution was apply | coated by the dip coating on the mold, and the protective film was formed. The mold of the seventh experiment is such that a line-and-space pattern having a groove width of 50 nm and a groove space of 50 nm is formed on a quartz substrate.

  When the thickness of the protective film was determined by X-ray photoelectron spectroscopy and infrared spectrophotometer, the film thickness was 9 nm. In addition, when the surface energy of the mold with the protective film was measured using a contact angle meter, the surface free energy before the protective film was formed was larger than 50 mN / m, whereas the surface free energy after the protective film was formed. Decreased to 25 mN / m or less.

  A resist material (OEBR-1000; manufactured by Tokyo Ohka Kogyo Co., Ltd.) containing commercially available polymethyl methacrylate (PMMA) was spin-coated on a silicon substrate, and then baked at 110 ° C. to form a liquid resist film.

  Then, the mold was pressed onto the resist film, the resist film was cooled and cured, and the mold was separated to form a resist pattern. For comparison, a resist pattern was similarly formed using a mold without a protective film.

  A resist pattern was formed on a plurality of wafers by repeatedly pressing, and the yield of 21 points in the wafer surface was evaluated for the resist pattern of each wafer. For comparison, the same evaluation was performed for a mold without a protective film.

  When a mold without a protective film was used, the yield decreased to 48% by the second press. On the other hand, when a mold with a protective film was used, the yield was 90% or more even when the press was repeated five times. It is considered that the mold with the protective film can suppress the adhesion of the resist material due to the low surface free energy and can form a good pattern even after repeated pressing.

  Thus, the protective film forming material of the first embodiment is not limited to the contact exposure photomask protective film, but can also be used to form a nanoimprinting mold protective film. The mold is made of, for example, quartz and contains silicon oxide on the surface. The amphiphilic molecule of the first embodiment has high adhesion because the terminal hydroxyl group is hydrogen-bonded to the oxide surface (oxygen) of the mold. It is thought that a protective film is formed. The protective film forming material of the second embodiment can be used in the same way for forming a mold protective film for nanoimprinting.

  The contact exposure photomask and the nanoimprint mold can be collectively regarded as a resist pattern forming member used in close contact with the resist film for forming a resist pattern. The protective film of the above embodiment is suitable as a protective film for such a resist pattern forming member.

  In addition, the solvent for forming the protective film forming material dissolves amphiphilic molecules having a straight chain, a main chain containing perfluoropolyether and a hydroxyl group in the terminal group, and does not react with the resist pattern forming member to be applied. Although it will not be limited if it is a material, the solvent containing a fluorine is especially preferable. Moreover, an additive and a surfactant can be added to the protective film forming material as necessary.

  Note that the method for applying the protective film forming material to the resist pattern forming member is not particularly limited, and methods such as dip coating, spin coating, spray coating, and vapor coating can be used. From the viewpoint, dip coating is particularly preferable. Convenience can be improved by combining the coating device for the protective film forming material with an exposure device, a developing device, a mask cleaning device, or the like.

  Although the present invention has been described with reference to the embodiments, the present invention is not limited thereto. It will be apparent to those skilled in the art that various modifications, improvements, combinations, and the like can be made.

The following additional notes are further disclosed regarding the embodiment including the first to third examples described above.
(Appendix 1)
A resist pattern forming member having a surface containing an oxide and used in close contact with the resist film for forming a resist pattern;
A resist pattern forming member with a protective film, which is formed on the resist pattern forming member, and has a protective film that is linear and has a main chain containing perfluoropolyether and an amphiphilic molecule containing a hydroxyl group at a terminal group.
(Appendix 2)
The member for forming a resist pattern with a protective film according to supplementary note 1, wherein the thickness of the protective film is 10 nm or less.
(Appendix 3)
The resist pattern forming member is a contact exposure photomask having a light-transmitting portion containing silicon oxide on the surface and a light-shielding portion containing chromium oxide on the surface, and the protective film is on the light-transmitting portion The member for forming a resist pattern with a protective film according to Supplementary Note 1 or 2, which is formed on the light shielding portion.
(Appendix 4)
The resist pattern forming member according to appendix 1 or 2, wherein the resist pattern forming member is a nanoimprint mold including silicon oxide on a surface thereof.
(Appendix 5)
Preparing a solution of an amphiphilic molecule which is linear and has a main chain containing perfluoropolyether and a terminal group containing a hydroxyl group;
Applying the solution onto a resist pattern forming member having a surface containing an oxide and used in close contact with a resist material for forming a resist pattern. .
(Appendix 6)
The resist film-coated resist according to appendix 5, wherein the step of preparing the solution containing the amphiphilic molecule prepares a solution of the amphiphilic molecule having a dispersity of 1.4 or less and an average molecular weight of 1000 or more and 5000 or less. A method for producing a pattern forming member.
(Appendix 7)
The method for preparing a resist pattern-forming member with a protective film according to appendix 5 or 6, wherein the step of preparing the solution containing the amphiphilic molecule prepares a solution in which the amphiphilic molecule is dissolved at a concentration of 1% or less. .
(Appendix 8)
A resist pattern forming member that has an oxide-containing surface and is used in close contact with a resist material for forming a resist pattern, and is formed on the resist pattern forming member. Preparing a resist pattern forming member with a protective film having a protective film containing an amphiphilic molecule containing a polyether and containing a hydroxyl group at a terminal group;
Preparing a substrate on which a resist film is formed;
A method for producing a resist pattern, comprising: adhering the member for forming a resist pattern with a protective film to the resist film.
(Appendix 9)
The resist pattern forming member is a contact exposure photomask,
further,
Exposing the resist film in a state where the contact exposure photomask with a protective film is in close contact with the resist film;
The method for producing a resist pattern according to appendix 8, further comprising a step of separating the photomask for contact exposure with a protective film from the resist film and developing the resist film.
(Appendix 10)
The resist pattern forming member is a nanoimprint mold,
further,
Curing the resist film in a state where the mold for imprint with a protective film is in close contact with the resist film;
The method for producing a resist pattern according to appendix 8, further comprising a step of separating the nanoimprint mold with a protective film from the resist film.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Resist film 3 Photomask 3a Translucent substrate 3b Light-shielding film Pa Light-transmitting part Pb Light-shielding part 4 Protective film L Light RP1 Resist pattern 11 Substrate 12 Resist film 13 Mold 14 Protective film RP11 Resist pattern

Claims (5)

A resist pattern forming member having a surface containing an oxide and used in close contact with the resist film for forming a resist pattern;
A resist pattern forming member with a protective film, which is formed on the resist pattern forming member, and has a protective film that is linear and has a main chain containing perfluoropolyether and an amphiphilic molecule containing a hydroxyl group at a terminal group.   The resist pattern forming member is a contact exposure photomask having a light-transmitting portion containing silicon oxide on the surface and a light-shielding portion containing chromium oxide on the surface, and the protective film is on the light-transmitting portion The member for forming a resist pattern with a protective film according to claim 1, which is formed on the light shielding portion. Preparing a solution of an amphiphilic molecule which is linear and has a main chain containing perfluoropolyether and a terminal group containing a hydroxyl group;
Applying the solution onto a resist pattern forming member having a surface containing an oxide and used in close contact with a resist material for forming a resist pattern. .   The step of preparing the solution containing the amphiphilic molecule prepares a solution of the amphiphilic molecule having a dispersity of 1.4 or less and an average molecular weight of 1000 or more and 5000 or less. A method for producing a resist pattern forming member. A resist pattern forming member that has an oxide-containing surface and is used in close contact with a resist material for forming a resist pattern, and is formed on the resist pattern forming member. Preparing a resist pattern forming member with a protective film having a protective film containing an amphiphilic molecule containing a polyether and containing a hydroxyl group at a terminal group;
Preparing a substrate on which a resist film is formed;
A method for producing a resist pattern, comprising: adhering the member for forming a resist pattern with a protective film to the resist film.

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